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2023 Volume 34 Issue 12
2023, 34(12): 108145
doi: 10.1016/j.cclet.2023.108145
Abstract:
Highly enantioselective sulfa-Michael additions (SMA) between 2-alkenyl quinoxalines and aromatic thiols are accomplished using a low loading of chiral phosphoric acid catalyst (1 mol%). It was confirmed by an investigation of a lot of azaarenes that the two C=N units of quinoxalines are indispensable for controlling the reaction enantioselectivities. A series of non-terminal 2-alkenes substituted with aryls or alkyls, even other electro-withdrawing groups such as ketones, esters, or amides, selectively reacted and afforded the desired SMA products (48 examples) in good regioselectivities with high yields (up to 99%) and good ee values (up to 97%).
Highly enantioselective sulfa-Michael additions (SMA) between 2-alkenyl quinoxalines and aromatic thiols are accomplished using a low loading of chiral phosphoric acid catalyst (1 mol%). It was confirmed by an investigation of a lot of azaarenes that the two C=N units of quinoxalines are indispensable for controlling the reaction enantioselectivities. A series of non-terminal 2-alkenes substituted with aryls or alkyls, even other electro-withdrawing groups such as ketones, esters, or amides, selectively reacted and afforded the desired SMA products (48 examples) in good regioselectivities with high yields (up to 99%) and good ee values (up to 97%).
2023, 34(12): 108183
doi: 10.1016/j.cclet.2023.108183
Abstract:
A photocycloaddition reaction of ethyl 1,4-diaryl-1,4-dihydropyridine-3-carboxylate for the construction of 3,9-diazatetraasteranes (P1) and 3,9-diazatetracyclododecanes (P2) is reported for the first time. The types of reaction product clearly differ with solvent, regardless of the irradiation wavelength. The difference in P1 and P2 lies in the second step of the intramolecular [2 + 2] photocyclization. In order to further investigate this phenomenon and gain a deeper understanding of the photochemical behavior of 1,4-dihydropyridines, DFT and TDDFT theoretical calculations are performed. The results provide a good explanation for the formation of 3,9-diazatetraasteranes and 3,9-diazatetracyclododecanes.
A photocycloaddition reaction of ethyl 1,4-diaryl-1,4-dihydropyridine-3-carboxylate for the construction of 3,9-diazatetraasteranes (P1) and 3,9-diazatetracyclododecanes (P2) is reported for the first time. The types of reaction product clearly differ with solvent, regardless of the irradiation wavelength. The difference in P1 and P2 lies in the second step of the intramolecular [2 + 2] photocyclization. In order to further investigate this phenomenon and gain a deeper understanding of the photochemical behavior of 1,4-dihydropyridines, DFT and TDDFT theoretical calculations are performed. The results provide a good explanation for the formation of 3,9-diazatetraasteranes and 3,9-diazatetracyclododecanes.
2023, 34(12): 108237
doi: 10.1016/j.cclet.2023.108237
Abstract:
Detection of mercury ions (Hg2+) in actual samples is of significant importance due to the toxicity of Hg2+ to human health. In this work, a simple tetraphenylethene (TPE) derived fluorescent probe TPE-Hg based on aggregation-induced emission (AIE) mechanism was synthesized. TPE-Hg can visually recognize Hg2+ in THF/HEPES (1:9, v/v, HEPES 20 mmol/L, pH 7.3) system with rapid response, strong anti-interference ability, large Stokes shift (203 nm), and low detection limit (7.548 × 10−7 mol/L). The results show that Hg2+ triggered elimination of TPE-Hg lead to releasing of an AIE-active compound 2 is responsible to the sensing mechanism. TPE-Hg is applicable to detect Hg2+ in actual water samples and image Hg2+ in living MCF-7 cells. In addition, TPE-Hg is suitable to assay the Hg2+ level in seafood and tea samples, and it is also applicable in test strips.
Detection of mercury ions (Hg2+) in actual samples is of significant importance due to the toxicity of Hg2+ to human health. In this work, a simple tetraphenylethene (TPE) derived fluorescent probe TPE-Hg based on aggregation-induced emission (AIE) mechanism was synthesized. TPE-Hg can visually recognize Hg2+ in THF/HEPES (1:9, v/v, HEPES 20 mmol/L, pH 7.3) system with rapid response, strong anti-interference ability, large Stokes shift (203 nm), and low detection limit (7.548 × 10−7 mol/L). The results show that Hg2+ triggered elimination of TPE-Hg lead to releasing of an AIE-active compound 2 is responsible to the sensing mechanism. TPE-Hg is applicable to detect Hg2+ in actual water samples and image Hg2+ in living MCF-7 cells. In addition, TPE-Hg is suitable to assay the Hg2+ level in seafood and tea samples, and it is also applicable in test strips.
2023, 34(12): 108249
doi: 10.1016/j.cclet.2023.108249
Abstract:
Three isomorphic polytungstates, Cs9K18H10{[Sm2(H2O)4W4O10(AsW9O33)3]2(N(CH2PO3)2)}·46.5H2O (1), Cs10K9H18{[Eu2(H2O)4W4O10(AsW9O33)3]2(N(CH2PO3)2)}·41.5H2O (2), Cs10K9H18{[Gd2(H2O)4W4O10 (AsW9O33)3]2(N(CH2PO3)2)}·46H2O (3), have been successfully synthesized and characterized by routine methods, and demonstrated excellent catalytic activities in Knoevenagel condensation reaction as heterogeneous catalysts. Notably, catalyst 1 achieved higher reaction activity than catalysts 2 and 3, where a satisfactory reaction yield (95%) and high TON value (6380) could be obtained at moderate reaction condition. In addition, in the scale-up experiment, with the help of catalyst 1, 7.8 g benzaldehyde and 5.7 g ethyl cyanoacetate could transform into corresponding condensation product with a satisfactory yield (83%) and impressive TON value (13,883).
Three isomorphic polytungstates, Cs9K18H10{[Sm2(H2O)4W4O10(AsW9O33)3]2(N(CH2PO3)2)}·46.5H2O (1), Cs10K9H18{[Eu2(H2O)4W4O10(AsW9O33)3]2(N(CH2PO3)2)}·41.5H2O (2), Cs10K9H18{[Gd2(H2O)4W4O10 (AsW9O33)3]2(N(CH2PO3)2)}·46H2O (3), have been successfully synthesized and characterized by routine methods, and demonstrated excellent catalytic activities in Knoevenagel condensation reaction as heterogeneous catalysts. Notably, catalyst 1 achieved higher reaction activity than catalysts 2 and 3, where a satisfactory reaction yield (95%) and high TON value (6380) could be obtained at moderate reaction condition. In addition, in the scale-up experiment, with the help of catalyst 1, 7.8 g benzaldehyde and 5.7 g ethyl cyanoacetate could transform into corresponding condensation product with a satisfactory yield (83%) and impressive TON value (13,883).
2023, 34(12): 108251
doi: 10.1016/j.cclet.2023.108251
Abstract:
Herein, we report a semi-synthetic strategy affording a nitrophorin 2 (NP2) variant with a N,N′-bis(2-pyridylmethyl)amine (Dpa) ligand as sidechain selectively installed at position 27, which was assembled from a synthetic peptide thioester bearing the Dpa ligand and an expressed protein segment via native chemical ligation. The semi-synthetic NP2 was able to accept the natural heme b cofactor and the Dpa ligand was able to bind Cu(Ⅱ)/Fe(Ⅲ) ions, leading to heteronuclear active site.
Herein, we report a semi-synthetic strategy affording a nitrophorin 2 (NP2) variant with a N,N′-bis(2-pyridylmethyl)amine (Dpa) ligand as sidechain selectively installed at position 27, which was assembled from a synthetic peptide thioester bearing the Dpa ligand and an expressed protein segment via native chemical ligation. The semi-synthetic NP2 was able to accept the natural heme b cofactor and the Dpa ligand was able to bind Cu(Ⅱ)/Fe(Ⅲ) ions, leading to heteronuclear active site.
2023, 34(12): 108261
doi: 10.1016/j.cclet.2023.108261
Abstract:
Following our previous work on human immunodeficiency virus-1 (HIV-1) non-nucleoside reverse transcriptase inhibitors (NNRTIs), a series of novel biphenyl-pyridone derivatives were synthesized and evaluated for their anti-HIV-1 activity to expand their structure–activity relationship. Some of them exhibited low nanomolar activity toward wild-type HIV-1 and clinically relevant single/double mutant strains. The most active compound B1 was 231-fold more potent (EC50 = 17 nmol/L) than the lead compound 2 (EC50 = 3.93 µmol/L) against wild-type (WT) HIV-1. This compound was approximately 3.5-fold less cytotoxic (CC50 = 100.58 µmol/L) than compound 2 (CC50 = 28.24 µmol/L), presenting a higher selectivity index (SI) value of 5923. Compared with 2, the antiviral potency of B1 was significantly increased against five single mutant strains (L100I, K103N, E138K, Y181C and Y188L) and two double mutant strains (F227L+V106A and K103N+Y181C). Especially, K103N, Y181C and K103N+Y181C were more sensitive to B1 than both 2 and doravirine. Besides, the enzymatic inhibitory activity of B1 against wild-type HIV-1 reverse transcriptase was approximately 32-fold higher (IC50 = 100 nmol/L) than 2 (IC50 = 3.21 µmol/L). Molecular docking studies and dynamic simulations were conducted to explain their potent activity. Taken together, this research represents an important step toward the discovery of novel biphenyl-pyridone drug candidates for HIV therapy.
Following our previous work on human immunodeficiency virus-1 (HIV-1) non-nucleoside reverse transcriptase inhibitors (NNRTIs), a series of novel biphenyl-pyridone derivatives were synthesized and evaluated for their anti-HIV-1 activity to expand their structure–activity relationship. Some of them exhibited low nanomolar activity toward wild-type HIV-1 and clinically relevant single/double mutant strains. The most active compound B1 was 231-fold more potent (EC50 = 17 nmol/L) than the lead compound 2 (EC50 = 3.93 µmol/L) against wild-type (WT) HIV-1. This compound was approximately 3.5-fold less cytotoxic (CC50 = 100.58 µmol/L) than compound 2 (CC50 = 28.24 µmol/L), presenting a higher selectivity index (SI) value of 5923. Compared with 2, the antiviral potency of B1 was significantly increased against five single mutant strains (L100I, K103N, E138K, Y181C and Y188L) and two double mutant strains (F227L+V106A and K103N+Y181C). Especially, K103N, Y181C and K103N+Y181C were more sensitive to B1 than both 2 and doravirine. Besides, the enzymatic inhibitory activity of B1 against wild-type HIV-1 reverse transcriptase was approximately 32-fold higher (IC50 = 100 nmol/L) than 2 (IC50 = 3.21 µmol/L). Molecular docking studies and dynamic simulations were conducted to explain their potent activity. Taken together, this research represents an important step toward the discovery of novel biphenyl-pyridone drug candidates for HIV therapy.
2023, 34(12): 108267
doi: 10.1016/j.cclet.2023.108267
Abstract:
Superlattices in crystals, particularly in perovskite oxides with strong correlation effects, can create new states of matter and produce peculiar physicochemical phenomena. However, the newfangled perovskite superlattices depend on physical deposition with unit-cell precision. It has been challenging to explore a new suitable chemical method to tailor perovskite superlattices. Herein, we present a new bottom-up strategy to precisely prepare atomic-scale oxide superlattices of (LaMnO3)1-(La1-x-yCaxKyMnO3)2 in a monodispersed perovskite La0.66Ca0.29K0.05MnO3 (LCKMO). The special atomic-scale perovskite superlattices are demonstrated using SAED, HAADF-STEM, XRD, and atomic-resolution elemental mapping. Our experiments reveal that the perovskite superlattices can be fabricated under extreme hydrothermal conditions utilizing ultra-high concentrations of KOH. An approximate molten salt system in the hydrothermal process can induce the disproportionation reaction of MnO2 solids, which is vital to the growth of ordered perovskite superlattices. This work not only clarifies the hydrothermal growth process of perovskite oxides in extreme conditions, but also proposes a novel engineering route toward perovskite superlattices.
Superlattices in crystals, particularly in perovskite oxides with strong correlation effects, can create new states of matter and produce peculiar physicochemical phenomena. However, the newfangled perovskite superlattices depend on physical deposition with unit-cell precision. It has been challenging to explore a new suitable chemical method to tailor perovskite superlattices. Herein, we present a new bottom-up strategy to precisely prepare atomic-scale oxide superlattices of (LaMnO3)1-(La1-x-yCaxKyMnO3)2 in a monodispersed perovskite La0.66Ca0.29K0.05MnO3 (LCKMO). The special atomic-scale perovskite superlattices are demonstrated using SAED, HAADF-STEM, XRD, and atomic-resolution elemental mapping. Our experiments reveal that the perovskite superlattices can be fabricated under extreme hydrothermal conditions utilizing ultra-high concentrations of KOH. An approximate molten salt system in the hydrothermal process can induce the disproportionation reaction of MnO2 solids, which is vital to the growth of ordered perovskite superlattices. This work not only clarifies the hydrothermal growth process of perovskite oxides in extreme conditions, but also proposes a novel engineering route toward perovskite superlattices.
2023, 34(12): 108268
doi: 10.1016/j.cclet.2023.108268
Abstract:
Anode SnO2 in lithium-ion batteries suffers from volume expansion and agglomeration. Here, the SnO2 nanoparticles are hybrided with ZrO2 particles by the support of carbon nanotube networks. The obtained SnO2/C/ZrO2 composite shows improved electrochemical performances. Investigations reveal that the carbon nanotubes shorten the transmission path of electrons and Li+ ions. Ball milling with ZrO2 promotes the formation of nanosized SnO2 to weaken the internal strain change, being beneficial to buffering volume change during electrochemical cycling afterwards. High-resolution 6, 7Li NMR investigations indicate that conversion and alloying reactions are stepwise involved for SnO2/C/ZrO2 anode. The strategy of designing SnO2/C/ZrO2 composite from the morphology-controlled metal-organic frameworks for energy storage widens the possibility to fabricate promising materials with enhanced performances.
Anode SnO2 in lithium-ion batteries suffers from volume expansion and agglomeration. Here, the SnO2 nanoparticles are hybrided with ZrO2 particles by the support of carbon nanotube networks. The obtained SnO2/C/ZrO2 composite shows improved electrochemical performances. Investigations reveal that the carbon nanotubes shorten the transmission path of electrons and Li+ ions. Ball milling with ZrO2 promotes the formation of nanosized SnO2 to weaken the internal strain change, being beneficial to buffering volume change during electrochemical cycling afterwards. High-resolution 6, 7Li NMR investigations indicate that conversion and alloying reactions are stepwise involved for SnO2/C/ZrO2 anode. The strategy of designing SnO2/C/ZrO2 composite from the morphology-controlled metal-organic frameworks for energy storage widens the possibility to fabricate promising materials with enhanced performances.
2023, 34(12): 108269
doi: 10.1016/j.cclet.2023.108269
Abstract:
Epoxidation is an important chemical process for the production of epoxides, key building blocks in chemical industry. Despite great efforts being made to facilitate this process, it remains a significant challenge to develop cost-effective, environmental-friendly, and selective catalysts. Herein, we reported a highly dispersed Mn supported by g-C3N4 (Mn/g-C3N4) with Mn loading up to 2.56 wt%. The Mn/g-C3N4 exhibited satisfied catalytic performance for olefin epoxidation with excellent conversion (91%), high selectivity (93%) as well as outstanding recycling stability. Further analysis revealed the importance of Mn-N structure for the generation of active oxo-containing species and subsequent oxygen atom transfer. Besides, an efficient synthesis of cyclic carbonates from styrene epoxide and CO2 has been achieved (88% conversion, 89% selectivity) based on the polar Mn-N coordinated characteristics of Mn/g-C3N4 catalyst.
Epoxidation is an important chemical process for the production of epoxides, key building blocks in chemical industry. Despite great efforts being made to facilitate this process, it remains a significant challenge to develop cost-effective, environmental-friendly, and selective catalysts. Herein, we reported a highly dispersed Mn supported by g-C3N4 (Mn/g-C3N4) with Mn loading up to 2.56 wt%. The Mn/g-C3N4 exhibited satisfied catalytic performance for olefin epoxidation with excellent conversion (91%), high selectivity (93%) as well as outstanding recycling stability. Further analysis revealed the importance of Mn-N structure for the generation of active oxo-containing species and subsequent oxygen atom transfer. Besides, an efficient synthesis of cyclic carbonates from styrene epoxide and CO2 has been achieved (88% conversion, 89% selectivity) based on the polar Mn-N coordinated characteristics of Mn/g-C3N4 catalyst.
2023, 34(12): 108270
doi: 10.1016/j.cclet.2023.108270
Abstract:
To solve the problem of energy scarcity and widespread environmental contamination, it is necessary to design green and low-cost photocatalysts for water splitting. In this paper, a new penta-graphene/AlAs5 (PG/AlAs5) van der Waals (vdW) heterostructure is proposed and its performance for photocatalytic hydrolysis is calculated using the first-principles method. The findings suggest that the PG/AlAs5 heterostructure belong to type-Ⅱ indirect semiconductor, and the edge position and band gap width of this heterostructure satisfy the requests of redox reaction. Furthermore, the oxidation reaction (OER) on the AlAs5 side and the hydrogen evolution reaction (HER) on the PG side are thermodynamically spontaneous under different conditions. Surprisingly, the introduction of strain engineering has changed the position of the band edge and light absorption performance of PG/AlAs5 heterostructure, which is powerful for the performance of photocatalytic water splitting. The PG/AlAs5 vdW heterostructure exhibits well visible light absorption intensity without applying strain and biaxial strain of 2%. In conclusion, the findings suggest that the PG/AlAs5 vdW heterostructure is a prospecting catalyst for visible-light hydrolysis.
