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2025 Volume 36 Issue 9
2025, 36(9): 110303
doi: 10.1016/j.cclet.2024.110303
Abstract:
An Fe-doped bimetallic ZnFe–MOF precursor was prepared using a microchannel reactor, and carbonization was conducted to synthesize a bimetallic catalyst (ZnFe–NC). The fundamental reason for the efficient activity of the catalyst was determined through an in-depth analysis of its structural composition and close correlation with the oxygen reduction reaction (ORR). The ZnFe–NC catalyst maintains a stable truncated rhombohedral morphology and a rich microporous structure, exhibiting excellent ORR activity and long-term stability. The experimental results show that compared with the reversible hydrogen electrode, it has a high half-wave potential of 0.902 V (E1/2), retains 94% of activity after 35,000 s of stability testing, and exhibits significant methanol tolerance in alkaline media. Density functional theory calculations confirm the synergistic effect between the Zn and Fe sites. Furthermore, the results indicate that the interaction between ZnFe–N6 coordination structures reduces the reaction energy barrier, thus enhancing intermediate adsorption during the ORR.
An Fe-doped bimetallic ZnFe–MOF precursor was prepared using a microchannel reactor, and carbonization was conducted to synthesize a bimetallic catalyst (ZnFe–NC). The fundamental reason for the efficient activity of the catalyst was determined through an in-depth analysis of its structural composition and close correlation with the oxygen reduction reaction (ORR). The ZnFe–NC catalyst maintains a stable truncated rhombohedral morphology and a rich microporous structure, exhibiting excellent ORR activity and long-term stability. The experimental results show that compared with the reversible hydrogen electrode, it has a high half-wave potential of 0.902 V (E1/2), retains 94% of activity after 35,000 s of stability testing, and exhibits significant methanol tolerance in alkaline media. Density functional theory calculations confirm the synergistic effect between the Zn and Fe sites. Furthermore, the results indicate that the interaction between ZnFe–N6 coordination structures reduces the reaction energy barrier, thus enhancing intermediate adsorption during the ORR.
2025, 36(9): 110304
doi: 10.1016/j.cclet.2024.110304
Abstract:
Due to the ionic feature of the lanthanide ions, to straightly bridge two lanthanide (Ln) ions is rather challenging though this bridging mode is much beneficial to suppress the zero-field quantum tunneling of the magnetization (QTM) for single-molecule magnets (SMMs), a kind of nanosized magnetic materials for high-density information storage and magnetic resonance imaging contrast agent. Here we used an unusual terminal amino pyridine ligand which utilizes extensive supramolecular interactions to stabilize such an unusual linear bridging mode and obtained a series of such dimeric Ln(Ⅲ) complexes - {[LnLA(4-NH2py)5]2(µ-Cl)}[BPh4]3 (For LA- = 1-AdO-, 1Ln; for LA- = tBuO-, 2Ln; Ln = Dy, Gd). More uniquely, the bridging chloride sits in the center of two improper rotation symmetry related Ln(Ⅲ) ions with local C5v symmetry. The dimeric compounds 1Dy and 2Dy exhibit much slower low-temperature magnetic relaxation and thousands of times longer relaxation times at 2 K (τ2K = 2706.89 and 1437.05 s for 1Dy and 2Dy) compared to the diluted ones with the approaching magnetic property of the C5v motifs (τ2K = 0.77 and 1.29 s for 1Dy@1Y and 2Dy@2Y). Though magnetic interactions mediated via the chloride bridge in both 1Dy and 2Dy are weak and antiferromagnetic, it is still very effective due to such a linear geometry to reduce the QTM effect in SMMs.
Due to the ionic feature of the lanthanide ions, to straightly bridge two lanthanide (Ln) ions is rather challenging though this bridging mode is much beneficial to suppress the zero-field quantum tunneling of the magnetization (QTM) for single-molecule magnets (SMMs), a kind of nanosized magnetic materials for high-density information storage and magnetic resonance imaging contrast agent. Here we used an unusual terminal amino pyridine ligand which utilizes extensive supramolecular interactions to stabilize such an unusual linear bridging mode and obtained a series of such dimeric Ln(Ⅲ) complexes - {[LnLA(4-NH2py)5]2(µ-Cl)}[BPh4]3 (For LA- = 1-AdO-, 1Ln; for LA- = tBuO-, 2Ln; Ln = Dy, Gd). More uniquely, the bridging chloride sits in the center of two improper rotation symmetry related Ln(Ⅲ) ions with local C5v symmetry. The dimeric compounds 1Dy and 2Dy exhibit much slower low-temperature magnetic relaxation and thousands of times longer relaxation times at 2 K (τ2K = 2706.89 and 1437.05 s for 1Dy and 2Dy) compared to the diluted ones with the approaching magnetic property of the C5v motifs (τ2K = 0.77 and 1.29 s for 1Dy@1Y and 2Dy@2Y). Though magnetic interactions mediated via the chloride bridge in both 1Dy and 2Dy are weak and antiferromagnetic, it is still very effective due to such a linear geometry to reduce the QTM effect in SMMs.
2025, 36(9): 110305
doi: 10.1016/j.cclet.2024.110305
Abstract:
Lithium-ion capacitors (LICs) hold promise as next-generation energy storage devices due to the synergy of the advantageous features of lithium-ion batteries (LIBs) and supercapacitors (SCs). Recently, the use of nanostructured conjugated carboxylate organic anode materials in LICs has attracted tremendous attention due to their high capacity, excellent capacitive behavior, design flexibility, and environmental friendliness. Nevertheless, no studies have reported the use of non-conjugated organic compounds in LICs. In this study, we report for the first time that non-conjugated adipamide (ADIPAM) nanocrystals fabricated using a dissolution-recrystallization self-assembly technique serve as an excellent anode material for LICs. The unique ADIPAM nanocrystals–PVDF–Super P conductive integrated network architecture accelerates Li+ ion and electron diffusion and enhances lithium storage capability. Consequently, ADIPAM electrodes exhibit a high capacity of 705.8 mAh/g, exceptional cycling stability (308 mAh/g after 2100 cycles at 5 A/g), and remarkable rate capability. Furthermore, a LIC full cell comprising the ADIPAM anode with a porous activated carbon cathode demonstrates a wide working window (4.5 V), high energy density (238.3 Wh/kg), and superb power density (22,500 W/kg). We believe this work may introduce a new approach to the design of non-conjugated organic materials for LICs.
Lithium-ion capacitors (LICs) hold promise as next-generation energy storage devices due to the synergy of the advantageous features of lithium-ion batteries (LIBs) and supercapacitors (SCs). Recently, the use of nanostructured conjugated carboxylate organic anode materials in LICs has attracted tremendous attention due to their high capacity, excellent capacitive behavior, design flexibility, and environmental friendliness. Nevertheless, no studies have reported the use of non-conjugated organic compounds in LICs. In this study, we report for the first time that non-conjugated adipamide (ADIPAM) nanocrystals fabricated using a dissolution-recrystallization self-assembly technique serve as an excellent anode material for LICs. The unique ADIPAM nanocrystals–PVDF–Super P conductive integrated network architecture accelerates Li+ ion and electron diffusion and enhances lithium storage capability. Consequently, ADIPAM electrodes exhibit a high capacity of 705.8 mAh/g, exceptional cycling stability (308 mAh/g after 2100 cycles at 5 A/g), and remarkable rate capability. Furthermore, a LIC full cell comprising the ADIPAM anode with a porous activated carbon cathode demonstrates a wide working window (4.5 V), high energy density (238.3 Wh/kg), and superb power density (22,500 W/kg). We believe this work may introduce a new approach to the design of non-conjugated organic materials for LICs.
2025, 36(9): 110307
doi: 10.1016/j.cclet.2024.110307
Abstract:
Nickel-rich layered oxide cathode materials such as LiNi0.8Co0.1Mn0.1O2 (NCM811) undergo deleterious side reactions when coupled with sulfide solid-state electrolytes (SSEs). To address this issue, we propose a dual-functional Ti3(PO4)4 coating for NCM811 cathode to achieve a highly stable interface between NCM811 and sulfide SSEs. The electrochemically stabilized Ti3(PO4)4 coating prevents direct contact between the SSEs and NCM811, thereby inhibiting interfacial side reactions. In addition, the internal structure of NCM811 can be stabilized by Ti doping, which inhibits the oxygen release behavior of NCM811 at high charge state, preventing further electrochemical oxidation of the SSEs. The modified NCM811@TiP cathode exhibits excellent long cycle stability, with 74.4% capacity retention after 100 cycles at a cut-off voltage of 4.2 V. This work provides a new insight for cathode modification based on nickel-rich layered oxides and sulfide-based all-solid-state lithium batteries.
Nickel-rich layered oxide cathode materials such as LiNi0.8Co0.1Mn0.1O2 (NCM811) undergo deleterious side reactions when coupled with sulfide solid-state electrolytes (SSEs). To address this issue, we propose a dual-functional Ti3(PO4)4 coating for NCM811 cathode to achieve a highly stable interface between NCM811 and sulfide SSEs. The electrochemically stabilized Ti3(PO4)4 coating prevents direct contact between the SSEs and NCM811, thereby inhibiting interfacial side reactions. In addition, the internal structure of NCM811 can be stabilized by Ti doping, which inhibits the oxygen release behavior of NCM811 at high charge state, preventing further electrochemical oxidation of the SSEs. The modified NCM811@TiP cathode exhibits excellent long cycle stability, with 74.4% capacity retention after 100 cycles at a cut-off voltage of 4.2 V. This work provides a new insight for cathode modification based on nickel-rich layered oxides and sulfide-based all-solid-state lithium batteries.
2025, 36(9): 110326
doi: 10.1016/j.cclet.2024.110326
Abstract:
Non-covalent interactions-driven host-guest assembly based on metallo-tweezers has been used to construct varied optical functional materials with attractive structures and properties. We reported here two pairs of chiral gold(Ⅰ)-based metallo-tweezers as hosts to clip AgⅠ or CuⅠ cations for circularly polarized phosphorescence (CPP), driven by the integration of two-fold coordination and heterometallophilic interactions. The AuⅠ-based hosts and metal ions-guests formed sandwich structures in 1:1 ratio with high binding affinity. The achieved tweezer/cation adducts exhibited red-shifted absorption bands and circular dichroism signals, which were attributed to the newly formed ligand to metal-metal charge transfer process. Remarkably, the host-guest supramolecular adducts showed turn-on phosphorescence and CPP, which benefited from rigidifying effect of multiple intermolecular interactions and shorter excited-state lifetime. Overall, our findings bring new insights into the feasibility to achieve and modulate CPP performance by fabricating metallo-tweezer-based host-guest complexes.
Non-covalent interactions-driven host-guest assembly based on metallo-tweezers has been used to construct varied optical functional materials with attractive structures and properties. We reported here two pairs of chiral gold(Ⅰ)-based metallo-tweezers as hosts to clip AgⅠ or CuⅠ cations for circularly polarized phosphorescence (CPP), driven by the integration of two-fold coordination and heterometallophilic interactions. The AuⅠ-based hosts and metal ions-guests formed sandwich structures in 1:1 ratio with high binding affinity. The achieved tweezer/cation adducts exhibited red-shifted absorption bands and circular dichroism signals, which were attributed to the newly formed ligand to metal-metal charge transfer process. Remarkably, the host-guest supramolecular adducts showed turn-on phosphorescence and CPP, which benefited from rigidifying effect of multiple intermolecular interactions and shorter excited-state lifetime. Overall, our findings bring new insights into the feasibility to achieve and modulate CPP performance by fabricating metallo-tweezer-based host-guest complexes.
2025, 36(9): 110327
doi: 10.1016/j.cclet.2024.110327
Abstract:
Here, we present a regulation strategy involving heteroatom doping and structural construction to adjust zincophilic sites and electric field distribution, achieving a robust and dendrite-free Zn host anode. Theoretical calculations and experimental results confirm that sulfur atoms can provide moderate zincophilicity, while graphene-like nanosheets can even the electric field distribution, imparting the sulfur-doped graphene-like network (S-GP) with a longer lifespan (exceeding 500 h) and acceptable coulombic efficiency. Importantly, the S-GP host is used as the substrate for flexible Zn-ion batteries, exhibiting impressive electrochemical performance and great mechanical flexibility, indicating a broad application prospect in portable and wearable electronic devices.
Here, we present a regulation strategy involving heteroatom doping and structural construction to adjust zincophilic sites and electric field distribution, achieving a robust and dendrite-free Zn host anode. Theoretical calculations and experimental results confirm that sulfur atoms can provide moderate zincophilicity, while graphene-like nanosheets can even the electric field distribution, imparting the sulfur-doped graphene-like network (S-GP) with a longer lifespan (exceeding 500 h) and acceptable coulombic efficiency. Importantly, the S-GP host is used as the substrate for flexible Zn-ion batteries, exhibiting impressive electrochemical performance and great mechanical flexibility, indicating a broad application prospect in portable and wearable electronic devices.
2025, 36(9): 110328
doi: 10.1016/j.cclet.2024.110328
Abstract:
The NASICON-structured Na3MnTi(PO4)3 (NMTP) cathode has attracted widespread attention due to its prominent thermal stability, stable 3D structure and rapid sodium ion transport channel. However, the poor cycling stability, limited electronic conductivity and phase transition represent significant obstacles to for its commercialization. Herein, an innovative mixed-conducting interphase, comprising amorphous carbon and Ti3C2-MXene, was developed for NMTP. NMTP particles are evenly dispersed on the MXene sheets through electrostatic adsorption, and MXenes can also regulate the growth of NMTP crystals and provide a large number of active sites in contact with the electrolyte. Furthermore, DFT calculations demonstrate that MXene enhances both electron and ion transport processes. Therefore, the mixed-conducting interphase, forming an interconnected network on the NMTP surface, serves as an artificial cathode electrolyte interface, significantly enhancing the dynamic processes and cycle stability of the NMTP cathode. The NMTP/C@Ti3C2 exhibits a fully reversible three-electron redox reaction and inhibited voltage hysteresis. An excellent reversible capacity of 158.2 mAh/g is achieved at 0.2 C, corresponding to an extremely high energy density of 466.6 Wh/kg. This study presents an effective approach for developing high-energy SIB cathodes.
The NASICON-structured Na3MnTi(PO4)3 (NMTP) cathode has attracted widespread attention due to its prominent thermal stability, stable 3D structure and rapid sodium ion transport channel. However, the poor cycling stability, limited electronic conductivity and phase transition represent significant obstacles to for its commercialization. Herein, an innovative mixed-conducting interphase, comprising amorphous carbon and Ti3C2-MXene, was developed for NMTP. NMTP particles are evenly dispersed on the MXene sheets through electrostatic adsorption, and MXenes can also regulate the growth of NMTP crystals and provide a large number of active sites in contact with the electrolyte. Furthermore, DFT calculations demonstrate that MXene enhances both electron and ion transport processes. Therefore, the mixed-conducting interphase, forming an interconnected network on the NMTP surface, serves as an artificial cathode electrolyte interface, significantly enhancing the dynamic processes and cycle stability of the NMTP cathode. The NMTP/C@Ti3C2 exhibits a fully reversible three-electron redox reaction and inhibited voltage hysteresis. An excellent reversible capacity of 158.2 mAh/g is achieved at 0.2 C, corresponding to an extremely high energy density of 466.6 Wh/kg. This study presents an effective approach for developing high-energy SIB cathodes.
2025, 36(9): 110329
doi: 10.1016/j.cclet.2024.110329
Abstract:
The synthesis of Ta-substituted polyoxometalates has always been an attractive but challenging goal. Three novel tantalum-containing 12-tungsto-2-phosphates were successfully prepared using the water bath method. The monomer, K11Li[P2W12(TaO2)6O56]·19H2O (1), is composed of {P2W12} and 6 {Ta(O2)} building blocks, similar to [P2W12(NbO2)6O56]12−. Monomer 1 polymerized to form two cis-trans dimers, K13Li6H-cis-[P2W12Ta4(TaO2)2O59]2·61H2O (2) and KNa3Li4H12-trans-[P2W12Ta4(TaO2)2O59]2·37H2O (3). Compounds 1–3 can serve as a structural motif to manufacture additional fascinating molecular clusters, promoting the advancement of POM chemistry. In contrast to [P2W12(NbO2)6O56]12−, compound 1 exhibits exceptional stability, evidenced by ESI-MS, IR, and NMR spectroscopy. In addition, 2 and 3 exhibit high proton conductivity and superior water adsorption properties.
The synthesis of Ta-substituted polyoxometalates has always been an attractive but challenging goal. Three novel tantalum-containing 12-tungsto-2-phosphates were successfully prepared using the water bath method. The monomer, K11Li[P2W12(TaO2)6O56]·19H2O (1), is composed of {P2W12} and 6 {Ta(O2)} building blocks, similar to [P2W12(NbO2)6O56]12−. Monomer 1 polymerized to form two cis-trans dimers, K13Li6H-cis-[P2W12Ta4(TaO2)2O59]2·61H2O (2) and KNa3Li4H12-trans-[P2W12Ta4(TaO2)2O59]2·37H2O (3). Compounds 1–3 can serve as a structural motif to manufacture additional fascinating molecular clusters, promoting the advancement of POM chemistry. In contrast to [P2W12(NbO2)6O56]12−, compound 1 exhibits exceptional stability, evidenced by ESI-MS, IR, and NMR spectroscopy. In addition, 2 and 3 exhibit high proton conductivity and superior water adsorption properties.
2025, 36(9): 110330
doi: 10.1016/j.cclet.2024.110330
Abstract:
Dimensionality has great influence on the photo/electro-catalysts properties of covalent organic frameworks (COFs) because of the different electronic and porous structures. However, very rare attention has been paid on the dimensionality and function correlations of COF materials. In the present work, one new two-dimensional phthalocyanine COF, namely 2D-NiPc-COF, and one new three-dimensional phthalocyanine COF, namely 3D-NiPc-COF, were fabricated according to the imide reaction between tetraanhydrides of 2, 3, 9, 10, 16, 17, 23, 24-octacarboxyphthalocyaninato nickel(Ⅱ) with [2, 2-bipyridine]-5, 5-diamine and tetrakis(4-aminophenyl) methane, respectively. The crystalline structures of both COFs are verified by the powder X-ray diffraction analysis, computational simulation, and high resolution transmission electron microscopy measurement. Notably, 3D-NiPc-COF with dispersed conjugated modules has high utilization efficiency of NiPc electroactive sites of 26.8%, almost two times higher than the in-plane stacking 2D-NiPc-COF measured by electrochemical measurement, in turn resulting in its superior electrocatalytic performance with high CO2-to-CO Faradaic efficiency over 90% in a wide potential window, a large partial CO current density of −13.97 mA/cm2 at −0.9 V (vs. reversible hydrogen electrode) to 2D-NiPc-COF. Moreover, 3D-NiPc-COF has higher turnover number and turnover frequency of 5741.6 and 0.18 s-1 at −0.8 V during 8 h lasting measurement. The present work provides an example for the investigation on the correlation between dimensionality and electrochemical properties of 2D and 3D phthalocyanine COFs.
Dimensionality has great influence on the photo/electro-catalysts properties of covalent organic frameworks (COFs) because of the different electronic and porous structures. However, very rare attention has been paid on the dimensionality and function correlations of COF materials. In the present work, one new two-dimensional phthalocyanine COF, namely 2D-NiPc-COF, and one new three-dimensional phthalocyanine COF, namely 3D-NiPc-COF, were fabricated according to the imide reaction between tetraanhydrides of 2, 3, 9, 10, 16, 17, 23, 24-octacarboxyphthalocyaninato nickel(Ⅱ) with [2, 2-bipyridine]-5, 5-diamine and tetrakis(4-aminophenyl) methane, respectively. The crystalline structures of both COFs are verified by the powder X-ray diffraction analysis, computational simulation, and high resolution transmission electron microscopy measurement. Notably, 3D-NiPc-COF with dispersed conjugated modules has high utilization efficiency of NiPc electroactive sites of 26.8%, almost two times higher than the in-plane stacking 2D-NiPc-COF measured by electrochemical measurement, in turn resulting in its superior electrocatalytic performance with high CO2-to-CO Faradaic efficiency over 90% in a wide potential window, a large partial CO current density of −13.97 mA/cm2 at −0.9 V (vs. reversible hydrogen electrode) to 2D-NiPc-COF. Moreover, 3D-NiPc-COF has higher turnover number and turnover frequency of 5741.6 and 0.18 s-1 at −0.8 V during 8 h lasting measurement. The present work provides an example for the investigation on the correlation between dimensionality and electrochemical properties of 2D and 3D phthalocyanine COFs.
2025, 36(9): 110345
doi: 10.1016/j.cclet.2024.110345
Abstract:
Conventional polycrystalline LiMn2O4 (PC-LMO) suffers from poor Li+ diffusion rates and structural instability, negatively affecting its electrochemical performance. Here, we design a single-crystal LMO cathode material using BaO flux (SC-LMOB) to address these issues. The BaO flux enables the fabrication of brick-like single-crystal particles, enhancing Li+ diffusion by shortening the diffusion path and increasing the unit cell volume. This process also reduces the specific surface area and stabilizes the crystal structure, effectively mitigating Mn dissolution and polarization. As a result, SC-LMOB exhibits ultra-high rate performance and superior structural stability, retaining 88.8% of its capacity at a 20 C discharge rate and achieving capacity retentions of 85.3% and 86.0% after 500 and 300 cycles at 1 C at room and elevated temperatures, respectively. This structural design offers a low-cost, scalable approach for fabricating single-crystal cathode materials with excellent performance.
Conventional polycrystalline LiMn2O4 (PC-LMO) suffers from poor Li+ diffusion rates and structural instability, negatively affecting its electrochemical performance. Here, we design a single-crystal LMO cathode material using BaO flux (SC-LMOB) to address these issues. The BaO flux enables the fabrication of brick-like single-crystal particles, enhancing Li+ diffusion by shortening the diffusion path and increasing the unit cell volume. This process also reduces the specific surface area and stabilizes the crystal structure, effectively mitigating Mn dissolution and polarization. As a result, SC-LMOB exhibits ultra-high rate performance and superior structural stability, retaining 88.8% of its capacity at a 20 C discharge rate and achieving capacity retentions of 85.3% and 86.0% after 500 and 300 cycles at 1 C at room and elevated temperatures, respectively. This structural design offers a low-cost, scalable approach for fabricating single-crystal cathode materials with excellent performance.
2025, 36(9): 110346
doi: 10.1016/j.cclet.2024.110346
Abstract:
Symmetric secondary batteries are expected to become promising storage devices on account of their low cost, environmentally friendly and high safety. Nevertheless, the further development of symmetric batteries needs to rely on bipolar electrodes with superior performance. Cation-disordered rocksalt (DRX) Li2FeTiO4 shows promising properties as symmetric electrodes, based on the ability of iron to undergo multiple electrochemical reactions over a wide voltage window. Unfortunately, this cation-disordered structure would not provide a cross-path for the rapid migration of Li+, ultimately resulting in inferior electrochemical dynamics and cycle stability. Herein, Li2FeTiO4 nanoparticles assembled by ultrafine nanocrystals are synthesized via a sol-gel method through an orderly reaction regulation strategy of precursor reactants. Such ultrafine nanocrystals increase the active sites to promote the reversibility of multi-cationic (e.g., stable Fe2+/Fe3+, Ti3+/Ti4+ and moderated Fe3+/Fe4+) and anionic redox, and maintain the DRX structure well during the cycling process. The half cells with nano-sized Li2FeTiO4 as the cathode/anode exhibit a high reversible capacity of 127.8/500.8 mAh/g, respectively. Besides, the Li2FeTiO4//Li2FeTiO4 symmetric full cell could provide a reversible capacity of 95.4 mAh/g at 0.1 A/g after 200 cycles. This hierarchical self-assembly by nanocrystal strategy could offer effective guidance for high-performance electrode design for rechargeable secondary batteries.
Symmetric secondary batteries are expected to become promising storage devices on account of their low cost, environmentally friendly and high safety. Nevertheless, the further development of symmetric batteries needs to rely on bipolar electrodes with superior performance. Cation-disordered rocksalt (DRX) Li2FeTiO4 shows promising properties as symmetric electrodes, based on the ability of iron to undergo multiple electrochemical reactions over a wide voltage window. Unfortunately, this cation-disordered structure would not provide a cross-path for the rapid migration of Li+, ultimately resulting in inferior electrochemical dynamics and cycle stability. Herein, Li2FeTiO4 nanoparticles assembled by ultrafine nanocrystals are synthesized via a sol-gel method through an orderly reaction regulation strategy of precursor reactants. Such ultrafine nanocrystals increase the active sites to promote the reversibility of multi-cationic (e.g., stable Fe2+/Fe3+, Ti3+/Ti4+ and moderated Fe3+/Fe4+) and anionic redox, and maintain the DRX structure well during the cycling process. The half cells with nano-sized Li2FeTiO4 as the cathode/anode exhibit a high reversible capacity of 127.8/500.8 mAh/g, respectively. Besides, the Li2FeTiO4//Li2FeTiO4 symmetric full cell could provide a reversible capacity of 95.4 mAh/g at 0.1 A/g after 200 cycles. This hierarchical self-assembly by nanocrystal strategy could offer effective guidance for high-performance electrode design for rechargeable secondary batteries.