To solve the problem of energy scarcity and widespread environmental contamination, it is necessary to design green and low-cost photocatalysts for water splitting. In this paper, a new penta-graphene/AlAs5 (PG/AlAs5) van der Waals (vdW) heterostructure is proposed and its performance for photocatalytic hydrolysis is calculated using the first-principles method. The findings suggest that the PG/AlAs5 heterostructure belong to type-Ⅱ indirect semiconductor, and the edge position and band gap width of this heterostructure satisfy the requests of redox reaction. Furthermore, the oxidation reaction (OER) on the AlAs5 side and the hydrogen evolution reaction (HER) on the PG side are thermodynamically spontaneous under different conditions. Surprisingly, the introduction of strain engineering has changed the position of the band edge and light absorption performance of PG/AlAs5 heterostructure, which is powerful for the performance of photocatalytic water splitting. The PG/AlAs5 vdW heterostructure exhibits well visible light absorption intensity without applying strain and biaxial strain of 2%. In conclusion, the findings suggest that the PG/AlAs5 vdW heterostructure is a prospecting catalyst for visible-light hydrolysis.
2023, 34(12): 108276
doi: 10.1016/j.cclet.2023.108276
Abstract:
Bacterial infection of wounds is an escalating medical problem, issuing threats to both global public health and personal health. Photothermal antibacterial technology as a novel sterilization strategy has outstanding sterilization efficiency, high safety and low risk of emergence of drug-resistant bacteria. By combining inherent antibacterial activity and light-assisted antibacterial treatment, developing novel multifunctional dressings with synergistic high-efficiency antibacterial effects and also promoting wound healing possesses attractive advantages in the field of treating bacterial wound infections in clinical care. Herein, a multifunctional hydrogel formed by in situ photo-cross linking was designed and prepared by first grafting methacrylic anhydride as a photosensitizer onto chitosan, and then introducing oxidatively synthesized polydopamine (PDA). The physicochemical characterizations of the synthesized hydrogels demonstrated their tunability certainly associated with PDA concentration, including pore size, water swelling, rheological properties and in vitro degradability. In addition, the composite hydrogels exhibited good adhesion, anti-oxidation and photothermal properties due to the existence of PDA. Within 10 min upon exposure to 808 nm near-infrared (NIR) light irradiation, this hydrogel system displayed outstanding antibacterial activity against Staphylococcus aureus with almost 100% killing efficiency, of which rapid efficient sterilization plays a significant role in wound healing. Moreover, the hydrogel is capable of cytocompatibility and has low toxicity to murine fibroblasts (L929 and NIH/3T3). In the full-thickness wound defect infection model in mice, the wound closure ratio, inflammatory response, fibroblasts, neovascularization and epithelialization were measured. Animal experiments also reveal that the hydrogel assisted with NIR laser irradiation can inhibit effectively infection at an early stage and accelerate the wound healing process. In summary, this novel multifunctional injectable hydrogel exhibits excellent swelling capacity, bio-adhesion, antioxidant property, photothermal activity, efficient antibacterial property and facilitates skin healing, which has great promising application as a medical dressing biomaterial in infected wound care fields.
Bacterial infection of wounds is an escalating medical problem, issuing threats to both global public health and personal health. Photothermal antibacterial technology as a novel sterilization strategy has outstanding sterilization efficiency, high safety and low risk of emergence of drug-resistant bacteria. By combining inherent antibacterial activity and light-assisted antibacterial treatment, developing novel multifunctional dressings with synergistic high-efficiency antibacterial effects and also promoting wound healing possesses attractive advantages in the field of treating bacterial wound infections in clinical care. Herein, a multifunctional hydrogel formed by in situ photo-cross linking was designed and prepared by first grafting methacrylic anhydride as a photosensitizer onto chitosan, and then introducing oxidatively synthesized polydopamine (PDA). The physicochemical characterizations of the synthesized hydrogels demonstrated their tunability certainly associated with PDA concentration, including pore size, water swelling, rheological properties and in vitro degradability. In addition, the composite hydrogels exhibited good adhesion, anti-oxidation and photothermal properties due to the existence of PDA. Within 10 min upon exposure to 808 nm near-infrared (NIR) light irradiation, this hydrogel system displayed outstanding antibacterial activity against Staphylococcus aureus with almost 100% killing efficiency, of which rapid efficient sterilization plays a significant role in wound healing. Moreover, the hydrogel is capable of cytocompatibility and has low toxicity to murine fibroblasts (L929 and NIH/3T3). In the full-thickness wound defect infection model in mice, the wound closure ratio, inflammatory response, fibroblasts, neovascularization and epithelialization were measured. Animal experiments also reveal that the hydrogel assisted with NIR laser irradiation can inhibit effectively infection at an early stage and accelerate the wound healing process. In summary, this novel multifunctional injectable hydrogel exhibits excellent swelling capacity, bio-adhesion, antioxidant property, photothermal activity, efficient antibacterial property and facilitates skin healing, which has great promising application as a medical dressing biomaterial in infected wound care fields.
2023, 34(12): 108282
doi: 10.1016/j.cclet.2023.108282
Abstract:
Two-dimensional organic-inorganic hybrid ferroelastics with high-temperature reversible phase transitions are very rare and have become one of the research hotspots in the field of ferroelastic materials. Herein, we report three new layered organic-inorganic hybrid perovskites based on halogen-substituted phenethylaminium, (3-XC6H5CH2CH2NH3)2[CdCl4] (X = F (1), Cl (2) and Br (3)). They undergo structural phase transitions at 376/371 K, 436/430 K, and 421/411 K, respectively, between the isomorphic high-temperature phases (space group I4/mmm, Z = 2) and different room-temperature phases with the reduced structural symmetries, i.e., P21/a (Z = 2) in 1, (Z = 4) in 2, and P21/a (Z = 4) in 3, respectively. These ferroelastic transitions arise from the order-disorder transition of organic cations together with the synchronous displacement of inorganic layers, accompanying with ferroelastic spontaneous strains of 0.16, 0.13 and 0.12 for 1−3, respectively. By enriching layered perovskite ferroelastics based on halogen-substituted cations, this work provides important clues for exploring new ferroic materials based on hybrid crystals.
Two-dimensional organic-inorganic hybrid ferroelastics with high-temperature reversible phase transitions are very rare and have become one of the research hotspots in the field of ferroelastic materials. Herein, we report three new layered organic-inorganic hybrid perovskites based on halogen-substituted phenethylaminium, (3-XC6H5CH2CH2NH3)2[CdCl4] (X = F (1), Cl (2) and Br (3)). They undergo structural phase transitions at 376/371 K, 436/430 K, and 421/411 K, respectively, between the isomorphic high-temperature phases (space group I4/mmm, Z = 2) and different room-temperature phases with the reduced structural symmetries, i.e., P21/a (Z = 2) in 1, (Z = 4) in 2, and P21/a (Z = 4) in 3, respectively. These ferroelastic transitions arise from the order-disorder transition of organic cations together with the synchronous displacement of inorganic layers, accompanying with ferroelastic spontaneous strains of 0.16, 0.13 and 0.12 for 1−3, respectively. By enriching layered perovskite ferroelastics based on halogen-substituted cations, this work provides important clues for exploring new ferroic materials based on hybrid crystals.
2023, 34(12): 108283
doi: 10.1016/j.cclet.2023.108283
Abstract:
The trade-off between mass-loading and cycling stability is always a big challenge for iron oxide-based electrodes. Herein, α-Fe2O3 nanoparticles uniformly anchored on nitrogen-doped wood carbons with high mass-loading have been synthesized via a facile electrodeposition method accompanied by post-heating treatment. The resultant composite delivers a high specific capacitance of 603 F/g at 0.1 A/g and superior capacitance retention of 85.5% after 10,000 cycles at 10 A/g, indicating excellent long-term cycling stability. Such excellent electrochemical performance can be attributed to the synergistic effects of α-Fe2O3 nanoparticles and the conductive matrix as well as the formation of interfacial Fe-O-C bonding, which enables the composite electrode to provide plenty of accessible redox active sites, sufficient electron transport and electrolyte ions diffusion, and robust interfacial interaction. Consequently, the asymmetrical supercapacitor exhibits a high energy density of 30.3 Wh/kg at 125 W/kg, suggesting its great potential for practical applications.
The trade-off between mass-loading and cycling stability is always a big challenge for iron oxide-based electrodes. Herein, α-Fe2O3 nanoparticles uniformly anchored on nitrogen-doped wood carbons with high mass-loading have been synthesized via a facile electrodeposition method accompanied by post-heating treatment. The resultant composite delivers a high specific capacitance of 603 F/g at 0.1 A/g and superior capacitance retention of 85.5% after 10,000 cycles at 10 A/g, indicating excellent long-term cycling stability. Such excellent electrochemical performance can be attributed to the synergistic effects of α-Fe2O3 nanoparticles and the conductive matrix as well as the formation of interfacial Fe-O-C bonding, which enables the composite electrode to provide plenty of accessible redox active sites, sufficient electron transport and electrolyte ions diffusion, and robust interfacial interaction. Consequently, the asymmetrical supercapacitor exhibits a high energy density of 30.3 Wh/kg at 125 W/kg, suggesting its great potential for practical applications.
2023, 34(12): 108288
doi: 10.1016/j.cclet.2023.108288
Abstract:
Carbon is a promising capacitive electrode material for Zn-ion hybrid supercapacitors (ZHSCs), as it is low-cost, environmentally friendly, controllable and adjustable. By now, achieving both high energy and high power with carbon electrodes is still challenging, limited by their intrinsic properties. In this work, we have designed and presented an amorphous hollow carbon bowl material with surface chemical modifications of oxygen groups to figure out these concerns. The preparation of bowl-like structures and the storage behavior between Zn2+ and oxygen functional groups have also been discussed. With the contributions from its unique hollow structure and surface functional groups, it can significantly enhance the electrode pseudocapacitance and the entire electrochemical performance.
Carbon is a promising capacitive electrode material for Zn-ion hybrid supercapacitors (ZHSCs), as it is low-cost, environmentally friendly, controllable and adjustable. By now, achieving both high energy and high power with carbon electrodes is still challenging, limited by their intrinsic properties. In this work, we have designed and presented an amorphous hollow carbon bowl material with surface chemical modifications of oxygen groups to figure out these concerns. The preparation of bowl-like structures and the storage behavior between Zn2+ and oxygen functional groups have also been discussed. With the contributions from its unique hollow structure and surface functional groups, it can significantly enhance the electrode pseudocapacitance and the entire electrochemical performance.
2023, 34(12): 108294
doi: 10.1016/j.cclet.2023.108294
Abstract:
Tetra(amino)azacalix[4]arene skeleton was functionalized at the bridging NH sites using various aromatic aldehydes via formation of imidazobenzimidazole fused heterocycles. X-ray single crystal analysis revealed distorted 1,3-alternate conformations for the resulting macrocycles. Anthracenyl and pyrenyl modified imidazobenzimidazole fused aza-calix[4]arenes existed as dimers in the solid state, associated mainly through π-π stacking interactions between the planar polycyclic fluorophores. The tetrapyrenyl modified product was further used as a Zn2+-selective sensor, which showed naked-eye detected color change and enhanced excimer emission. The stoichiometry between the sensor and Zn2+ was determined to be 1:1 and the association constant was 1.1 × 105 L/mol. The sensing process was highly selective and showed strong anti-interference with presence of other cations. The UV-vis spectral changes in the sensing process were completely reversible by alternate addition of Zn2+ and F−, showing an efficient ''on–off-on'' result.
Tetra(amino)azacalix[4]arene skeleton was functionalized at the bridging NH sites using various aromatic aldehydes via formation of imidazobenzimidazole fused heterocycles. X-ray single crystal analysis revealed distorted 1,3-alternate conformations for the resulting macrocycles. Anthracenyl and pyrenyl modified imidazobenzimidazole fused aza-calix[4]arenes existed as dimers in the solid state, associated mainly through π-π stacking interactions between the planar polycyclic fluorophores. The tetrapyrenyl modified product was further used as a Zn2+-selective sensor, which showed naked-eye detected color change and enhanced excimer emission. The stoichiometry between the sensor and Zn2+ was determined to be 1:1 and the association constant was 1.1 × 105 L/mol. The sensing process was highly selective and showed strong anti-interference with presence of other cations. The UV-vis spectral changes in the sensing process were completely reversible by alternate addition of Zn2+ and F−, showing an efficient ''on–off-on'' result.
2023, 34(12): 108296
doi: 10.1016/j.cclet.2023.108296
Abstract:
Present research on the antimalarial mechanisms of artemisinin (ART) is mainly focused on covalent drug binding targets alkylated by free radicals, while non-covalent binding targets have rarely been reported. Here, we developed a novel photoaffinity probe of ART to globally capture and identify the antimalarial target proteins of ART through chemical proteomics. The results demonstrated that ART can bind to parasite proteins by both covalent and non-covalent modification, and these may jointly contribute to the antimalarial effects. Our work enriches the research on the antimalarial targets of ART, and provides a new perspective for further exploring the antimalarial mechanism of ART.
Present research on the antimalarial mechanisms of artemisinin (ART) is mainly focused on covalent drug binding targets alkylated by free radicals, while non-covalent binding targets have rarely been reported. Here, we developed a novel photoaffinity probe of ART to globally capture and identify the antimalarial target proteins of ART through chemical proteomics. The results demonstrated that ART can bind to parasite proteins by both covalent and non-covalent modification, and these may jointly contribute to the antimalarial effects. Our work enriches the research on the antimalarial targets of ART, and provides a new perspective for further exploring the antimalarial mechanism of ART.
2023, 34(12): 108310
doi: 10.1016/j.cclet.2023.108310
Abstract:
Recognized as one of the important active species involved in various reactions, singlet oxygen (1O2) shows potential applications in chemical, biological, and environmental related fields. However, the controlled capture and release of 1O2 are still facing huge challenges due to its short lifetime and high reactivity. Herein, a framework-interpenetration tuning strategy was applied on a metal-organic framework (MOF) that aiming to improve the capture and release rate of 1O2. The porosity of the MOF was remarkably enhanced with the structural evolution from seven-fold (termed NKM-181) to six-fold interpenetration (termed NKM-182), and the active anthracene sites became much more accessible. Such drastic process can be achieved as simple as exchanging the primitive MOF in selected solvent and occurred surprisingly as single-crystal to single-crystal transformation. Also, additionally owing to the unblocked regular channels, NKM-182 shown significantly improved 1O2 trapping and releasing rates compared to that of in NKM-181. This work demonstrates an unprecedented regulation of 1O2 capture and release process, along with achieving the highest 1O2 capture and release rate among reported porous materials. Furthermore, the obtained endoperoxides with 1O2 loaded (termed EPO-NKM-181 and EPO-NKM-182) can be used as a high efficiency smart material for anti-fake application
Recognized as one of the important active species involved in various reactions, singlet oxygen (1O2) shows potential applications in chemical, biological, and environmental related fields. However, the controlled capture and release of 1O2 are still facing huge challenges due to its short lifetime and high reactivity. Herein, a framework-interpenetration tuning strategy was applied on a metal-organic framework (MOF) that aiming to improve the capture and release rate of 1O2. The porosity of the MOF was remarkably enhanced with the structural evolution from seven-fold (termed NKM-181) to six-fold interpenetration (termed NKM-182), and the active anthracene sites became much more accessible. Such drastic process can be achieved as simple as exchanging the primitive MOF in selected solvent and occurred surprisingly as single-crystal to single-crystal transformation. Also, additionally owing to the unblocked regular channels, NKM-182 shown significantly improved 1O2 trapping and releasing rates compared to that of in NKM-181. This work demonstrates an unprecedented regulation of 1O2 capture and release process, along with achieving the highest 1O2 capture and release rate among reported porous materials. Furthermore, the obtained endoperoxides with 1O2 loaded (termed EPO-NKM-181 and EPO-NKM-182) can be used as a high efficiency smart material for anti-fake application
2023, 34(12): 108311
doi: 10.1016/j.cclet.2023.108311
Abstract:
The currently reported axial chiral molecules based on the 3,3′-substitution of the binaphthyl skeleton are limited by intrinsic fluorescence properties, resulting in generally low device efficiencies (EQE < 5%) of related organic light emitting diodes (OLEDs). Herein, we designed and synthesized four pair of chiral binaphthyl enantiomers (R/S-1 − R/S-4) adopting acceptor-donor-donor-acceptor (ADDA) structure by introducing different thioxanthone modification groups on the 3,3′-position of 2,2′-dimethoxy-1,1′-binaphthalene. Among them, emitter R/S-2 and R/S-4 obtained by enhancing intramolecular charge transfer exhibited TADF characteristics due to relatively small ΔEST of 0.12 eV and 0.17 eV, and relatively moderate SOC matrix elements of 0.28 cm−1 and 0.10 cm−1 between the 1CT and 3LE states. The CD spectra of these enantiomers in diluted solutions showed perfect mirror images and reasonable gabs for small organic molecules (10−4–10−3). And the external quantum efficiencies (EQE) of 10.9% and 8.32% for device A and B based on emitter S-2 and S-4 were highest compared with currently reported axial chiral molecules based on the 3,3′-position substitution of binaphthyl skeleton, providing simple molecular design strategies to construct efficient CP-OLED device.