2025, 36(9): 110371
doi: 10.1016/j.cclet.2024.110371
Abstract:
In recent years, metal phosphosulfides have attracted great attention as the promising anode materials in sodium/potassium batteries because of their incorporation of the advantages of metal phosphides and sulfides. However, they are also confronted with the problem of unstable battery performance due to the heavy volume expansion and sluggish ion reaction kinetics. Herein, yolk-shell cobalt phosphosulfide nanocrystals encapsulating into multi-heterogeneous atom (N, P, S)-doped carbon framework (Co9S8/CoP@NPSC) were constructed by employing dodecahedral ZIF-67 as precursor and a polymer as carbon sources through simultaneous sulfidation and phosphorization processes. The synergistic effect of Co9S8 and CoP component and the yolk-shell structure greatly improve the bettery performance and structural stability. In addition, the multiple hetero-atoms doped carbon frameworks enhance the conductivity of the electrode materials and increase the spacing of carbon layers to supply sufficient active sites and facilitate the Na+/K+ transport. The electrochemical results demonstrated that Co9S8/CoP@NPSC exhibited the pleasant reversible capacity (360.47 mAh/g at 1 A/g) after 300 cycles and an unpredictable cycling stability (103.22 mAh/g after 1000 cycles) in the SIBs application. The ex-situ XRD and XPS analyses were further applied to study the sodium ion storage mechanism and the multi-step phase transition reaction of the yolk-shell heterogeneous structure. This work provides new perspectives for the preparation of novel structure metal phosphosulfide and their applications in anode materials for sodium/potassium batteries and other secondary batteries.
In recent years, metal phosphosulfides have attracted great attention as the promising anode materials in sodium/potassium batteries because of their incorporation of the advantages of metal phosphides and sulfides. However, they are also confronted with the problem of unstable battery performance due to the heavy volume expansion and sluggish ion reaction kinetics. Herein, yolk-shell cobalt phosphosulfide nanocrystals encapsulating into multi-heterogeneous atom (N, P, S)-doped carbon framework (Co9S8/CoP@NPSC) were constructed by employing dodecahedral ZIF-67 as precursor and a polymer as carbon sources through simultaneous sulfidation and phosphorization processes. The synergistic effect of Co9S8 and CoP component and the yolk-shell structure greatly improve the bettery performance and structural stability. In addition, the multiple hetero-atoms doped carbon frameworks enhance the conductivity of the electrode materials and increase the spacing of carbon layers to supply sufficient active sites and facilitate the Na+/K+ transport. The electrochemical results demonstrated that Co9S8/CoP@NPSC exhibited the pleasant reversible capacity (360.47 mAh/g at 1 A/g) after 300 cycles and an unpredictable cycling stability (103.22 mAh/g after 1000 cycles) in the SIBs application. The ex-situ XRD and XPS analyses were further applied to study the sodium ion storage mechanism and the multi-step phase transition reaction of the yolk-shell heterogeneous structure. This work provides new perspectives for the preparation of novel structure metal phosphosulfide and their applications in anode materials for sodium/potassium batteries and other secondary batteries.
2025, 36(9): 110547
doi: 10.1016/j.cclet.2024.110547
Abstract:
The photocatalytic reduction of CO2 presents a promising avenue for carbon fuel conversion. However, the efficiency of charge utilization remains a critical barrier to industrial applications. In this study, we introduce a tandem design of Bi2WO6-BiOCl with an atomically matched interface, achieving highly efficient photoreduction of CO2 to CO. By incorporating WO42− ions and tuning coordination environment, the (110) facet of BiOCl was in-situ grown on the (200) facet of Bi2WO6. Compared to single phases and ball-milling samples, Bi2WO6-BiOCl exhibits a remarkable CO yield of 68.03 µmol g−1 h−1 with a selectivity of 98%. Atomic visualization and coordination analysis confirm the formation of a coherent interface that facilitates charge migration for efficient electron transport. Density functional theory (DFT) calculations and in-situ Fourier transform infrared (FTIR) spectroscopy provide insights into the intrinsic active sites and reaction mechanisms. The proposed lattice engineering strategies offer a new paradigm for the rational design of heterostructures beyond traditional band alignment at the atomic scale.
The photocatalytic reduction of CO2 presents a promising avenue for carbon fuel conversion. However, the efficiency of charge utilization remains a critical barrier to industrial applications. In this study, we introduce a tandem design of Bi2WO6-BiOCl with an atomically matched interface, achieving highly efficient photoreduction of CO2 to CO. By incorporating WO42− ions and tuning coordination environment, the (110) facet of BiOCl was in-situ grown on the (200) facet of Bi2WO6. Compared to single phases and ball-milling samples, Bi2WO6-BiOCl exhibits a remarkable CO yield of 68.03 µmol g−1 h−1 with a selectivity of 98%. Atomic visualization and coordination analysis confirm the formation of a coherent interface that facilitates charge migration for efficient electron transport. Density functional theory (DFT) calculations and in-situ Fourier transform infrared (FTIR) spectroscopy provide insights into the intrinsic active sites and reaction mechanisms. The proposed lattice engineering strategies offer a new paradigm for the rational design of heterostructures beyond traditional band alignment at the atomic scale.
2025, 36(9): 110653
doi: 10.1016/j.cclet.2024.110653
Abstract:
Dye-based color films are increasingly considered as viable alternatives to pigment-based color films in complementary metal-oxide-semiconductor (CMOS) image sensors. Herein, a series of azo dyes utilizing 5-methyl-2-phenyl-4-(2-phenylhydrazono)-2,4-dihydro-3H-pyrazol-3-one as the coupling component and aromatic amines with various electron-withdrawing groups (NO2, CN, Br) as diazo components were designed and synthesized. The presence of intermolecular hydrogen bonding between the hydrogen atom on the NH group and the oxygen atom of the C=O group of the hydrazo structure facilitates the formation of a stable six-membered ring. Additionally, the electron-withdrawing groups in the diazo component further stabilize this hydrogen-bonded structure. As a result, these azo dyes (P-2, P-3, P-4, P-5) exhibit not only excellent light stability but also ultra-highly thermal stability (Td > 260 ℃). Therein, the synthesized dyes P-2 and P-3 with great bright yellow color (~400 nm), proper solubility (~6.00 g/100 g) were selected to make for color films. And their dye-based color films displayed ultra-highly thermal and light stability (color difference ΔE < 3). Notably, the increased planarity of the molecular structure by hydrogen bonding for the novel dyes ensures a balance between high transmittance (>90%) in the 550–780 nm wavelength range and the solvent resistance of the dye-based color films. This work contributes to the advancement of next-generation smart CMOS devices and offers valuable insights into the design of azo dyes for applications in the field of organic electronics.
Dye-based color films are increasingly considered as viable alternatives to pigment-based color films in complementary metal-oxide-semiconductor (CMOS) image sensors. Herein, a series of azo dyes utilizing 5-methyl-2-phenyl-4-(2-phenylhydrazono)-2,4-dihydro-3H-pyrazol-3-one as the coupling component and aromatic amines with various electron-withdrawing groups (NO2, CN, Br) as diazo components were designed and synthesized. The presence of intermolecular hydrogen bonding between the hydrogen atom on the NH group and the oxygen atom of the C=O group of the hydrazo structure facilitates the formation of a stable six-membered ring. Additionally, the electron-withdrawing groups in the diazo component further stabilize this hydrogen-bonded structure. As a result, these azo dyes (P-2, P-3, P-4, P-5) exhibit not only excellent light stability but also ultra-highly thermal stability (Td > 260 ℃). Therein, the synthesized dyes P-2 and P-3 with great bright yellow color (~400 nm), proper solubility (~6.00 g/100 g) were selected to make for color films. And their dye-based color films displayed ultra-highly thermal and light stability (color difference ΔE < 3). Notably, the increased planarity of the molecular structure by hydrogen bonding for the novel dyes ensures a balance between high transmittance (>90%) in the 550–780 nm wavelength range and the solvent resistance of the dye-based color films. This work contributes to the advancement of next-generation smart CMOS devices and offers valuable insights into the design of azo dyes for applications in the field of organic electronics.
2025, 36(9): 110658
doi: 10.1016/j.cclet.2024.110658
Abstract:
Rheumatoid arthritis (RA) is a refractory autoimmune disease with limited treatment options. Plant-derived exosomes-like nanovesicles (PDENs) have emerged as a novel nanomedical approach, with the inherent bioactive compounds from their source plants. The roots of Morinda officinalis How. (MO), a Chinese herb, exhibit notable anti-inflammatory activities and hold promising therapeutic value. We engineered a joint-targeting delivery system (termed MOE@EM) by masking MO-derived exosomes-like nanovesicles (MOE) with erythrocyte membrane (EM). This biomimetic strategy, using EM camouflage, is intended to improve the in vivo fate of MOE. We investigated the antioxidative and anti-inflammatory activities, immunogenicity, drug accumulation in the joint, and therapeutic efficacy to ascertain its suitability for RA therapy. UV irradiation significantly increased the activities of catalase and peroxidase of MOE, and enhanced the anti-inflammatory effects via the Wnt/β-catenin pathway. Furthermore, MOE@EM markedly attenuated dendritic cell activation. MOE@EM exhibited joint-specific delivery, with substantial reduction in paw swelling, and favorable modulation of immune microenvironment.
Rheumatoid arthritis (RA) is a refractory autoimmune disease with limited treatment options. Plant-derived exosomes-like nanovesicles (PDENs) have emerged as a novel nanomedical approach, with the inherent bioactive compounds from their source plants. The roots of Morinda officinalis How. (MO), a Chinese herb, exhibit notable anti-inflammatory activities and hold promising therapeutic value. We engineered a joint-targeting delivery system (termed MOE@EM) by masking MO-derived exosomes-like nanovesicles (MOE) with erythrocyte membrane (EM). This biomimetic strategy, using EM camouflage, is intended to improve the in vivo fate of MOE. We investigated the antioxidative and anti-inflammatory activities, immunogenicity, drug accumulation in the joint, and therapeutic efficacy to ascertain its suitability for RA therapy. UV irradiation significantly increased the activities of catalase and peroxidase of MOE, and enhanced the anti-inflammatory effects via the Wnt/β-catenin pathway. Furthermore, MOE@EM markedly attenuated dendritic cell activation. MOE@EM exhibited joint-specific delivery, with substantial reduction in paw swelling, and favorable modulation of immune microenvironment.
2025, 36(9): 110659
doi: 10.1016/j.cclet.2024.110659
Abstract:
In this work, atomic Co catalysts are anchored on a three-dimensional (3D) interconnected g-C3N4 (SACo-CN) through Co-N coordination, which exhibit efficient charge carrier transition and low activation energy barriers for peroxymonosulfate (PMS). The incorporation of Co atoms extends the absorption spectrum and enhances the photoelectron-hole separation efficiency of the SACo-CN samples. The 3D interconnected structure, combined with the synergistic interplay between Co-N coordination and visible light irradiation, results in SACo-CN catalysts demonstrating excellent catalytic activity and stability for PMS activation. This leads to a degradation rate of 98.8% for oxytetracycline (OTC) within 30 min under visible light. The research proposes three potential mineralization pathways with eight intermediates, leading to a significant decrease in the toxicity of the intermediates. This work provides a facile and promising approach for the preparation of metal single atom catalysts with highly efficient PMS activation performance.
In this work, atomic Co catalysts are anchored on a three-dimensional (3D) interconnected g-C3N4 (SACo-CN) through Co-N coordination, which exhibit efficient charge carrier transition and low activation energy barriers for peroxymonosulfate (PMS). The incorporation of Co atoms extends the absorption spectrum and enhances the photoelectron-hole separation efficiency of the SACo-CN samples. The 3D interconnected structure, combined with the synergistic interplay between Co-N coordination and visible light irradiation, results in SACo-CN catalysts demonstrating excellent catalytic activity and stability for PMS activation. This leads to a degradation rate of 98.8% for oxytetracycline (OTC) within 30 min under visible light. The research proposes three potential mineralization pathways with eight intermediates, leading to a significant decrease in the toxicity of the intermediates. This work provides a facile and promising approach for the preparation of metal single atom catalysts with highly efficient PMS activation performance.
2025, 36(9): 110661
doi: 10.1016/j.cclet.2024.110661
Abstract:
The healing of diabetic wounds poses a significant healthcare burden due to persistent inflammation, M1 macrophage aggregation, and high glucose levels in the microenvironment. Previous studies have demonstrated that immunomodulatory hydrogel dressings can facilitate diabetic wound healing. However, current immunomodulatory hydrogels require costly and complex treatments such as cell therapy and cytokines. Herein, a hierarchical hydrogel dressing with continuous biochemical gradient based on glycyrrhizic acid (GA) was constructed to modulate immunomodulatory processes in diabetic wounds. The hydrogels present many desirable features, such as tunable mechanical properties, broad antibacterial ability, outstanding conductive, transparent, and self-adhesive properties. The resultant hydrogel can promote diabetic wound healing by preventing bacterial infection, promoting macrophage polarization, improving the inflammatory microenvironment, and inducing angiogenesis and neurogenesis. Furthermore, electrical stimulation (ES) can further promote the healing of chronic diabetic wounds, providing valuable guidance for relevant clinical practice.
The healing of diabetic wounds poses a significant healthcare burden due to persistent inflammation, M1 macrophage aggregation, and high glucose levels in the microenvironment. Previous studies have demonstrated that immunomodulatory hydrogel dressings can facilitate diabetic wound healing. However, current immunomodulatory hydrogels require costly and complex treatments such as cell therapy and cytokines. Herein, a hierarchical hydrogel dressing with continuous biochemical gradient based on glycyrrhizic acid (GA) was constructed to modulate immunomodulatory processes in diabetic wounds. The hydrogels present many desirable features, such as tunable mechanical properties, broad antibacterial ability, outstanding conductive, transparent, and self-adhesive properties. The resultant hydrogel can promote diabetic wound healing by preventing bacterial infection, promoting macrophage polarization, improving the inflammatory microenvironment, and inducing angiogenesis and neurogenesis. Furthermore, electrical stimulation (ES) can further promote the healing of chronic diabetic wounds, providing valuable guidance for relevant clinical practice.
2025, 36(9): 110671
doi: 10.1016/j.cclet.2024.110671
Abstract:
Worsened air pollution has been linked to elevated rates of cardiovascular disease (CVD) morbidity and mortality. Atherosclerosis, a shared pathophysiological foundation for various CVD manifestations, plays a crucial role. Although foam cell formation is hypothesized to be a contributing factor, the precise mechanisms by which air pollution accelerates the advancement of atherosclerotic plaques remain unidentified. In this study, an atherosclerosis-susceptible apolipoprotein E-deficient (ApoE−/−) mouse model was employed to examine the influence of real-world environmental PM2.5 exposure on atherosclerosis. Metabolomic analysis was performed to identify potential biomarkers that may play a role in atherogenesis following PM2.5 exposure. Our findings revealed that mice fed a high-cholesterol diet (HCD) exhibited susceptibility to PM2.5 exposure, as evidenced by increased inflammation, enhanced fibrosis, and enlarged foam cell formation in the aorta. The interactive effects between PM2.5 exposure and HCD disrupted the secretion of certain chemokines. The metabolomic data provided additional insights into how PM2.5 exposure alters prostaglandin levels, contributing to the progression of atherosclerotic lesions. These findings enhance our understanding of the pivotal role of arachidonic acid metabolism in the etiology of PM2.5-induced cardiovascular risks and elucidate the mechanisms by which PM2.5 exposure leads to vascular damage in populations with high cholesterol intake.
Worsened air pollution has been linked to elevated rates of cardiovascular disease (CVD) morbidity and mortality. Atherosclerosis, a shared pathophysiological foundation for various CVD manifestations, plays a crucial role. Although foam cell formation is hypothesized to be a contributing factor, the precise mechanisms by which air pollution accelerates the advancement of atherosclerotic plaques remain unidentified. In this study, an atherosclerosis-susceptible apolipoprotein E-deficient (ApoE−/−) mouse model was employed to examine the influence of real-world environmental PM2.5 exposure on atherosclerosis. Metabolomic analysis was performed to identify potential biomarkers that may play a role in atherogenesis following PM2.5 exposure. Our findings revealed that mice fed a high-cholesterol diet (HCD) exhibited susceptibility to PM2.5 exposure, as evidenced by increased inflammation, enhanced fibrosis, and enlarged foam cell formation in the aorta. The interactive effects between PM2.5 exposure and HCD disrupted the secretion of certain chemokines. The metabolomic data provided additional insights into how PM2.5 exposure alters prostaglandin levels, contributing to the progression of atherosclerotic lesions. These findings enhance our understanding of the pivotal role of arachidonic acid metabolism in the etiology of PM2.5-induced cardiovascular risks and elucidate the mechanisms by which PM2.5 exposure leads to vascular damage in populations with high cholesterol intake.
2025, 36(9): 110673
doi: 10.1016/j.cclet.2024.110673
Abstract:
In this study, we present a self-driven photoelectrocatalytic (SD-PEC) system that effectively treats complex uranium-bearing wastewaters for both uranium recovery and organic matter decomposition while generating power. The system utilizes a titanium dioxide nanorod array (TNR) photoelectrode coupled with a silicon solar cell to optimize electron transport, while the cathode is composed of a carbon fiber coated with carboxylated carbon nanotubes (CCNT/CF), which efficiently reduce UO22+. The results demonstrate significant removal efficiency of uranium (complete removal in 25 min at a rate constant of ~0.248 min-1), as well as substantial degradation of organic impurities. Furthermore, the system generates sufficient power output to light an LED lamp and exhibits superior performance under various complex wastewater conditions, including simulated seawater and real uranium tailings wastewater. These findings underscore the potential of the SD-PEC system as a versatile approach for sustainable treatment and energy recovery of radioactive wastewater. The significance of this research extends to global environmental challenges, offering an innovative solution for managing radioactive wastewater while simultaneously contributing to renewable energy generation.
In this study, we present a self-driven photoelectrocatalytic (SD-PEC) system that effectively treats complex uranium-bearing wastewaters for both uranium recovery and organic matter decomposition while generating power. The system utilizes a titanium dioxide nanorod array (TNR) photoelectrode coupled with a silicon solar cell to optimize electron transport, while the cathode is composed of a carbon fiber coated with carboxylated carbon nanotubes (CCNT/CF), which efficiently reduce UO22+. The results demonstrate significant removal efficiency of uranium (complete removal in 25 min at a rate constant of ~0.248 min-1), as well as substantial degradation of organic impurities. Furthermore, the system generates sufficient power output to light an LED lamp and exhibits superior performance under various complex wastewater conditions, including simulated seawater and real uranium tailings wastewater. These findings underscore the potential of the SD-PEC system as a versatile approach for sustainable treatment and energy recovery of radioactive wastewater. The significance of this research extends to global environmental challenges, offering an innovative solution for managing radioactive wastewater while simultaneously contributing to renewable energy generation.
2025, 36(9): 110674
doi: 10.1016/j.cclet.2024.110674
Abstract:
Periodontitis is a chronic inflammatory disease caused by oral pathogens, and the osteogenic potential of human periodontal ligament stem cells (hPDLSCs) is severely impaired under the inflammatory environment. Current clinical periodontitis treatment strategies such as surgical interventions and antibiotic delivery still suffer from poor antibacterial efficacy, difficulty in ameliorating excessive inflammatory responses and slow periodontal tissue regeneration. Here, we have innovatively developed a non-surgical treatment strategy based on a functional composite hydrogel. A composite hydrogel system (Pt@ZIF-8/ALN-ac/Gel) containing bioactive zeolite imidazolate framework-8 (ZIF-8) integrated with platinum nanoparticles (Pt@ZIF-8) and alendronate acrylamide (ALN-ac) was constructed on the basis of gelatin methacryloyl (GelMA) to achieve enhanced antibacterial effect and reactive oxygen species (ROS) scavenging ability while promoting the osteogenic potential of hPDLSCs. We confirmed that Pt@ZIF-8/ALN-ac/Gel was able to continuously release Zn2+ and exerted an obvious antibacterial effect against Porphyromonas gingivalis. In vitro experiments proved that Pt@ZIF-8/ALN-ac/Gel had good biocompatibility, while efficiently featuring excellent reactive oxygen species (ROS) scavenging capacity, increasing alkaline phosphatase activity, and promoting extracellular matrix mineralization by hPDLSCs. In vivo, Pt@ZIF-8/ALN-ac/Gel significantly inhibited the alveolar bone deterioration and reduced osteoclast activation and inflammation, thereby promoting the regeneration of damaged tissues. These findings demonstrated superior therapeutic efficacy in the reported clinical periodontitis treatment, exhibiting great potential for application.
Periodontitis is a chronic inflammatory disease caused by oral pathogens, and the osteogenic potential of human periodontal ligament stem cells (hPDLSCs) is severely impaired under the inflammatory environment. Current clinical periodontitis treatment strategies such as surgical interventions and antibiotic delivery still suffer from poor antibacterial efficacy, difficulty in ameliorating excessive inflammatory responses and slow periodontal tissue regeneration. Here, we have innovatively developed a non-surgical treatment strategy based on a functional composite hydrogel. A composite hydrogel system (Pt@ZIF-8/ALN-ac/Gel) containing bioactive zeolite imidazolate framework-8 (ZIF-8) integrated with platinum nanoparticles (Pt@ZIF-8) and alendronate acrylamide (ALN-ac) was constructed on the basis of gelatin methacryloyl (GelMA) to achieve enhanced antibacterial effect and reactive oxygen species (ROS) scavenging ability while promoting the osteogenic potential of hPDLSCs. We confirmed that Pt@ZIF-8/ALN-ac/Gel was able to continuously release Zn2+ and exerted an obvious antibacterial effect against Porphyromonas gingivalis. In vitro experiments proved that Pt@ZIF-8/ALN-ac/Gel had good biocompatibility, while efficiently featuring excellent reactive oxygen species (ROS) scavenging capacity, increasing alkaline phosphatase activity, and promoting extracellular matrix mineralization by hPDLSCs. In vivo, Pt@ZIF-8/ALN-ac/Gel significantly inhibited the alveolar bone deterioration and reduced osteoclast activation and inflammation, thereby promoting the regeneration of damaged tissues. These findings demonstrated superior therapeutic efficacy in the reported clinical periodontitis treatment, exhibiting great potential for application.
2025, 36(9): 110687
doi: 10.1016/j.cclet.2024.110687
Abstract:
Two racemic pairs of new stilbenoid dimers, (±)-heterosmilaxones A (1) and B (2), with unique 6/6/6and 6/5/7 tricyclic core systems, respectively, were isolated from the rhizomes of Heterosmilax yunnanensis. Their structures were elucidated through comprehensive spectroscopic analyses, quantum chemical calculations and X-ray diffraction crystallography. Compound (+)-1, initially reported as syagrusin Awith a 1,4,4a,9a-tetrahydrofluoren-9-one skeleton, is now revised to a new structure characteristic witha benzo bicyclo[3.3.1] nonene scaffold. And compound 2 bears an unprecedented carbon skeleton withfour continuous chiral centers in the central benzo bicyclo[4.2.1]nonene motif. Biogenetically, both 1 and 2 were proposed to derive from 3,3',4,5,5'-pentahydroxy stilbene and could be generated through keyinverse-electron-demand [4 + 2] and [5 + 2] cycloadditions, respectively. Interestingly, both (±)-1 and(±)-2 showed significant inhibition against α-glucosidase. (±)-1 and its pure enantiomers could modulate protein tyrosine phosphatase-1B (PTP1B) enzyme activities and increased glucose consumption inHepG2 cells in a dose-dependent manner.
Two racemic pairs of new stilbenoid dimers, (±)-heterosmilaxones A (1) and B (2), with unique 6/6/6and 6/5/7 tricyclic core systems, respectively, were isolated from the rhizomes of Heterosmilax yunnanensis. Their structures were elucidated through comprehensive spectroscopic analyses, quantum chemical calculations and X-ray diffraction crystallography. Compound (+)-1, initially reported as syagrusin Awith a 1,4,4a,9a-tetrahydrofluoren-9-one skeleton, is now revised to a new structure characteristic witha benzo bicyclo[3.3.1] nonene scaffold. And compound 2 bears an unprecedented carbon skeleton withfour continuous chiral centers in the central benzo bicyclo[4.2.1]nonene motif. Biogenetically, both 1 and 2 were proposed to derive from 3,3',4,5,5'-pentahydroxy stilbene and could be generated through keyinverse-electron-demand [4 + 2] and [5 + 2] cycloadditions, respectively. Interestingly, both (±)-1 and(±)-2 showed significant inhibition against α-glucosidase. (±)-1 and its pure enantiomers could modulate protein tyrosine phosphatase-1B (PTP1B) enzyme activities and increased glucose consumption inHepG2 cells in a dose-dependent manner.