The currently reported axial chiral molecules based on the 3,3′-substitution of the binaphthyl skeleton are limited by intrinsic fluorescence properties, resulting in generally low device efficiencies (EQE < 5%) of related organic light emitting diodes (OLEDs). Herein, we designed and synthesized four pair of chiral binaphthyl enantiomers (R/S-1 − R/S-4) adopting acceptor-donor-donor-acceptor (ADDA) structure by introducing different thioxanthone modification groups on the 3,3′-position of 2,2′-dimethoxy-1,1′-binaphthalene. Among them, emitter R/S-2 and R/S-4 obtained by enhancing intramolecular charge transfer exhibited TADF characteristics due to relatively small ΔEST of 0.12 eV and 0.17 eV, and relatively moderate SOC matrix elements of 0.28 cm−1 and 0.10 cm−1 between the 1CT and 3LE states. The CD spectra of these enantiomers in diluted solutions showed perfect mirror images and reasonable gabs for small organic molecules (10−4–10−3). And the external quantum efficiencies (EQE) of 10.9% and 8.32% for device A and B based on emitter S-2 and S-4 were highest compared with currently reported axial chiral molecules based on the 3,3′-position substitution of binaphthyl skeleton, providing simple molecular design strategies to construct efficient CP-OLED device.
2023, 34(12): 108314
doi: 10.1016/j.cclet.2023.108314
Abstract:
Electrochemistry with antifouling sensing interfaces that effectively resist the adsorption of nonspecific biomolecules provides a powerful mean for the accurate and sensitive detection of disease biomarkers in complex biofluids. However, there are few strategies to acquire a stable and solid antifouling coating on any substrate by a simple way. Herein, a simple one-step assembly method has been adopted to construct phase-transited bovine serum albumin (PTB) antifouling layers. Prior to construction of the antifouling layers, the poly(3,4-ethylenedioxythiophene) (PEDOT) doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (ionic liquid, IL) were firstly electrodeposited on bare electrodes, endowing good conductivity and catalytic capability for the developed sensor. Subsequently, with the assist of tris(2-carboxyethyl)phosphine (TCEP), the disulfide bonds of bovine serum albumin (BSA) were reduced to form PTB, which can be coated on the PEDOT-IL modified electrode to construct an antifouling electrochemical senor (PTB/PEDOT-IL/GCE) for the detection of uric acid (UA) in human serum. The UA sensor demonstrated a good linear range from 1.11 µmol/L to 798.9 µmol/L, with a high sensitivity of 0.556 µA µmol L−1 cm−2. The combination of conducting polymers with one-step assembly of PTB offers a universal and reliable method for the modification of various electrodes to determine target molecules in complex human body fluids.
Electrochemistry with antifouling sensing interfaces that effectively resist the adsorption of nonspecific biomolecules provides a powerful mean for the accurate and sensitive detection of disease biomarkers in complex biofluids. However, there are few strategies to acquire a stable and solid antifouling coating on any substrate by a simple way. Herein, a simple one-step assembly method has been adopted to construct phase-transited bovine serum albumin (PTB) antifouling layers. Prior to construction of the antifouling layers, the poly(3,4-ethylenedioxythiophene) (PEDOT) doped with 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (ionic liquid, IL) were firstly electrodeposited on bare electrodes, endowing good conductivity and catalytic capability for the developed sensor. Subsequently, with the assist of tris(2-carboxyethyl)phosphine (TCEP), the disulfide bonds of bovine serum albumin (BSA) were reduced to form PTB, which can be coated on the PEDOT-IL modified electrode to construct an antifouling electrochemical senor (PTB/PEDOT-IL/GCE) for the detection of uric acid (UA) in human serum. The UA sensor demonstrated a good linear range from 1.11 µmol/L to 798.9 µmol/L, with a high sensitivity of 0.556 µA µmol L−1 cm−2. The combination of conducting polymers with one-step assembly of PTB offers a universal and reliable method for the modification of various electrodes to determine target molecules in complex human body fluids.
2023, 34(12): 108317
doi: 10.1016/j.cclet.2023.108317
Abstract:
Photo-catalytic oxidation of intracellular nicotinamide adenine dinucleotide (2′-phosphate) (NAD(P)H) has attracted much attention for cancer therapy. However, the general oxygen-dependent mechanism heavily depresses the efficacy in hypoxic tumors. To solve this problem, herein platinum nanoparticles (Pt NPs) with catalase-like (CAT-like) and catalytic H2 evolution activities were introduced as a powerful assistant to enhance the photo-catalytic NAD(P)H oxidation of Ru1 ([Ru(phen)2(PIP-OCH3)]2+, phen = 1,10-phenanthroline, PIP-OCH3 = 2-(4–methoxy phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline) under hypoxic and even oxygen-free conditions. Firstly, Pt NPs can transform the original and in situ formed H2O2 once again into O2 by the CAT-like activity, thus relieving tumor hypoxia and realizing cyclic utilization (at least in part) of the precious oxygen in hypoxia. Secondly, Pt NPs can also be served as H2 evolution catalysts while using Ru1 as the photosensitizer and NAD(P)H as the electron and proton donor. In this process, NAD(P)H is oxidized without the participation of oxygen, which can provide an effective way even under oxygen-free conditions. Via co-encapsulation of Ru1 and Pt NPs in bovine serum albumin (BSA) with tumor targeting ability, the resultant Ru/Pt@BSA could photo-catalyze intracellular NAD(P)H oxidation under hypoxic conditions (3% O2), and exhibited an efficient and selective anticancer activity both in vitro and in vivo. Our results may provide new sights for efficient and targeted cancer treatment under hypoxic conditions.
Photo-catalytic oxidation of intracellular nicotinamide adenine dinucleotide (2′-phosphate) (NAD(P)H) has attracted much attention for cancer therapy. However, the general oxygen-dependent mechanism heavily depresses the efficacy in hypoxic tumors. To solve this problem, herein platinum nanoparticles (Pt NPs) with catalase-like (CAT-like) and catalytic H2 evolution activities were introduced as a powerful assistant to enhance the photo-catalytic NAD(P)H oxidation of Ru1 ([Ru(phen)2(PIP-OCH3)]2+, phen = 1,10-phenanthroline, PIP-OCH3 = 2-(4–methoxy phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline) under hypoxic and even oxygen-free conditions. Firstly, Pt NPs can transform the original and in situ formed H2O2 once again into O2 by the CAT-like activity, thus relieving tumor hypoxia and realizing cyclic utilization (at least in part) of the precious oxygen in hypoxia. Secondly, Pt NPs can also be served as H2 evolution catalysts while using Ru1 as the photosensitizer and NAD(P)H as the electron and proton donor. In this process, NAD(P)H is oxidized without the participation of oxygen, which can provide an effective way even under oxygen-free conditions. Via co-encapsulation of Ru1 and Pt NPs in bovine serum albumin (BSA) with tumor targeting ability, the resultant Ru/Pt@BSA could photo-catalyze intracellular NAD(P)H oxidation under hypoxic conditions (3% O2), and exhibited an efficient and selective anticancer activity both in vitro and in vivo. Our results may provide new sights for efficient and targeted cancer treatment under hypoxic conditions.
2023, 34(12): 108318
doi: 10.1016/j.cclet.2023.108318
Abstract:
Zinc-air batteries (ZABs) are regarded as promising next-generation energy storage devices but limited by their sluggish oxygen reduction/evolution reactions (ORR/OER). Herein, the bifunctional catalyst consisting of MXene and metal compounds has been constructed via a controllable strategy. For demonstration, a 3D MXene framework with anchored heterostructure CoNi/CoNiP and nitrogen-doped carbon (NC) called H-CNP@M is constructed by metal-ion inducement and phosphorization. The bimetal-semiconductor heterostructure greatly enhances the catalytic performance. The H-CNP@M exhibits superior activities toward ORR (E1/2 = 0.833 V) and OER (η10 = 294 mV). Both aqueous and all-solid-state ZAB assembled with H-CNP@M demonstrate superior performance (peak power density of 166.5 mW/cm2 in aqueous case). This work provides a facile and general strategy to prepare MXene-supported bimetallic heterostructure for high-performance electrochemical energy devices.
Zinc-air batteries (ZABs) are regarded as promising next-generation energy storage devices but limited by their sluggish oxygen reduction/evolution reactions (ORR/OER). Herein, the bifunctional catalyst consisting of MXene and metal compounds has been constructed via a controllable strategy. For demonstration, a 3D MXene framework with anchored heterostructure CoNi/CoNiP and nitrogen-doped carbon (NC) called H-CNP@M is constructed by metal-ion inducement and phosphorization. The bimetal-semiconductor heterostructure greatly enhances the catalytic performance. The H-CNP@M exhibits superior activities toward ORR (E1/2 = 0.833 V) and OER (η10 = 294 mV). Both aqueous and all-solid-state ZAB assembled with H-CNP@M demonstrate superior performance (peak power density of 166.5 mW/cm2 in aqueous case). This work provides a facile and general strategy to prepare MXene-supported bimetallic heterostructure for high-performance electrochemical energy devices.
2023, 34(12): 108321
doi: 10.1016/j.cclet.2023.108321
Abstract:
Aging-related diseases are gradually becoming a major problem with the rapid development of aged population in human society. Although many fluorescent probes have been employed to diagnosis senescence via imaging senescence-associated β-galactosidase (SA-β-Gal), which is proved to be closely associated with senescent cells, the similar catalytic effectiveness of enzymatic reaction of ovarian cancer-associated β-Gal (OA-β-Gal) will interfere with imaging accuracy. Herein, a near-infrared (NIR) hemicyanine based fluorescent probe HCyXA-βGal was designed for light-up imaging of live cells containing β-Gal. With the organelle-targeting morpholinyl and positive charge moieties, HCyXA-βGal was successfully applicated to image the difference of enzymatic location in senescent cells and ovarian cancer cells. Furthermore, inspired by the fast response performance, fast and precise imaging of the two cell lines was realized via covering another dimension of fluorescence signal: time-dependent intensity.
Aging-related diseases are gradually becoming a major problem with the rapid development of aged population in human society. Although many fluorescent probes have been employed to diagnosis senescence via imaging senescence-associated β-galactosidase (SA-β-Gal), which is proved to be closely associated with senescent cells, the similar catalytic effectiveness of enzymatic reaction of ovarian cancer-associated β-Gal (OA-β-Gal) will interfere with imaging accuracy. Herein, a near-infrared (NIR) hemicyanine based fluorescent probe HCyXA-βGal was designed for light-up imaging of live cells containing β-Gal. With the organelle-targeting morpholinyl and positive charge moieties, HCyXA-βGal was successfully applicated to image the difference of enzymatic location in senescent cells and ovarian cancer cells. Furthermore, inspired by the fast response performance, fast and precise imaging of the two cell lines was realized via covering another dimension of fluorescence signal: time-dependent intensity.
2023, 34(12): 108329
doi: 10.1016/j.cclet.2023.108329
Abstract:
We here present a Förster resonance energy transfer (FRET)-based and environment-sensitive fluorescent probe VG-1 for vicinal-dithiol-containing proteins (VDPs). VG-1 uniquely contains two sites sensitive to the protein environment (SPE), thus it shows weak fluorescence in both blue and green channels (a low FRET efficiency) in solution. After specifically binding with VDPs, its fluorescence in the green channel increases, while that in the blue channel disappears, achieving the specific detection of VDPs. The obvious signal changes in fluorescence may be attributed to that the increased rigidity of the molecular skeletons causes the enhanced FRET efficiency. The probe also achieved the cell super-resolution imaging of VDPs and the confocal imaging of VDPs in zebrafish.
We here present a Förster resonance energy transfer (FRET)-based and environment-sensitive fluorescent probe VG-1 for vicinal-dithiol-containing proteins (VDPs). VG-1 uniquely contains two sites sensitive to the protein environment (SPE), thus it shows weak fluorescence in both blue and green channels (a low FRET efficiency) in solution. After specifically binding with VDPs, its fluorescence in the green channel increases, while that in the blue channel disappears, achieving the specific detection of VDPs. The obvious signal changes in fluorescence may be attributed to that the increased rigidity of the molecular skeletons causes the enhanced FRET efficiency. The probe also achieved the cell super-resolution imaging of VDPs and the confocal imaging of VDPs in zebrafish.
2023, 34(12): 108332
doi: 10.1016/j.cclet.2023.108332
Abstract:
Photodynamic therapy (PDT) has emerged as an efficient cancer treatment method with minimal invasiveness. However, the majority of current photosensitizers (PSs) display severe dark toxicity and low tumor specificity due to their "always-on" photoactivity in blood circulation. To address this concern, we herein report a series of acid-activatable PSs for ultrasensitive PDT of triple-negative breast tumors. These set of novel PSs are synthesized by covalently modifying tetrakis(4-carboxyphenyl)porphyrin (TCPP) with a variety of tertiary amines for acidity-activatable fluorescence imaging and reactive oxygen species (ROS) generation. The resultant TCPP derivatives are grafted with a poly(ethylene glycol) (PEG) chain via a matrix metalloproteinase-2 (MMP-2)-liable peptide spacer and chelated with Mn2+ for magnetic resonance imaging (MRI) capability. The PEGylated TCPP derivatives are amphiphilic and self-assemble into micellar nanoparticles to elongate blood circulation and for tumor-specific PDT. We further demonstrate that the PEGylated TCPP nanoparticles could serve as a nanoplatform to deliver the anticancer drug doxorubicin (DOX) and perform fluorescence image-guided combinatorial PDT and chemotherapy, which efficiently suppress the growth of 4T1 breast tumors and lung metastases in a mouse model. These acid-activatable PS-incorporated nanoparticles might provide a versatile platform for precise PDT and combinatorial breast cancer therapy.
Photodynamic therapy (PDT) has emerged as an efficient cancer treatment method with minimal invasiveness. However, the majority of current photosensitizers (PSs) display severe dark toxicity and low tumor specificity due to their "always-on" photoactivity in blood circulation. To address this concern, we herein report a series of acid-activatable PSs for ultrasensitive PDT of triple-negative breast tumors. These set of novel PSs are synthesized by covalently modifying tetrakis(4-carboxyphenyl)porphyrin (TCPP) with a variety of tertiary amines for acidity-activatable fluorescence imaging and reactive oxygen species (ROS) generation. The resultant TCPP derivatives are grafted with a poly(ethylene glycol) (PEG) chain via a matrix metalloproteinase-2 (MMP-2)-liable peptide spacer and chelated with Mn2+ for magnetic resonance imaging (MRI) capability. The PEGylated TCPP derivatives are amphiphilic and self-assemble into micellar nanoparticles to elongate blood circulation and for tumor-specific PDT. We further demonstrate that the PEGylated TCPP nanoparticles could serve as a nanoplatform to deliver the anticancer drug doxorubicin (DOX) and perform fluorescence image-guided combinatorial PDT and chemotherapy, which efficiently suppress the growth of 4T1 breast tumors and lung metastases in a mouse model. These acid-activatable PS-incorporated nanoparticles might provide a versatile platform for precise PDT and combinatorial breast cancer therapy.
2023, 34(12): 108334
doi: 10.1016/j.cclet.2023.108334
Abstract:
Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional (2D) and three-dimensional (3D) supramolecules, but designing and constructing heteroleptic and controllable self-assembly without unexpected by-products remains a challenge. Here we report two discrete trefoil-shaped metallacycle S1 and metallacage S2 by heteroleptic self-assembly using one hexaphenylbenzene core ligand and two capping ligands. The 2D trefoil-shaped metallacycle S1 could resemble the emblem of the classic 'Mitsubishi' motif. The use of template-oriented ligand and bent spacer ligand promotes the quantitative formation of the desired 3D trefoil-shaped metallacage S2. The formed metallacage S2 possesses a molecular weight up to 36 kDa, diameter 6.6 nm and height 3.0 nm. All supramolecular coordination complexes were fully characterized by NMR spectroscopy (1H NMR, 2D COSY, 2D NOESY, 2D DOSY), high-resolution electrospray ionization mass spectrometry ESI-MS, ESI-TWIM-MS, TEM and AFM.
Template-oriented multi-component synthesis method has been proven to be an exceedingly reasonable and excellent method for the synthesis of giant two-dimensional (2D) and three-dimensional (3D) supramolecules, but designing and constructing heteroleptic and controllable self-assembly without unexpected by-products remains a challenge. Here we report two discrete trefoil-shaped metallacycle S1 and metallacage S2 by heteroleptic self-assembly using one hexaphenylbenzene core ligand and two capping ligands. The 2D trefoil-shaped metallacycle S1 could resemble the emblem of the classic 'Mitsubishi' motif. The use of template-oriented ligand and bent spacer ligand promotes the quantitative formation of the desired 3D trefoil-shaped metallacage S2. The formed metallacage S2 possesses a molecular weight up to 36 kDa, diameter 6.6 nm and height 3.0 nm. All supramolecular coordination complexes were fully characterized by NMR spectroscopy (1H NMR, 2D COSY, 2D NOESY, 2D DOSY), high-resolution electrospray ionization mass spectrometry ESI-MS, ESI-TWIM-MS, TEM and AFM.
2023, 34(12): 108342
doi: 10.1016/j.cclet.2023.108342
Abstract:
Researchers engrossed in enantioseparation keep seeking for versatile chiral separation selectors. This work proposes a concept of quasi-dual-chiral-channel (QDCC) enantioseparation platform, where the surface sequentially grafted quinine (QN) and functional cyclodextrin (CD) can imitate two independent chiral channels without mutual interference to achieve wide spectrum chiral resolution. Chiral separation results combined with molecular docking simulation indicates that the different interaction mode of QN and functional CD layer renders QDCC the wide separation capability. This work provides a valuable insight into the rational design of versatile enantioseparation materials.
Researchers engrossed in enantioseparation keep seeking for versatile chiral separation selectors. This work proposes a concept of quasi-dual-chiral-channel (QDCC) enantioseparation platform, where the surface sequentially grafted quinine (QN) and functional cyclodextrin (CD) can imitate two independent chiral channels without mutual interference to achieve wide spectrum chiral resolution. Chiral separation results combined with molecular docking simulation indicates that the different interaction mode of QN and functional CD layer renders QDCC the wide separation capability. This work provides a valuable insight into the rational design of versatile enantioseparation materials.
2023, 34(12): 108345
doi: 10.1016/j.cclet.2023.108345
Abstract:
A novel BINOL-based fluorescence probe (S)-6 featuring a sodium sulfonate fragment at the 2′-position was designed and synthesized via simple synthetic procedures under mild reaction conditions. The water-soluble probe (S)-6 displays excellent enantioselective recognition toward 15 common amino acids, and it can be used for enantiomeric excess determination of amino acids. The fluorescence intensity of (S)-6 treated with amino acids reaches the maximum after standing for only 30 min at room temperature and remains stable in the following 5.5 h, which has great potential in the application of chiral fluorescence analysis due to its timeliness and outstanding fluorescent stability.
A novel BINOL-based fluorescence probe (S)-6 featuring a sodium sulfonate fragment at the 2′-position was designed and synthesized via simple synthetic procedures under mild reaction conditions. The water-soluble probe (S)-6 displays excellent enantioselective recognition toward 15 common amino acids, and it can be used for enantiomeric excess determination of amino acids. The fluorescence intensity of (S)-6 treated with amino acids reaches the maximum after standing for only 30 min at room temperature and remains stable in the following 5.5 h, which has great potential in the application of chiral fluorescence analysis due to its timeliness and outstanding fluorescent stability.
2023, 34(12): 108350
doi: 10.1016/j.cclet.2023.108350
Abstract:
Poly(m-phthaloyl-m-phenylenediamine) (PMIA) is promising as the separator in lithium-ion batteries (LIBs) for its excellent thermostability, insulation and self-extinguishing properties. However, its low mechanical strength and poor electrolyte affinity limit its application in LIBs. In this work, a new PMIA@polyacrylonitrile-polyvinylidene fluoride hexafluoropropylene-titanium dioxide (PMIA@PAN/PVDF-HFP/TiO2) composite fibrous separator with a coaxial core-shell structure was developed by combining coaxial electrospinning, hot pressing, and heat treatment techniques. This separator not only inherits the exceptional thermostability of PMIA, showing no evident thermal shrinkage at 220 ℃, but also reveals improved mechanical strength (29.7 MPa) due to the formation of firm connections between fibers with the melted PVDF-HFP. Meanwhile, the massive polar groups in PVDF-HFP play a vital role in improving the electrolyte affinity, which renders the separator a high ionic conductivity of 1.36 × 10−3 S/cm. Therefore, the LIBs with PMIA@PAN/PVDF-HFP/TiO2 separators exhibited excellent cycling and rate performance at 25 ℃, and a high capacity retention rate (76.2%) at 80 ℃ for 200 cycles at 1 C. Besides, the lithium metal symmetric battery assembled by the separator showed a small overpotential, indicating that the separator had a role in inhibiting lithium dendrites. In short, the PMIA@PAN/PVDF-HFP/TiO2 separator possesses a wide application prospect in the domain of LIBs.
Poly(m-phthaloyl-m-phenylenediamine) (PMIA) is promising as the separator in lithium-ion batteries (LIBs) for its excellent thermostability, insulation and self-extinguishing properties. However, its low mechanical strength and poor electrolyte affinity limit its application in LIBs. In this work, a new PMIA@polyacrylonitrile-polyvinylidene fluoride hexafluoropropylene-titanium dioxide (PMIA@PAN/PVDF-HFP/TiO2) composite fibrous separator with a coaxial core-shell structure was developed by combining coaxial electrospinning, hot pressing, and heat treatment techniques. This separator not only inherits the exceptional thermostability of PMIA, showing no evident thermal shrinkage at 220 ℃, but also reveals improved mechanical strength (29.7 MPa) due to the formation of firm connections between fibers with the melted PVDF-HFP. Meanwhile, the massive polar groups in PVDF-HFP play a vital role in improving the electrolyte affinity, which renders the separator a high ionic conductivity of 1.36 × 10−3 S/cm. Therefore, the LIBs with PMIA@PAN/PVDF-HFP/TiO2 separators exhibited excellent cycling and rate performance at 25 ℃, and a high capacity retention rate (76.2%) at 80 ℃ for 200 cycles at 1 C. Besides, the lithium metal symmetric battery assembled by the separator showed a small overpotential, indicating that the separator had a role in inhibiting lithium dendrites. In short, the PMIA@PAN/PVDF-HFP/TiO2 separator possesses a wide application prospect in the domain of LIBs.
2023, 34(12): 108355
doi: 10.1016/j.cclet.2023.108355
Abstract:
Replicating extraordinarily high membrane transport selectivity of protein channels in artificial channel is a challenging task. In this work, we demonstrate that a strategic application of steric code-based social self-sorting offers a novel means to enhance ion transport selectivities of artificial ion channels, alongside with boosted ion transport activities. More specifically, two types of mutually compatible sterically bulky groups (benzo-crown ether and tert-butyl group) were appended onto a monopeptide-based scaffold, which can order the bulky groups onto the same side of a one-dimensionally aligned H-bonded structure. Strong steric repulsions among the same type of bulky groups (either benzo-crown ethers or tert-butyl groups), which are forced into proximity by H-bonds, favor the formation of hetero-oligomeric ensembles that carry an alternative arrangement of sterically compatible benzo-crown ethers and tert-butyl groups, rather than homo-oligomeric ensembles containing a single type of either benzo-crown ethers or tert-butyl groups. Coupled with side chain tuning, this social self-sorting strategy delivers highly active hetero-oligomeric K+-selective ion channel (5F12·BF12)n, displaying the highest K+/Na+ selectivity of 20.1 among artificial potassium channels and an excellent EC50 value of 0.50 µmol/L (0.62 mol% relative to lipids) in terms of single channel concentration
Replicating extraordinarily high membrane transport selectivity of protein channels in artificial channel is a challenging task. In this work, we demonstrate that a strategic application of steric code-based social self-sorting offers a novel means to enhance ion transport selectivities of artificial ion channels, alongside with boosted ion transport activities. More specifically, two types of mutually compatible sterically bulky groups (benzo-crown ether and tert-butyl group) were appended onto a monopeptide-based scaffold, which can order the bulky groups onto the same side of a one-dimensionally aligned H-bonded structure. Strong steric repulsions among the same type of bulky groups (either benzo-crown ethers or tert-butyl groups), which are forced into proximity by H-bonds, favor the formation of hetero-oligomeric ensembles that carry an alternative arrangement of sterically compatible benzo-crown ethers and tert-butyl groups, rather than homo-oligomeric ensembles containing a single type of either benzo-crown ethers or tert-butyl groups. Coupled with side chain tuning, this social self-sorting strategy delivers highly active hetero-oligomeric K+-selective ion channel (5F12·BF12)n, displaying the highest K+/Na+ selectivity of 20.1 among artificial potassium channels and an excellent EC50 value of 0.50 µmol/L (0.62 mol% relative to lipids) in terms of single channel concentration
2023, 34(12): 108362
doi: 10.1016/j.cclet.2023.108362
Abstract:
Electrode materials with strong desalting ability is an important research direction of capacitive deionization. In this study, HKUST-1 was successfully synthesized by the solvothermal method, and MOFs-derived porous carbon/Cu@Cu2O composites were prepared by simple pyrolysis as cathode materials for CDI. After high-temperature pyrolysis, the Cu+ site with unsaturated coordination is generated, and the structure changes from micropores to the coexistence of mesoporous and micropores. The complex pore structure is conducive to strengthening ion migration and diffusion. The results show that the porous carbon/Cu@Cu2O materials derived from MOFs depend on the pseudocapacitance behavior for capacitive deionization and desalination. At a voltage window of -1.2 V~1.2 V, a current density of 40 mA/g, and 5 mmol/L NaCl, the HDC-1100 exhibited the best desalting capacity of 30.9 mg/g. HDC-1100 also has good cycle stability. After 20 cycles of adsorption and desorption, the desalting capacity almost does not decrease. Therefore, MOFs derived porous carbon/Cu@Cu2O composites are expected to be an excellent choice for CDI cathode materials.
Electrode materials with strong desalting ability is an important research direction of capacitive deionization. In this study, HKUST-1 was successfully synthesized by the solvothermal method, and MOFs-derived porous carbon/Cu@Cu2O composites were prepared by simple pyrolysis as cathode materials for CDI. After high-temperature pyrolysis, the Cu+ site with unsaturated coordination is generated, and the structure changes from micropores to the coexistence of mesoporous and micropores. The complex pore structure is conducive to strengthening ion migration and diffusion. The results show that the porous carbon/Cu@Cu2O materials derived from MOFs depend on the pseudocapacitance behavior for capacitive deionization and desalination. At a voltage window of -1.2 V~1.2 V, a current density of 40 mA/g, and 5 mmol/L NaCl, the HDC-1100 exhibited the best desalting capacity of 30.9 mg/g. HDC-1100 also has good cycle stability. After 20 cycles of adsorption and desorption, the desalting capacity almost does not decrease. Therefore, MOFs derived porous carbon/Cu@Cu2O composites are expected to be an excellent choice for CDI cathode materials.
2023, 34(12): 108363
doi: 10.1016/j.cclet.2023.108363
Abstract:
Phenylspirodrimanes are a kind of meroterpenoids with structural diversity and complexity, exhibiting a wide of biological properties, especially for the lactam derivatives consisting a γ-lactam moiety and N-linked side chains. These compounds were derived from multi-step combination of enzymatic and non-enzymatic conversions of intermediates in their biosynthetic pathways. Stachbotrydial (2) with an o-phthalaldehyde unit was supposed as the high-reactivity intermediate of phenylspirodrimane lactams via nonenzymatic reaction with amines. In the present work, an effective and non-enzymatic diversification strategy was developed for the structural diversification of phenylspirodrimane lactams including monomers and dimers from 2 by feeding structurally various mono- and diamines in the fungus Stachybotrys chartarum cultures. In total, 24 phenylspirodrimane lactams (1, 3–25) including 18 new compounds were synthesized. Among them, stachybocin A (1), a bioactive phenylspirodrimane lactam dimer, was produced with the yield of 18.7 mg/g of cell dry weight. The structures of these compounds were elucidated by extensive spectroscopic data, single-crystal X-ray diffraction (Cu Kα), and calculated electronic circular dichroism (ECD) analyses. Bioassay revealed that compounds 1, 17, and 24 displayed significant inhibitory effect on the inactivated state of hNaV 1.2 channels with IC50 values of 0.22, 2.08, and 0.53 µmol/L, respectively. In addition, 1 showed potent protein tyrosine phosphatase 1B (PTP1B) inhibitory, N-methyl-D-aspartate (NMDA) receptor antagonistic, and anti-inflammatory activities.
Phenylspirodrimanes are a kind of meroterpenoids with structural diversity and complexity, exhibiting a wide of biological properties, especially for the lactam derivatives consisting a γ-lactam moiety and N-linked side chains. These compounds were derived from multi-step combination of enzymatic and non-enzymatic conversions of intermediates in their biosynthetic pathways. Stachbotrydial (2) with an o-phthalaldehyde unit was supposed as the high-reactivity intermediate of phenylspirodrimane lactams via nonenzymatic reaction with amines. In the present work, an effective and non-enzymatic diversification strategy was developed for the structural diversification of phenylspirodrimane lactams including monomers and dimers from 2 by feeding structurally various mono- and diamines in the fungus Stachybotrys chartarum cultures. In total, 24 phenylspirodrimane lactams (1, 3–25) including 18 new compounds were synthesized. Among them, stachybocin A (1), a bioactive phenylspirodrimane lactam dimer, was produced with the yield of 18.7 mg/g of cell dry weight. The structures of these compounds were elucidated by extensive spectroscopic data, single-crystal X-ray diffraction (Cu Kα), and calculated electronic circular dichroism (ECD) analyses. Bioassay revealed that compounds 1, 17, and 24 displayed significant inhibitory effect on the inactivated state of hNaV 1.2 channels with IC50 values of 0.22, 2.08, and 0.53 µmol/L, respectively. In addition, 1 showed potent protein tyrosine phosphatase 1B (PTP1B) inhibitory, N-methyl-D-aspartate (NMDA) receptor antagonistic, and anti-inflammatory activities.
2023, 34(12): 108369
doi: 10.1016/j.cclet.2023.108369
Abstract:
To improve operation efficiency, an interlayered thin-film composite forward osmosis (iTFC-FO) membrane was designed by introducing an ultrathin and porous interlayer based on aluminum tetra-(4-carboxyphenyl)porphyrin (a stable metal−organic framework nanosheet, Al-MOF). Surface characterization results revealed that Al-MOF spread evenly in the macro-porous substrate, and provided a flat and smooth reaction interface with moderate hydrophilicity and uniform small aperture. The resultant polyamide (PA) layer had a thin base (without intrusion into substrate) and crumpled surface (with abundant leaves). The leaves size and cross-linking degree of PA layer firstly increased and then decreased with the Al-MOF loading. Compared to the original membrane, the iTFC-FO showed an enhanced water permeability and a reduced reverse sodium flux in both modes of active layer facing feed solution (AL-FS) and active layer facing draw solution (AL-DS). To be specific, the specific reverse sodium flux (reverse sodium flux/pure water flux) decreased from 0.27 g/L to 0.04 g/L in the AL-FS mode, while from 1.36 g/L to 0.23 g/L in the AL-DS mode with 2 mol/L NaCl as DS. Moreover, the iTFC-FO maintained high stability and high permeability under high-salinity and contaminated environment. This study offers a new possibility for the rational fabrication of high-performance TFC-FO membranes.
To improve operation efficiency, an interlayered thin-film composite forward osmosis (iTFC-FO) membrane was designed by introducing an ultrathin and porous interlayer based on aluminum tetra-(4-carboxyphenyl)porphyrin (a stable metal−organic framework nanosheet, Al-MOF). Surface characterization results revealed that Al-MOF spread evenly in the macro-porous substrate, and provided a flat and smooth reaction interface with moderate hydrophilicity and uniform small aperture. The resultant polyamide (PA) layer had a thin base (without intrusion into substrate) and crumpled surface (with abundant leaves). The leaves size and cross-linking degree of PA layer firstly increased and then decreased with the Al-MOF loading. Compared to the original membrane, the iTFC-FO showed an enhanced water permeability and a reduced reverse sodium flux in both modes of active layer facing feed solution (AL-FS) and active layer facing draw solution (AL-DS). To be specific, the specific reverse sodium flux (reverse sodium flux/pure water flux) decreased from 0.27 g/L to 0.04 g/L in the AL-FS mode, while from 1.36 g/L to 0.23 g/L in the AL-DS mode with 2 mol/L NaCl as DS. Moreover, the iTFC-FO maintained high stability and high permeability under high-salinity and contaminated environment. This study offers a new possibility for the rational fabrication of high-performance TFC-FO membranes.
2023, 34(12): 108371
doi: 10.1016/j.cclet.2023.108371
Abstract:
Because of the widespread applications of optically active alkyl fluorides in medicinal and agro chemicals, enantioselective and even stereodivergent construction of alkyl fluorides remains highly desirable but underdeveloped. Transition-metal-catalyzed asymmetric hydrofluoroalkylation of readily available dienes represents a novel route to achieve this goal, yet receives scarce study. Here we report an intriguing palladium-catalyzed enantioselective hydromonofluoroalkylation reaction of conjugated dienes. Both monosubstituted and internal dienes proceed well with the transformation and furnish alkyl fluorides in generally > 80% yield and > 90% ee. A stereodivergent hydromonofluoroalkylation protocol via Pd/Cu co-catalysis is also established for the access to all four stereoisomers of corresponding moieties bearing a fully-substituted F-stereogenic center and vicinal tertiary carbon center. In addition, asymmetric migratory hydromonofluoroalkylation of skipped dienes is developed to realize the direct allylic CH fluoroalkylation. A compound library of enantioenriched cyclic fluorides is thus built to highlight the transformation potential of present methodology.
Because of the widespread applications of optically active alkyl fluorides in medicinal and agro chemicals, enantioselective and even stereodivergent construction of alkyl fluorides remains highly desirable but underdeveloped. Transition-metal-catalyzed asymmetric hydrofluoroalkylation of readily available dienes represents a novel route to achieve this goal, yet receives scarce study. Here we report an intriguing palladium-catalyzed enantioselective hydromonofluoroalkylation reaction of conjugated dienes. Both monosubstituted and internal dienes proceed well with the transformation and furnish alkyl fluorides in generally > 80% yield and > 90% ee. A stereodivergent hydromonofluoroalkylation protocol via Pd/Cu co-catalysis is also established for the access to all four stereoisomers of corresponding moieties bearing a fully-substituted F-stereogenic center and vicinal tertiary carbon center. In addition, asymmetric migratory hydromonofluoroalkylation of skipped dienes is developed to realize the direct allylic CH fluoroalkylation. A compound library of enantioenriched cyclic fluorides is thus built to highlight the transformation potential of present methodology.