2025, 36(9): 110703
doi: 10.1016/j.cclet.2024.110703
Abstract:
The traditional nanozymes-based ratiometric fluorescence sensing platforms usually necessitate the supplementary addition of fluorescent probes, therefore greatly restricting its convenient and broad application. In this study, a highly sensitive and selective ratiometric fluorescence platform for alkaline phosphatase (ALP) detection was established, only employing Prussian blue (PB) nanozymes and a commercially available chromogen of o-phenylenediamine (OPD). PB nanozymes with remarkable peroxidase-like (POD-like) activity can effectively catalyze OPD chromogen to yield 2,3-diaminophenazine (OPDox) with an intense yellow fluorescence at 573 nm emission peak. Target ALP can facilitate ascorbic acid 2-phosphate (AAP) dephosphorylation to generate phosphate and ascorbic acid (AA). Significantly, both these two resultant hydrolysis products could effectively decrease the OPDox generation via a dual-path based inhibition on the PB nanozymes POD-like activity. On the other hand, the generated dehydroascorbic acid (DHAA) from AA oxidation would exclusively react with OPD chromogen to yield 3-(dihydroxyethyl)furo[3,4-b]quinoxaline-1-one (DFQ) with a strong blue fluorescent signal at 434 nm, which further providing a significant enhancement on the sensing selectivity of ALP detection. As a result, an increased yellow fluorescence of OPDox and decreased blue fluorescence of DFQ could be clearly observed with different ALP addition. A robust linear relationship between the fluorescence ratio of F434/F573 and ALP activity ranging from 0.25 U/L to 6 U/L was obtained, with a low detection limit of 0.112 U/L. This proposed method demonstrates high sensitivity, excellent selectivity, cost-effectiveness, and operational simplicity, yet enabling an effective detection of ALP levels in human serum.
The traditional nanozymes-based ratiometric fluorescence sensing platforms usually necessitate the supplementary addition of fluorescent probes, therefore greatly restricting its convenient and broad application. In this study, a highly sensitive and selective ratiometric fluorescence platform for alkaline phosphatase (ALP) detection was established, only employing Prussian blue (PB) nanozymes and a commercially available chromogen of o-phenylenediamine (OPD). PB nanozymes with remarkable peroxidase-like (POD-like) activity can effectively catalyze OPD chromogen to yield 2,3-diaminophenazine (OPDox) with an intense yellow fluorescence at 573 nm emission peak. Target ALP can facilitate ascorbic acid 2-phosphate (AAP) dephosphorylation to generate phosphate and ascorbic acid (AA). Significantly, both these two resultant hydrolysis products could effectively decrease the OPDox generation via a dual-path based inhibition on the PB nanozymes POD-like activity. On the other hand, the generated dehydroascorbic acid (DHAA) from AA oxidation would exclusively react with OPD chromogen to yield 3-(dihydroxyethyl)furo[3,4-b]quinoxaline-1-one (DFQ) with a strong blue fluorescent signal at 434 nm, which further providing a significant enhancement on the sensing selectivity of ALP detection. As a result, an increased yellow fluorescence of OPDox and decreased blue fluorescence of DFQ could be clearly observed with different ALP addition. A robust linear relationship between the fluorescence ratio of F434/F573 and ALP activity ranging from 0.25 U/L to 6 U/L was obtained, with a low detection limit of 0.112 U/L. This proposed method demonstrates high sensitivity, excellent selectivity, cost-effectiveness, and operational simplicity, yet enabling an effective detection of ALP levels in human serum.
2025, 36(9): 110704
doi: 10.1016/j.cclet.2024.110704
Abstract:
Nanomaterials that can sequentially respond to internal and external stimuli, functioning as a sequential gate, have great potential for targeting different aspects of antitumor immunity. Herein, we construct a mannose-modified, pH and reactive oxygen species (ROS) sequential-responsive, transformable dual-immunofunction nanoprodrug (MpRTNP). This nanoprodrug encapsulates a transforming growth factor-β (TGF-β) receptor inhibitor SD-208 (MpRTNP@SD), to simultaneously alleviate the immunosuppressive effects of TGF-β and tumor-associated macrophages (TAMs). In the weakly acidic tumor microenvironment (TME), the vesicle-micelle morphology transformation occurs owing to the protonation of PC7A, which is accompanied by SD-208 release to inhibit cancer-associated fibroblasts and regulatory T cells. The transformed micelles then target TAMs via mannose receptor-mediated endocytosis. Upon laser irradiation, the thioketal linker is cleaved, releasing conjugated chlorin e6 and generating ROS, which facilitates TAM polarization. The PC7A+ segment activates the stimulator of the interferon gene in TAMs with elevated phosphorylation of TANK binding kinase 1 and interferon regulatory factor 3, and type Ⅰ interferon secretion. MpRTNP@SD displays superior abscopal effects and robust antitumor immunity, as evidenced by increased CD8+/CD4+ T cell infiltration and reduced regulatory T cell (Treg) ratios. Mouse survival time is prolonged after combination with the CD47 antibody. This study provides a novel strategy for potent antitumor immunotherapy through pH and ROS sequential-gated spatiotemporal regulation of the TME.
Nanomaterials that can sequentially respond to internal and external stimuli, functioning as a sequential gate, have great potential for targeting different aspects of antitumor immunity. Herein, we construct a mannose-modified, pH and reactive oxygen species (ROS) sequential-responsive, transformable dual-immunofunction nanoprodrug (MpRTNP). This nanoprodrug encapsulates a transforming growth factor-β (TGF-β) receptor inhibitor SD-208 (MpRTNP@SD), to simultaneously alleviate the immunosuppressive effects of TGF-β and tumor-associated macrophages (TAMs). In the weakly acidic tumor microenvironment (TME), the vesicle-micelle morphology transformation occurs owing to the protonation of PC7A, which is accompanied by SD-208 release to inhibit cancer-associated fibroblasts and regulatory T cells. The transformed micelles then target TAMs via mannose receptor-mediated endocytosis. Upon laser irradiation, the thioketal linker is cleaved, releasing conjugated chlorin e6 and generating ROS, which facilitates TAM polarization. The PC7A+ segment activates the stimulator of the interferon gene in TAMs with elevated phosphorylation of TANK binding kinase 1 and interferon regulatory factor 3, and type Ⅰ interferon secretion. MpRTNP@SD displays superior abscopal effects and robust antitumor immunity, as evidenced by increased CD8+/CD4+ T cell infiltration and reduced regulatory T cell (Treg) ratios. Mouse survival time is prolonged after combination with the CD47 antibody. This study provides a novel strategy for potent antitumor immunotherapy through pH and ROS sequential-gated spatiotemporal regulation of the TME.
2025, 36(9): 110708
doi: 10.1016/j.cclet.2024.110708
Abstract:
The investigation of reaction kinetics is the key to understanding the nature of reaction processes. However, monitoring fast photochemical reactions by mass spectrometry remains challenging. Herein, we developed an optical focusing inductive electrospray (OF-iESI) mass spectrometry platform for real-time and in-situ photoreaction monitoring. Coaxial irradiation from back of nanoelectrospray emitter with a taper section was utilized, so the emitter could act as optical lens to help achieving much larger optical power density at emitter tip compared to other sections, which allowed for in-situ reaction monitoring of photoreactions. Through theoretical calculations, the highest optical power density region volume was ca. 45 nL. We also integrated a controller for the laser source (450 nm), enabling the modulation of pulse duration (>1 ms). This facilitates the study of photochemical reaction kinetics. The in-situ capability of this device was proved by capturing the short-lived photogenerated intermediates during the dehydrogenation of tetrahydroquinoline. This device was further used to investigate the kinetics of triplet energy transfer based Paternò–Büchi reaction. The reaction order has hitherto remained undetermined while the result of OF-iESI suggested it followed pseudo-second-order reaction kinetics. The short-lived donor-acceptor collision complex intermediate was also successfully identified by tandem mass spectrometry.
The investigation of reaction kinetics is the key to understanding the nature of reaction processes. However, monitoring fast photochemical reactions by mass spectrometry remains challenging. Herein, we developed an optical focusing inductive electrospray (OF-iESI) mass spectrometry platform for real-time and in-situ photoreaction monitoring. Coaxial irradiation from back of nanoelectrospray emitter with a taper section was utilized, so the emitter could act as optical lens to help achieving much larger optical power density at emitter tip compared to other sections, which allowed for in-situ reaction monitoring of photoreactions. Through theoretical calculations, the highest optical power density region volume was ca. 45 nL. We also integrated a controller for the laser source (450 nm), enabling the modulation of pulse duration (>1 ms). This facilitates the study of photochemical reaction kinetics. The in-situ capability of this device was proved by capturing the short-lived photogenerated intermediates during the dehydrogenation of tetrahydroquinoline. This device was further used to investigate the kinetics of triplet energy transfer based Paternò–Büchi reaction. The reaction order has hitherto remained undetermined while the result of OF-iESI suggested it followed pseudo-second-order reaction kinetics. The short-lived donor-acceptor collision complex intermediate was also successfully identified by tandem mass spectrometry.
2025, 36(9): 110712
doi: 10.1016/j.cclet.2024.110712
Abstract:
Active sulfur dissolution and shuttle effect of lithium polysulfides (LiPSs) are the main obstacles hindering the practical application of lithium-sulfur batteries (LSBs), which is primarily induced by the direct interaction between sulfur-loading cathode and liquid electrolyte. The introduction of functional interlayer within the separator and cathode is an effective strategy to stabilize the electrode/electrolyte interface reaction and improve the utilization rate of active sulfur. Herein, conductive composite nanofabrics (CCN) with multifunctional groups are employed as the interlayer of sulfur-loading cathode, in which the PMIA/PAN supporting fibers offer robust mechanical strength and high thermostable performance, and gelatin/polypyrrole functional fibers ensure high electrical conductivity and strong chemical interaction for LiPSs. As demonstrated by the experimental data and material characterizations, the presence of CCN interlayer not only blocks the shuttle behavior of LiPSs, but also strengthens the interface stability of both Li anode and sulfur-loading cathode. Interestingly, the assembled LSBs with CCN interlayer can maintain stable capacity of 686 mAh/g after 200 cycles at 0.5 A/g. This work will provide new ideas for the elaborate design of functional interlayers/separators for LSBs and lithium metal batteries.
Active sulfur dissolution and shuttle effect of lithium polysulfides (LiPSs) are the main obstacles hindering the practical application of lithium-sulfur batteries (LSBs), which is primarily induced by the direct interaction between sulfur-loading cathode and liquid electrolyte. The introduction of functional interlayer within the separator and cathode is an effective strategy to stabilize the electrode/electrolyte interface reaction and improve the utilization rate of active sulfur. Herein, conductive composite nanofabrics (CCN) with multifunctional groups are employed as the interlayer of sulfur-loading cathode, in which the PMIA/PAN supporting fibers offer robust mechanical strength and high thermostable performance, and gelatin/polypyrrole functional fibers ensure high electrical conductivity and strong chemical interaction for LiPSs. As demonstrated by the experimental data and material characterizations, the presence of CCN interlayer not only blocks the shuttle behavior of LiPSs, but also strengthens the interface stability of both Li anode and sulfur-loading cathode. Interestingly, the assembled LSBs with CCN interlayer can maintain stable capacity of 686 mAh/g after 200 cycles at 0.5 A/g. This work will provide new ideas for the elaborate design of functional interlayers/separators for LSBs and lithium metal batteries.
2025, 36(9): 110713
doi: 10.1016/j.cclet.2024.110713
Abstract:
Rheumatoid arthritis (RA) is a chronic inflammatory disease with multi-system damage and autoimmune features. The main clinical manifestations of RA include joint pain, swelling, and stiffness, and RA may lead to joint deformity and dysfunction in severe cases. The pathologic development of RA involves complex interactions of multiple biomarkers, and detecting a single biomarker may produce false-positive results due to other confounding factors. Therefore, fluorescent probes that can detect multiple biomarkers simultaneously are crucial for precise RA diagnosis. Peroxynitrite (ONOO−) and viscosity are inflammation-related factors in cells. In this study, we developed a dual responsive near-infrared fluorescent probe, YLS, for ONOO− and viscosity. The probe features dual-channel turn-on fluorescence responses at 625 and 760 nm upon the presence of ONOO− and viscosity, respectively. Supported by YLS, we found that during RA pathology, lymphocyte infiltration not only increases the concentration of proteins in the joint fluid resulting in elevated viscosity; at the same time, the overproduction of ONOO− exacerbates oxidative stress and inflammatory responses. This multiparameter assay is expected to improve the diagnostic accuracy of the early stages of RA, thus providing a scientific basis for early intervention and personalized treatment.
Rheumatoid arthritis (RA) is a chronic inflammatory disease with multi-system damage and autoimmune features. The main clinical manifestations of RA include joint pain, swelling, and stiffness, and RA may lead to joint deformity and dysfunction in severe cases. The pathologic development of RA involves complex interactions of multiple biomarkers, and detecting a single biomarker may produce false-positive results due to other confounding factors. Therefore, fluorescent probes that can detect multiple biomarkers simultaneously are crucial for precise RA diagnosis. Peroxynitrite (ONOO−) and viscosity are inflammation-related factors in cells. In this study, we developed a dual responsive near-infrared fluorescent probe, YLS, for ONOO− and viscosity. The probe features dual-channel turn-on fluorescence responses at 625 and 760 nm upon the presence of ONOO− and viscosity, respectively. Supported by YLS, we found that during RA pathology, lymphocyte infiltration not only increases the concentration of proteins in the joint fluid resulting in elevated viscosity; at the same time, the overproduction of ONOO− exacerbates oxidative stress and inflammatory responses. This multiparameter assay is expected to improve the diagnostic accuracy of the early stages of RA, thus providing a scientific basis for early intervention and personalized treatment.
2025, 36(9): 110715
doi: 10.1016/j.cclet.2024.110715
Abstract:
Although aggregation-induced emission (AIE) units enabled fluorophores as rotor-based probes for advancing biomedical imaging, the quantum-mechanism through which AIEgens enhanced fluorescence via aggregation or rotor effects remains poorly understood. Herein, we elucidate the mechanisms governing the tetraphenylethene (TPE)’s function (rotor-effect or aggregation-effect) in cyanine systems by tuning the methine-chain length from Cy3 to Cy5 to Cy7. Our study shows that modulating the frontier orbital energy difference (ΔE (DA)) between the cyanine and TPE allows TPE to display AIE property in Cy3, act as a rotor in Cy5 uniquely devoid of aggregation activation, or neither in Cy7. In vitro and in vivo results further demonstrate that rotor-specific TPE-Cy5 can serve as a sensitive probe for imaging tumor rigidity. We anticipate that continued advancements in TPE rotor visualization will open new avenues for understanding the biophysical behaviors of tumors.
Although aggregation-induced emission (AIE) units enabled fluorophores as rotor-based probes for advancing biomedical imaging, the quantum-mechanism through which AIEgens enhanced fluorescence via aggregation or rotor effects remains poorly understood. Herein, we elucidate the mechanisms governing the tetraphenylethene (TPE)’s function (rotor-effect or aggregation-effect) in cyanine systems by tuning the methine-chain length from Cy3 to Cy5 to Cy7. Our study shows that modulating the frontier orbital energy difference (ΔE (DA)) between the cyanine and TPE allows TPE to display AIE property in Cy3, act as a rotor in Cy5 uniquely devoid of aggregation activation, or neither in Cy7. In vitro and in vivo results further demonstrate that rotor-specific TPE-Cy5 can serve as a sensitive probe for imaging tumor rigidity. We anticipate that continued advancements in TPE rotor visualization will open new avenues for understanding the biophysical behaviors of tumors.
2025, 36(9): 110716
doi: 10.1016/j.cclet.2024.110716
Abstract:
The advancement of efficient, cheap, and durable catalysts for oxygen reduction reaction (ORR) to substitute Pt/C in metal-air batteries is of paramount importance. However, traditional solvent-based methods fall short in terms of environmental benign and scalability. Herein, a solvent-free organic-inorganic self-assembly approach is explored to construct cobalt single atom and cobalt nanocluster decorated nitrogen-doped porous carbon spheres (Co-SA/NC@NCS). The solvent-free synthesis demonstrates an impressively high yield (282 g/L) and the resultant Co-SA/NC@NCS possesses a high N content (6.9 wt%). Density functional theory calculations disclose that the Co-SAs and Co-NCs are able to optimize the surface oxygen adsorption capability and enhance the conductivity of the NCS, thereby facilitating the ORR performance. The solvent-free synthesis is also feasible for the synthesis of other non-noble metal element (Fe, Ni, and Zn) decorated nitrogen-doped porous carbon spheres.
The advancement of efficient, cheap, and durable catalysts for oxygen reduction reaction (ORR) to substitute Pt/C in metal-air batteries is of paramount importance. However, traditional solvent-based methods fall short in terms of environmental benign and scalability. Herein, a solvent-free organic-inorganic self-assembly approach is explored to construct cobalt single atom and cobalt nanocluster decorated nitrogen-doped porous carbon spheres (Co-SA/NC@NCS). The solvent-free synthesis demonstrates an impressively high yield (282 g/L) and the resultant Co-SA/NC@NCS possesses a high N content (6.9 wt%). Density functional theory calculations disclose that the Co-SAs and Co-NCs are able to optimize the surface oxygen adsorption capability and enhance the conductivity of the NCS, thereby facilitating the ORR performance. The solvent-free synthesis is also feasible for the synthesis of other non-noble metal element (Fe, Ni, and Zn) decorated nitrogen-doped porous carbon spheres.
2025, 36(9): 110717
doi: 10.1016/j.cclet.2024.110717
Abstract:
Majority of photodynamic therapy (PDT) or photothermal therapy (PTT) is achieved by the integration of photosensitizers or photothermal agents into nanocarriers, which may bring risks due to uncertain leakage with serious nonspecific damage to normal tissues. Thus, we report an imine-linked nanoscale covalent organic framework (COF) with intrinsic photo-response ability, showing a high singlet oxygen generation ability by 660 nm irradiation, followed by the surface fabrication of polydopamine (PDA) that displays an excellent photothermal conversion performance under 808 nm irradiation. Furthermore, therapeutic agents with the modulation capacity of subcellular organelle such as mitochondria, shows more precision and effectiveness in cancer therapy. Herein, the obtained COF@PDA nanoplatform not only provides an excellent PDT/PTT-in-one therapeutic effect on inhibition of MCF-7 cancer cells, but also gives a prominent photo-induced mitochondrial regulation performance for enhanced treatment.
Majority of photodynamic therapy (PDT) or photothermal therapy (PTT) is achieved by the integration of photosensitizers or photothermal agents into nanocarriers, which may bring risks due to uncertain leakage with serious nonspecific damage to normal tissues. Thus, we report an imine-linked nanoscale covalent organic framework (COF) with intrinsic photo-response ability, showing a high singlet oxygen generation ability by 660 nm irradiation, followed by the surface fabrication of polydopamine (PDA) that displays an excellent photothermal conversion performance under 808 nm irradiation. Furthermore, therapeutic agents with the modulation capacity of subcellular organelle such as mitochondria, shows more precision and effectiveness in cancer therapy. Herein, the obtained COF@PDA nanoplatform not only provides an excellent PDT/PTT-in-one therapeutic effect on inhibition of MCF-7 cancer cells, but also gives a prominent photo-induced mitochondrial regulation performance for enhanced treatment.
2025, 36(9): 110718
doi: 10.1016/j.cclet.2024.110718
Abstract:
Drug resistance poses a significant challenge to effective long-term treatment across various medical fields. This study proposed a feasible strategy to enhance lysosomal alkalinization by transporting mitochondria-targeting quaternary ammonium salts into lysosomes, creating a deprotonated environment. This environment allows drugs to bypass protonation issues in lysosomes, thereby reversing drug resistance and improving therapeutic efficacy. As a proof of concept, a quaternary ammonium salt-based pH indicator was developed, berberrubine (BRB), enhancing the action of the anticancer drug hydroxycamptothecin (HCPT) in resistant cells. BRB-induced alkalinization increased lysosomal pH and deactivated lysosomal activity, enabling HCPT to bypass protonation constraints. This enhancement markedly improved the anticancer efficacy of HCPT in resistant cells, providing an innovative approach to address drug resistance and advancing therapeutic technologies.
Drug resistance poses a significant challenge to effective long-term treatment across various medical fields. This study proposed a feasible strategy to enhance lysosomal alkalinization by transporting mitochondria-targeting quaternary ammonium salts into lysosomes, creating a deprotonated environment. This environment allows drugs to bypass protonation issues in lysosomes, thereby reversing drug resistance and improving therapeutic efficacy. As a proof of concept, a quaternary ammonium salt-based pH indicator was developed, berberrubine (BRB), enhancing the action of the anticancer drug hydroxycamptothecin (HCPT) in resistant cells. BRB-induced alkalinization increased lysosomal pH and deactivated lysosomal activity, enabling HCPT to bypass protonation constraints. This enhancement markedly improved the anticancer efficacy of HCPT in resistant cells, providing an innovative approach to address drug resistance and advancing therapeutic technologies.
2025, 36(9): 110720
doi: 10.1016/j.cclet.2024.110720
Abstract:
For chromatographic separation, the reasonable modulation of stationary phases is the key factor to achieve high separation performance. We proposed that developing MOF stationary phases through precisely modulating the thermodynamic interactions between MOFs and analytes is conducive to improving the separation resolution. MIL-125, MIL-125-NH2, MIL-143-BTB, and MIL-143-TATB were developed as stationary phases with the careful modulation of organic ligands. MIL-125-NH2 and MIL-143-TATB coated columns exhibited much better separation performance than their counterparts, MIL-125 and MIL-143-BTB, respectively. The investigation of the separation mechanism indicated that thermodynamic interaction, rather than kinetic diffusion, was responsible for the separation improvement. MIL-125-NH2 and MIL-143-TATB provided stronger and distinguishable interactions with targets than corresponding MIL-125 and MIL-143-BTB, respectively, resulting in enhanced separation performance. This work demonstrates a guide to improving the separation performance of MOF stationary phases by increasing the thermodynamic interactions between MOFs and analytes.
For chromatographic separation, the reasonable modulation of stationary phases is the key factor to achieve high separation performance. We proposed that developing MOF stationary phases through precisely modulating the thermodynamic interactions between MOFs and analytes is conducive to improving the separation resolution. MIL-125, MIL-125-NH2, MIL-143-BTB, and MIL-143-TATB were developed as stationary phases with the careful modulation of organic ligands. MIL-125-NH2 and MIL-143-TATB coated columns exhibited much better separation performance than their counterparts, MIL-125 and MIL-143-BTB, respectively. The investigation of the separation mechanism indicated that thermodynamic interaction, rather than kinetic diffusion, was responsible for the separation improvement. MIL-125-NH2 and MIL-143-TATB provided stronger and distinguishable interactions with targets than corresponding MIL-125 and MIL-143-BTB, respectively, resulting in enhanced separation performance. This work demonstrates a guide to improving the separation performance of MOF stationary phases by increasing the thermodynamic interactions between MOFs and analytes.
2025, 36(9): 110721
doi: 10.1016/j.cclet.2024.110721
Abstract:
DNA repair enzymes are important in the repair of DNA lesions for maintaining the genome stability, and their abnormal expression induced various human cancers. Simultaneous detection of these DNA enzymes could provide convincing evidence based on the comparison of the activity of multiple enzymes than on that of single enzyme. Although fluorescence approach has been applied for the simultaneous detection both of DNA repair enzymes, the spectral overlap and multiwavelength excitation severely restrict the number of available fluorophores. Thus, it is difficult to simultaneously detect three enzymes in a single analysis by fluorescence detection. Herein, we developed a method for the simultaneous determination of three DNA repair enzymes including human flap DNA endonuclease 1 (FEN1), human alkyladenine DNA glycosylase (hAAG) and uracil DNA glycosylase (UDG) based on the combination of template-free amplification system with capillary electrophoresis-laser induced fluorescence (CE-LIF) detection. The amplification system was adopted to transfer and amplify the enzymatic products into different length DNA fragments which could be separated effectively by CE-LIF without the complicated modification of the capillary inner wall or labeling different tails on signal probes for separation. The method demonstrated a detection limit of 0.07 U/mL (0.08-160 U/mL) for FEN1, 2.40 U/mL (2.5-250 U/mL) for hAAG and 2.1 × 10−4 U/mL (0.0004-2.5 U/mL) for UDG, the relative standard deviations (RSDs) of peak time and peak area for different analytes were as follows: 2.50%-4.37% and 3.24%-7.18% (inter-day); 1.37%-2.71% and 1.43%-3.02% (intra-day), 4.28%-6.08% and 4.16%-7.57% (column to column), respectively. And it can identify the inhibitor-like drugs, evaluate enzymatic kinetics and achieve the detection of three enzymes in cell extracts, providing a simple and powerful platform for simultaneous detection of more DNA repair enzymes.
DNA repair enzymes are important in the repair of DNA lesions for maintaining the genome stability, and their abnormal expression induced various human cancers. Simultaneous detection of these DNA enzymes could provide convincing evidence based on the comparison of the activity of multiple enzymes than on that of single enzyme. Although fluorescence approach has been applied for the simultaneous detection both of DNA repair enzymes, the spectral overlap and multiwavelength excitation severely restrict the number of available fluorophores. Thus, it is difficult to simultaneously detect three enzymes in a single analysis by fluorescence detection. Herein, we developed a method for the simultaneous determination of three DNA repair enzymes including human flap DNA endonuclease 1 (FEN1), human alkyladenine DNA glycosylase (hAAG) and uracil DNA glycosylase (UDG) based on the combination of template-free amplification system with capillary electrophoresis-laser induced fluorescence (CE-LIF) detection. The amplification system was adopted to transfer and amplify the enzymatic products into different length DNA fragments which could be separated effectively by CE-LIF without the complicated modification of the capillary inner wall or labeling different tails on signal probes for separation. The method demonstrated a detection limit of 0.07 U/mL (0.08-160 U/mL) for FEN1, 2.40 U/mL (2.5-250 U/mL) for hAAG and 2.1 × 10−4 U/mL (0.0004-2.5 U/mL) for UDG, the relative standard deviations (RSDs) of peak time and peak area for different analytes were as follows: 2.50%-4.37% and 3.24%-7.18% (inter-day); 1.37%-2.71% and 1.43%-3.02% (intra-day), 4.28%-6.08% and 4.16%-7.57% (column to column), respectively. And it can identify the inhibitor-like drugs, evaluate enzymatic kinetics and achieve the detection of three enzymes in cell extracts, providing a simple and powerful platform for simultaneous detection of more DNA repair enzymes.