2023, 34(12): 108379
doi: 10.1016/j.cclet.2023.108379
Abstract:
The deterioration of water caused by industrial production is a thorny problem. Solving the problem cogently through innovative coagulationstrategies has been recognized of important practical significance. In this work, a simple enhanced coagulation by using ferric chloride (FC) and poly-ferric chloride (PFC) coupled with polyamidine (PA) were tried to remove the toxic organics. The results shown that PA addition could obviously enhance coagulation performances of the iron-based coagulants. The synergic coagulation process and mechanism were studied and discussed in detail based on the coagulation behaviors, flocs properties, removal efficiency and zeta potentials. FC and PFC remove organics mainly through charge neutralization and adsorption-bridging, resulting in a good purification performance. While PA with a higher charge density showed better purification performance due to enhanced charge neutralization. It is worth mentioning that the addition of PA could make the coagulants adapt to a wider pH range, and remove the toxic organics more effectively. That is to say, the practical adaptability of the coagulant was enhanced. This work thus provides a simple strategy to effectively purify wastewater and further improve the water safety.
The deterioration of water caused by industrial production is a thorny problem. Solving the problem cogently through innovative coagulationstrategies has been recognized of important practical significance. In this work, a simple enhanced coagulation by using ferric chloride (FC) and poly-ferric chloride (PFC) coupled with polyamidine (PA) were tried to remove the toxic organics. The results shown that PA addition could obviously enhance coagulation performances of the iron-based coagulants. The synergic coagulation process and mechanism were studied and discussed in detail based on the coagulation behaviors, flocs properties, removal efficiency and zeta potentials. FC and PFC remove organics mainly through charge neutralization and adsorption-bridging, resulting in a good purification performance. While PA with a higher charge density showed better purification performance due to enhanced charge neutralization. It is worth mentioning that the addition of PA could make the coagulants adapt to a wider pH range, and remove the toxic organics more effectively. That is to say, the practical adaptability of the coagulant was enhanced. This work thus provides a simple strategy to effectively purify wastewater and further improve the water safety.
2023, 34(12): 108383
doi: 10.1016/j.cclet.2023.108383
Abstract:
A wavelength-dependent three-dimensional (3D) superlocalization imaging method on gold nanoislands (GNIs) chip was developed as a supersensitive single-molecule thyroid-stimulating hormone (TSH) nanobiosensor. Scattered and fluorescent signals from gold nanoislands on the substrate and quantum dots (QDs) nanoprobes were simultaneously isolated and acquired within an evanescent field layer generated by total internal reflection (TIR) of incident light using a dual-view device. The 3D TIR fluorescence images of TSH-bound QDs on the GNIs were obtained using z-axis optical sectioning at 10 nm intervals before/after immunoreaction to identify the optimal conditions for detection. The localized centroid position of QD nanoprobes and GNI were distinguished at a subdiffraction limit resolution using 3D Gaussian fitting to the point spread function. The QD TSH nanobiosensor using wavelength-dependent 3D TIR fluorescence-based single-molecule localization microscopy (3D TIRF-SLM) imaging technique showed an excellent detection limit of 90 yoctomoles (~54 molecules) and a wide linear dynamic range of 1.14 zmol/L − 100 pmol/L for TSH. The detection sensitivity was about 4.4 × 109 times higher than conventional enzyme-linked immunosorbent assay and could successfully quantify TSH in human serum. The wavelength-dependent 3D TIRF-SLM technique may emerge as a reliable platform for ultrahigh-sensitive nanobiosensors at the single-molecule level and early diagnosis with quantification of disease-related ultra-trace biomolecules.
A wavelength-dependent three-dimensional (3D) superlocalization imaging method on gold nanoislands (GNIs) chip was developed as a supersensitive single-molecule thyroid-stimulating hormone (TSH) nanobiosensor. Scattered and fluorescent signals from gold nanoislands on the substrate and quantum dots (QDs) nanoprobes were simultaneously isolated and acquired within an evanescent field layer generated by total internal reflection (TIR) of incident light using a dual-view device. The 3D TIR fluorescence images of TSH-bound QDs on the GNIs were obtained using z-axis optical sectioning at 10 nm intervals before/after immunoreaction to identify the optimal conditions for detection. The localized centroid position of QD nanoprobes and GNI were distinguished at a subdiffraction limit resolution using 3D Gaussian fitting to the point spread function. The QD TSH nanobiosensor using wavelength-dependent 3D TIR fluorescence-based single-molecule localization microscopy (3D TIRF-SLM) imaging technique showed an excellent detection limit of 90 yoctomoles (~54 molecules) and a wide linear dynamic range of 1.14 zmol/L − 100 pmol/L for TSH. The detection sensitivity was about 4.4 × 109 times higher than conventional enzyme-linked immunosorbent assay and could successfully quantify TSH in human serum. The wavelength-dependent 3D TIRF-SLM technique may emerge as a reliable platform for ultrahigh-sensitive nanobiosensors at the single-molecule level and early diagnosis with quantification of disease-related ultra-trace biomolecules.
2023, 34(12): 108395
doi: 10.1016/j.cclet.2023.108395
Abstract:
Direct synthesis of glycerol carbonate (GC) from CO2 and glycerol (a byproduct of biodiesel production) is a route to obtain a high-value chemical from waste and low-cost byproducts but has not yet industrialized due to the lack of efficient catalysts. Ceria (CeO2) exhibits the highest catalytic activity and GC selectivity among the heterogeneous catalysts studied so far. However, the mechanism of this reaction over CeO2 catalysts has not been studied in detail. Herein, we synthesized CeO2 nanocrystals with different morphologies as model catalysts that can predominantly expose {111}, {110}, and {100} facets, and their surface acid-base properties were characterized using high-sensitivity temperature-programmed desorption of NH3 and CO2 with quadrupole mass spectrometry as detector (NH3-TPD-QMS and CO2-TPD-QMS). We found that the catalytic performance (GC formation rate) is strictly linearly dependent on the density of basic sites, which is relevant to the adsorption and activation of CO2. In addition, to illustrate a more microscopic reaction mechanisms underlying the formation of GC from CO2 and glycerol on all three low-index surfaces (111), (110) and (100), we also performed comprehensive first principles calculations. A three-step Langmuir–Hinshelwood (LH) mechanism was identified in which the annulation reaction is the rate-limiting step. The CeO2 (111) surface exhibits the lowest overall activation energy, which agrees well with the catalytic performance that the CeO2 nano-octahedra, predominantly exposing {111} facets, have the highest GC formation rate. This work is the first to combine experiments on shaped CeO2 model catalysts with first-principles calculations to gain insight into the mechanism of direct synthesis of GC from CO2 and glycerol, and will aid in the development of catalysts with improved performance.
Direct synthesis of glycerol carbonate (GC) from CO2 and glycerol (a byproduct of biodiesel production) is a route to obtain a high-value chemical from waste and low-cost byproducts but has not yet industrialized due to the lack of efficient catalysts. Ceria (CeO2) exhibits the highest catalytic activity and GC selectivity among the heterogeneous catalysts studied so far. However, the mechanism of this reaction over CeO2 catalysts has not been studied in detail. Herein, we synthesized CeO2 nanocrystals with different morphologies as model catalysts that can predominantly expose {111}, {110}, and {100} facets, and their surface acid-base properties were characterized using high-sensitivity temperature-programmed desorption of NH3 and CO2 with quadrupole mass spectrometry as detector (NH3-TPD-QMS and CO2-TPD-QMS). We found that the catalytic performance (GC formation rate) is strictly linearly dependent on the density of basic sites, which is relevant to the adsorption and activation of CO2. In addition, to illustrate a more microscopic reaction mechanisms underlying the formation of GC from CO2 and glycerol on all three low-index surfaces (111), (110) and (100), we also performed comprehensive first principles calculations. A three-step Langmuir–Hinshelwood (LH) mechanism was identified in which the annulation reaction is the rate-limiting step. The CeO2 (111) surface exhibits the lowest overall activation energy, which agrees well with the catalytic performance that the CeO2 nano-octahedra, predominantly exposing {111} facets, have the highest GC formation rate. This work is the first to combine experiments on shaped CeO2 model catalysts with first-principles calculations to gain insight into the mechanism of direct synthesis of GC from CO2 and glycerol, and will aid in the development of catalysts with improved performance.
2023, 34(12): 108397
doi: 10.1016/j.cclet.2023.108397
Abstract:
Rational design of heterogeneous catalysts with high activity and stability is crucial in peroxymonosulfate (PMS)-based oxidation treatment of wastewater. Herein, the graphite oxide-cobalt ferrite (GO-CoFe2O4) composite was constructed, and its morphological, component and structural characteristics were thoroughly examined, respectively. GO-CoFe2O4 obviously boosted PMS catalytic performance on di-n–butyl phthalate removal (DBP, RDBP = 90%, RTOC = 37%), which indicated by the first-order kinetic constant (kDBP = 0.060 min−1) being roughly 4 times than pure CoFe2O4 (kDBP = 0.015 min−1). The fabrication of GO-CoFe2O4 brought the favorable stability and repeatability up to six cycles. Moreover, the method of batch dosing catalyst was creatively proposed to improve the PMS utilization efficiency. The coupling of GO enhanced the dispersion of CoFe2O4 particles to obtain sufficient active sites, additionally, the plentiful C=O groups and free-flowing electrons on GO promoted GO-CoFe2O4 to coordinate a redox process during PMS activation. With the aid of theoretical calculations, GO-CoFe2O4 was revealed to exhibit a strong affinity toward PMS adsorption, where PMS spontaneously dissociated into sulfate radical (SO4•−), hydroxyl radical (•OH) and singlet oxygen (1O2), acting as the reactive oxygen species (ROSs). Electrons cycling between Co, Fe and O species ensured continuous ROSs generation and excellent catalytic performance.
Rational design of heterogeneous catalysts with high activity and stability is crucial in peroxymonosulfate (PMS)-based oxidation treatment of wastewater. Herein, the graphite oxide-cobalt ferrite (GO-CoFe2O4) composite was constructed, and its morphological, component and structural characteristics were thoroughly examined, respectively. GO-CoFe2O4 obviously boosted PMS catalytic performance on di-n–butyl phthalate removal (DBP, RDBP = 90%, RTOC = 37%), which indicated by the first-order kinetic constant (kDBP = 0.060 min−1) being roughly 4 times than pure CoFe2O4 (kDBP = 0.015 min−1). The fabrication of GO-CoFe2O4 brought the favorable stability and repeatability up to six cycles. Moreover, the method of batch dosing catalyst was creatively proposed to improve the PMS utilization efficiency. The coupling of GO enhanced the dispersion of CoFe2O4 particles to obtain sufficient active sites, additionally, the plentiful C=O groups and free-flowing electrons on GO promoted GO-CoFe2O4 to coordinate a redox process during PMS activation. With the aid of theoretical calculations, GO-CoFe2O4 was revealed to exhibit a strong affinity toward PMS adsorption, where PMS spontaneously dissociated into sulfate radical (SO4•−), hydroxyl radical (•OH) and singlet oxygen (1O2), acting as the reactive oxygen species (ROSs). Electrons cycling between Co, Fe and O species ensured continuous ROSs generation and excellent catalytic performance.
2023, 34(12): 108398
doi: 10.1016/j.cclet.2023.108398
Abstract:
A new palladium-catalyzed annulative allylic alkylation (AAA) reaction of 2-(indol-2-yl)phenols with dual allylic electrophiles such as isobutylene dicarbonate and butene dicarbonate is described, leading to the regioselective synthesis of tetracyclic medium-sized cyclic ethers possessing a bridged aryl-indole scaffold, namely, benzo[2,3]oxocino[4,5-b]indoles and benzo[2,3]oxepino[4,5-b]indoles, in good to excellent yields. This protocol demonstrates a broad substrate scope, good compatibility with substituents and high regioselectivity, providing a catalytic and flexible method for creating bridged aryl-indole skeletons.
A new palladium-catalyzed annulative allylic alkylation (AAA) reaction of 2-(indol-2-yl)phenols with dual allylic electrophiles such as isobutylene dicarbonate and butene dicarbonate is described, leading to the regioselective synthesis of tetracyclic medium-sized cyclic ethers possessing a bridged aryl-indole scaffold, namely, benzo[2,3]oxocino[4,5-b]indoles and benzo[2,3]oxepino[4,5-b]indoles, in good to excellent yields. This protocol demonstrates a broad substrate scope, good compatibility with substituents and high regioselectivity, providing a catalytic and flexible method for creating bridged aryl-indole skeletons.
2023, 34(12): 108399
doi: 10.1016/j.cclet.2023.108399
Abstract:
Accurate and sensitive detection of cancer cells is of significant importance for early diagnosis and treatment of cancer. Here, we developed an extracellular ATP-activated hybridization chain reaction (HCR) amplification strategy to meet this purpose. This strategy relies on three DNA probes, Apt-trigger, H1-ATP aptamer duplex and hairpin H2. The Apt-trigger probe consists of two components: an aptamer sequence for specific recognition of the target cells, and a trigger sequence for the HCR assembly. The duplex structure of H1-ATP aptamer causes the toehold in hairpin H1 to be hidden, preventing the strand-displacement reaction between hairpin H1 and Apt-trigger. Upon activation with ATP, the ATP aptamer will bind to ATP to dissociate from hairpin H1, thus leading to an Apt-trigger-induced strand-displacement reaction and subsequent HCR with hairpin H2 on the target cell surface. Benefiting from aptamer recognition and ATP-activated HCR amplification, this strategy can not only perform sensitive quantitative analysis with a detection limit of 25 cells in 200 µL of binding buffer, but also show desirable specificity and accuracy for identifying target cells from control cells and mixed cell samples. Importantly, this method retains stable and good performance for target cell detection in 10% fetal bovine serum, demonstrating great potential for clinical diagnosis in complex biological matrices. Furthermore, this strategy can be adapted to detect various types of cancer cells by changing the corresponding aptamer sequence.
Accurate and sensitive detection of cancer cells is of significant importance for early diagnosis and treatment of cancer. Here, we developed an extracellular ATP-activated hybridization chain reaction (HCR) amplification strategy to meet this purpose. This strategy relies on three DNA probes, Apt-trigger, H1-ATP aptamer duplex and hairpin H2. The Apt-trigger probe consists of two components: an aptamer sequence for specific recognition of the target cells, and a trigger sequence for the HCR assembly. The duplex structure of H1-ATP aptamer causes the toehold in hairpin H1 to be hidden, preventing the strand-displacement reaction between hairpin H1 and Apt-trigger. Upon activation with ATP, the ATP aptamer will bind to ATP to dissociate from hairpin H1, thus leading to an Apt-trigger-induced strand-displacement reaction and subsequent HCR with hairpin H2 on the target cell surface. Benefiting from aptamer recognition and ATP-activated HCR amplification, this strategy can not only perform sensitive quantitative analysis with a detection limit of 25 cells in 200 µL of binding buffer, but also show desirable specificity and accuracy for identifying target cells from control cells and mixed cell samples. Importantly, this method retains stable and good performance for target cell detection in 10% fetal bovine serum, demonstrating great potential for clinical diagnosis in complex biological matrices. Furthermore, this strategy can be adapted to detect various types of cancer cells by changing the corresponding aptamer sequence.
2023, 34(12): 108407
doi: 10.1016/j.cclet.2023.108407
Abstract:
Manganese oxides show a strong catalytic activity in the peroxymonosulfate (PMS) advanced oxidation process but have poor chemical stability and a propensity to cause the aggregation of nanoparticles. Here, a novel composite material (abbreviated as MnOx@ACF) was synthesized, characterized, and applied. Activated carbon fiber (ACF) was selected as a carrier, which modulated the composition of manganese oxides. The results showed that MnOx@ACF had a strong adsorption ability and successfully activated PMS to degrade tetracycline hydrochloride (TCH), with a removal efficiency of 89.0% in 30 min. Influencing factors such as pH and coexisting ion species were investigated, and a five-cycle test was conducted. Singlet oxygen (1O2) was predominated in the MnOx@ACF/PMS system. A possible explanatory pathway of TCH was proposed based on the results of the high performance liquid chromatography-mass spectrometry. It was concluded that this study provides a novel insight into the activation of PMS for the degradation of organic matter by carbon-loaded multivalent manganese oxides.
Manganese oxides show a strong catalytic activity in the peroxymonosulfate (PMS) advanced oxidation process but have poor chemical stability and a propensity to cause the aggregation of nanoparticles. Here, a novel composite material (abbreviated as MnOx@ACF) was synthesized, characterized, and applied. Activated carbon fiber (ACF) was selected as a carrier, which modulated the composition of manganese oxides. The results showed that MnOx@ACF had a strong adsorption ability and successfully activated PMS to degrade tetracycline hydrochloride (TCH), with a removal efficiency of 89.0% in 30 min. Influencing factors such as pH and coexisting ion species were investigated, and a five-cycle test was conducted. Singlet oxygen (1O2) was predominated in the MnOx@ACF/PMS system. A possible explanatory pathway of TCH was proposed based on the results of the high performance liquid chromatography-mass spectrometry. It was concluded that this study provides a novel insight into the activation of PMS for the degradation of organic matter by carbon-loaded multivalent manganese oxides.