2025, 36(9): 110723
doi: 10.1016/j.cclet.2024.110723
Abstract:
The androgenetic alopecia (AGA) is the most prevalent clinical manifestation of hair loss, believed to be associated with excessive dihydrotestosterone (DHT) caused by type Ⅱ 5α-reductase (5αR2). The utilization of oral finasteride (FNS), which selectively inhibits 5αR2, is frequently constrained by its adverse effects. Topical FNS formulations can mitigate adverse effects but often exhibit limited dermal permeability. Nanocarriers show great potential in augmenting the cutaneous permeation of loaded FNS due to their inherent properties of selective accumulation within the hair follicles (HFs). In this study, hollow mesoporous silica nanoparticles (HMSN) with varying sizes were utilized as the nanocarriers for FNS, following mixing with the Carbopol hydrogel (F@H/Gel) for direct topical application. Specifically, the influence of size on the targeted delivery of FNS to HFs, and its enhanced therapeutic efficacy for the AGA mice model was evaluated. Results showed that the HMSN, with a diameter of approximately 300 nm, exhibited significant enhancement in FNS retention within skin and HFs, as well as remarkably accelerated hair regrowth on an AGA mouse model. In conclusion, this FNS topical formulation has proved to be a viable approach in offering a secure and efficient treatment modality for AGA.
The androgenetic alopecia (AGA) is the most prevalent clinical manifestation of hair loss, believed to be associated with excessive dihydrotestosterone (DHT) caused by type Ⅱ 5α-reductase (5αR2). The utilization of oral finasteride (FNS), which selectively inhibits 5αR2, is frequently constrained by its adverse effects. Topical FNS formulations can mitigate adverse effects but often exhibit limited dermal permeability. Nanocarriers show great potential in augmenting the cutaneous permeation of loaded FNS due to their inherent properties of selective accumulation within the hair follicles (HFs). In this study, hollow mesoporous silica nanoparticles (HMSN) with varying sizes were utilized as the nanocarriers for FNS, following mixing with the Carbopol hydrogel (F@H/Gel) for direct topical application. Specifically, the influence of size on the targeted delivery of FNS to HFs, and its enhanced therapeutic efficacy for the AGA mice model was evaluated. Results showed that the HMSN, with a diameter of approximately 300 nm, exhibited significant enhancement in FNS retention within skin and HFs, as well as remarkably accelerated hair regrowth on an AGA mouse model. In conclusion, this FNS topical formulation has proved to be a viable approach in offering a secure and efficient treatment modality for AGA.
2025, 36(9): 110735
doi: 10.1016/j.cclet.2024.110735
Abstract:
In this work, we synthesize two luminescent Pt(Ⅱ) complexes using different π-conjugated bidentate ligands. Both complexes are assembled into three-dimensional (3D) networks through non-classical intermolecular interactions in the crystal state. Unexpectedly, substituting pyridine with the more extensively π-conjugated quinoline significantly increases the dihedral angles between the phenyl and quinolyl groups of the bidentate ligands. This alteration disrupts the π-π interactions between molecules, resulting in distinct optical properties upon exposure to external stimuli. By integrating these complexes into polymers, we fabricate electrospun films containing luminescent nanofibers that exhibit reversible optical changes. These findings have paved the way for the development of high-performance optical encryption and anti-counterfeiting materials, achieved through the employment of simple chromophores.
In this work, we synthesize two luminescent Pt(Ⅱ) complexes using different π-conjugated bidentate ligands. Both complexes are assembled into three-dimensional (3D) networks through non-classical intermolecular interactions in the crystal state. Unexpectedly, substituting pyridine with the more extensively π-conjugated quinoline significantly increases the dihedral angles between the phenyl and quinolyl groups of the bidentate ligands. This alteration disrupts the π-π interactions between molecules, resulting in distinct optical properties upon exposure to external stimuli. By integrating these complexes into polymers, we fabricate electrospun films containing luminescent nanofibers that exhibit reversible optical changes. These findings have paved the way for the development of high-performance optical encryption and anti-counterfeiting materials, achieved through the employment of simple chromophores.
2025, 36(9): 110737
doi: 10.1016/j.cclet.2024.110737
Abstract:
Structure-based virtual screening utilizing the approved drugs is an intriguing and laudable approach to excavate novel alternatives for different indications based on the vast amount of reported experimental data. Virus superfamily 1 helicase could resolve hydrogen bonds between base pairs and participate in nucleic acid replication and has emerged as a potential target for managing virus infection. Nonetheless, current drug exploitation targeting viral helicases is still in infancy. This work establishes an intelligent multi-computational screening programme to screen potential inhibitors targeting tobacco mosaic virus (TMV) helicase using Food and Drug Administration (FDA)-approved commercially available molecule library. The ranked top 6 hits were further validated by root mean square deviations/fluctuations (RMSD/F), molecular mechanics Poisson Boltzmann surface area (MM-PBSA), density functional theory (DFT) calculations, and bioactivity evaluation. Encouragingly, lumacaftor (ΔEtotal = −29.0 kcal/mol, Kd = 0.22 µmol/L, half maximal inhibitory concentration (IC50) = 162.5 µmol/L) displayed superior binding strength and enzyme inhibition against TMV helicase compared to ningnanmycin (Kd = 9.35 µmol/L, IC50 > 200 µmol/L). Therefore, lumacaftor may be able to inhibit TMV replication by binding to helicase and interfering with its biofunctionability. Besides, the lumacaftor-helicase binding mode changes from H-bonding/electrostatic interactions to hydrophobic interactions in trajectory analysis. Overall, current findings suggest this state-of-the-art stratagem is fruitful and has the potential to be engaged in rapid mining of other target inhibitors for disease treatment.
Structure-based virtual screening utilizing the approved drugs is an intriguing and laudable approach to excavate novel alternatives for different indications based on the vast amount of reported experimental data. Virus superfamily 1 helicase could resolve hydrogen bonds between base pairs and participate in nucleic acid replication and has emerged as a potential target for managing virus infection. Nonetheless, current drug exploitation targeting viral helicases is still in infancy. This work establishes an intelligent multi-computational screening programme to screen potential inhibitors targeting tobacco mosaic virus (TMV) helicase using Food and Drug Administration (FDA)-approved commercially available molecule library. The ranked top 6 hits were further validated by root mean square deviations/fluctuations (RMSD/F), molecular mechanics Poisson Boltzmann surface area (MM-PBSA), density functional theory (DFT) calculations, and bioactivity evaluation. Encouragingly, lumacaftor (ΔEtotal = −29.0 kcal/mol, Kd = 0.22 µmol/L, half maximal inhibitory concentration (IC50) = 162.5 µmol/L) displayed superior binding strength and enzyme inhibition against TMV helicase compared to ningnanmycin (Kd = 9.35 µmol/L, IC50 > 200 µmol/L). Therefore, lumacaftor may be able to inhibit TMV replication by binding to helicase and interfering with its biofunctionability. Besides, the lumacaftor-helicase binding mode changes from H-bonding/electrostatic interactions to hydrophobic interactions in trajectory analysis. Overall, current findings suggest this state-of-the-art stratagem is fruitful and has the potential to be engaged in rapid mining of other target inhibitors for disease treatment.
2025, 36(9): 110740
doi: 10.1016/j.cclet.2024.110740
Abstract:
The induction of antitumor immunity by tumor antigens released from cancer cells following regional photothermal therapy (PTT) alone may not be adequate for achieving complete tumor elimination. Combination therapy with immune adjuvants enhances antitumor immune responses, but faces challenges such as targeting deficiencies, systemic toxicity, and uncontrolled release behavior. Herein, we introduce a novel dual-functional hybrid membrane nanoparticle (HM-NP) incorporating gold nanorods (GNRs) and a thermally responsive polymer shell. HM-NP demonstrates exceptional homotypic targeting efficacy beneath the tumor cell membrane (TM), leading to substantial tumor accumulation. Upon in situ near-infrared (NIR) stimulation, GNRs within HM-NP generate heat, triggering the burst release of HM by facilitating the contraction and disintegration of the thermally responsive polymer shell. HM-NP exhibits excellent photothermal conversion efficiency under NIR irradiation, enabling effective destruction of primary tumors, release of tumor-associated antigens, and stimulation of potent anti- cancer immune. Simultaneously, the immune responses are strengthened by TM and Escherichia coli membrane (EM) through promoting the maturation of antigen presenting cells (APCs) and activating cytotoxic T lymphocytes (CTLs). Moreover, the use of polymer shells enables efficient cancer therapy with minimal host clearance and adverse effects. This photothermally triggered immunotherapy holds promise for precise and personalized treatment of tumors.
The induction of antitumor immunity by tumor antigens released from cancer cells following regional photothermal therapy (PTT) alone may not be adequate for achieving complete tumor elimination. Combination therapy with immune adjuvants enhances antitumor immune responses, but faces challenges such as targeting deficiencies, systemic toxicity, and uncontrolled release behavior. Herein, we introduce a novel dual-functional hybrid membrane nanoparticle (HM-NP) incorporating gold nanorods (GNRs) and a thermally responsive polymer shell. HM-NP demonstrates exceptional homotypic targeting efficacy beneath the tumor cell membrane (TM), leading to substantial tumor accumulation. Upon in situ near-infrared (NIR) stimulation, GNRs within HM-NP generate heat, triggering the burst release of HM by facilitating the contraction and disintegration of the thermally responsive polymer shell. HM-NP exhibits excellent photothermal conversion efficiency under NIR irradiation, enabling effective destruction of primary tumors, release of tumor-associated antigens, and stimulation of potent anti- cancer immune. Simultaneously, the immune responses are strengthened by TM and Escherichia coli membrane (EM) through promoting the maturation of antigen presenting cells (APCs) and activating cytotoxic T lymphocytes (CTLs). Moreover, the use of polymer shells enables efficient cancer therapy with minimal host clearance and adverse effects. This photothermally triggered immunotherapy holds promise for precise and personalized treatment of tumors.
2025, 36(9): 110742
doi: 10.1016/j.cclet.2024.110742
Abstract:
Current research in the direction of electrocatalytic reduction of CO2 (ECO2R) focuses on the preparation of catalysts with excellent performance, but little has been reported on the effect of electrolyte type on the selectivity of ECO2R gas products. In this work, the ECO2R performance of unmodified Cu foam (CF) was systematically investigated in four electrolytes (KCl, NaCl, KHCO3, and NaHCO3) at different concentrations (0.1, 0.5 and 1.0 mol/L), using CF as the working electrode. The results showed that CF exhibited high selectivity for C2H4 in KCl solution, while high selectivity for CH4 in low concentration NaCl and NaHCO3 solutions containing Na+. In addition, serious hydrogen evolution reactions (HERs) were observed in both KHCO3 and NaHCO3 solutions at higher concentrations, which were attributed to the lower local pH of the two buffer solutions. It was also shown that solution resistance of the cathode electrolyte during ECO2R process decreased consistently due to the trans-membrane diffusion of K+ and Na+, especially at the low concentration of electrolyte of 0.1 mol/L. It was detrimental to keep the reduction process stabilized for a long period of time. Furthermore, the non-buffered solutions KCl and NaCl also maintained a neutral pH (≈ 6.7) after a period of ECO2R, resulting in a stable ECO2R. The results of this work will provide significant insights into the design of reaction systems of ECO2R in the future.
Current research in the direction of electrocatalytic reduction of CO2 (ECO2R) focuses on the preparation of catalysts with excellent performance, but little has been reported on the effect of electrolyte type on the selectivity of ECO2R gas products. In this work, the ECO2R performance of unmodified Cu foam (CF) was systematically investigated in four electrolytes (KCl, NaCl, KHCO3, and NaHCO3) at different concentrations (0.1, 0.5 and 1.0 mol/L), using CF as the working electrode. The results showed that CF exhibited high selectivity for C2H4 in KCl solution, while high selectivity for CH4 in low concentration NaCl and NaHCO3 solutions containing Na+. In addition, serious hydrogen evolution reactions (HERs) were observed in both KHCO3 and NaHCO3 solutions at higher concentrations, which were attributed to the lower local pH of the two buffer solutions. It was also shown that solution resistance of the cathode electrolyte during ECO2R process decreased consistently due to the trans-membrane diffusion of K+ and Na+, especially at the low concentration of electrolyte of 0.1 mol/L. It was detrimental to keep the reduction process stabilized for a long period of time. Furthermore, the non-buffered solutions KCl and NaCl also maintained a neutral pH (≈ 6.7) after a period of ECO2R, resulting in a stable ECO2R. The results of this work will provide significant insights into the design of reaction systems of ECO2R in the future.
2025, 36(9): 110768
doi: 10.1016/j.cclet.2024.110768
Abstract:
The objective of this study was to predict, screen, synthesize, and investigate cocrystals of poorly soluble flavonoids that are commonly found in dietary supplements with bipolar compound picolinic acid (PA). To improve the efficiency and success rate of experimental screening, two virtual tools based on hydrogen bond propensity (HBP) and modified molecular electrostatic potential (MEP) maps were used. The prediction accuracy of HBP and MEP is 58.82% and 94.11%, respectively, presenting that the MEP model is very powerful in the discovery of pharmaceutical cocrystals. Among the 12 successfully obtained cocrystals, 4 single crystals of PA with luteolin (LUT), genistein (GEN), taxifolin (TAX), dihydromyricetin (DHM) were obtained for the first time. Charged-assisted OH···O and NH···O hydrogen bonds appear as main hydrogen bonding synthons, and PA adopts a zwitterionic form after cocrystallization. GEN-PA, TAX-PA, and DHM-PA showed higher DPPH• radical-scavenging capacities; LUT-PA and DHM-PA showed higher ABTS+ radical-scavenging capacities; GEN-PA and DHM-PA possessed better protective effects on H9c2 cells from hypoxic injury caused by CoCl2 than corresponding pure flavonoids.
The objective of this study was to predict, screen, synthesize, and investigate cocrystals of poorly soluble flavonoids that are commonly found in dietary supplements with bipolar compound picolinic acid (PA). To improve the efficiency and success rate of experimental screening, two virtual tools based on hydrogen bond propensity (HBP) and modified molecular electrostatic potential (MEP) maps were used. The prediction accuracy of HBP and MEP is 58.82% and 94.11%, respectively, presenting that the MEP model is very powerful in the discovery of pharmaceutical cocrystals. Among the 12 successfully obtained cocrystals, 4 single crystals of PA with luteolin (LUT), genistein (GEN), taxifolin (TAX), dihydromyricetin (DHM) were obtained for the first time. Charged-assisted OH···O and NH···O hydrogen bonds appear as main hydrogen bonding synthons, and PA adopts a zwitterionic form after cocrystallization. GEN-PA, TAX-PA, and DHM-PA showed higher DPPH• radical-scavenging capacities; LUT-PA and DHM-PA showed higher ABTS+ radical-scavenging capacities; GEN-PA and DHM-PA possessed better protective effects on H9c2 cells from hypoxic injury caused by CoCl2 than corresponding pure flavonoids.
2025, 36(9): 110783
doi: 10.1016/j.cclet.2024.110783
Abstract:
Chondroitin sulfate (CS) B and T are rare subtypes of CS, which are scare in nature. There are also limited synthetic methods to prepare them. Here we report an ingenious semisynthetic approach to prepare a library of disaccharides, tetrasaccharides and hexasaccharides of CS-B and CS-T based on the acid or enzymatic degradation of natural CS polysaccharide in 9 or 10 steps. Our approach is the shortest synthetic route toward size-defined CS-B and CS-T oligosaccharides reported to date. In addition, a regioselective protection method of hydroxyls is highlighted, which has achieved the regioselective protection of 4 hydroxyl groups among 7 equatorial hydroxyl groups. By preparing size-defined rare CS oligosaccharides from commercially available natural CS polysaccharides, this strategy has the potential to meet the need of rare natural oligosaccharides.
Chondroitin sulfate (CS) B and T are rare subtypes of CS, which are scare in nature. There are also limited synthetic methods to prepare them. Here we report an ingenious semisynthetic approach to prepare a library of disaccharides, tetrasaccharides and hexasaccharides of CS-B and CS-T based on the acid or enzymatic degradation of natural CS polysaccharide in 9 or 10 steps. Our approach is the shortest synthetic route toward size-defined CS-B and CS-T oligosaccharides reported to date. In addition, a regioselective protection method of hydroxyls is highlighted, which has achieved the regioselective protection of 4 hydroxyl groups among 7 equatorial hydroxyl groups. By preparing size-defined rare CS oligosaccharides from commercially available natural CS polysaccharides, this strategy has the potential to meet the need of rare natural oligosaccharides.
2025, 36(9): 110785
doi: 10.1016/j.cclet.2024.110785
Abstract:
Developing novel building blocks with predictable side-chain orientations and minimal intramolecular interactions is essential for peptide-based self-assembling materials. Traditional structures like α-helices and β-sheets rely on such interactions for stability, limiting control over exposed interacting moieties. Here, we reported a novel, frame-like peptide scaffold that maintains exceptional stability without intramolecular interactions. This structure exposes its backbone and orients side chains for hierarchical self-assembly into micron-scale cubes. By introducing mutations at specific sites, we controlled packing orientations, offering new options for tunable self-assembly. Our scaffold provides a versatile platform for designing advanced peptide materials, with applications in nanotechnology and biomaterials.
Developing novel building blocks with predictable side-chain orientations and minimal intramolecular interactions is essential for peptide-based self-assembling materials. Traditional structures like α-helices and β-sheets rely on such interactions for stability, limiting control over exposed interacting moieties. Here, we reported a novel, frame-like peptide scaffold that maintains exceptional stability without intramolecular interactions. This structure exposes its backbone and orients side chains for hierarchical self-assembly into micron-scale cubes. By introducing mutations at specific sites, we controlled packing orientations, offering new options for tunable self-assembly. Our scaffold provides a versatile platform for designing advanced peptide materials, with applications in nanotechnology and biomaterials.
2025, 36(9): 110786
doi: 10.1016/j.cclet.2024.110786
Abstract:
Advances in controllable growth of ultrathin two-dimensional molecular crystals (2DMCs) or even monolayer molecular crystals (MMCs) propelled their application in high-performance, high-sensitivity, low-contact-resistance optoelectronic devices. However, the rational molecular design strategies for materials prone to grow into ultrathin 2DMC or MMC have rarely been addressed. Here, systematically tailoring the π-conjugation and alkyl chain types of asymmetric anthracene derivatives, 2DMCs and even MMCs were obtained under the synergetic regulation of inter- and intralayer interactions. High-quality MMCs were obtained for SAP-C6 by traditional physical vapor transport technique (PVT), and corresponding organic field-effect transistors (OFETs) exhibited high mobility of 3.22 cm2 V-1 s-1. In addition, band-like charge transport with low activation energy was achieved by SAP-C6 MMC-OFETs. Furthermore, the SAP-C6 MMC-based device exhibits excellent thermal stability, retaining ~70% of its initial performance at 140 ℃ in air, which is the first report on the thermal stability of MMC devices. This research highlights the potential of alkyl-substituted asymmetric molecules as a design strategy to achieve ultrathin 2DMC or MMC growth, and improve the mobility and thermal stability in OFETs.
Advances in controllable growth of ultrathin two-dimensional molecular crystals (2DMCs) or even monolayer molecular crystals (MMCs) propelled their application in high-performance, high-sensitivity, low-contact-resistance optoelectronic devices. However, the rational molecular design strategies for materials prone to grow into ultrathin 2DMC or MMC have rarely been addressed. Here, systematically tailoring the π-conjugation and alkyl chain types of asymmetric anthracene derivatives, 2DMCs and even MMCs were obtained under the synergetic regulation of inter- and intralayer interactions. High-quality MMCs were obtained for SAP-C6 by traditional physical vapor transport technique (PVT), and corresponding organic field-effect transistors (OFETs) exhibited high mobility of 3.22 cm2 V-1 s-1. In addition, band-like charge transport with low activation energy was achieved by SAP-C6 MMC-OFETs. Furthermore, the SAP-C6 MMC-based device exhibits excellent thermal stability, retaining ~70% of its initial performance at 140 ℃ in air, which is the first report on the thermal stability of MMC devices. This research highlights the potential of alkyl-substituted asymmetric molecules as a design strategy to achieve ultrathin 2DMC or MMC growth, and improve the mobility and thermal stability in OFETs.
2025, 36(9): 110797
doi: 10.1016/j.cclet.2024.110797
Abstract:
The gut pathogen Enterocloster bolteae (E. bolteae) has been associated with autism spectrum disorder (ASD). The development of an E. bolteae vaccine to prevent gastrointestinal diseases, might be beneficial for understanding and treating ASD. Capsular polysaccharide (CPS) is a major virulence factor for E. bolteae. Based on an antigenicity evaluation of oligosaccharides associated with E. bolteae CPS and a structural revision of this carbohydrate antigen, two series of glycans including the d-Manp-d-Rhap type oligosaccharides 13–18 and the d-Ribp-d-Rhap type disaccharides 19–23 related to E. bolteae WAL-16351 CPS were prepared. The hydrogen-bond mediated glycosylation and conformational locking strategy facilitated the constructions of two 1,2-cis-β-glycosidic linkages. Glycan microarray analysis revealed that oligosaccharides 4, 5, and 19 are recognized by antibodies in the anti-E. bolteae sera. The sera IgG antibodies induced by glycoconjugate 19-CRM197 recognize the CPS and bacteria specifically, whereas the IgG antibodies induced respectively by glycoconjugates 4-CRM197 and 5-CRM197 showed almost no binding to the CPS and bacteria. These results indicated that disaccharide 19 is a potential candidate for the development of E. bolteae vaccines.
The gut pathogen Enterocloster bolteae (E. bolteae) has been associated with autism spectrum disorder (ASD). The development of an E. bolteae vaccine to prevent gastrointestinal diseases, might be beneficial for understanding and treating ASD. Capsular polysaccharide (CPS) is a major virulence factor for E. bolteae. Based on an antigenicity evaluation of oligosaccharides associated with E. bolteae CPS and a structural revision of this carbohydrate antigen, two series of glycans including the d-Manp-d-Rhap type oligosaccharides 13–18 and the d-Ribp-d-Rhap type disaccharides 19–23 related to E. bolteae WAL-16351 CPS were prepared. The hydrogen-bond mediated glycosylation and conformational locking strategy facilitated the constructions of two 1,2-cis-β-glycosidic linkages. Glycan microarray analysis revealed that oligosaccharides 4, 5, and 19 are recognized by antibodies in the anti-E. bolteae sera. The sera IgG antibodies induced by glycoconjugate 19-CRM197 recognize the CPS and bacteria specifically, whereas the IgG antibodies induced respectively by glycoconjugates 4-CRM197 and 5-CRM197 showed almost no binding to the CPS and bacteria. These results indicated that disaccharide 19 is a potential candidate for the development of E. bolteae vaccines.
2025, 36(9): 110807
doi: 10.1016/j.cclet.2024.110807
Abstract:
Pyridine (Py) and 3-methylpyridine (3-MP) are crucial intermediates in chemical industrial processes. Here, we provide a simple and energy-efficient approach for the isolation of Py and 3-MP by employing crystalline cucurbit[6]uril (Q[6]). The crystal exhibit high selectivity for Py from the mixture of Py and 3-MP in both vapor and liquid phases, with separation purities close to 100%. The selectivity is attributed to the varying stability of the host–guest complexes after the absorption of Py or 3-MP, as revealed by the single-crystal structure analysis. ITC experimental results and DFT calculations indicate that, compared to 3-MP, Q[6] has a higher binding strength and lower binding energy with Py. In addition, pyridine can be removed from the Q[6] cavity through vacuum heating or organic solvent immersion, enabling Q[6] reuse via reversible guest loading. This method offers a promising approach for high-purity Py and 3-MP separation with significant economic and environmental benefits.
Pyridine (Py) and 3-methylpyridine (3-MP) are crucial intermediates in chemical industrial processes. Here, we provide a simple and energy-efficient approach for the isolation of Py and 3-MP by employing crystalline cucurbit[6]uril (Q[6]). The crystal exhibit high selectivity for Py from the mixture of Py and 3-MP in both vapor and liquid phases, with separation purities close to 100%. The selectivity is attributed to the varying stability of the host–guest complexes after the absorption of Py or 3-MP, as revealed by the single-crystal structure analysis. ITC experimental results and DFT calculations indicate that, compared to 3-MP, Q[6] has a higher binding strength and lower binding energy with Py. In addition, pyridine can be removed from the Q[6] cavity through vacuum heating or organic solvent immersion, enabling Q[6] reuse via reversible guest loading. This method offers a promising approach for high-purity Py and 3-MP separation with significant economic and environmental benefits.
2025, 36(9): 110808
doi: 10.1016/j.cclet.2024.110808
Abstract:
Sulfur dioxide (SO2), being one of the therapeutic gaseous molecules, has been widely utilized in cancer therapy because of its high therapeutic efficacy and biosafety. Nevertheless, the in situ-triggered and efficient transportation of SO2 to tumors are the main obstacles that restrict its clinical application. To overcome this impediment, we functionalized pillar[5]arene with 2, 4-dinitrobenzene sulfonic acid (DNSB) and then self-assembled it with tetraphenyl-PEG (TPE-PEG) in aqueous media to form fluorescent nanoparticles (PSTPE NPs). Meanwhile, the target guest (NH2-PEG-FA) was encapsulated within the spacious cavity of pillar[5]arene via host-guest interaction. The resulting nanoparticles possess distinctive characteristics: (Ⅰ) dual GSH recognition motifs for enhanced SO2 release kinetics; (Ⅱ) incorporation of targeting ligands for selective cytotoxicity towards tumor cells while sparing normal tissues and cells; and (Ⅲ) surface modification of pillar[5]arene with TPE-PEG conferring excellent dispersibility, biocompatibility, and fluorescence properties in aqueous environments. Collectively, this novel nanoparticle represents an innovative approach that utilizes macrocyclics as SO2 gas donors to induce cellular apoptosis and provides new insights into gas-based therapy.
Sulfur dioxide (SO2), being one of the therapeutic gaseous molecules, has been widely utilized in cancer therapy because of its high therapeutic efficacy and biosafety. Nevertheless, the in situ-triggered and efficient transportation of SO2 to tumors are the main obstacles that restrict its clinical application. To overcome this impediment, we functionalized pillar[5]arene with 2, 4-dinitrobenzene sulfonic acid (DNSB) and then self-assembled it with tetraphenyl-PEG (TPE-PEG) in aqueous media to form fluorescent nanoparticles (PSTPE NPs). Meanwhile, the target guest (NH2-PEG-FA) was encapsulated within the spacious cavity of pillar[5]arene via host-guest interaction. The resulting nanoparticles possess distinctive characteristics: (Ⅰ) dual GSH recognition motifs for enhanced SO2 release kinetics; (Ⅱ) incorporation of targeting ligands for selective cytotoxicity towards tumor cells while sparing normal tissues and cells; and (Ⅲ) surface modification of pillar[5]arene with TPE-PEG conferring excellent dispersibility, biocompatibility, and fluorescence properties in aqueous environments. Collectively, this novel nanoparticle represents an innovative approach that utilizes macrocyclics as SO2 gas donors to induce cellular apoptosis and provides new insights into gas-based therapy.
2025, 36(9): 110809
doi: 10.1016/j.cclet.2024.110809
Abstract:
Mechanistic studies of the cleavage and transformation of unactivated Csp3–H bonds are a significant field of chemistry. Overcoming the inherent low acidity of C–H bonds to activate the inert substrates is challenge under mild conditions. And their complex multi-step transformations may also hinder mechanistic understanding. Herein, we perform theoretical calculations and experimental studies to explore the Csp3–H bonds activation and acylation mechanisms of toluene/thioether using the relatively weak base LDA. A synergistic "main and auxiliary" model was revealed involving dual lithium metal by LDA dimers, and the aryl dilithium species as an intermediate base can facilitate Csp3–H activation. This model not only aids in understanding the acidity of unactivated Csp3–H bonds and the nucleophilicity of their conjugate bases for their kinetic control through cooperative interactions, but also predicts unusual kinetic isotope effects (KIE) for newly designed 2-(methylthio)naphthalene that are experimentally validated. This research is expected to provide a crucial scenario for the cleavage and transformation of unactivated Csp3–H bonds and the development of new functionalities for alkali metal reagents.
Mechanistic studies of the cleavage and transformation of unactivated Csp3–H bonds are a significant field of chemistry. Overcoming the inherent low acidity of C–H bonds to activate the inert substrates is challenge under mild conditions. And their complex multi-step transformations may also hinder mechanistic understanding. Herein, we perform theoretical calculations and experimental studies to explore the Csp3–H bonds activation and acylation mechanisms of toluene/thioether using the relatively weak base LDA. A synergistic "main and auxiliary" model was revealed involving dual lithium metal by LDA dimers, and the aryl dilithium species as an intermediate base can facilitate Csp3–H activation. This model not only aids in understanding the acidity of unactivated Csp3–H bonds and the nucleophilicity of their conjugate bases for their kinetic control through cooperative interactions, but also predicts unusual kinetic isotope effects (KIE) for newly designed 2-(methylthio)naphthalene that are experimentally validated. This research is expected to provide a crucial scenario for the cleavage and transformation of unactivated Csp3–H bonds and the development of new functionalities for alkali metal reagents.
2025, 36(9): 110810
doi: 10.1016/j.cclet.2024.110810
Abstract:
Herein, a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution (SNAr) using TMSCN as a cheap cyanide source under mild conditions has been presented. This transformation utilizes commercially available reagents, cheap electrodes, and simple equipment. Diverse aryl nitriles were successfully obtained in a direct and efficient way with broad substrate scope, excellent functional group tolerance, and selective C−O bond cleavage. Furthermore, late-stage modification of biorelevant compounds and gram-scale synthesis highlighted the potential application of the strategy. Mechanistic investigations suggest that the arene cation radical was considered as the key intermediate for the transformation, and undergoing the followed SNAr process.
Herein, a metal-free electrochemical demethoxyl-cyanation of methoxyarenes via aromatic nucleophilic substitution (SNAr) using TMSCN as a cheap cyanide source under mild conditions has been presented. This transformation utilizes commercially available reagents, cheap electrodes, and simple equipment. Diverse aryl nitriles were successfully obtained in a direct and efficient way with broad substrate scope, excellent functional group tolerance, and selective C−O bond cleavage. Furthermore, late-stage modification of biorelevant compounds and gram-scale synthesis highlighted the potential application of the strategy. Mechanistic investigations suggest that the arene cation radical was considered as the key intermediate for the transformation, and undergoing the followed SNAr process.
2025, 36(9): 110820
doi: 10.1016/j.cclet.2025.110820
Abstract:
Chiral anticancer drugs are the subject of ongoing research due to their optical characterization and pharmacological effects. Achieving a single enantiomer of a chiral anticancer drug is arduous, but it can significantly improve its pharmacokinetics for tumor therapy. Here, the chiral nanocatchers, known as d-biotin-P5⊃MCC NCs, were designed and prepared based on host-guest self-assembly between d-biotin anchored pillar[5]arene (d-biotin-P5) and myristoyl chloride choline (MCC). d-Biotin-P5⊃MCC NCs featuring the chiral separation and enzyme-induced disassemble were evaluated for their ability to selectively capture and subsequently target the release of (R,R)-OXA enantiomers into tumor cells. Furthermore, the use of d-biotin-P5⊃MCC NCs has demonstrated a significant enhancement in the intracellular uptake of OXA, with the drug being efficiently released to MCF-7 breast cancer cells. This has led to a superior inhibitory effect on MCF-7 cells when compared to free OXA, while also reducing the cytotoxicity of the drug in HEK 293 human embryonic kidney cells. This research not only paves a promising way for the fabrication of chiral supramolecular nanocarriers but also holds the potential to improve the processes of chiral drug separation and targeted therapy.
Chiral anticancer drugs are the subject of ongoing research due to their optical characterization and pharmacological effects. Achieving a single enantiomer of a chiral anticancer drug is arduous, but it can significantly improve its pharmacokinetics for tumor therapy. Here, the chiral nanocatchers, known as d-biotin-P5⊃MCC NCs, were designed and prepared based on host-guest self-assembly between d-biotin anchored pillar[5]arene (d-biotin-P5) and myristoyl chloride choline (MCC). d-Biotin-P5⊃MCC NCs featuring the chiral separation and enzyme-induced disassemble were evaluated for their ability to selectively capture and subsequently target the release of (R,R)-OXA enantiomers into tumor cells. Furthermore, the use of d-biotin-P5⊃MCC NCs has demonstrated a significant enhancement in the intracellular uptake of OXA, with the drug being efficiently released to MCF-7 breast cancer cells. This has led to a superior inhibitory effect on MCF-7 cells when compared to free OXA, while also reducing the cytotoxicity of the drug in HEK 293 human embryonic kidney cells. This research not only paves a promising way for the fabrication of chiral supramolecular nanocarriers but also holds the potential to improve the processes of chiral drug separation and targeted therapy.
2025, 36(9): 110821
doi: 10.1016/j.cclet.2025.110821
Abstract:
This investigation focuses on the utilization of cucurbit[6]uril (Q[6]) as the host compound for the development of long-lasting afterglow materials. By strategically manipulating the outer surface interactions of Q[6], classical aggregation-caused quenching (ACQ) compounds such as fluorescein sodium (FluNa) and calcein sodium (CalNa) were transformed into afterglow materials with varying colors and durations upon exposure to ultraviolet light. This transformation was facilitated through a host-guest doping method combined with coordination with metal ions. Even at a reduced doping concentration of 5 × 10–5 wt%, the materials exhibit remarkable afterglow properties, lasting up to 2 s, with a phosphorescence lifetime of up to 150 ms. Moreover, by adjusting the concentration of the guest compound, the persistent luminescence color of the materials could be easily transitioned from orange to yellow and subsequently to green. These findings suggest that the developed afterglow materials hold significant potential for multi-level anti-counterfeiting and information encryption applications when exposed to ultraviolet light. The supramolecular assembly strategy, which relies on the outer surface interactions of cucurbit[n]uril, offers a simpler and more efficient approach to crafting multi-color luminescent materials. Additionally, this method opens avenues for enhancing the application potential of aggregation-caused quenching (ACQ) compounds in various technological domains.
This investigation focuses on the utilization of cucurbit[6]uril (Q[6]) as the host compound for the development of long-lasting afterglow materials. By strategically manipulating the outer surface interactions of Q[6], classical aggregation-caused quenching (ACQ) compounds such as fluorescein sodium (FluNa) and calcein sodium (CalNa) were transformed into afterglow materials with varying colors and durations upon exposure to ultraviolet light. This transformation was facilitated through a host-guest doping method combined with coordination with metal ions. Even at a reduced doping concentration of 5 × 10–5 wt%, the materials exhibit remarkable afterglow properties, lasting up to 2 s, with a phosphorescence lifetime of up to 150 ms. Moreover, by adjusting the concentration of the guest compound, the persistent luminescence color of the materials could be easily transitioned from orange to yellow and subsequently to green. These findings suggest that the developed afterglow materials hold significant potential for multi-level anti-counterfeiting and information encryption applications when exposed to ultraviolet light. The supramolecular assembly strategy, which relies on the outer surface interactions of cucurbit[n]uril, offers a simpler and more efficient approach to crafting multi-color luminescent materials. Additionally, this method opens avenues for enhancing the application potential of aggregation-caused quenching (ACQ) compounds in various technological domains.
2025, 36(9): 110822
doi: 10.1016/j.cclet.2025.110822
Abstract:
The direct difunctionalization of alkenes serves as one of the most straightforward strategies toward complex nitrogen-containing compounds. The existing approach is extensively promoted by using C/X-centered radicals and N-nucleophiles to conduct 1,2-difunctional amination/azolization of alkenes. In contrast, 2,1-difunctional amination/azolization of alkenes by using nitrogen-centered radicals (NCRs) and nucleophiles still remains rarely underexplored. It is possibly due to the highly active electron properties of NCRs and the relatively poor nucleophilicity of aromatic NCRs to be trapped by arylalkenes. Herein, we demonstrate an unprecedented 2,1-hydroxazolization reactions of arylalkenes through electrochemically enabled addition of NCRs from azoles and nucleophiles (NuH) in high yields and with high regioselectivity. This conversion is characterized by the fact that neither metal catalysts nor external chemical oxidants are required. This electrochemical oxidation synthesis method can also be applied for a broad range of NuH including pyridine hydrofluoride, ammonia, water, alcohols, and acids which enables the formation of C-N and C–X (X = F/N/O) bonds in one-pot fashion to furnish efficient fluoroamination, diamination and oxoamination of alkenes.
The direct difunctionalization of alkenes serves as one of the most straightforward strategies toward complex nitrogen-containing compounds. The existing approach is extensively promoted by using C/X-centered radicals and N-nucleophiles to conduct 1,2-difunctional amination/azolization of alkenes. In contrast, 2,1-difunctional amination/azolization of alkenes by using nitrogen-centered radicals (NCRs) and nucleophiles still remains rarely underexplored. It is possibly due to the highly active electron properties of NCRs and the relatively poor nucleophilicity of aromatic NCRs to be trapped by arylalkenes. Herein, we demonstrate an unprecedented 2,1-hydroxazolization reactions of arylalkenes through electrochemically enabled addition of NCRs from azoles and nucleophiles (NuH) in high yields and with high regioselectivity. This conversion is characterized by the fact that neither metal catalysts nor external chemical oxidants are required. This electrochemical oxidation synthesis method can also be applied for a broad range of NuH including pyridine hydrofluoride, ammonia, water, alcohols, and acids which enables the formation of C-N and C–X (X = F/N/O) bonds in one-pot fashion to furnish efficient fluoroamination, diamination and oxoamination of alkenes.
2025, 36(9): 110831
doi: 10.1016/j.cclet.2025.110831
Abstract:
The ongoing development of small molecule drugs underscores the urgent need for novel excipients to formulate poorly soluble drug candidates. Cucurbit[7]uril (CB[7]) possesses high binding affinities for a variety of molecular guests. However, its moderate water solubility limits broader application. Here we report the synthesis of three CB[7] derivatives M1-M3 by modifying an average of 4.2, 5.5, and 5.9 sulfonatopropoxy groups onto their "equator" carbons. Compared to CB[7], their water-solubility increased by at least 26.6-, 23.6-, and 19.2-fold, respectively, while the maximum tolerated doses (MTD) of M1 and M2 improved by 2.5- and 2.3-fold. Phase solubility diagram studies demonstrate that M1 and M2 significantly enhance the water-solubility of eighteen poorly soluble drugs. In vivo experiments in rat complete Freund's arthritis reveal that M1 not only improves the anti-inflammatory efficacy of indomethacin by up to 52%, but also substantially reduces its side effect of gastric ulcer.
The ongoing development of small molecule drugs underscores the urgent need for novel excipients to formulate poorly soluble drug candidates. Cucurbit[7]uril (CB[7]) possesses high binding affinities for a variety of molecular guests. However, its moderate water solubility limits broader application. Here we report the synthesis of three CB[7] derivatives M1-M3 by modifying an average of 4.2, 5.5, and 5.9 sulfonatopropoxy groups onto their "equator" carbons. Compared to CB[7], their water-solubility increased by at least 26.6-, 23.6-, and 19.2-fold, respectively, while the maximum tolerated doses (MTD) of M1 and M2 improved by 2.5- and 2.3-fold. Phase solubility diagram studies demonstrate that M1 and M2 significantly enhance the water-solubility of eighteen poorly soluble drugs. In vivo experiments in rat complete Freund's arthritis reveal that M1 not only improves the anti-inflammatory efficacy of indomethacin by up to 52%, but also substantially reduces its side effect of gastric ulcer.
2025, 36(9): 110842
doi: 10.1016/j.cclet.2025.110842
Abstract:
A novel [3]rotaxane, featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites, a secondary dialkylammonium (AM) unit and a 4,4′-bipyridinium (BP) unit, has been synthesized. This multi-stimuli-responsive [3]rotaxane exhibits unique molecular motion, with the macrocycles shuttling along the axle in response to acid-base reactions, temperature changes, solvent variations, and light irradiation. The molecular shuttle and reversibility were investigated by 1H NMR, 2D NOESY, HRESI-MS, and UV-vis spectroscopy. This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness, highlighting its potential for multi-state control over the motion of interlocked rings on an axle. The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.
A novel [3]rotaxane, featuring two hydrogen-bonded aramide azo-macrocycles mechanically interlocked on a dumbbell with distinct recognition sites, a secondary dialkylammonium (AM) unit and a 4,4′-bipyridinium (BP) unit, has been synthesized. This multi-stimuli-responsive [3]rotaxane exhibits unique molecular motion, with the macrocycles shuttling along the axle in response to acid-base reactions, temperature changes, solvent variations, and light irradiation. The molecular shuttle and reversibility were investigated by 1H NMR, 2D NOESY, HRESI-MS, and UV-vis spectroscopy. This study provides a rare example of a higher order rotaxane with multi-stimuli responsiveness, highlighting its potential for multi-state control over the motion of interlocked rings on an axle. The ability to manipulate the molecular motion of the macrocycles through various external triggers offers insights for future developments in molecular machinery and adaptive materials.
2025, 36(9): 110843
doi: 10.1016/j.cclet.2025.110843
Abstract:
The amide moiety plays an important role as a powerful bioactive backbone, and as the synthetic chemistry community moves toward more sp3-rich scaffolds, alkyl halides have become the feedstock of choice for obtaining carbonylation products. With the development of photoredox catalysis, several aminocarbonylation systems for alkyl halides were developed which usually require transition metal catalysis. Considering the demands for green sustainable chemical synthesis, here we report a metal-free, exogenous catalyst-free aminocarbonylation reaction of alkyl iodides under atmospheric pressure of carbon monoxide. Through a combination of EDA and XAT strategies, the reaction occurs efficiently under only light irradiation at room temperature.
The amide moiety plays an important role as a powerful bioactive backbone, and as the synthetic chemistry community moves toward more sp3-rich scaffolds, alkyl halides have become the feedstock of choice for obtaining carbonylation products. With the development of photoredox catalysis, several aminocarbonylation systems for alkyl halides were developed which usually require transition metal catalysis. Considering the demands for green sustainable chemical synthesis, here we report a metal-free, exogenous catalyst-free aminocarbonylation reaction of alkyl iodides under atmospheric pressure of carbon monoxide. Through a combination of EDA and XAT strategies, the reaction occurs efficiently under only light irradiation at room temperature.
2025, 36(9): 110861
doi: 10.1016/j.cclet.2025.110861
Abstract:
Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development. Compared with the kinetically sluggish oxygen evolution reaction (OER), the thermodynamically advantageous sulfion oxidation reaction (SOR) enables the S2- pollutants recovery while reducing the energy input of water electrolysis. Here, a nanoporous NiMo alloy ligament (np-NiMo) with AlNi3/Al5Mo heterostructure was prepared for hydrogen evolution reaction (HER, -0.134 V versus reversible hydrogen electrode (vs. RHE) at 50 mA/cm2), which needs an Al89Ni10Mo1 as a precursor and dealloying operation. Further, the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS2 (np-NiMo-S) for OER (1.544 V vs. RHE at 50 mA/cm2) and SOR (0.364 V vs. RHE at 50 mA/cm2), while still maintaining the nanostructuring advantages. Moreover, for a two-electrode electrolyzer system with np-NiMo cathode (1 M KOH + seawater) coupling np-NiMo-S anode (1 mol/L KOH + seawater + 1 mol/L Na2S), a remarkably ultra-low cell potential of 0.532 V is acquired at 50 mA/cm2, which is about 1.015 V below that of normal alkaline seawater splitting. The theory calculations confirmed that the AlNi3/Al5Mo heterostructure within np-NiMo promotes H2O dissociation for excellent HER, while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from *S4 to *S8. This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.
Establishing an energy-saving and affordable hydrogen production route from infinite seawater presents a promising strategy for achieving carbon neutrality and low-carbon development. Compared with the kinetically sluggish oxygen evolution reaction (OER), the thermodynamically advantageous sulfion oxidation reaction (SOR) enables the S2- pollutants recovery while reducing the energy input of water electrolysis. Here, a nanoporous NiMo alloy ligament (np-NiMo) with AlNi3/Al5Mo heterostructure was prepared for hydrogen evolution reaction (HER, -0.134 V versus reversible hydrogen electrode (vs. RHE) at 50 mA/cm2), which needs an Al89Ni10Mo1 as a precursor and dealloying operation. Further, the np-NiMo alloy was thermal-treated with S powder to generate Mo-doped NiS2 (np-NiMo-S) for OER (1.544 V vs. RHE at 50 mA/cm2) and SOR (0.364 V vs. RHE at 50 mA/cm2), while still maintaining the nanostructuring advantages. Moreover, for a two-electrode electrolyzer system with np-NiMo cathode (1 M KOH + seawater) coupling np-NiMo-S anode (1 mol/L KOH + seawater + 1 mol/L Na2S), a remarkably ultra-low cell potential of 0.532 V is acquired at 50 mA/cm2, which is about 1.015 V below that of normal alkaline seawater splitting. The theory calculations confirmed that the AlNi3/Al5Mo heterostructure within np-NiMo promotes H2O dissociation for excellent HER, while the Mo-dopant of np-NiMo-S lowers energy barriers for the rate-determining step from *S4 to *S8. This work develops two kinds of NiMo alloy with tremendous prominence for achieving energy-efficient hydrogen production from alkaline seawater and sulfur recycling from sulfion-rich sewage.
2025, 36(9): 110870
doi: 10.1016/j.cclet.2025.110870
Abstract:
The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis. However, examples of asymmetric Meinwald rearrangements are quite scarce, and these reactions have so far been limited to the use of chiral Brønsted acids as catalysts. Here, we report a copper-catalyzed asymmetric cascade cyclization/Meinwald rearrangement reaction, allowing the practical and atom-economic synthesis of a range of chiral tricyclic pyrroles bearing a chiral oxa-quaternary carbon stereocenter in high yields and enantioselectivities. Thus, this protocol not only represents the first transition-metal-catalyzed enantioselective Meinwald rearrangement, but also constitutes the first example of asymmetric formal monocarbon insertion into C–O bond of ester. Moreover, theoretical calculations provide further evidence for this multiple cascade cyclization and elucidate the origin of enantioselectivity.
The Meinwald rearrangement has proven to be one of the most useful tools in organic synthesis. However, examples of asymmetric Meinwald rearrangements are quite scarce, and these reactions have so far been limited to the use of chiral Brønsted acids as catalysts. Here, we report a copper-catalyzed asymmetric cascade cyclization/Meinwald rearrangement reaction, allowing the practical and atom-economic synthesis of a range of chiral tricyclic pyrroles bearing a chiral oxa-quaternary carbon stereocenter in high yields and enantioselectivities. Thus, this protocol not only represents the first transition-metal-catalyzed enantioselective Meinwald rearrangement, but also constitutes the first example of asymmetric formal monocarbon insertion into C–O bond of ester. Moreover, theoretical calculations provide further evidence for this multiple cascade cyclization and elucidate the origin of enantioselectivity.
2025, 36(9): 110896
doi: 10.1016/j.cclet.2025.110896
Abstract:
Many azo compounds and their intermediates are toxic and have been linked to various health issues, representing a growing global problem. Molecular engineering for selective encapsulation of azobenzene compounds is critical, given their significant use in smart materials and prevalence as environmental micropollutants released from the food and dye industries. However, the current host molecules catering to azobenzene compounds are mainly limited to cyclodextrins, pillar[n]arenes and cucurbit[n]urils, demonstrating a moderate affinity. This report describes that a novel 3,3′-bipyridinium-based cyclophane was capable of encapsulating anionic azobenzene compounds in water with high binding affinity and pH stability through electrostatic attraction-enhanced mechanism, surpassing the extensively reported supramolecular systems. 1D & 2D NMR experiments, UV–vis spectrum, X-ray crystallography and computational modeling were carried out to understand the host-guest complexation. It's worth noting that the tetracationic cyclophane exhibited good selective and anti-interference encapsulation properties in binary, ternary and seawater systems. Furthermore, upon UV/white light irradiation, the reversible conversion between (E)-4,4′-azobisbenzoate and (Z)-4,4′-azobisbenzoate triggers the dissociation/recomplexation of the host-guest complex within 3 min. This reversible photo-switchable (E)-disodium 4,4′-azobisbenzoate-BPy-Box4+ supramolecular system holds promise for designing novel materials for extraction/release of azo compounds and other small smart materials.
Many azo compounds and their intermediates are toxic and have been linked to various health issues, representing a growing global problem. Molecular engineering for selective encapsulation of azobenzene compounds is critical, given their significant use in smart materials and prevalence as environmental micropollutants released from the food and dye industries. However, the current host molecules catering to azobenzene compounds are mainly limited to cyclodextrins, pillar[n]arenes and cucurbit[n]urils, demonstrating a moderate affinity. This report describes that a novel 3,3′-bipyridinium-based cyclophane was capable of encapsulating anionic azobenzene compounds in water with high binding affinity and pH stability through electrostatic attraction-enhanced mechanism, surpassing the extensively reported supramolecular systems. 1D & 2D NMR experiments, UV–vis spectrum, X-ray crystallography and computational modeling were carried out to understand the host-guest complexation. It's worth noting that the tetracationic cyclophane exhibited good selective and anti-interference encapsulation properties in binary, ternary and seawater systems. Furthermore, upon UV/white light irradiation, the reversible conversion between (E)-4,4′-azobisbenzoate and (Z)-4,4′-azobisbenzoate triggers the dissociation/recomplexation of the host-guest complex within 3 min. This reversible photo-switchable (E)-disodium 4,4′-azobisbenzoate-BPy-Box4+ supramolecular system holds promise for designing novel materials for extraction/release of azo compounds and other small smart materials.