2023, 34(12): 108410
doi: 10.1016/j.cclet.2023.108410
Abstract:
This work reported a facile approach to surface oxygen vacancy (OV)-enriched urchin-like TiO2 microparticles (U-TiO2), which were highly effective and durable in catalyzing selective nitrate reduction to ammonia (NO3RR). Specifically, the U-TiO2 delivered a mass activity of 1.15 min−1 mgcatalyst−1, a low yield of toxic NO2−-N intermediate (≤0.4 mg/L) and an exceptional high NH3-N selectivity of 98.1% in treating 22.5 mg/L of NO3−-N under a potential of -0.60 V vs. RHE, outperforming most of the reported oxide-based catalysts. When comparing the performance of U-TiO2 with that of the solid amorphous TiO2 counterpart (A-TiO2) that had close particle size but more OV on surfaces, we identified that the OV was the reactive sites, but rather than its content, the NO3RR kinetics were primarily limited by the electron and mass transfer at U-TiO2/water interfaces. Accordingly, the superior performance of U-TiO2 to A-TiO2 could be ascribed to the hierarchical urchin-like structure in U-TiO2. The in-situ DEMS test revealed that the NO3RR on U-TiO2 followed a pathway of *NO3− → *NO2−→ *NO → *N → *NH → *NH2 → *NH3. We also demonstrated that the U-TiO2 could keep its robust performance under a wide NO3−-N concentration range and in the presence of some co-existing ions (such as Ca2+, Cl−, Mg2+). However, the presence of humic acid and CO32− in water slowed down the NO3RR on U-TiO2. This work provides a more fundamental insight into the OV-driven NO3RR process on TiO2, which should benefit for the development of efficient TiO2-based catalysts.
This work reported a facile approach to surface oxygen vacancy (OV)-enriched urchin-like TiO2 microparticles (U-TiO2), which were highly effective and durable in catalyzing selective nitrate reduction to ammonia (NO3RR). Specifically, the U-TiO2 delivered a mass activity of 1.15 min−1 mgcatalyst−1, a low yield of toxic NO2−-N intermediate (≤0.4 mg/L) and an exceptional high NH3-N selectivity of 98.1% in treating 22.5 mg/L of NO3−-N under a potential of -0.60 V vs. RHE, outperforming most of the reported oxide-based catalysts. When comparing the performance of U-TiO2 with that of the solid amorphous TiO2 counterpart (A-TiO2) that had close particle size but more OV on surfaces, we identified that the OV was the reactive sites, but rather than its content, the NO3RR kinetics were primarily limited by the electron and mass transfer at U-TiO2/water interfaces. Accordingly, the superior performance of U-TiO2 to A-TiO2 could be ascribed to the hierarchical urchin-like structure in U-TiO2. The in-situ DEMS test revealed that the NO3RR on U-TiO2 followed a pathway of *NO3− → *NO2−→ *NO → *N → *NH → *NH2 → *NH3. We also demonstrated that the U-TiO2 could keep its robust performance under a wide NO3−-N concentration range and in the presence of some co-existing ions (such as Ca2+, Cl−, Mg2+). However, the presence of humic acid and CO32− in water slowed down the NO3RR on U-TiO2. This work provides a more fundamental insight into the OV-driven NO3RR process on TiO2, which should benefit for the development of efficient TiO2-based catalysts.
2023, 34(12): 108419
doi: 10.1016/j.cclet.2023.108419
Abstract:
A flexible organic artificial synapse (OAS) for tunable time-frequency signal processing was fabricated using a tri-blend film that had been fabricated using a one-step solution method. When combined with a chitosan film, this OAS can achieve an ultrashort-term retention time of only 49 ms for instant electrical-computing applications; this is the shortest retention time yet achieved by a two-terminal artificial synapse. An array of these flexible OASs can withstand a high bending strain of 5% for 104 cycles; this deformation endurance is a new record. The OAS was also sensitive to the number and frequency of electrical inputs; a tunable cut-off frequency enables dynamic filtering for use in image detail enhancement. This work provides a new resource for development of future neuromorphic computing devices
A flexible organic artificial synapse (OAS) for tunable time-frequency signal processing was fabricated using a tri-blend film that had been fabricated using a one-step solution method. When combined with a chitosan film, this OAS can achieve an ultrashort-term retention time of only 49 ms for instant electrical-computing applications; this is the shortest retention time yet achieved by a two-terminal artificial synapse. An array of these flexible OASs can withstand a high bending strain of 5% for 104 cycles; this deformation endurance is a new record. The OAS was also sensitive to the number and frequency of electrical inputs; a tunable cut-off frequency enables dynamic filtering for use in image detail enhancement. This work provides a new resource for development of future neuromorphic computing devices
2023, 34(12): 108424
doi: 10.1016/j.cclet.2023.108424
Abstract:
There are some critical issues hindering the practical applications of aqueous zinc-ion batteries (ZIBs), although they possess high safety and low cost as one of promising energy storge devices, such as the Zn dendrite growth and the by-product of Zn4SO4(OH)6·xH2O (ZHS) resulted from some side reactions in a mild electrolyte. Herein, a compact and self-repairing solid electrolyte interface (SEI) film, as labeled the PVDF-Zn(TFSI)2-ZHS coating [The PVDF and Zn(TFSI)2 are polyvinylidene fluoride and zinc bis(trifluoromethanesulfonyl)imide, respectively], which turns the in-situ generated ZHS into a beneficial ingredient onto the pre-coated PVDF-based composite coating layer containing Zn(TFSI)2, was designed and fabricated by a simple doctor blade method. It is shown that the SEI layer can effectively isolate Zn from the electrolyte and homogenize the Zn2+ flux, and thus effectively suppress side reactions and dendrites growth. Benefiting from the hybrid SEI layer, a symmetric cell exhibits a high cycling stability over 750 h at 2.0 mA/cm2 and 2.0 mAh/cm2, and meanwhile, a full-cell, coupled with K+ pre-intercalation α-MnO2 (KMO) cathode, displays excellent rate performance, stable coulombic efficiency and an acceptable cycle life. This work provides a feasible approach for simple and scalable modification of Zn anodes to achieve high performance.
There are some critical issues hindering the practical applications of aqueous zinc-ion batteries (ZIBs), although they possess high safety and low cost as one of promising energy storge devices, such as the Zn dendrite growth and the by-product of Zn4SO4(OH)6·xH2O (ZHS) resulted from some side reactions in a mild electrolyte. Herein, a compact and self-repairing solid electrolyte interface (SEI) film, as labeled the PVDF-Zn(TFSI)2-ZHS coating [The PVDF and Zn(TFSI)2 are polyvinylidene fluoride and zinc bis(trifluoromethanesulfonyl)imide, respectively], which turns the in-situ generated ZHS into a beneficial ingredient onto the pre-coated PVDF-based composite coating layer containing Zn(TFSI)2, was designed and fabricated by a simple doctor blade method. It is shown that the SEI layer can effectively isolate Zn from the electrolyte and homogenize the Zn2+ flux, and thus effectively suppress side reactions and dendrites growth. Benefiting from the hybrid SEI layer, a symmetric cell exhibits a high cycling stability over 750 h at 2.0 mA/cm2 and 2.0 mAh/cm2, and meanwhile, a full-cell, coupled with K+ pre-intercalation α-MnO2 (KMO) cathode, displays excellent rate performance, stable coulombic efficiency and an acceptable cycle life. This work provides a feasible approach for simple and scalable modification of Zn anodes to achieve high performance.
2023, 34(12): 108437
doi: 10.1016/j.cclet.2023.108437
Abstract:
The structure-activity relationships for vinyl acetate catalytic oxidation are challenging to explore at the atomic scale due to the ambiguity of the structural defect types and sites of manganese oxides. Our work elaborates, at the atomic level, through in-situ experimental and theoretical methods, the synergistic effects of two types of structural defect sites of VO-e (edge-sharing oxygen) and VO-c (corner-sharing oxygen) and MnO6 structural motifs of manganese oxides. Multi-dimensional manganese oxides, namely those with corner-connected MnO6 structural motifs and VO-c structural oxygen defect sites, significantly improved the activation of vinyl acetate. Enhancement of enol structure formation, acetate and formate intermediate species, and tautomerism between enol structure and acetaldehyde were detected when oxygen vacancies of manganese oxides were present in combination with corner/edge-connected MnO6. Moreover, the activation of chemical bonds and deep catalytic oxidation of vinyl acetate depend on the presence of a redox couple, surface oxygen species, and weakened MnO bonds. It provides a valuable notion for investigating and designing catalytic systems and reaction processes for the purpose of emission reduction and the management of environmental contaminants.
The structure-activity relationships for vinyl acetate catalytic oxidation are challenging to explore at the atomic scale due to the ambiguity of the structural defect types and sites of manganese oxides. Our work elaborates, at the atomic level, through in-situ experimental and theoretical methods, the synergistic effects of two types of structural defect sites of VO-e (edge-sharing oxygen) and VO-c (corner-sharing oxygen) and MnO6 structural motifs of manganese oxides. Multi-dimensional manganese oxides, namely those with corner-connected MnO6 structural motifs and VO-c structural oxygen defect sites, significantly improved the activation of vinyl acetate. Enhancement of enol structure formation, acetate and formate intermediate species, and tautomerism between enol structure and acetaldehyde were detected when oxygen vacancies of manganese oxides were present in combination with corner/edge-connected MnO6. Moreover, the activation of chemical bonds and deep catalytic oxidation of vinyl acetate depend on the presence of a redox couple, surface oxygen species, and weakened MnO bonds. It provides a valuable notion for investigating and designing catalytic systems and reaction processes for the purpose of emission reduction and the management of environmental contaminants.
2023, 34(12): 108439
doi: 10.1016/j.cclet.2023.108439
Abstract:
Developing novel emissive supramolecular assemblies with elegant architectures and tunable performance remains highly desirable yet challenging. Herein, we report the design and synthesis of several 9,10-bis(diphenylmethylene)-9,10-dihydroanthracene-based metal-organic assembles with aggregation-induced emission characteristics. Such assemblies feature intriguing thermochromic and mechanochromic properties, i.e., distinguishable fluorescence responses in terms of emission wavelength and intensity under variable temperatures and pressures. Moreover, these assemblies can serve as excellent fluorescent sensors for the detection of polysaccharide molecules. Due to the differentiated charge type and density, the assembles display distinct sensing mechanisms toward different polysaccharide molecules. This study provides novel perspectives for the synthesis of butterfly-like platinum(Ⅱ) supramolecular coordination complexes with multistimuli-responsiveness for polysaccharide sensing, which will facilitate the development of stimuli-responsive materials
Developing novel emissive supramolecular assemblies with elegant architectures and tunable performance remains highly desirable yet challenging. Herein, we report the design and synthesis of several 9,10-bis(diphenylmethylene)-9,10-dihydroanthracene-based metal-organic assembles with aggregation-induced emission characteristics. Such assemblies feature intriguing thermochromic and mechanochromic properties, i.e., distinguishable fluorescence responses in terms of emission wavelength and intensity under variable temperatures and pressures. Moreover, these assemblies can serve as excellent fluorescent sensors for the detection of polysaccharide molecules. Due to the differentiated charge type and density, the assembles display distinct sensing mechanisms toward different polysaccharide molecules. This study provides novel perspectives for the synthesis of butterfly-like platinum(Ⅱ) supramolecular coordination complexes with multistimuli-responsiveness for polysaccharide sensing, which will facilitate the development of stimuli-responsive materials
2023, 34(12): 108448
doi: 10.1016/j.cclet.2023.108448
Abstract:
Optimal bulk-heterojunction (BHJ) morphology is crucial for efficient charge transport and good photovoltaic performance in organic solar cells (OSCs). Yet, the correlation between chemical structures of nonfullerene acceptors (NFAs) and molecular interaction in the BHJ blends remains opaque. Herein, we study three isomeric NFAs referred to as MQ1-x (x = β, γ, or δ) that shared an asymmetric selenophene-fused heteroheptacene backbone end-capped by two monochlorinated end groups. Remarkably, miscibility between the polymer donor of PM6 and MQ1-x successively elevates as the chlorine atoms move from β-, to γ-, to δ-position of terminals. Combined with the varied molecular crystallinity of these NFAs, diverse BHJ morphologies are observed in their blend films. As a result, the MQ1-δ-based devices present the highest PCE of 12.08% owing to the efficient charge dissociation and transport induced by the compact molecular packing and optimal BHJ morphology. Our investigation provides a new insight in the material design that has a good balance in molecular packing and film morphology for high-performance OSCs.
Optimal bulk-heterojunction (BHJ) morphology is crucial for efficient charge transport and good photovoltaic performance in organic solar cells (OSCs). Yet, the correlation between chemical structures of nonfullerene acceptors (NFAs) and molecular interaction in the BHJ blends remains opaque. Herein, we study three isomeric NFAs referred to as MQ1-x (x = β, γ, or δ) that shared an asymmetric selenophene-fused heteroheptacene backbone end-capped by two monochlorinated end groups. Remarkably, miscibility between the polymer donor of PM6 and MQ1-x successively elevates as the chlorine atoms move from β-, to γ-, to δ-position of terminals. Combined with the varied molecular crystallinity of these NFAs, diverse BHJ morphologies are observed in their blend films. As a result, the MQ1-δ-based devices present the highest PCE of 12.08% owing to the efficient charge dissociation and transport induced by the compact molecular packing and optimal BHJ morphology. Our investigation provides a new insight in the material design that has a good balance in molecular packing and film morphology for high-performance OSCs.
2023, 34(12): 108452
doi: 10.1016/j.cclet.2023.108452
Abstract:
α-Cyanostilbene (CS) based organic luminescent materials with efficient electrical conductivity, aggregation-induced enhanced emission, and controllable multi-colour emission properties, have been aroused wide attention by scientists over the past few years. Self-assembly of CS-motif in aqueous media refers to an environment-friendly method for preparing luminescent materials. However, it is still challenging to control the intrinsic hydrophobic properties of the organic components in aqueous media. In this study, an amphiphilic dicyanostilbene-functionalized thiophene (ACSTP) derivative was synthesized. Z-ACSTP was identified to dissolve in different organic solvents, accompanied with strong and tunable fluorescence emission. However, when Z-ACSTP was dispersed in water, it was self-assembled into nanofibers, and the fluorescence was red shifted, accompanied with sharp decrease of intensity compared with that in DMSO. Furthermore, Z-form of ACSTP to its E-form under 365 nm irradiation led to the morphology transformation from nanofibers to nanosheets. Notably, upon addition of water-soluble pillar[5]arene (WP5), the nanofibers were transformed into fluorescent hollow particles due to the host–guest interactions between the pyridinium group and WP5 and the obtained fluorescent particles can be further applied in living cell imaging.
α-Cyanostilbene (CS) based organic luminescent materials with efficient electrical conductivity, aggregation-induced enhanced emission, and controllable multi-colour emission properties, have been aroused wide attention by scientists over the past few years. Self-assembly of CS-motif in aqueous media refers to an environment-friendly method for preparing luminescent materials. However, it is still challenging to control the intrinsic hydrophobic properties of the organic components in aqueous media. In this study, an amphiphilic dicyanostilbene-functionalized thiophene (ACSTP) derivative was synthesized. Z-ACSTP was identified to dissolve in different organic solvents, accompanied with strong and tunable fluorescence emission. However, when Z-ACSTP was dispersed in water, it was self-assembled into nanofibers, and the fluorescence was red shifted, accompanied with sharp decrease of intensity compared with that in DMSO. Furthermore, Z-form of ACSTP to its E-form under 365 nm irradiation led to the morphology transformation from nanofibers to nanosheets. Notably, upon addition of water-soluble pillar[5]arene (WP5), the nanofibers were transformed into fluorescent hollow particles due to the host–guest interactions between the pyridinium group and WP5 and the obtained fluorescent particles can be further applied in living cell imaging.
2023, 34(12): 108453
doi: 10.1016/j.cclet.2023.108453
Abstract:
A cooperative Pd/Cu-catalyzed three-component cross-coupling reaction of alkynes, B2Pin2 and alkene-tethered aryl halides is reported. This reaction proceeds under mild conditions and shows broad substrate scope, providing a variety of heterocycles containing tetrasubstituted alkenylboronate moieties in synthetically useful yields with excellent chemoselectivity and regioselectivity. This transformation features the catalytic generation of β-borylalkenylcopper intermediates and their use in Pd-catalyzed Heck cyclization/cross-couplings. An enantioselective cascade cyclization/cross-coupling process has also been developed for the synthesis of enantiomerically enriched oxindole bearing a tetrasubstituted alkenylboronate moiety.
A cooperative Pd/Cu-catalyzed three-component cross-coupling reaction of alkynes, B2Pin2 and alkene-tethered aryl halides is reported. This reaction proceeds under mild conditions and shows broad substrate scope, providing a variety of heterocycles containing tetrasubstituted alkenylboronate moieties in synthetically useful yields with excellent chemoselectivity and regioselectivity. This transformation features the catalytic generation of β-borylalkenylcopper intermediates and their use in Pd-catalyzed Heck cyclization/cross-couplings. An enantioselective cascade cyclization/cross-coupling process has also been developed for the synthesis of enantiomerically enriched oxindole bearing a tetrasubstituted alkenylboronate moiety.