2025, 36(9): 110937
doi: 10.1016/j.cclet.2025.110937
Abstract:
Microporous organic networks (MONs) are attractive adsorbents for use in sample pretreatment owning to their unique structure and properties. However, methods for constructing functional MONs are still limited because the lack of monomers via direct synthesis and their complex procedures via post-modification. To address this issue, a facile one-pot in situ doping strategy was proposed herein for synthesis a novel phenylboronic acid-functionalized magnetic cyclodextrin-based microporous organic network ([PBA]3/4−MCD-MON-0.04). [PBA]3/4−MCD-MON-0.04 was used for the selective and efficient extraction of sulfonylurea herbicides (SUHs) from complex food and environmental water samples via the synergistic hydrogen bonding, host-guest, hydrophobic and π-π interactions and the specific B-N coordination. [PBA]3/4−MCD-MON-0.04 had a large surface area, high saturation magnetism, good reusability, and remarkable stability. A rapid, sensitive, and selective method was proposed for monitoring SUHs from diverse matrices. This study provides a new strategy for synthesizing novel and multifunctional magnetic CD-MONs-based adsorbents and reveals the considerable potential of CD-MONs in sample pretreatment.
Microporous organic networks (MONs) are attractive adsorbents for use in sample pretreatment owning to their unique structure and properties. However, methods for constructing functional MONs are still limited because the lack of monomers via direct synthesis and their complex procedures via post-modification. To address this issue, a facile one-pot in situ doping strategy was proposed herein for synthesis a novel phenylboronic acid-functionalized magnetic cyclodextrin-based microporous organic network ([PBA]3/4−MCD-MON-0.04). [PBA]3/4−MCD-MON-0.04 was used for the selective and efficient extraction of sulfonylurea herbicides (SUHs) from complex food and environmental water samples via the synergistic hydrogen bonding, host-guest, hydrophobic and π-π interactions and the specific B-N coordination. [PBA]3/4−MCD-MON-0.04 had a large surface area, high saturation magnetism, good reusability, and remarkable stability. A rapid, sensitive, and selective method was proposed for monitoring SUHs from diverse matrices. This study provides a new strategy for synthesizing novel and multifunctional magnetic CD-MONs-based adsorbents and reveals the considerable potential of CD-MONs in sample pretreatment.
2025, 36(9): 110955
doi: 10.1016/j.cclet.2025.110955
Abstract:
In this study, different types of small molecular carbon sources such as melamine, dicyandiamine, pyrocatechol, and o-phenylenediamine were used to regulate the surface structures of iron/nitrogen/carbon-based composites (Fe-N/C), which were used to activate peroxymonosulfate (PMS). The relationship between different small molecular carbon sources and the electronic structure was investigated. The characteristics of metal-carrier interaction in the Fe-N/C were clarified. As a result, there were significant differences in the degradation efficiency of catalysts prepared with different small molecular carbon sources, which was related to the types of active sites. Density functional theory (DFT) and experiments results showed that the catalyst rich in CO-C and FeNx exhibited better catalytic activity, which may be attributed to the higher adsorption energy for PMS. The main active species for catalytic degradation of ofloxacin were identified as sulfate radical (SO4•-) and hydroxyl radical (•OH) by electron paramagnetic resonance (EPR) spectra. The introduction of different small molecular carbon sources can significantly affect the distribution and electronic structure of active sites on the catalyst surface, thereby regulating the generation and migration of radicals.
In this study, different types of small molecular carbon sources such as melamine, dicyandiamine, pyrocatechol, and o-phenylenediamine were used to regulate the surface structures of iron/nitrogen/carbon-based composites (Fe-N/C), which were used to activate peroxymonosulfate (PMS). The relationship between different small molecular carbon sources and the electronic structure was investigated. The characteristics of metal-carrier interaction in the Fe-N/C were clarified. As a result, there were significant differences in the degradation efficiency of catalysts prepared with different small molecular carbon sources, which was related to the types of active sites. Density functional theory (DFT) and experiments results showed that the catalyst rich in CO-C and FeNx exhibited better catalytic activity, which may be attributed to the higher adsorption energy for PMS. The main active species for catalytic degradation of ofloxacin were identified as sulfate radical (SO4•-) and hydroxyl radical (•OH) by electron paramagnetic resonance (EPR) spectra. The introduction of different small molecular carbon sources can significantly affect the distribution and electronic structure of active sites on the catalyst surface, thereby regulating the generation and migration of radicals.
Metallic cobalt mediated molybdenum nitride for efficient glycerol upgrading with water electrolysis
2025, 36(9): 111010
doi: 10.1016/j.cclet.2025.111010
Abstract:
Integrating electrochemical upgrading of glycerol and water electrolysis is regarded as a promising and energy-saving approach for the co-production of chemicals and hydrogen. However, developing efficient electrocatalyst towards this technology remains challenging. Herein, a metallic cobalt mediated molybdenum nitride heterostructural material has been exploited on nickel foam (Co@Mo2N/NF) for the glycerol oxidation reaction (GOR) and hydrogen evolution reaction (HER). Remarkably, the obtained Co@Mo2N/NF realizes eminent performance with low overpotential of 49 mV at 50 mA/cm2 for HER and high Faradaic efficiency of formate of 95.03% at 1.35 Ⅴ vs. RHE for GOR, respectively. The systematic in-situ experiments reveal that the Co@Mo2N heterostructure promotes the cleavage of CC bond in glycerol by active CoOOH species and boosts the conversion of glycerol to aldehyde intermediates to formate product. Moreover, the density functional theory (DFT) calculations confirm the strong interaction at Co@Mo2N interface, which contributes to the optimized water dissociation and the transformation of H* to H2. Benefiting from those advantages, the built HERGOR electrolyzer delivers a low voltage of 1.61 Ⅴ at 50 mA/cm2, high Faradaic efficiency, and robust stability over 120 h for sustained and stable electrolysis.
Integrating electrochemical upgrading of glycerol and water electrolysis is regarded as a promising and energy-saving approach for the co-production of chemicals and hydrogen. However, developing efficient electrocatalyst towards this technology remains challenging. Herein, a metallic cobalt mediated molybdenum nitride heterostructural material has been exploited on nickel foam (Co@Mo2N/NF) for the glycerol oxidation reaction (GOR) and hydrogen evolution reaction (HER). Remarkably, the obtained Co@Mo2N/NF realizes eminent performance with low overpotential of 49 mV at 50 mA/cm2 for HER and high Faradaic efficiency of formate of 95.03% at 1.35 Ⅴ vs. RHE for GOR, respectively. The systematic in-situ experiments reveal that the Co@Mo2N heterostructure promotes the cleavage of CC bond in glycerol by active CoOOH species and boosts the conversion of glycerol to aldehyde intermediates to formate product. Moreover, the density functional theory (DFT) calculations confirm the strong interaction at Co@Mo2N interface, which contributes to the optimized water dissociation and the transformation of H* to H2. Benefiting from those advantages, the built HERGOR electrolyzer delivers a low voltage of 1.61 Ⅴ at 50 mA/cm2, high Faradaic efficiency, and robust stability over 120 h for sustained and stable electrolysis.
2025, 36(9): 111030
doi: 10.1016/j.cclet.2025.111030
Abstract:
Tumor heterogeneity and diversity significantly undermine the effectiveness of monotherapy. Collaborative therapy emerges as a promising approach to mitigate tumor recurrence resulting from monotherapy. Combining chemodynamic therapy (CDT) with photothermal therapy (PTT) offers a compelling solution for eradicating residual tumor cells post-PTT. In this study, we harness the Fenton-like response facilitated by glucose oxidase (GOD) and the mild hyperthermia induced by polyethyleneimine (PEI) functionalized nitrogen-containing graphene oxide to enhance tumor therapy through a metal-free bionic nanozyme. GOD catalyzes a substantial amount of hydrogen peroxide, and, with the carrier's involvement, triggers a Fenton-like reaction, yielding a wealth of hydroxyl radicals. These hydroxyl radicals effectively target tumor cells following photothermal action, bolstering CDT and culminating in a bidirectional amplification treatment that effectively prevents tumor recurrence and metastasis. This research amalgamates the physical and chemical attributes of nanomaterials with the unique characteristics of the tumor microenvironment, presenting a compelling and efficacious alternative for tumor treatment.
Tumor heterogeneity and diversity significantly undermine the effectiveness of monotherapy. Collaborative therapy emerges as a promising approach to mitigate tumor recurrence resulting from monotherapy. Combining chemodynamic therapy (CDT) with photothermal therapy (PTT) offers a compelling solution for eradicating residual tumor cells post-PTT. In this study, we harness the Fenton-like response facilitated by glucose oxidase (GOD) and the mild hyperthermia induced by polyethyleneimine (PEI) functionalized nitrogen-containing graphene oxide to enhance tumor therapy through a metal-free bionic nanozyme. GOD catalyzes a substantial amount of hydrogen peroxide, and, with the carrier's involvement, triggers a Fenton-like reaction, yielding a wealth of hydroxyl radicals. These hydroxyl radicals effectively target tumor cells following photothermal action, bolstering CDT and culminating in a bidirectional amplification treatment that effectively prevents tumor recurrence and metastasis. This research amalgamates the physical and chemical attributes of nanomaterials with the unique characteristics of the tumor microenvironment, presenting a compelling and efficacious alternative for tumor treatment.
2025, 36(9): 111152
doi: 10.1016/j.cclet.2025.111152
Abstract:
Amorphous bimetallic borides, as a new generation of catalytic nanomaterials with modifiable electronic properties, are of great importance in the design of high-efficiency catalysts for NaBH4 hydrolysis. This study synthesizes an amorphous Co3B-Mo2B5 catalyst using a self-sacrificial template strategy and NaBH4 reduction for both NaBH4 hydrolysis and the reduction of 4-nitrophenol. The catalyst delivers an impressive hydrogen generation rate of 7690.5 mL min−1 g−1 at 25 ℃, coupled with a rapid reaction rate of 0.701 min−1 in the reduction of 4-nitrophenol. The enhanced catalytic performance is attributed to the unique amorphous structure and the electron rearrangement between Co3B and Mo2B5. Experimental and theoretical analyses suggest electron transfer from Co3B to the Mo2B5, with the electron-deficient Co3B site favoring BH4− adsorption, while the electron-rich Mo2B5 site favoring H2O adsorption. Furthermore, Co3B-Mo2B5 demonstrated potential for energy applications, delivering a power output of 0.3 V in a hydrogen-air fuel cell.
Amorphous bimetallic borides, as a new generation of catalytic nanomaterials with modifiable electronic properties, are of great importance in the design of high-efficiency catalysts for NaBH4 hydrolysis. This study synthesizes an amorphous Co3B-Mo2B5 catalyst using a self-sacrificial template strategy and NaBH4 reduction for both NaBH4 hydrolysis and the reduction of 4-nitrophenol. The catalyst delivers an impressive hydrogen generation rate of 7690.5 mL min−1 g−1 at 25 ℃, coupled with a rapid reaction rate of 0.701 min−1 in the reduction of 4-nitrophenol. The enhanced catalytic performance is attributed to the unique amorphous structure and the electron rearrangement between Co3B and Mo2B5. Experimental and theoretical analyses suggest electron transfer from Co3B to the Mo2B5, with the electron-deficient Co3B site favoring BH4− adsorption, while the electron-rich Mo2B5 site favoring H2O adsorption. Furthermore, Co3B-Mo2B5 demonstrated potential for energy applications, delivering a power output of 0.3 V in a hydrogen-air fuel cell.
2025, 36(9): 111194
doi: 10.1016/j.cclet.2025.111194
Abstract:
Organic afterglow materials hold significant potential for applications in information storage, anti-counterfeiting, and biological imaging. However, studies on afterglow materials capable of ultra-wide range excitation and emission simultaneously are limited. To enhance the practicality of strong emission single-component organic afterglow systems, overcoming the constraints of crystalline or other rigid environments is essential. We have developed solid-state dual-persistent thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) emissions spanning yellow to red under visible light excitation, utilizing a single-molecule terminal group regulation strategy. The RTP lifetime extends from 4.19 ms to 399.70 ms. These afterglow materials exhibit an ultra-wide absorption range from 200 nm to 800 nm, rendering them capable of being excited by both sunlight simulator and near-infrared radiation. The upconversion phosphorescence lifetime under 808 nm excitation reaches 13.72 µs. The double persistent emission of these compounds is temperature-sensitive. Moreover, following grinding or heat treatment, accompanied by extensive afterglow color conversion due to planarization of excited state conformations and additional efficient kRISC generation. In addition, the amorphous state post melt annealing facilitates the afterglow transition from yellow to green. Crucially, these compounds also maintain stable ultra-long afterglow emission in aqueous and acid-base environments. Overall, we have successfully developed a series of single-component intelligent luminescent materials that demonstrate significant benefits, including dual TADF and RTP emissions, adjustable afterglow lifetimes, a broad range of excitation and emission wavelengths, multi-modal luminescence not restricted to crystalline states, and robust afterglow performance in challenging environments, setting the stage for the practical deployment of afterglow materials in engineering applications, the upconversion afterglow emission also holds promising potential for applications in the field of biological imaging.
Organic afterglow materials hold significant potential for applications in information storage, anti-counterfeiting, and biological imaging. However, studies on afterglow materials capable of ultra-wide range excitation and emission simultaneously are limited. To enhance the practicality of strong emission single-component organic afterglow systems, overcoming the constraints of crystalline or other rigid environments is essential. We have developed solid-state dual-persistent thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) emissions spanning yellow to red under visible light excitation, utilizing a single-molecule terminal group regulation strategy. The RTP lifetime extends from 4.19 ms to 399.70 ms. These afterglow materials exhibit an ultra-wide absorption range from 200 nm to 800 nm, rendering them capable of being excited by both sunlight simulator and near-infrared radiation. The upconversion phosphorescence lifetime under 808 nm excitation reaches 13.72 µs. The double persistent emission of these compounds is temperature-sensitive. Moreover, following grinding or heat treatment, accompanied by extensive afterglow color conversion due to planarization of excited state conformations and additional efficient kRISC generation. In addition, the amorphous state post melt annealing facilitates the afterglow transition from yellow to green. Crucially, these compounds also maintain stable ultra-long afterglow emission in aqueous and acid-base environments. Overall, we have successfully developed a series of single-component intelligent luminescent materials that demonstrate significant benefits, including dual TADF and RTP emissions, adjustable afterglow lifetimes, a broad range of excitation and emission wavelengths, multi-modal luminescence not restricted to crystalline states, and robust afterglow performance in challenging environments, setting the stage for the practical deployment of afterglow materials in engineering applications, the upconversion afterglow emission also holds promising potential for applications in the field of biological imaging.
2025, 36(9): 111205
doi: 10.1016/j.cclet.2025.111205
Abstract:
Directly occluding polymer nanoparticles into growing host crystals provides a versatile pathway for synthesizing polymer-inorganic composite crystals, where guest nanoparticles are distributed within the crystal matrix. However, systematically controlling the extent of nanoparticle occlusion within a host crystal remains a significant challenge. In this study, we employ a one-step, soap-free emulsion polymerization method to synthesize polyethyleneimine-functionalized poly(tert‑butyl methacrylate) (PtBMA/PEI) nanoparticles. These cationic nanoparticles are subsequently modified using formaldehyde to systematically tune the content of surface amine group via the Eschweiler-Clarke reaction. This approach yields a series of model nanoparticles that allow us to investigate how surface chemistry influences the extent of nanoparticle occlusion within calcite crystals. Our findings reveal that the extent of nanoparticle occlusion within calcite crystals is proportional to the surface amine group content. This study offers a new design rule for creating composite crystals with tailored compositions through a nanoparticle occlusion strategy.
Directly occluding polymer nanoparticles into growing host crystals provides a versatile pathway for synthesizing polymer-inorganic composite crystals, where guest nanoparticles are distributed within the crystal matrix. However, systematically controlling the extent of nanoparticle occlusion within a host crystal remains a significant challenge. In this study, we employ a one-step, soap-free emulsion polymerization method to synthesize polyethyleneimine-functionalized poly(tert‑butyl methacrylate) (PtBMA/PEI) nanoparticles. These cationic nanoparticles are subsequently modified using formaldehyde to systematically tune the content of surface amine group via the Eschweiler-Clarke reaction. This approach yields a series of model nanoparticles that allow us to investigate how surface chemistry influences the extent of nanoparticle occlusion within calcite crystals. Our findings reveal that the extent of nanoparticle occlusion within calcite crystals is proportional to the surface amine group content. This study offers a new design rule for creating composite crystals with tailored compositions through a nanoparticle occlusion strategy.
2025, 36(9): 111223
doi: 10.1016/j.cclet.2025.111223
Abstract:
Hydrogen-bonded framework (HOF) offers an attractive platform to encapsulate enzymes and stabilize their conformation, due to the advantages of mild synthesis conditions, tailorable pore structure, and backbone biocompatibility. However, the efficiency of this HOF approach relies on the interfacial interactions between enzyme guest and the ligand precursors, limiting its adaptability to enzymes with varying surface chemistry property. In this study, we report a site-specific surface modification strategy to positively tailor the enzyme surface charge, facilitating the biomimetic encapsulation of enzymes within HOF in situ. Both experimental results and computational simulation reveal that site-specific amination of enzyme surface's acidic residues contributes to the interfacial accumulation of carboxylic ligand precursors in aqueous solutions via synergistic electrostatic and hydrogen bonding interactions. This substantially facilitates the in situ growth of porous HOF surrounding the aminated enzyme biotemplates, with up to 100% enzyme loading efficiency. The resultant hydrogen-bonded biohybrid framework (HBF) retains high biocatalytic functions while exhibiting exceptional stability under harsh conditions. By leveraging the marked catalytic activity of GOx-NH2@HBF-1 and a H2O2-sensitive QD, a highly sensitive glucose fluorescence sensor is fabricated with a wide linear range (5–2000 µmol/L) and a low quantification limit of 5 µmol/L. This work presents a simple yet effective enzyme surface engineering approach for integrating enzyme into HOF, opening new avenues for the construction of multifunctional HOF biocomposites.
Hydrogen-bonded framework (HOF) offers an attractive platform to encapsulate enzymes and stabilize their conformation, due to the advantages of mild synthesis conditions, tailorable pore structure, and backbone biocompatibility. However, the efficiency of this HOF approach relies on the interfacial interactions between enzyme guest and the ligand precursors, limiting its adaptability to enzymes with varying surface chemistry property. In this study, we report a site-specific surface modification strategy to positively tailor the enzyme surface charge, facilitating the biomimetic encapsulation of enzymes within HOF in situ. Both experimental results and computational simulation reveal that site-specific amination of enzyme surface's acidic residues contributes to the interfacial accumulation of carboxylic ligand precursors in aqueous solutions via synergistic electrostatic and hydrogen bonding interactions. This substantially facilitates the in situ growth of porous HOF surrounding the aminated enzyme biotemplates, with up to 100% enzyme loading efficiency. The resultant hydrogen-bonded biohybrid framework (HBF) retains high biocatalytic functions while exhibiting exceptional stability under harsh conditions. By leveraging the marked catalytic activity of GOx-NH2@HBF-1 and a H2O2-sensitive QD, a highly sensitive glucose fluorescence sensor is fabricated with a wide linear range (5–2000 µmol/L) and a low quantification limit of 5 µmol/L. This work presents a simple yet effective enzyme surface engineering approach for integrating enzyme into HOF, opening new avenues for the construction of multifunctional HOF biocomposites.
2025, 36(9): 111234
doi: 10.1016/j.cclet.2025.111234
Abstract:
Two pairs of novel 6/6/6/9 tetracyclic merosesquiterpenoid enantiomers, dauroxonanols A (1) and B (2), possessing an unprecedented 9,15-dioxatetracyclo[8.5.3.04,17.014,18]octadecane core skeleton, were isolated from Rhododendron dauricum. The nuclear magnetic resonance (NMR) spectra of 1 and 2 showed very broad resonances, and 13C NMR spectrum of 1 exhibited only 13 instead of 22 carbon resonances. These broadening or missing NMR resonances led to a great challenge to elucidate their structures using NMR data analysis. Their structures and absolute configurations of 1 and 2 were finally determined by single crystal X-ray diffraction analysis, chiral separation, and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for 1 and 2 are proposed. Conformational analysis, density functional theory (DFT) calculations, and dynamic NMR assigned the coalescent NMR phenomena of 1 and 2 to the conformational changes of the flexible oxonane ring. Dauroxonanols A (1) and B (2) showed potent α-glucosidase inhibitory activities, 2–8 times potent than acarbose, an antidiabetic drug targeting α-glucosidase in clinic.
Two pairs of novel 6/6/6/9 tetracyclic merosesquiterpenoid enantiomers, dauroxonanols A (1) and B (2), possessing an unprecedented 9,15-dioxatetracyclo[8.5.3.04,17.014,18]octadecane core skeleton, were isolated from Rhododendron dauricum. The nuclear magnetic resonance (NMR) spectra of 1 and 2 showed very broad resonances, and 13C NMR spectrum of 1 exhibited only 13 instead of 22 carbon resonances. These broadening or missing NMR resonances led to a great challenge to elucidate their structures using NMR data analysis. Their structures and absolute configurations of 1 and 2 were finally determined by single crystal X-ray diffraction analysis, chiral separation, and electronic circular dichroism (ECD) calculations. Plausible biosynthetic pathways for 1 and 2 are proposed. Conformational analysis, density functional theory (DFT) calculations, and dynamic NMR assigned the coalescent NMR phenomena of 1 and 2 to the conformational changes of the flexible oxonane ring. Dauroxonanols A (1) and B (2) showed potent α-glucosidase inhibitory activities, 2–8 times potent than acarbose, an antidiabetic drug targeting α-glucosidase in clinic.
2025, 36(9): 111271
doi: 10.1016/j.cclet.2025.111271
Abstract:
The biomass electrochemical oxidation coupled with hydrogen evolution reaction has received widespread attention due to its carbon-neutral and sustainable properties. The electrosynthesis of 2,5-furanodicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF) oxidation is one of the most promising means for the production of bioplastic monomers. In this work, we constructed a novel P-doped Ni3S2 and Ni heterojunction on nickel foam (P-Ni3S2/Ni/NF) using electrodeposition methods and thermal sulfuration techniques as a bifunctional catalyst for the simultaneous anodic oxidation of HMF to FDCA (HMFOR) and the cathodic hydrogen evolution reaction (HER). On one hand, the synergistic promotion of P doping and the heterojunction of Ni3S2 and Ni accelerated electron transfer, and on the other hand, the structure of three-dimensional microsphere stacking on NF surface to form macropores enhances the exposure of catalytically active sites. The prepared P-Ni3S2/Ni/NF exhibited remarkable performance with high HMF conversion (99.2%), FDCA yield (98.1%), and Faraday efficiency (98.8%), and excellent stability with good product selectivity for 7 consecutive cycles, which stands at a higher level than majority of previously published electrocatalysts. Furthermore, P-Ni3S2/Ni/NF also shows a significant response in HER. By using HMFOR and HER as the anodic reaction and cathodic reaction, respectively, the biomass upgrading and hydrogen production can be carried out simultaneously. The synthesized P-Ni3S2/Ni/NF only need a voltage of 1.31 V to achieve a current density of 10 mA/cm2 in a two-electrode system of HMFOR and HER, which is much lower than that of 1.48 V in OER and HER process, thus potentially reducing the cost of this process.
The biomass electrochemical oxidation coupled with hydrogen evolution reaction has received widespread attention due to its carbon-neutral and sustainable properties. The electrosynthesis of 2,5-furanodicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF) oxidation is one of the most promising means for the production of bioplastic monomers. In this work, we constructed a novel P-doped Ni3S2 and Ni heterojunction on nickel foam (P-Ni3S2/Ni/NF) using electrodeposition methods and thermal sulfuration techniques as a bifunctional catalyst for the simultaneous anodic oxidation of HMF to FDCA (HMFOR) and the cathodic hydrogen evolution reaction (HER). On one hand, the synergistic promotion of P doping and the heterojunction of Ni3S2 and Ni accelerated electron transfer, and on the other hand, the structure of three-dimensional microsphere stacking on NF surface to form macropores enhances the exposure of catalytically active sites. The prepared P-Ni3S2/Ni/NF exhibited remarkable performance with high HMF conversion (99.2%), FDCA yield (98.1%), and Faraday efficiency (98.8%), and excellent stability with good product selectivity for 7 consecutive cycles, which stands at a higher level than majority of previously published electrocatalysts. Furthermore, P-Ni3S2/Ni/NF also shows a significant response in HER. By using HMFOR and HER as the anodic reaction and cathodic reaction, respectively, the biomass upgrading and hydrogen production can be carried out simultaneously. The synthesized P-Ni3S2/Ni/NF only need a voltage of 1.31 V to achieve a current density of 10 mA/cm2 in a two-electrode system of HMFOR and HER, which is much lower than that of 1.48 V in OER and HER process, thus potentially reducing the cost of this process.
2025, 36(9): 111272
doi: 10.1016/j.cclet.2025.111272
Abstract:
Photocatalytic hydrogen peroxide (H2O2) production (PHP) offers significant advantages to traditional production methods, including solar energy utilization, mild reaction conditions, environmental friendliness, pollution-free processes, sustainability, and high selectivity. However, despite its potential as a green and sustainable technology, photocatalytic H2O2 production (PHP) is constrained by limited visible light absorption by photocatalysts and the rapid recombination of photogenerated charge carriers, which reduce yield and efficiency. In this study, we synthesized an organic amine constrained Zn0.5Cd0.5S-DETA/g-C3N4 (ZCS-D/CN) S-scheme heterojunction via a hydrothermal method to enhance PHP. Anchoring ZCS-D on the surface of CN and forming an S-scheme heterojunction effectively prevented ZCS-D agglomeration, modulated the band structure of CN, and enhanced the migration and redox capabilities of photogenerated charge carriers. The optimized heterojunction (ZCS-D/CN) achieved a H2O2 yield of 5124 µmol g-1 h-1 in pure H2O, significantly outperforming pure CN (24 µmol g-1 h-1) and ZCS-D (4012 µmol g-1 h-1). These results demonstrate that ZCS-D/CN S-scheme heterojunction holds substantial potential for photocatalytic applications, particularly in the efficient production of H2O2.
Photocatalytic hydrogen peroxide (H2O2) production (PHP) offers significant advantages to traditional production methods, including solar energy utilization, mild reaction conditions, environmental friendliness, pollution-free processes, sustainability, and high selectivity. However, despite its potential as a green and sustainable technology, photocatalytic H2O2 production (PHP) is constrained by limited visible light absorption by photocatalysts and the rapid recombination of photogenerated charge carriers, which reduce yield and efficiency. In this study, we synthesized an organic amine constrained Zn0.5Cd0.5S-DETA/g-C3N4 (ZCS-D/CN) S-scheme heterojunction via a hydrothermal method to enhance PHP. Anchoring ZCS-D on the surface of CN and forming an S-scheme heterojunction effectively prevented ZCS-D agglomeration, modulated the band structure of CN, and enhanced the migration and redox capabilities of photogenerated charge carriers. The optimized heterojunction (ZCS-D/CN) achieved a H2O2 yield of 5124 µmol g-1 h-1 in pure H2O, significantly outperforming pure CN (24 µmol g-1 h-1) and ZCS-D (4012 µmol g-1 h-1). These results demonstrate that ZCS-D/CN S-scheme heterojunction holds substantial potential for photocatalytic applications, particularly in the efficient production of H2O2.
2025, 36(9): 111295
doi: 10.1016/j.cclet.2025.111295
Abstract:
The electrocatalytic nitrogen reduction reaction (NRR) is challenging but crucial for the sustainable development of both industry and agriculture. To enhance NRR performance, it is critically important to construct advanced electrocatalysts that offer satisfactory performance containing high activity and selectivity. However, the strong affinity of nitrogen-containing species on the Ru surface resulted in suboptimal NRR activity. Herein, we propose a dual-site catalyst, RuNi, to optimize the binding strength, which leads to superior electrocatalytic performance, achieving a high NH3 yield rate of 5.07 µg h-1 cm-2 at -0.2 V vs. RHE and a Faradaic efficiency (FE) of 26.2% at -0.1 V vs. RHE in 0.1 mol/L Na2SO4. Owing to the synergistic interaction between Ru and Ni, a remarkable performance is realized over the RuNi catalyst. In-situ characterization evidenced that hydrogen radicals (H*) on the Ni site of the RuNi catalyst participate in the dissociation of N2 adsorbed on the Ru site, and theoretical investigations indicated that RuNi reduces the adsorption strength of intermediates. This offers an effective approach to the synthesis of dual-site catalysts for electrocatalytic ammonia synthesis.
The electrocatalytic nitrogen reduction reaction (NRR) is challenging but crucial for the sustainable development of both industry and agriculture. To enhance NRR performance, it is critically important to construct advanced electrocatalysts that offer satisfactory performance containing high activity and selectivity. However, the strong affinity of nitrogen-containing species on the Ru surface resulted in suboptimal NRR activity. Herein, we propose a dual-site catalyst, RuNi, to optimize the binding strength, which leads to superior electrocatalytic performance, achieving a high NH3 yield rate of 5.07 µg h-1 cm-2 at -0.2 V vs. RHE and a Faradaic efficiency (FE) of 26.2% at -0.1 V vs. RHE in 0.1 mol/L Na2SO4. Owing to the synergistic interaction between Ru and Ni, a remarkable performance is realized over the RuNi catalyst. In-situ characterization evidenced that hydrogen radicals (H*) on the Ni site of the RuNi catalyst participate in the dissociation of N2 adsorbed on the Ru site, and theoretical investigations indicated that RuNi reduces the adsorption strength of intermediates. This offers an effective approach to the synthesis of dual-site catalysts for electrocatalytic ammonia synthesis.
2025, 36(9): 111400
doi: 10.1016/j.cclet.2025.111400
Abstract:
Wound dressings with tissue adhesion, good mechanical, antioxidant and anti-inflammatory performance are urgently needed. In this work, we present a multifunctional selenium nanoparticles (SeNPs)/citric acid/gelatin/hydroxysuccinimide-grafted polyacrylic acid nanocomposite hydrogel adhesive (SCA) specifically designed for wound healing applications. The SCA was prepared via a one-pot processing, where SeNPs synthesized via chemical reduction were incorporated. These SeNPs not only endowed SCA with robust wet adhesion ability, excellent stretchability, and skin-matched elasticity modulus by serving as a physical crosslinker to modulate swelling equilibrium and molecular slippage, but also enhanced the biocompatibility and free radical scavenging capacity of SCA. Furthermore, in vivo evaluation of full-thickness cutaneous defects of rats revealed that SCA effectively reduced inflammation, promoted wound closure, and increased collagen deposition. All these results demonstrated that the developed SCA offers a promising therapeutic strategy for wound healing applications.
Wound dressings with tissue adhesion, good mechanical, antioxidant and anti-inflammatory performance are urgently needed. In this work, we present a multifunctional selenium nanoparticles (SeNPs)/citric acid/gelatin/hydroxysuccinimide-grafted polyacrylic acid nanocomposite hydrogel adhesive (SCA) specifically designed for wound healing applications. The SCA was prepared via a one-pot processing, where SeNPs synthesized via chemical reduction were incorporated. These SeNPs not only endowed SCA with robust wet adhesion ability, excellent stretchability, and skin-matched elasticity modulus by serving as a physical crosslinker to modulate swelling equilibrium and molecular slippage, but also enhanced the biocompatibility and free radical scavenging capacity of SCA. Furthermore, in vivo evaluation of full-thickness cutaneous defects of rats revealed that SCA effectively reduced inflammation, promoted wound closure, and increased collagen deposition. All these results demonstrated that the developed SCA offers a promising therapeutic strategy for wound healing applications.
2025, 36(9): 110325
doi: 10.1016/j.cclet.2024.110325
Abstract:
Flexible and stretchable energy storage devices are highly desirable for wearable electronics, particularly in the emerging fields of smart clothes, medical instruments, and stretchable skin. Lithium metal batteries (LMBs) with high power density and long cycle life are one of the ideal power sources for flexible and stretchable energy storage devices. However, the current LMBs are usually too rigid and bulky to meet the requirements of these devices. The electrolyte is the critical component that determines the energy density and security of flexible and stretchable LMBs. Among various electrolytes, gel polymer electrolytes (GPEs) perform excellent flexibility, safety, and high ionic conductivity compared with traditional liquid electrolytes and solid electrolytes, fulfilling the next generation deformable LMBs. This essay mainly reviews and highlights the recent progress in GPEs for flexible/stretchable LMBs and provides some useful insights for people interested in this field. Additionally, the multifunctional GPEs with self-healing, flame retardant, and temperature tolerance abilities are summarized. Finally, the perspectives and opportunities for flexible and stretchable GPEs are discussed.
Flexible and stretchable energy storage devices are highly desirable for wearable electronics, particularly in the emerging fields of smart clothes, medical instruments, and stretchable skin. Lithium metal batteries (LMBs) with high power density and long cycle life are one of the ideal power sources for flexible and stretchable energy storage devices. However, the current LMBs are usually too rigid and bulky to meet the requirements of these devices. The electrolyte is the critical component that determines the energy density and security of flexible and stretchable LMBs. Among various electrolytes, gel polymer electrolytes (GPEs) perform excellent flexibility, safety, and high ionic conductivity compared with traditional liquid electrolytes and solid electrolytes, fulfilling the next generation deformable LMBs. This essay mainly reviews and highlights the recent progress in GPEs for flexible/stretchable LMBs and provides some useful insights for people interested in this field. Additionally, the multifunctional GPEs with self-healing, flame retardant, and temperature tolerance abilities are summarized. Finally, the perspectives and opportunities for flexible and stretchable GPEs are discussed.
2025, 36(9): 110370
doi: 10.1016/j.cclet.2024.110370
Abstract:
As an emergent energy carrier, ammonia benefits from a well-established industrial infrastructure for its transportation and production, positioning it as a promising candidate toward a carbon-free energy landscape. Within this context, the electrocatalytic ammonia oxidation reaction (AOR) is pivotal. Platinum (Pt), recognized as the most efficient AOR catalyst, has undergone extensive development over the years, yielding notable advancements across various domains, ranging from elucidating the reaction mechanism to exploring innovative materials. This review begins by elucidating the mechanism of ammonia oxidation, summarizing the evolution of the mechanism and the diverse intermediates identified through various detection methods. Subsequently, it outlines the research progress surrounding different Pt-based catalysts, followed by a discussion on standard protocols for electrochemical ammonia oxidation testing, which facilitates meaningful comparisons across studies and catalyzes the development of more efficient and potent catalysts. Moreover, the review addresses current challenges in ammonia oxidation and outlines potential future directions, providing a comprehensive outlook on the field.
As an emergent energy carrier, ammonia benefits from a well-established industrial infrastructure for its transportation and production, positioning it as a promising candidate toward a carbon-free energy landscape. Within this context, the electrocatalytic ammonia oxidation reaction (AOR) is pivotal. Platinum (Pt), recognized as the most efficient AOR catalyst, has undergone extensive development over the years, yielding notable advancements across various domains, ranging from elucidating the reaction mechanism to exploring innovative materials. This review begins by elucidating the mechanism of ammonia oxidation, summarizing the evolution of the mechanism and the diverse intermediates identified through various detection methods. Subsequently, it outlines the research progress surrounding different Pt-based catalysts, followed by a discussion on standard protocols for electrochemical ammonia oxidation testing, which facilitates meaningful comparisons across studies and catalyzes the development of more efficient and potent catalysts. Moreover, the review addresses current challenges in ammonia oxidation and outlines potential future directions, providing a comprehensive outlook on the field.
2025, 36(9): 110652
doi: 10.1016/j.cclet.2024.110652
Abstract:
Natural enzymes are able to precisely bind substrates and catalyze activities because of their distinct framework structures. To mimic this ability, chemists are designing framework structures that resemble real enzymes. The use of metal-organic frameworks (MOFs) to mimic natural enzymes has advanced recently; this paper reviews these developments. This research specifically focuses on how the catalytically active center of natural enzymes can be exactly replicated by carefully controlling the composition and structure of MOFs. By identifying and attaching to substrates, MOFs can accelerate changes in a manner akin to that of real enzymes. The role of MOFs in simulating catalytic processes, enzyme activity, and potential uses in brain chemistry are also investigated in this work. It also discusses the most recent MOF applications in detecting and treating chemical abnormalities of the brain. The report finishes with a discussion of future research areas and potential applications, providing useful insights for researchers in the subject.
Natural enzymes are able to precisely bind substrates and catalyze activities because of their distinct framework structures. To mimic this ability, chemists are designing framework structures that resemble real enzymes. The use of metal-organic frameworks (MOFs) to mimic natural enzymes has advanced recently; this paper reviews these developments. This research specifically focuses on how the catalytically active center of natural enzymes can be exactly replicated by carefully controlling the composition and structure of MOFs. By identifying and attaching to substrates, MOFs can accelerate changes in a manner akin to that of real enzymes. The role of MOFs in simulating catalytic processes, enzyme activity, and potential uses in brain chemistry are also investigated in this work. It also discusses the most recent MOF applications in detecting and treating chemical abnormalities of the brain. The report finishes with a discussion of future research areas and potential applications, providing useful insights for researchers in the subject.
2025, 36(9): 110664
doi: 10.1016/j.cclet.2024.110664
Abstract:
Low-valent sulfur oxy-acid salts (LVSOs) represent a category of oxygen-containing salts characterized by their potent reducing capabilities. Notably, sulfite, dithionite, and thiosulfate are prevalent reducing agents that are readily available, cost-effective, and exhibit minimal ecological toxicity. These LVSOs have the ability to generate or promote the generation of strong oxidants or reductants, which makes them widely used in advanced oxidation processes (AOPs) and advanced reduction processes (ARPs). This article provides a comprehensive review of the recent advancements in AOPs and ARPs involving LVSOs, alongside an examination of the fundamental principles governing the generation of active species within these processes. LVSOs fulfill three primary functions in AOPs: Serving as sources of reactive oxygen species (ROS), auxiliary agents, and activators. Particular attention is devoted to elucidating the reaction mechanisms through which LVSOs, in conjunction with metal ions, metal oxides, ultraviolet light (UV), and ozone, produce potent oxidizing agents in both homogeneous and heterogeneous systems. Regarding ARPs, this review delineates the mechanisms by which LVSOs generate strong reducing agents, including hydrated electrons, hydrogen radicals, and sulfite radicals, under UV irradiation, while also exploring the interactions between these reductants and pollutants. The review identifies existing gaps within the current framework and proposes future research avenues to address these challenges.
Low-valent sulfur oxy-acid salts (LVSOs) represent a category of oxygen-containing salts characterized by their potent reducing capabilities. Notably, sulfite, dithionite, and thiosulfate are prevalent reducing agents that are readily available, cost-effective, and exhibit minimal ecological toxicity. These LVSOs have the ability to generate or promote the generation of strong oxidants or reductants, which makes them widely used in advanced oxidation processes (AOPs) and advanced reduction processes (ARPs). This article provides a comprehensive review of the recent advancements in AOPs and ARPs involving LVSOs, alongside an examination of the fundamental principles governing the generation of active species within these processes. LVSOs fulfill three primary functions in AOPs: Serving as sources of reactive oxygen species (ROS), auxiliary agents, and activators. Particular attention is devoted to elucidating the reaction mechanisms through which LVSOs, in conjunction with metal ions, metal oxides, ultraviolet light (UV), and ozone, produce potent oxidizing agents in both homogeneous and heterogeneous systems. Regarding ARPs, this review delineates the mechanisms by which LVSOs generate strong reducing agents, including hydrated electrons, hydrogen radicals, and sulfite radicals, under UV irradiation, while also exploring the interactions between these reductants and pollutants. The review identifies existing gaps within the current framework and proposes future research avenues to address these challenges.
2025, 36(9): 110677
doi: 10.1016/j.cclet.2024.110677
Abstract:
Stochastic optical reconstruction microscopy (STORM), as a typical technique of single-molecule localization microscopy (SMLM), has overcome the diffraction limit by randomly switching fluorophores between fluorescent and dark states, allowing for the precise localization of isolated emission patterns and the super-resolution reconstruction from millions of localized positions of single fluorophores. A critical factor influencing localization precision is the photo-switching behavior of fluorophores, which is affected by the imaging buffer. The imaging buffer typically comprises oxygen scavengers, photo-switching reagents, and refractive index regulators. Oxygen scavengers help prevent photobleaching, photo-switching reagents assist in facilitating the conversion of fluorophores, and refractive index regulators are used to adjust the refractive index of the solution. The synergistic interaction of these components promotes stable blinking of fluorophores, reduces irreversible photobleaching, and thereby ensures high-quality super-resolution imaging. This review provides a comprehensive overview of the essential compositions and functionalities of imaging buffers used in STORM, serving as a valuable resource for researchers seeking to select appropriate imaging buffers for their experiments.
Stochastic optical reconstruction microscopy (STORM), as a typical technique of single-molecule localization microscopy (SMLM), has overcome the diffraction limit by randomly switching fluorophores between fluorescent and dark states, allowing for the precise localization of isolated emission patterns and the super-resolution reconstruction from millions of localized positions of single fluorophores. A critical factor influencing localization precision is the photo-switching behavior of fluorophores, which is affected by the imaging buffer. The imaging buffer typically comprises oxygen scavengers, photo-switching reagents, and refractive index regulators. Oxygen scavengers help prevent photobleaching, photo-switching reagents assist in facilitating the conversion of fluorophores, and refractive index regulators are used to adjust the refractive index of the solution. The synergistic interaction of these components promotes stable blinking of fluorophores, reduces irreversible photobleaching, and thereby ensures high-quality super-resolution imaging. This review provides a comprehensive overview of the essential compositions and functionalities of imaging buffers used in STORM, serving as a valuable resource for researchers seeking to select appropriate imaging buffers for their experiments.
2025, 36(9): 110685
doi: 10.1016/j.cclet.2024.110685
Abstract:
Thanks to its abundant reserves, relatively high energy density, and low reduction potential, potassium ion batteries (PIBs) have a high potential for large-scale energy storage applications. Due to the large radius of potassium ions, most conventional anode materials undergo severe volume expansion, making it difficult to achieve stable and reversible energy storage. Therefore, developing high-performance anode materials is one of the critical factors in developing PIBs. In this sense, antimony (Sb)-based anode materials with high theoretical capacity and safe reaction potentials have a broad potential for application in PIBs. However, overcoming the rapid capacity decay induced by the large radius of potassium ions is still an issue that needs to be focused on. This paper reviews the latest research on different types of Sb-based anode materials and provides an in-depth analysis of their optimization strategies. We focus on material selection, structural design, and storage mechanisms to develop a detailed description of the material. In addition, the current challenges still faced by Sb-based anode materials are summarized, and some further optimization strategies have been added. We hope to provide some insights for researchers developing Sb-based anode materials for next-generation advanced PIBs.
Thanks to its abundant reserves, relatively high energy density, and low reduction potential, potassium ion batteries (PIBs) have a high potential for large-scale energy storage applications. Due to the large radius of potassium ions, most conventional anode materials undergo severe volume expansion, making it difficult to achieve stable and reversible energy storage. Therefore, developing high-performance anode materials is one of the critical factors in developing PIBs. In this sense, antimony (Sb)-based anode materials with high theoretical capacity and safe reaction potentials have a broad potential for application in PIBs. However, overcoming the rapid capacity decay induced by the large radius of potassium ions is still an issue that needs to be focused on. This paper reviews the latest research on different types of Sb-based anode materials and provides an in-depth analysis of their optimization strategies. We focus on material selection, structural design, and storage mechanisms to develop a detailed description of the material. In addition, the current challenges still faced by Sb-based anode materials are summarized, and some further optimization strategies have been added. We hope to provide some insights for researchers developing Sb-based anode materials for next-generation advanced PIBs.
2025, 36(9): 110686
doi: 10.1016/j.cclet.2024.110686
Abstract:
The technology of three dimensional (3D) printing, also known as additive manufacturing, is a cutting-edge type of fabrication method that utilizes a computer-aided design platform and employs layer-by-layer stacking to construct objects with exceptional flexibility. Due to its capacity to produce a substantial quantity of products within a short period of time, 3D printing has emerged as one of the most significant manufacturing technology. Over the past two decades, remarkable advancements have been made in the application of 3D printing technology in the realm of bone tissue engineering. This review presents an innovative and systematic discussion on the potential application of 3D printing technology in bone tissue engineering, particularly in the treatment of infected bone defects. It comprehensively evaluates the materials utilized in 3D printing, highlights the interplay between cells and bone regeneration, and addresses and resolves challenges associated with current 3D printing technology. These challenges include material selection, fabrication of intricate 3D structures, integration of different cell types, streamlining design processes and material selection procedures, enhancing the clinical translational potential of 3D printing technology, and ultimately exploring future applications of four dimensional (4D) printing technology. The 3D printing technology has demonstrated significant potential in the synthesis of bone substitutes, offering consistent mechanical properties and ease of use. It has found extensive applications in personalized implant customization, prosthetic limb manufacturing, surgical tool production, tissue engineering, biological modeling, and cell diagnostics. Simultaneously, 3D bioprinting provides an effective solution to address the issue of organ donor shortage. However, challenges still exist in material selection, management of structural complexity, integration of different cell types, and construction of functionally mature tissues. With advancements in multi-material printing techniques as well as bioprinting and 4D printing technologies emerging on the horizon; 3D printing holds immense prospects for revolutionizing the means by which infectious bone defects are repaired.
The technology of three dimensional (3D) printing, also known as additive manufacturing, is a cutting-edge type of fabrication method that utilizes a computer-aided design platform and employs layer-by-layer stacking to construct objects with exceptional flexibility. Due to its capacity to produce a substantial quantity of products within a short period of time, 3D printing has emerged as one of the most significant manufacturing technology. Over the past two decades, remarkable advancements have been made in the application of 3D printing technology in the realm of bone tissue engineering. This review presents an innovative and systematic discussion on the potential application of 3D printing technology in bone tissue engineering, particularly in the treatment of infected bone defects. It comprehensively evaluates the materials utilized in 3D printing, highlights the interplay between cells and bone regeneration, and addresses and resolves challenges associated with current 3D printing technology. These challenges include material selection, fabrication of intricate 3D structures, integration of different cell types, streamlining design processes and material selection procedures, enhancing the clinical translational potential of 3D printing technology, and ultimately exploring future applications of four dimensional (4D) printing technology. The 3D printing technology has demonstrated significant potential in the synthesis of bone substitutes, offering consistent mechanical properties and ease of use. It has found extensive applications in personalized implant customization, prosthetic limb manufacturing, surgical tool production, tissue engineering, biological modeling, and cell diagnostics. Simultaneously, 3D bioprinting provides an effective solution to address the issue of organ donor shortage. However, challenges still exist in material selection, management of structural complexity, integration of different cell types, and construction of functionally mature tissues. With advancements in multi-material printing techniques as well as bioprinting and 4D printing technologies emerging on the horizon; 3D printing holds immense prospects for revolutionizing the means by which infectious bone defects are repaired.
2025, 36(9): 110698
doi: 10.1016/j.cclet.2024.110698
Abstract:
Rare earth metal elements include lanthanide elements as well as scandium and yttrium, totaling seventeen metal elements. Due to the wide application prospects of rare earth metal elements in various fields such as luminescent materials, magnetic materials, catalytic materials, electronic devices, they have an important strategic position. In the field of electrocatalysis, rare earth metal elements have great potential for development due to their unique 4f electron layer structure, spin orbit coupling, high reactivity, controllable coordination number, and rich optical properties. However, there is currently a lack of systematic reviews on the modification strategies of rare earth metal elements and the latest developments in electrocatalysis. Therefore, in order to stimulate the enthusiasm of researchers, this review focuses on the application progress of rare earth metal element modified metal oxides in multiple fields such as wastewater treatment, hydrogen peroxide synthesis, hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), nitrogen reduction reaction (NRR) and machine learning assisted research. In depth analysis of its electrocatalytic mechanism in various application scenarios and key factors affecting electrocatalytic performance. This review is of great significance for further developing high-performance and multifunctional electrocatalysts, and is expected to provide strong support for the development of energy, environment, and chemical industries.
Rare earth metal elements include lanthanide elements as well as scandium and yttrium, totaling seventeen metal elements. Due to the wide application prospects of rare earth metal elements in various fields such as luminescent materials, magnetic materials, catalytic materials, electronic devices, they have an important strategic position. In the field of electrocatalysis, rare earth metal elements have great potential for development due to their unique 4f electron layer structure, spin orbit coupling, high reactivity, controllable coordination number, and rich optical properties. However, there is currently a lack of systematic reviews on the modification strategies of rare earth metal elements and the latest developments in electrocatalysis. Therefore, in order to stimulate the enthusiasm of researchers, this review focuses on the application progress of rare earth metal element modified metal oxides in multiple fields such as wastewater treatment, hydrogen peroxide synthesis, hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), nitrogen reduction reaction (NRR) and machine learning assisted research. In depth analysis of its electrocatalytic mechanism in various application scenarios and key factors affecting electrocatalytic performance. This review is of great significance for further developing high-performance and multifunctional electrocatalysts, and is expected to provide strong support for the development of energy, environment, and chemical industries.
2025, 36(9): 110722
doi: 10.1016/j.cclet.2024.110722
Abstract:
To develop more efficient catalysts and discover new materials to work towards efficient solutions to the growing environmental problems, machine learning (ML) offers viable new ideas. Due to its ability to process large-scale data and mine underlying patterns, ML has been widely used in the design and development of materials in recent years. The purpose of this manuscript is to summarize the research progress of ML to guide the development of materials in the environmental field and open new horizons for environmental pollution control. This manuscript firstly details the basic ML definitions and operational procedures. Secondly, it summarizes the main ways of applying ML in materials. Then it unfolds to introduce the specific application examples of ML in different materials. Finally, we summarize the shortcomings and research trends of ML in predicting material design.
To develop more efficient catalysts and discover new materials to work towards efficient solutions to the growing environmental problems, machine learning (ML) offers viable new ideas. Due to its ability to process large-scale data and mine underlying patterns, ML has been widely used in the design and development of materials in recent years. The purpose of this manuscript is to summarize the research progress of ML to guide the development of materials in the environmental field and open new horizons for environmental pollution control. This manuscript firstly details the basic ML definitions and operational procedures. Secondly, it summarizes the main ways of applying ML in materials. Then it unfolds to introduce the specific application examples of ML in different materials. Finally, we summarize the shortcomings and research trends of ML in predicting material design.