2023, 34(12): 108457
doi: 10.1016/j.cclet.2023.108457
Abstract:
A novel solid–liquid-core fiber-optic biosensor was fabricated for highly sensitive and selective detection of 4-chlorophenol in water. The sensor comprised horseradish peroxidase (HRP)-coated U-shaped liquid-core optical fiber (LCOF) and 4-chlorophenol permselective polymer membrane. The U-shaped LCOF was filled with ethanol suspension of SiO2 particles and the polymer membrane was composed of molecularly imprinted polymer, sulfonated polyethersulfone, and polysulfone. The morphology, composition, and surface luminous properties of the sensing region were examined. The effects of the diameter and content of SiO2 particles and temperature of 4-chlorophenol solutions on the sensitivity of the biosensors were investigated. Further, the sensitivity, selectivity, response time, and limit of detection (LOD) of the biosensors was investigated. In addition, the effects of fiber core materials on the light transmission in sensing region were investigated and a biosensor sensing model was established. The proposed sensor exhibited high selectivity for 4-chlorophenol with satisfactory sensitivity, LOD, and response time: -1.18 (µg/L)−1, 30 µg/L, and 400 s, respectively. The results are expected to aid in the development of methods for enhancing sensitivity of fiber-optic sensors and surface luminous intensity of optical fibers.
A novel solid–liquid-core fiber-optic biosensor was fabricated for highly sensitive and selective detection of 4-chlorophenol in water. The sensor comprised horseradish peroxidase (HRP)-coated U-shaped liquid-core optical fiber (LCOF) and 4-chlorophenol permselective polymer membrane. The U-shaped LCOF was filled with ethanol suspension of SiO2 particles and the polymer membrane was composed of molecularly imprinted polymer, sulfonated polyethersulfone, and polysulfone. The morphology, composition, and surface luminous properties of the sensing region were examined. The effects of the diameter and content of SiO2 particles and temperature of 4-chlorophenol solutions on the sensitivity of the biosensors were investigated. Further, the sensitivity, selectivity, response time, and limit of detection (LOD) of the biosensors was investigated. In addition, the effects of fiber core materials on the light transmission in sensing region were investigated and a biosensor sensing model was established. The proposed sensor exhibited high selectivity for 4-chlorophenol with satisfactory sensitivity, LOD, and response time: -1.18 (µg/L)−1, 30 µg/L, and 400 s, respectively. The results are expected to aid in the development of methods for enhancing sensitivity of fiber-optic sensors and surface luminous intensity of optical fibers.
2023, 34(12): 108465
doi: 10.1016/j.cclet.2023.108465
Abstract:
Environmental economics is accelerating the urgency to develop recycling technologies for the ever-growing quantity of discarded thermoset polymers. Herein, we developed a mild and energy-saving process for high-efficiency degradation and reuse of anhydride-cured epoxy thermoset with the aid of hydrazine hydrate. The degradation degree of the epoxy resin reached 99.6% at 120 ℃ within a short time of 60 min. During the reaction, the ester bonds in the cross-linked network were selectively cleaved by the amination of hydrazine hydrate, and the epoxy resin was fully converted to new monomers that contained hydrazide and hydroxyl groups, respectively. Moreover, the degradation mechanism of the epoxy resin in hydrazine hydrate was studied and a nucleation model was utilized to predict the actual degradation behavior of the system. Finally, the degradation products can be directly mixed with epoxy precursor to prepare a new waterborne epoxy coating with good comprehensive properties. This work not only demonstrates a new way to realize the efficient degradation of epoxy resins, but also provides a facile and efficient recycling protocol for thermosets.
Environmental economics is accelerating the urgency to develop recycling technologies for the ever-growing quantity of discarded thermoset polymers. Herein, we developed a mild and energy-saving process for high-efficiency degradation and reuse of anhydride-cured epoxy thermoset with the aid of hydrazine hydrate. The degradation degree of the epoxy resin reached 99.6% at 120 ℃ within a short time of 60 min. During the reaction, the ester bonds in the cross-linked network were selectively cleaved by the amination of hydrazine hydrate, and the epoxy resin was fully converted to new monomers that contained hydrazide and hydroxyl groups, respectively. Moreover, the degradation mechanism of the epoxy resin in hydrazine hydrate was studied and a nucleation model was utilized to predict the actual degradation behavior of the system. Finally, the degradation products can be directly mixed with epoxy precursor to prepare a new waterborne epoxy coating with good comprehensive properties. This work not only demonstrates a new way to realize the efficient degradation of epoxy resins, but also provides a facile and efficient recycling protocol for thermosets.
2023, 34(12): 108471
doi: 10.1016/j.cclet.2023.108471
Abstract:
Generally, the metal sulfide itself has poor conductivity, and the volume expansion occurs when it is converted with sodium, which will destroy the integrity of the electrode structure, resulting in poor cycle performance and rate performance. To solve the problems of low initial coulombic efficiency (ICE) and volume expansion of metal compounds used as anodes in sodium-ion batteries (SIBs). Inspired by nature, the CoSO4/hard carbon/graphene (CHG) fractal structure electrode was designed. Self-fractal structures with electron/ion transport channels and high strain tolerance proved to be an effective strategy to overcome these challenges. The fractal dimension (D) is measured by synchronous Small Angle X-ray scattering, and the D remains stable during charging and discharging. The fractal CHG also showed excellent electrochemical performance, especially 97.4% ICE. Theoretical calculation shows that self-fractal CHG can promote the formation of a thin solid electrolyte interface (SEI). Synchrotron radiation absorption spectrum proved the reaction mechanism of CHG. This study not only proves that cobalt sulfate is a feasible strategy for developing high-performance SIBs anodes but also provides an advanced method for measuring the fractal dimension of energy storage electrode materials.
Generally, the metal sulfide itself has poor conductivity, and the volume expansion occurs when it is converted with sodium, which will destroy the integrity of the electrode structure, resulting in poor cycle performance and rate performance. To solve the problems of low initial coulombic efficiency (ICE) and volume expansion of metal compounds used as anodes in sodium-ion batteries (SIBs). Inspired by nature, the CoSO4/hard carbon/graphene (CHG) fractal structure electrode was designed. Self-fractal structures with electron/ion transport channels and high strain tolerance proved to be an effective strategy to overcome these challenges. The fractal dimension (D) is measured by synchronous Small Angle X-ray scattering, and the D remains stable during charging and discharging. The fractal CHG also showed excellent electrochemical performance, especially 97.4% ICE. Theoretical calculation shows that self-fractal CHG can promote the formation of a thin solid electrolyte interface (SEI). Synchrotron radiation absorption spectrum proved the reaction mechanism of CHG. This study not only proves that cobalt sulfate is a feasible strategy for developing high-performance SIBs anodes but also provides an advanced method for measuring the fractal dimension of energy storage electrode materials.
2023, 34(12): 108479
doi: 10.1016/j.cclet.2023.108479
Abstract:
Supramolecular interactions such as π-π stacking interaction and charge transfer interaction have drawn much attention in the design and construction of various supramolecular assemblies. Herein, partially oxidized pillar[5]arene (P5A), pillar[4]arene[1]quinone (P4A1Q), pillar[3]arene[2]quinone (P3A2Q), and pillar[2]arene[3]quinone (P2A3Q) were synthesized by one-step reaction. As indicated by experimental characterization data and density function theory modeling results, charge transfer interaction among partially oxidized P5A plays a significant role in host-host self-assembly behavior and corresponding packing morphology. This work provides a unique strategy for the construction of functional macrocyclic assemblies through host-host self-assembly.
Supramolecular interactions such as π-π stacking interaction and charge transfer interaction have drawn much attention in the design and construction of various supramolecular assemblies. Herein, partially oxidized pillar[5]arene (P5A), pillar[4]arene[1]quinone (P4A1Q), pillar[3]arene[2]quinone (P3A2Q), and pillar[2]arene[3]quinone (P2A3Q) were synthesized by one-step reaction. As indicated by experimental characterization data and density function theory modeling results, charge transfer interaction among partially oxidized P5A plays a significant role in host-host self-assembly behavior and corresponding packing morphology. This work provides a unique strategy for the construction of functional macrocyclic assemblies through host-host self-assembly.
2023, 34(12): 108517
doi: 10.1016/j.cclet.2023.108517
Abstract:
The CO2 photoconversion is sensitive to the local reaction environment, of which activity and selectivity can be regulated by the change of reaction systems. This paper focuses on investigating the photocatalytic CO2 reduction behaviors of MOFs with the involvement of water under different reaction modes, including gas-solid and liquid-solid systems. The CO2 photoreduction in a liquid-solid system shows high performance in generating HCOOH with the selectivity of 100%. In contrast, the gas-solid system referring to the synergistic interaction of MOFs and H2O vapor benefits to the formation of gas-phase products, such as CO and CH4. The possible mechanisms of photocatalytic CO2 reaction in two modes were investigated by in-situ Fourier-transform infrared spectroscopy, which indicates that the distinction in reaction consequence may result from the difference in CO2 chemisorbed modes and the proton provision. The choice of reaction system plays an important role in the achievement of high efficiency and selectivity for photocatalytic CO2 reduction, which is of great practical value in real-world applications.
The CO2 photoconversion is sensitive to the local reaction environment, of which activity and selectivity can be regulated by the change of reaction systems. This paper focuses on investigating the photocatalytic CO2 reduction behaviors of MOFs with the involvement of water under different reaction modes, including gas-solid and liquid-solid systems. The CO2 photoreduction in a liquid-solid system shows high performance in generating HCOOH with the selectivity of 100%. In contrast, the gas-solid system referring to the synergistic interaction of MOFs and H2O vapor benefits to the formation of gas-phase products, such as CO and CH4. The possible mechanisms of photocatalytic CO2 reaction in two modes were investigated by in-situ Fourier-transform infrared spectroscopy, which indicates that the distinction in reaction consequence may result from the difference in CO2 chemisorbed modes and the proton provision. The choice of reaction system plays an important role in the achievement of high efficiency and selectivity for photocatalytic CO2 reduction, which is of great practical value in real-world applications.
2023, 34(12): 108520
doi: 10.1016/j.cclet.2023.108520
Abstract:
High efficiency and low-cost catalyst-driven electrocatalytic CO2 reduction to CO production are of great significance for energy storage and development. The severe competitive hydrogen evolution reaction occurs at large negative potential window limits the achievement of the target product from CO2 at high efficiency. Here, we successfully prepared Cux/CdCO3 composite catalyst rich in interfaces, in which achieved high CO Faraday efficiency exceeded 90% in a wide potential window of 700 mV and highest value up to 97.9% at −0.90 V vs. RHE. The excellent performance can be ascribed to the positive contribution of Cux/CdCO3, which maintains a suitable high local pH value during electrochemical reduction, thus inhibiting the competitive hydrogen evolution reaction. Moreover, the compact structure between Cu and CdCO3 ensures fast electron transfer both inside catalysts and interface, thus speeding up the reaction kinetics of CO2 to CO conversion. Theoretically calculations further prove that the combination of Cu and CdCO3 provides the well-defined electronic structure for intermediates adsorption, significantly reducing the reaction barrier for the formation of CO. This work provides new insights into the design of efficient electrochemical CO2 reduction catalysts for inhibiting hydrogen evolution by adjusting the local pH effect.
High efficiency and low-cost catalyst-driven electrocatalytic CO2 reduction to CO production are of great significance for energy storage and development. The severe competitive hydrogen evolution reaction occurs at large negative potential window limits the achievement of the target product from CO2 at high efficiency. Here, we successfully prepared Cux/CdCO3 composite catalyst rich in interfaces, in which achieved high CO Faraday efficiency exceeded 90% in a wide potential window of 700 mV and highest value up to 97.9% at −0.90 V vs. RHE. The excellent performance can be ascribed to the positive contribution of Cux/CdCO3, which maintains a suitable high local pH value during electrochemical reduction, thus inhibiting the competitive hydrogen evolution reaction. Moreover, the compact structure between Cu and CdCO3 ensures fast electron transfer both inside catalysts and interface, thus speeding up the reaction kinetics of CO2 to CO conversion. Theoretically calculations further prove that the combination of Cu and CdCO3 provides the well-defined electronic structure for intermediates adsorption, significantly reducing the reaction barrier for the formation of CO. This work provides new insights into the design of efficient electrochemical CO2 reduction catalysts for inhibiting hydrogen evolution by adjusting the local pH effect.
2023, 34(12): 108527
doi: 10.1016/j.cclet.2023.108527
Abstract:
A double-cable conjugated polymer DCPIC-BO is designed via introducing a long-branched alkyl chains 2-buthyloctyl into the acceptor side unit. Compared with the double-cable polymer (DCPIC-EH) with the 2-ethylhexyl alkyl chains, the solubility of the DCPIC-BO in non-halogen solvents is substantially improved. Therefore, a power conversion efficiency (PCE) of 9.77% can be obtained by the devices processed from o-xylene at 40 ℃, while the DCPIC-EH cannot be processed due to its poor solubility under this condition. Moreover, PCEs of 10.10% for small-area (0.04 cm2) devices and nearly 9% for devices with an area of 1 cm2 are achieved using a non-halogenated solid additive in o-xylene, realizing the "absolutely halogen-free" OSC fabrication.
A double-cable conjugated polymer DCPIC-BO is designed via introducing a long-branched alkyl chains 2-buthyloctyl into the acceptor side unit. Compared with the double-cable polymer (DCPIC-EH) with the 2-ethylhexyl alkyl chains, the solubility of the DCPIC-BO in non-halogen solvents is substantially improved. Therefore, a power conversion efficiency (PCE) of 9.77% can be obtained by the devices processed from o-xylene at 40 ℃, while the DCPIC-EH cannot be processed due to its poor solubility under this condition. Moreover, PCEs of 10.10% for small-area (0.04 cm2) devices and nearly 9% for devices with an area of 1 cm2 are achieved using a non-halogenated solid additive in o-xylene, realizing the "absolutely halogen-free" OSC fabrication.
2023, 34(12): 108531
doi: 10.1016/j.cclet.2023.108531
Abstract:
Herein, we describe the selective formation of a barrel-shaped or a ball-shaped fluorescent metallacage by controlling the shape and stoichiometry of the building blocks. Specifically, the tetraphenylethylene-based donor and two acceptors with different numbers of Pt(Ⅱ) centers were combined via coordination-driven self-assembly. Owing to the differences in the shapes of the assemblies, the resultant ball-shaped metallacage displayed stronger and blue-shifted fluorescence compared to the barrel-shaped one in dilute solutions, while a reversal of fluorescence intensities was observed in the aggregation process. Overall, this work demonstrates that the photophysical properties of supramolecular coordination complexes can be affected by subtle geometrical factors, which can be controlled precisely at the molecular level.
Herein, we describe the selective formation of a barrel-shaped or a ball-shaped fluorescent metallacage by controlling the shape and stoichiometry of the building blocks. Specifically, the tetraphenylethylene-based donor and two acceptors with different numbers of Pt(Ⅱ) centers were combined via coordination-driven self-assembly. Owing to the differences in the shapes of the assemblies, the resultant ball-shaped metallacage displayed stronger and blue-shifted fluorescence compared to the barrel-shaped one in dilute solutions, while a reversal of fluorescence intensities was observed in the aggregation process. Overall, this work demonstrates that the photophysical properties of supramolecular coordination complexes can be affected by subtle geometrical factors, which can be controlled precisely at the molecular level.
2023, 34(12): 108538
doi: 10.1016/j.cclet.2023.108538
Abstract:
Wettability transition is a significant responsive mechanism which is widely applied to construct smart materials and systems. The broad-spectrum responsiveness of the wettability transition makes it a promising way to expand innovative applications. Here, we develop a track-guided self-transportation system mediated by sequential wettability transition accompanied with capillary transportation. Alkaline fuel is loaded into polydimethylsiloxane (PDMS) cuboid to trigger the wettability transition of distributed superhydrophobic tracks laid in shallow water. After the wettability transition, the induced capillary force can propel the repetitive track-to-track transportation of PDMS. Importantly, the spacing between adjacent tracks is rationally designed based on multiple factors including threshold of wettability transition, diffusion kinetics and capillary interaction. Furthermore, the track-guided transportation system is applied to realize directed self-assembly of multiple PDMS building blocks for designated configuration, which increases the complexity and intelligence of self-assembly systems.
Wettability transition is a significant responsive mechanism which is widely applied to construct smart materials and systems. The broad-spectrum responsiveness of the wettability transition makes it a promising way to expand innovative applications. Here, we develop a track-guided self-transportation system mediated by sequential wettability transition accompanied with capillary transportation. Alkaline fuel is loaded into polydimethylsiloxane (PDMS) cuboid to trigger the wettability transition of distributed superhydrophobic tracks laid in shallow water. After the wettability transition, the induced capillary force can propel the repetitive track-to-track transportation of PDMS. Importantly, the spacing between adjacent tracks is rationally designed based on multiple factors including threshold of wettability transition, diffusion kinetics and capillary interaction. Furthermore, the track-guided transportation system is applied to realize directed self-assembly of multiple PDMS building blocks for designated configuration, which increases the complexity and intelligence of self-assembly systems.