2025, 36(9): 110725
doi: 10.1016/j.cclet.2024.110725
Abstract:
Urbanization and industrialization have escalated water pollution, threatening ecosystems and human health. Water pollution not only degrades water quality but also poses long-term risks to human health through the food chain. The development of efficient wastewater detection and treatment methods is essential for mitigating this environmental hazard. Carbon dots (CDs), as emerging carbon-based nanomaterials, exhibit properties such as biocompatibility, photoluminescence (PL), water solubility, and strong adsorption, positioning them as promising candidates for environmental monitoring and management. Particularly in wastewater treatment, their optical and electron transfer properties make them ideal for pollutant detection and removal. Despite their potential, comprehensive reviews on CDs' role in wastewater treatment are scarce, often lacking detailed insights into their synthesis, PL mechanisms, and practical applications. This review systematically addresses the synthesis, PL mechanisms, and wastewater treatment applications of CDs, aiming to bridge existing research gaps. It begins with an overview of CDs structure and classification, essential for grasping their properties and uses. The paper then explores the pivotal PL mechanisms of CDs, crucial for their sensing capabilities. Next, comprehensive synthesis strategies are presented, encompassing both top-down and bottom-up strategies such as arc discharge, chemical oxidation, and hydrothermal/solvothermal synthesis. The diversity of these methods highlights the potential for tailored CDs production to suit specific environmental applications. Furthermore, the review systematically discusses the applications of CDs in wastewater treatment, including sensing, inorganic removal, and organic degradation. Finally, it delves into the research prospects and challenges of CDs, proposing future directions to enhance their role in wastewater treatment.
Urbanization and industrialization have escalated water pollution, threatening ecosystems and human health. Water pollution not only degrades water quality but also poses long-term risks to human health through the food chain. The development of efficient wastewater detection and treatment methods is essential for mitigating this environmental hazard. Carbon dots (CDs), as emerging carbon-based nanomaterials, exhibit properties such as biocompatibility, photoluminescence (PL), water solubility, and strong adsorption, positioning them as promising candidates for environmental monitoring and management. Particularly in wastewater treatment, their optical and electron transfer properties make them ideal for pollutant detection and removal. Despite their potential, comprehensive reviews on CDs' role in wastewater treatment are scarce, often lacking detailed insights into their synthesis, PL mechanisms, and practical applications. This review systematically addresses the synthesis, PL mechanisms, and wastewater treatment applications of CDs, aiming to bridge existing research gaps. It begins with an overview of CDs structure and classification, essential for grasping their properties and uses. The paper then explores the pivotal PL mechanisms of CDs, crucial for their sensing capabilities. Next, comprehensive synthesis strategies are presented, encompassing both top-down and bottom-up strategies such as arc discharge, chemical oxidation, and hydrothermal/solvothermal synthesis. The diversity of these methods highlights the potential for tailored CDs production to suit specific environmental applications. Furthermore, the review systematically discusses the applications of CDs in wastewater treatment, including sensing, inorganic removal, and organic degradation. Finally, it delves into the research prospects and challenges of CDs, proposing future directions to enhance their role in wastewater treatment.
2025, 36(9): 110736
doi: 10.1016/j.cclet.2024.110736
Abstract:
Small interfering RNAs (siRNA) provide a novel and highly specific therapy due to their ability to effectively silence target genes, to date six siRNA therapeutics are approved for clinical use. Even so, some critical challenges remain to overcome in the therapeutic application of siRNAs, with delivery issues at the forefront. Among them, endo/lysosomal barrier is one of the important but often-neglected limitations hindering the delivery of siRNA therapeutics. In this review, we summarize the promising strategies that facilitate siRNAs overcoming endo/lysosomal barriers based on the cellular uptake and intracellular transport pathways, including promoting escape once endocytosis into the endo/lysosomes and bypassing lysosomes via endosome-Golgi-endoplasmic reticulum (ER) pathway or nonendocytosis pathway, and discuss the principal considerations and the future directions of promoting endo/lysosomal escape in the development of therapeutic siRNAs.
Small interfering RNAs (siRNA) provide a novel and highly specific therapy due to their ability to effectively silence target genes, to date six siRNA therapeutics are approved for clinical use. Even so, some critical challenges remain to overcome in the therapeutic application of siRNAs, with delivery issues at the forefront. Among them, endo/lysosomal barrier is one of the important but often-neglected limitations hindering the delivery of siRNA therapeutics. In this review, we summarize the promising strategies that facilitate siRNAs overcoming endo/lysosomal barriers based on the cellular uptake and intracellular transport pathways, including promoting escape once endocytosis into the endo/lysosomes and bypassing lysosomes via endosome-Golgi-endoplasmic reticulum (ER) pathway or nonendocytosis pathway, and discuss the principal considerations and the future directions of promoting endo/lysosomal escape in the development of therapeutic siRNAs.
2025, 36(9): 110813
doi: 10.1016/j.cclet.2024.110813
Abstract:
Untreated water environments encourage the emergence of pathogenic microorganisms, which pose a significant risk to human health and sustainable development. Antimicrobial technologies in advanced photothermal materials offer a promising alternative strategy for solving water disinfection challenges. This technology effectively destroys bacterial biofilms by designing materials with controlled photothermal properties. Despite the potential of this technology, there is a lack of comprehensive reviews on the application of photothermal materials in water disinfection. The aim of this paper is to provide a comprehensive and up-to-date overview of the research and application of photothermal materials in water disinfection. It focuses on composites in photothermal materials, elucidates their basic mechanisms and sterilization properties, and provides a systematic and detailed overview of their recent progress in the field. The goal of this review is to offer insights into the future design of photothermal materials and to propose strategies for their practical application in disinfection processes.
Untreated water environments encourage the emergence of pathogenic microorganisms, which pose a significant risk to human health and sustainable development. Antimicrobial technologies in advanced photothermal materials offer a promising alternative strategy for solving water disinfection challenges. This technology effectively destroys bacterial biofilms by designing materials with controlled photothermal properties. Despite the potential of this technology, there is a lack of comprehensive reviews on the application of photothermal materials in water disinfection. The aim of this paper is to provide a comprehensive and up-to-date overview of the research and application of photothermal materials in water disinfection. It focuses on composites in photothermal materials, elucidates their basic mechanisms and sterilization properties, and provides a systematic and detailed overview of their recent progress in the field. The goal of this review is to offer insights into the future design of photothermal materials and to propose strategies for their practical application in disinfection processes.
2025, 36(9): 110857
doi: 10.1016/j.cclet.2025.110857
Abstract:
The development of efficient green energy technology is imperative in the face of energy crises and environmental concerns. Photocatalysis, which utilizes solar energy for processes such as carbon dioxide (CO2) reduction, organic pollutants degradation, and hydrogen (H2) production through water splitting, is a promising approach. The key to high-efficiency photocatalysis lies in the design of superior photocatalysts. Graphene quantum dots (GQDs) have sparked significant interest in photocatalysis due to their exceptional up conversion photoluminescence (UCPL), strong light-capturing capability, and unique photoinduced charge transfer properties. However, their standalone use is limited by stability and activity. By integrating GQDs into composite photocatalysts, the separation of photogenerated electron-hole pairs is enhanced, boosting photocatalytic performance. This review provides the first overview and summary of the preparation methods of GQDs in photocatalysts, encompassing top-down and bottom-up strategy. Subsequently, a pioneering detailed summary was made on the applications of GQDs-semiconductor composites (metal organic frameworks, CdS, and bismuth-based oxides, etc.) in photocatalytic reactions such as CO2 reduction, organic pollutant degradation, and H2 generation. Furthermore, the corresponding representative examples and mechanisms are also elaborated and discussed respectively. Finally, the challenges and prospects for GQDs-based photocatalysts in the field of photocatalysis are proposed. This review provides inspiration and guidance for the development of efficient GQDs-based photocatalysts.
The development of efficient green energy technology is imperative in the face of energy crises and environmental concerns. Photocatalysis, which utilizes solar energy for processes such as carbon dioxide (CO2) reduction, organic pollutants degradation, and hydrogen (H2) production through water splitting, is a promising approach. The key to high-efficiency photocatalysis lies in the design of superior photocatalysts. Graphene quantum dots (GQDs) have sparked significant interest in photocatalysis due to their exceptional up conversion photoluminescence (UCPL), strong light-capturing capability, and unique photoinduced charge transfer properties. However, their standalone use is limited by stability and activity. By integrating GQDs into composite photocatalysts, the separation of photogenerated electron-hole pairs is enhanced, boosting photocatalytic performance. This review provides the first overview and summary of the preparation methods of GQDs in photocatalysts, encompassing top-down and bottom-up strategy. Subsequently, a pioneering detailed summary was made on the applications of GQDs-semiconductor composites (metal organic frameworks, CdS, and bismuth-based oxides, etc.) in photocatalytic reactions such as CO2 reduction, organic pollutant degradation, and H2 generation. Furthermore, the corresponding representative examples and mechanisms are also elaborated and discussed respectively. Finally, the challenges and prospects for GQDs-based photocatalysts in the field of photocatalysis are proposed. This review provides inspiration and guidance for the development of efficient GQDs-based photocatalysts.
2025, 36(9): 110912
doi: 10.1016/j.cclet.2025.110912
Abstract:
Pyrazole derivatives have made impressive achievements in the discovery of new pesticides, especially novel fungicides, insecticides, and herbicides. The pyrazole ring containing two adjacent nitrogen atoms is an important active fragment, which showed broad-spectrum and efficient biological activities. With the great interest and focus on pyrazoles, it is necessary to keep up-to-date with the latest research progress on pyrazole derivatives in the discovery of new pesticides. Based on this, we reviewed the progress and applications of pyrazole derivatives in the discovery of fungicides, antibacterial agents, insecticides, herbicides, antiviral agents, and nematicides in the past decade, summarized the fungicidal, antibacterial, insecticidal, herbicidal, antiviral, and nematicidal activities of pyrazoles, as well as the synthetic methods of the representative compounds. We also discussed the structure-activity relationship (SAR) and mechanism of action of the active compounds, aiming to provide new clues and ideas for the search of new pyrazole pesticides with high efficiency, low toxicity, and unique mechanism of action.
Pyrazole derivatives have made impressive achievements in the discovery of new pesticides, especially novel fungicides, insecticides, and herbicides. The pyrazole ring containing two adjacent nitrogen atoms is an important active fragment, which showed broad-spectrum and efficient biological activities. With the great interest and focus on pyrazoles, it is necessary to keep up-to-date with the latest research progress on pyrazole derivatives in the discovery of new pesticides. Based on this, we reviewed the progress and applications of pyrazole derivatives in the discovery of fungicides, antibacterial agents, insecticides, herbicides, antiviral agents, and nematicides in the past decade, summarized the fungicidal, antibacterial, insecticidal, herbicidal, antiviral, and nematicidal activities of pyrazoles, as well as the synthetic methods of the representative compounds. We also discussed the structure-activity relationship (SAR) and mechanism of action of the active compounds, aiming to provide new clues and ideas for the search of new pyrazole pesticides with high efficiency, low toxicity, and unique mechanism of action.
2025, 36(9): 110988
doi: 10.1016/j.cclet.2025.110988
Abstract:
Environmental catalysis has been considered one of the important research topics. Some technologies (e.g., photocatalysis and electrocatalysis) have been intensively developed with the advance of synthetic technologies of catalytical materials. In 2019, we discussed the development trend of this field, and wrote a roadmap on this topic in Chinese Chemical Letters (30 (2019) 2065–2088). Nowadays, we discuss it again from a new viewpoint along this road. In this paper, several subtopics are discussed, e.g., photocatalysis based on titanium dioxide, violet phosphorus, graphitic carbon and covalent organic frameworks, electrocatalysts based on carbon, metal- and covalent-organic framework. Finally, we hope that this roadmap can enrich the development of two-dimensional materials in environmental catalysis with novel understanding, and give useful inspiration to explore new catalysts for practical applications.
Environmental catalysis has been considered one of the important research topics. Some technologies (e.g., photocatalysis and electrocatalysis) have been intensively developed with the advance of synthetic technologies of catalytical materials. In 2019, we discussed the development trend of this field, and wrote a roadmap on this topic in Chinese Chemical Letters (30 (2019) 2065–2088). Nowadays, we discuss it again from a new viewpoint along this road. In this paper, several subtopics are discussed, e.g., photocatalysis based on titanium dioxide, violet phosphorus, graphitic carbon and covalent organic frameworks, electrocatalysts based on carbon, metal- and covalent-organic framework. Finally, we hope that this roadmap can enrich the development of two-dimensional materials in environmental catalysis with novel understanding, and give useful inspiration to explore new catalysts for practical applications.
2025, 36(9): 111052
doi: 10.1016/j.cclet.2025.111052
Abstract:
P-stereogenic compounds play pivotal roles in natural products, pharmaceuticals, bioactive molecules, and catalysts/ligands, making their synthesis a highly researched area. Current studies have predominantly concentrated on fully carbon-substituted P-stereogenic species, despite the fact that many therapeutically relevant compounds feature P-O, P-N, or P-S bonds. The catalytic and stereoselective nucleophilic substitution at the P-center is acknowledged as a highly efficient and straightforward approach for constructing high-value P-stereogenic compounds, offering significant potential for further development. This review provides an overview of advancements in the construction of P-stereogenic centers based on P-centered nucleophilic substitution, highlighting key challenges, breakthroughs, and future opportunities in the field.
P-stereogenic compounds play pivotal roles in natural products, pharmaceuticals, bioactive molecules, and catalysts/ligands, making their synthesis a highly researched area. Current studies have predominantly concentrated on fully carbon-substituted P-stereogenic species, despite the fact that many therapeutically relevant compounds feature P-O, P-N, or P-S bonds. The catalytic and stereoselective nucleophilic substitution at the P-center is acknowledged as a highly efficient and straightforward approach for constructing high-value P-stereogenic compounds, offering significant potential for further development. This review provides an overview of advancements in the construction of P-stereogenic centers based on P-centered nucleophilic substitution, highlighting key challenges, breakthroughs, and future opportunities in the field.
2025, 36(9): 111093
doi: 10.1016/j.cclet.2025.111093
Abstract:
Immunotherapy offers the promise of a potential cure for cancer, yet achieving the desired therapeutic effect can be challenging due to the immunosuppressive tumor microenvironments (TMEs) present in some tumors. Therefore, robust immune system activation is crucial to enhance the efficacy of cancer immunotherapy in clinical applications. Bacteria have shown the ability to target the hypoxic TMEs while activating both innate and adaptive immune responses. Engineered bacteria, modified through chemical or biological methods, can be endowed with specific physiological properties, such as diverse surface antigens, metabolites, and improved biocompatibility. These unique characteristics give engineered bacteria distinct advantages in stimulating anti-cancer immune responses. This review explores the potential regulatory mechanisms of engineered bacteria in modulating both innate and adaptive immunity while also forecasting the future development and challenges of using engineered bacteria in clinical cancer immunotherapy.
Immunotherapy offers the promise of a potential cure for cancer, yet achieving the desired therapeutic effect can be challenging due to the immunosuppressive tumor microenvironments (TMEs) present in some tumors. Therefore, robust immune system activation is crucial to enhance the efficacy of cancer immunotherapy in clinical applications. Bacteria have shown the ability to target the hypoxic TMEs while activating both innate and adaptive immune responses. Engineered bacteria, modified through chemical or biological methods, can be endowed with specific physiological properties, such as diverse surface antigens, metabolites, and improved biocompatibility. These unique characteristics give engineered bacteria distinct advantages in stimulating anti-cancer immune responses. This review explores the potential regulatory mechanisms of engineered bacteria in modulating both innate and adaptive immunity while also forecasting the future development and challenges of using engineered bacteria in clinical cancer immunotherapy.
2025, 36(9): 111178
doi: 10.1016/j.cclet.2025.111178
Abstract:
Two-dimensional (2D) nanomaterials have always been regarded as having great development potential in the field of oil-based lubrication due to their designable structures, functional groups, and abundant active sites. However, understanding the structure-performance relationship between the chemical structure of 2D nanomaterials and their lubrication performance from a comprehensive perspective is crucial for guiding their future development. This review provides a timely and comprehensive overview of the applications of 2D nanomaterials in oil-based lubrication. First, the bottlenecks and mechanisms of action of 2D nanomaterials are outlined, including adsorption protective films, charge adsorption effects, tribochemical reaction films, interlayer slip, and synergistic effects. On this basis, the review summarizes recent structural regulation strategies for 2D nanomaterials, including doping engineering, surface modification, structural optimization, and interfacial mixing engineering. Then, the focus was on analyzing the structure-performance relationship between the chemical structure of 2D nanomaterials and their lubrication performance. The effects of thickness, number of layers, sheet diameter, interlayer spacing, Moiré patterns, wettability, functional groups, concentration, as well as interfacial compatibility and dispersion behavior of 2D nanomaterials were systematically investigated in oil-based lubrication, with the intrinsic correlations resolved through computational simulations. Finally, the review offers a preliminary summary of the significant challenges and future directions for 2D nanomaterials in oil-based lubrication. This review aims to provide valuable insights and development strategies for the rational design of high-performance oil-based lubrication materials.
Two-dimensional (2D) nanomaterials have always been regarded as having great development potential in the field of oil-based lubrication due to their designable structures, functional groups, and abundant active sites. However, understanding the structure-performance relationship between the chemical structure of 2D nanomaterials and their lubrication performance from a comprehensive perspective is crucial for guiding their future development. This review provides a timely and comprehensive overview of the applications of 2D nanomaterials in oil-based lubrication. First, the bottlenecks and mechanisms of action of 2D nanomaterials are outlined, including adsorption protective films, charge adsorption effects, tribochemical reaction films, interlayer slip, and synergistic effects. On this basis, the review summarizes recent structural regulation strategies for 2D nanomaterials, including doping engineering, surface modification, structural optimization, and interfacial mixing engineering. Then, the focus was on analyzing the structure-performance relationship between the chemical structure of 2D nanomaterials and their lubrication performance. The effects of thickness, number of layers, sheet diameter, interlayer spacing, Moiré patterns, wettability, functional groups, concentration, as well as interfacial compatibility and dispersion behavior of 2D nanomaterials were systematically investigated in oil-based lubrication, with the intrinsic correlations resolved through computational simulations. Finally, the review offers a preliminary summary of the significant challenges and future directions for 2D nanomaterials in oil-based lubrication. This review aims to provide valuable insights and development strategies for the rational design of high-performance oil-based lubrication materials.
2025, 36(9): 111297
doi: 10.1016/j.cclet.2025.111297
Abstract:
Introducing functional polar groups into polyolefins can significantly improve the material properties, but there are still challenges in achieving this goal, with the core difficulty being that polar groups are prone to interact with metal active species, affecting the efficiency of the copolymerization. With the rapid advancement in catalyst, a variety of copolymerization strategies are developed aimed at producing more versatile polyolefin materials. Although early transition metal catalysts play an indispensable role in the traditional polyolefin industry, their inherent strong oxophilicity becomes a significant constraint in copolymerization involving polar olefins, limiting their application scope. This review summarizes the progress made in recent years in the efficient copolymerization of non-polar olefins with polar comonomers catalyzed by groups 3 and 4 single-site catalysts. We classify the catalysts into four categories, Sc-, Ti-, Zr-, Hf-, based on the type of metal centers, and provide insights into the influence of catalyst structures and the type of comonomers on the copolymerization behavior. The introduction of polar monomers fundamentally improves the comprehensive performance of the products, greatly broadens the application scope of polyolefin materials, and meets the growing market demand for multifunctional and high-performance materials.
Introducing functional polar groups into polyolefins can significantly improve the material properties, but there are still challenges in achieving this goal, with the core difficulty being that polar groups are prone to interact with metal active species, affecting the efficiency of the copolymerization. With the rapid advancement in catalyst, a variety of copolymerization strategies are developed aimed at producing more versatile polyolefin materials. Although early transition metal catalysts play an indispensable role in the traditional polyolefin industry, their inherent strong oxophilicity becomes a significant constraint in copolymerization involving polar olefins, limiting their application scope. This review summarizes the progress made in recent years in the efficient copolymerization of non-polar olefins with polar comonomers catalyzed by groups 3 and 4 single-site catalysts. We classify the catalysts into four categories, Sc-, Ti-, Zr-, Hf-, based on the type of metal centers, and provide insights into the influence of catalyst structures and the type of comonomers on the copolymerization behavior. The introduction of polar monomers fundamentally improves the comprehensive performance of the products, greatly broadens the application scope of polyolefin materials, and meets the growing market demand for multifunctional and high-performance materials.
2025, 36(9): 111383
doi: 10.1016/j.cclet.2025.111383
Abstract:
Solid-state lithium-ion batteries (SSLIBs) offer significant advantages over traditional liquid-electrolyte-based batteries, including improved safety, higher energy density, and better thermal stability. Among various anode materials, silicon (Si)-based anodes have attracted significant attention due to their ultrahigh theoretical capacity (~4200 mAh/g) and abundant resources. However, widespread adoption of Si-based anodes in SSLIBs is still restricted by some critical challenges such as severe volume expansion, low electronic and ionic conductivity, high interfacial impedance, and low initial Coulombic efficiency (ICE). This review mainly focuses on the design strategies of Si-based anode for SSLIBs at the material, electrode and cell levels including nanostructuring, Si alloys, Si-carbon composites, conductive additives, advanced binder, external pressure, electrolyte infiltration, and prelithiation. The insights provided here aim to inspire future research and accelerate commercialization of high-performance Si-based anodes in next-generation SSLIBs.
Solid-state lithium-ion batteries (SSLIBs) offer significant advantages over traditional liquid-electrolyte-based batteries, including improved safety, higher energy density, and better thermal stability. Among various anode materials, silicon (Si)-based anodes have attracted significant attention due to their ultrahigh theoretical capacity (~4200 mAh/g) and abundant resources. However, widespread adoption of Si-based anodes in SSLIBs is still restricted by some critical challenges such as severe volume expansion, low electronic and ionic conductivity, high interfacial impedance, and low initial Coulombic efficiency (ICE). This review mainly focuses on the design strategies of Si-based anode for SSLIBs at the material, electrode and cell levels including nanostructuring, Si alloys, Si-carbon composites, conductive additives, advanced binder, external pressure, electrolyte infiltration, and prelithiation. The insights provided here aim to inspire future research and accelerate commercialization of high-performance Si-based anodes in next-generation SSLIBs.
2025, 36(9): 110679
doi: 10.1016/j.cclet.2024.110679
Abstract:
2025, 36(9): 110924
doi: 10.1016/j.cclet.2025.110924
Abstract:
Element Transfer Reaction (ETR) theory is a new fundamental theory guiding the design of synthetic routes. It analyses problems from a brand-new perspective of element circulation, decomposing the factors affecting synthetic efficiency into three elements: element sources, driving force, and output. Different from the retrosynthetic analysis method and the atom economy theory, the ETR theory places more emphasis on examining the problem as a whole and comprehensively considering various factors involved in industrial applications. This perspective intends to elaborate on the scientific connotation of the ETR theory and explore its characteristics by discussing the practical application cases.
Element Transfer Reaction (ETR) theory is a new fundamental theory guiding the design of synthetic routes. It analyses problems from a brand-new perspective of element circulation, decomposing the factors affecting synthetic efficiency into three elements: element sources, driving force, and output. Different from the retrosynthetic analysis method and the atom economy theory, the ETR theory places more emphasis on examining the problem as a whole and comprehensively considering various factors involved in industrial applications. This perspective intends to elaborate on the scientific connotation of the ETR theory and explore its characteristics by discussing the practical application cases.
2025, 36(9): 111160
doi: 10.1016/j.cclet.2025.111160
Abstract:
Linear mRNA vaccines are constrained by exonuclease susceptibility and instability, leading to compromised antigen expression. Circular RNA (circRNA) lacking canonical 5′ and 3′ untranslated regions demonstrates intrinsic exonuclease resistance. Current circularization strategies face three principal limitations: chemical methods produce non-native 2′, 5′-phosphodiester bonds; ribozyme-mediated approaches are restricted to RNA fragments shorter than 500 nucleotides; the Anabaena Group Ⅰ intron system retains immunogenic exon sequences. In contrast, the self-splicing Group Ⅰ intron ribozyme from Tetrahymena enables precisely controlled circularization through autonomous structural rearrangement, yielding exon-free constructs. Through optimized purification protocols, historical scalability challenges are systematically addressed. This Perspective establishes the mechanistic rationale and therapeutic superiority of this engineered RNA circularization platform.
Linear mRNA vaccines are constrained by exonuclease susceptibility and instability, leading to compromised antigen expression. Circular RNA (circRNA) lacking canonical 5′ and 3′ untranslated regions demonstrates intrinsic exonuclease resistance. Current circularization strategies face three principal limitations: chemical methods produce non-native 2′, 5′-phosphodiester bonds; ribozyme-mediated approaches are restricted to RNA fragments shorter than 500 nucleotides; the Anabaena Group Ⅰ intron system retains immunogenic exon sequences. In contrast, the self-splicing Group Ⅰ intron ribozyme from Tetrahymena enables precisely controlled circularization through autonomous structural rearrangement, yielding exon-free constructs. Through optimized purification protocols, historical scalability challenges are systematically addressed. This Perspective establishes the mechanistic rationale and therapeutic superiority of this engineered RNA circularization platform.