2023, 34(12): 108558
doi: 10.1016/j.cclet.2023.108558
Abstract:
Emerging organic pollutants (EOPs) in water are of great concern due to their high environmental risk, so urgent technologies are needed for effective removal of those pollutants. Herein, a heterogeneous advanced oxidation process (AOP) of peroxymonosulfate (PMS) activation by functional material was developed for degradation of a typical antibiotic, gatifloxacin (GAT). The reactive species including sulfate radical (SO4•−) and singlet oxygen (1O2) in this AOP were regulated by interlayered ions (Na+/H+) of titanate nanotubes that supported on Co(OH)2 hollow microsphere. Both the Na-type (NaTi-CoHS) and H-type (HTi-CoHS) materials achieved efficient PMS activation for GAT degradation, and HTi-CoHS even exhibited a relatively high degradation efficiency of 96.6% within 5 min. Co(OH)2 was considered the key component for generation of SO4•− after PMS activation, while hydrogen titanate nanotubes (H-TNTs) promoted the transformation of peroxysulfate radical (SO5•−) to 1O2 by hydrogen bond interaction. Therefore, when the interlayer ion of TNTs transformed from Na+ to H+, more 1O2 was produced for organic pollutant degradation. H-TNTs with lower symmetry preferred to adsorb PMS molecules to achieve interlayer electron transport through hydrogen bonding, rather than electrostatic interaction of Na+ for Na-TNTs. In addition, the degradation pathway of GAT mainly proceeded by the cleavage of C–N bond at the 8 N site of the piperazine ring, which was confirmed by condensed Fukui index and mass spectrographic analysis. This work gives new sights into the regulation of reactive species in AOPs by the composition of material and promotes the understanding of pollutant degradation mechanisms in water treatment process.
Emerging organic pollutants (EOPs) in water are of great concern due to their high environmental risk, so urgent technologies are needed for effective removal of those pollutants. Herein, a heterogeneous advanced oxidation process (AOP) of peroxymonosulfate (PMS) activation by functional material was developed for degradation of a typical antibiotic, gatifloxacin (GAT). The reactive species including sulfate radical (SO4•−) and singlet oxygen (1O2) in this AOP were regulated by interlayered ions (Na+/H+) of titanate nanotubes that supported on Co(OH)2 hollow microsphere. Both the Na-type (NaTi-CoHS) and H-type (HTi-CoHS) materials achieved efficient PMS activation for GAT degradation, and HTi-CoHS even exhibited a relatively high degradation efficiency of 96.6% within 5 min. Co(OH)2 was considered the key component for generation of SO4•− after PMS activation, while hydrogen titanate nanotubes (H-TNTs) promoted the transformation of peroxysulfate radical (SO5•−) to 1O2 by hydrogen bond interaction. Therefore, when the interlayer ion of TNTs transformed from Na+ to H+, more 1O2 was produced for organic pollutant degradation. H-TNTs with lower symmetry preferred to adsorb PMS molecules to achieve interlayer electron transport through hydrogen bonding, rather than electrostatic interaction of Na+ for Na-TNTs. In addition, the degradation pathway of GAT mainly proceeded by the cleavage of C–N bond at the 8 N site of the piperazine ring, which was confirmed by condensed Fukui index and mass spectrographic analysis. This work gives new sights into the regulation of reactive species in AOPs by the composition of material and promotes the understanding of pollutant degradation mechanisms in water treatment process.
2023, 34(12): 108564
doi: 10.1016/j.cclet.2023.108564
Abstract:
Reactive oxygen species (ROS) are essential for biological processes like cell signaling and chemical processes like organic oxidation. Moreover, the sufficient generation of ROS plays a significant role in targeted tumor treatments or oxidation of organics. Herein, a hydrazone-linked porphyrin covalent organic framework (Por-DETH-COF) is developed for red light-induced generation of ROS like singlet oxygen (1O2) or superoxide (O2•−) to undertake different but targeted oxidations. First, 1O2 is adopted in photodynamic therapy (PDT) for the oxidation of glioma cells. The PDT efficiency of Por-DETH-COF on the apoptosis of glioma cells is explored through flow cytometry and western blot assay. The apoptosis rate of glioma cells significantly increases over Por-DETH-COF under 660 nm red light illumination, suggestive of the potency of 1O2. Second, O2•− is employed for the targeted oxidation of thiols. A series of thiols could be efficiently oxidized to corresponding disulfides over Por-DETH-COF under 660 nm red light illumination, indicative of the significance of O2•−. This work highlights the potential of covalent organic frameworks in generating ROS for precise medical applications of complex chemical environments.
Reactive oxygen species (ROS) are essential for biological processes like cell signaling and chemical processes like organic oxidation. Moreover, the sufficient generation of ROS plays a significant role in targeted tumor treatments or oxidation of organics. Herein, a hydrazone-linked porphyrin covalent organic framework (Por-DETH-COF) is developed for red light-induced generation of ROS like singlet oxygen (1O2) or superoxide (O2•−) to undertake different but targeted oxidations. First, 1O2 is adopted in photodynamic therapy (PDT) for the oxidation of glioma cells. The PDT efficiency of Por-DETH-COF on the apoptosis of glioma cells is explored through flow cytometry and western blot assay. The apoptosis rate of glioma cells significantly increases over Por-DETH-COF under 660 nm red light illumination, suggestive of the potency of 1O2. Second, O2•− is employed for the targeted oxidation of thiols. A series of thiols could be efficiently oxidized to corresponding disulfides over Por-DETH-COF under 660 nm red light illumination, indicative of the significance of O2•−. This work highlights the potential of covalent organic frameworks in generating ROS for precise medical applications of complex chemical environments.
2023, 34(12): 108569
doi: 10.1016/j.cclet.2023.108569
Abstract:
Graphene and its derivatives have sparked intense research interest in wearable temperature sensing due to their excellent electric properties, mechanical flexibility, and good biocompatibility. Despite these advantages, the weak temperature dependence of charge transport makes them difficult to achieve a highly sensitive temperature response, which is one of the remaining bottlenecks in the progress towards practical applications. Unfortunately, detailed knowledge about the key factors of the charge transport temperature dependence in this material that determines the critical performance of electrical sensors is very limited up to now. Here, we reveal that oxygen absorption on the ultrathin reduced graphene oxide (RGO) films (~3 nm) can significantly increase their conductance activation energy over 200% and thus greatly improve the temperature dependence of thermal-activated charge transport. Further investigations suggest that oxygen introduces the deep acceptor states, distributed at an energy level ~0.175 eV from the valence-band maximum, which allows a highly temperature-dependent impurity ionization process and the resulting vast holes release in a wide temperature range. Remarkably, our temperature sensors based on oxygen-doped ultrathin RGO films show a high sensitivity with temperature conductive coefficient of 14.58% K−1, which is one order of magnitude higher than the reported CNT or graphene-based devices. Moreover, the ultrathin thickness and high thermal conductivity of RGO film allow an ultrafast response time of ~86 ms, which represents the best level of temperature sensors based on soft materials. Profiting from these advantages, our sensors show good capacity to identify the slight temperature difference of human body, monitor respiratory rate, and detect the environmental temperature. This work not only represents substantial performance advances in temperature sensing, but also provides a new approach to modulate the charge transport temperature dependence, which could be benefited to both device design and fundamental research.
Graphene and its derivatives have sparked intense research interest in wearable temperature sensing due to their excellent electric properties, mechanical flexibility, and good biocompatibility. Despite these advantages, the weak temperature dependence of charge transport makes them difficult to achieve a highly sensitive temperature response, which is one of the remaining bottlenecks in the progress towards practical applications. Unfortunately, detailed knowledge about the key factors of the charge transport temperature dependence in this material that determines the critical performance of electrical sensors is very limited up to now. Here, we reveal that oxygen absorption on the ultrathin reduced graphene oxide (RGO) films (~3 nm) can significantly increase their conductance activation energy over 200% and thus greatly improve the temperature dependence of thermal-activated charge transport. Further investigations suggest that oxygen introduces the deep acceptor states, distributed at an energy level ~0.175 eV from the valence-band maximum, which allows a highly temperature-dependent impurity ionization process and the resulting vast holes release in a wide temperature range. Remarkably, our temperature sensors based on oxygen-doped ultrathin RGO films show a high sensitivity with temperature conductive coefficient of 14.58% K−1, which is one order of magnitude higher than the reported CNT or graphene-based devices. Moreover, the ultrathin thickness and high thermal conductivity of RGO film allow an ultrafast response time of ~86 ms, which represents the best level of temperature sensors based on soft materials. Profiting from these advantages, our sensors show good capacity to identify the slight temperature difference of human body, monitor respiratory rate, and detect the environmental temperature. This work not only represents substantial performance advances in temperature sensing, but also provides a new approach to modulate the charge transport temperature dependence, which could be benefited to both device design and fundamental research.
2023, 34(12): 108584
doi: 10.1016/j.cclet.2023.108584
Abstract:
Drug-resistant bacteria present a severe threat to public health, emphasizing the importance of developing broad-spectrum antibacterial agents that are free from drug resistance. Among silver-based antibacterial agents, nano-silver has been found to exhibit the most promising and comprehensive performance. The exploration of the antibacterial capacity and morphological changes of silver nanoparticles (AgNPs) could offer a starting point for the development of safe and efficient antibacterial agents. In this study, three types of nano-silver-modified polyphosphazene (PRV) nanoparticles with different morphologies were synthesized using precipitation polymerization. These nanoparticles were characterized using various techniques, including Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The antibacterial activity of these nanoparticles against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) was assessed using minimum inhibitory concentration (MIC)/minimum bactericidal concentration (MBC) tests and inverted fluorescence microscopy. Our results revealed that the antibacterial activity of silver nanoparticles can vary significantly depending on their immobilized form. Ag@PRV Strawberry-like nanoparticles (NPs) exhibited higher antibacterial activity compared to Ag@PRV Yolk-Shell NPs and Ag@PRV Cable-like nanofibers (NFs). Notably, all three types of synthesized nanoparticles demonstrated a stronger bactericidal effect on Gram-positive bacteria than Gram-negative bacteria. Live/dead bacterial staining and scanning electron microscopy demonstrated that silver can kill bacteria by altering the permeability of their cell membranes. These findings offer valuable insights for designing and practically applying new silver-based antibacterial agents in the future.
Drug-resistant bacteria present a severe threat to public health, emphasizing the importance of developing broad-spectrum antibacterial agents that are free from drug resistance. Among silver-based antibacterial agents, nano-silver has been found to exhibit the most promising and comprehensive performance. The exploration of the antibacterial capacity and morphological changes of silver nanoparticles (AgNPs) could offer a starting point for the development of safe and efficient antibacterial agents. In this study, three types of nano-silver-modified polyphosphazene (PRV) nanoparticles with different morphologies were synthesized using precipitation polymerization. These nanoparticles were characterized using various techniques, including Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The antibacterial activity of these nanoparticles against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) was assessed using minimum inhibitory concentration (MIC)/minimum bactericidal concentration (MBC) tests and inverted fluorescence microscopy. Our results revealed that the antibacterial activity of silver nanoparticles can vary significantly depending on their immobilized form. Ag@PRV Strawberry-like nanoparticles (NPs) exhibited higher antibacterial activity compared to Ag@PRV Yolk-Shell NPs and Ag@PRV Cable-like nanofibers (NFs). Notably, all three types of synthesized nanoparticles demonstrated a stronger bactericidal effect on Gram-positive bacteria than Gram-negative bacteria. Live/dead bacterial staining and scanning electron microscopy demonstrated that silver can kill bacteria by altering the permeability of their cell membranes. These findings offer valuable insights for designing and practically applying new silver-based antibacterial agents in the future.
2023, 34(12): 108588
doi: 10.1016/j.cclet.2023.108588
Abstract:
Compared with the widespread exploitation of hot electrons in plasmonic nanoparticles (NPs), hot holes generated from plasmonic metal interband transitions, are often overlooked in photoelectrochemistry, including photoelectrochemical sensing. Motivated by the subtle spectral overlap between the characteristic plasmonic bands of Ag NPs and interband transitions of Au, herein, we construct unusual core-shell Ag@Au NPs via an anti-galvanic reaction to promote the generation of hot holes. Benefiting from the unique plasmon resonances of Ag cores in specific wavelength regimes, Ag@Au can excite multiplied hot holes while Au cannot under the same conditions. With satisfactory accuracy and good practicability, the photoelectrochemical sensing platform based on Ag@Au NPs possesses a detection limit of 77 nmol/L for glucose, exhibiting significantly higher sensitivity compared to that using Au NPs. This work exemplifies the applications of interband hot-hole accumulation initiated by plasmons and may inspire more strategies to explore the utilization of hot holes in photoelectrochemistry.
Compared with the widespread exploitation of hot electrons in plasmonic nanoparticles (NPs), hot holes generated from plasmonic metal interband transitions, are often overlooked in photoelectrochemistry, including photoelectrochemical sensing. Motivated by the subtle spectral overlap between the characteristic plasmonic bands of Ag NPs and interband transitions of Au, herein, we construct unusual core-shell Ag@Au NPs via an anti-galvanic reaction to promote the generation of hot holes. Benefiting from the unique plasmon resonances of Ag cores in specific wavelength regimes, Ag@Au can excite multiplied hot holes while Au cannot under the same conditions. With satisfactory accuracy and good practicability, the photoelectrochemical sensing platform based on Ag@Au NPs possesses a detection limit of 77 nmol/L for glucose, exhibiting significantly higher sensitivity compared to that using Au NPs. This work exemplifies the applications of interband hot-hole accumulation initiated by plasmons and may inspire more strategies to explore the utilization of hot holes in photoelectrochemistry.
2023, 34(12): 108604
doi: 10.1016/j.cclet.2023.108604
Abstract:
Electrochemical nitrogen reduction reaction (NRR) is a mild and sustainable method for ammonia synthesis. Therefore, developing high activity, selectivity, and economic efficiency catalysts with considering the synergistic effects between catalysts and carriers to design novel structural models is very important. Considering the non-noble metal NRR catalyst, Mo3, we tried to find a suitable carrier which is stable and economical. Herein, we used the largest atomically precise aluminum-pyrazole ring (AlOC-69) to date (diameter up to 2.3 nm). The larger ring cavities and the presence of abundant hydroxy groups make AlOC-69 an ideal molecular carrier model and provide a basis for studying its structure-activity relationship. The formation energy (−0.76 eV) and stable Mo-O bonds indicate that Mo3 can be stabilized on the Al10O10 surface. Additionally, N2 has fully activated due to the strong interaction between the p-orbital of N and the d-orbital of Mo. The low limiting potential (−0.28 V) emerges that Mo3@Al10O10 has ideal catalytic activity and selectivity. This research provides a promising catalyst model and an understanding of its catalytic process at the atomic level, providing a new approach for the co-design of catalyst and carrier in NRR.
Electrochemical nitrogen reduction reaction (NRR) is a mild and sustainable method for ammonia synthesis. Therefore, developing high activity, selectivity, and economic efficiency catalysts with considering the synergistic effects between catalysts and carriers to design novel structural models is very important. Considering the non-noble metal NRR catalyst, Mo3, we tried to find a suitable carrier which is stable and economical. Herein, we used the largest atomically precise aluminum-pyrazole ring (AlOC-69) to date (diameter up to 2.3 nm). The larger ring cavities and the presence of abundant hydroxy groups make AlOC-69 an ideal molecular carrier model and provide a basis for studying its structure-activity relationship. The formation energy (−0.76 eV) and stable Mo-O bonds indicate that Mo3 can be stabilized on the Al10O10 surface. Additionally, N2 has fully activated due to the strong interaction between the p-orbital of N and the d-orbital of Mo. The low limiting potential (−0.28 V) emerges that Mo3@Al10O10 has ideal catalytic activity and selectivity. This research provides a promising catalyst model and an understanding of its catalytic process at the atomic level, providing a new approach for the co-design of catalyst and carrier in NRR.
2023, 34(12): 108620
doi: 10.1016/j.cclet.2023.108620
Abstract:
Metal-organic frameworks (MOFs) received considerable attention to adsorption and removal of various environmental pollutants because of some inherent advantages. However, it is challenging but meaningful to design and fabricate hierarchical mixed-dimensional MOFs with synergistic effects to enhance the performance for removal and preconcentration of environmental pollutants. Herein, a new hierarchical two-dimensional (2D)-three-dimensional (3D) mixed-dimensional cactus‐like MOF@MOF hybrid material (PCN-134@Zr-BTB) was prepared by in-situ growth of 2D MOF nanosheets (Zr-BTB) on the surface of 3D MOF (PCN-134). The PCN-134@Zr-BTB composites combine the advantages of 2D and 3D MOFs with extensive mesoporous structures and large surface area for effective removal and enrichment of bisphenols (BPs). In comparison with pristine PCN-134 and Zr-BTB materials, the PCN-134@Zr-BTB hybrid material presented excellent adsorption performance for BPs. The adsorption isotherms are consistent with the Langmuir model, and the maximum adsorption capacity of four bisphenols (BPs) ranged from 135.1 mg/g to 628.9 mg/g. The adsorption kinetics are in accordance with the pseudo-second-order model. The recoveries ranged from 72.8% to 108%. The limits of detection were calculated at 0.02–0.03 ng/mL. The enrichment factors were calculated in the range of 310–374. According to FT-IR and XPS analysis, the main adsorption mechanisms are hydrogen bonding and π-π stacking. Nevertheless, this work provides a new and convenient strategy for the preparation of new hierarchical mixed-dimensional MOF@MOF (PCN-134@Zr-BTB) hybrid material for extraction and enrichment of BPs from aqueous matrix.
Metal-organic frameworks (MOFs) received considerable attention to adsorption and removal of various environmental pollutants because of some inherent advantages. However, it is challenging but meaningful to design and fabricate hierarchical mixed-dimensional MOFs with synergistic effects to enhance the performance for removal and preconcentration of environmental pollutants. Herein, a new hierarchical two-dimensional (2D)-three-dimensional (3D) mixed-dimensional cactus‐like MOF@MOF hybrid material (PCN-134@Zr-BTB) was prepared by in-situ growth of 2D MOF nanosheets (Zr-BTB) on the surface of 3D MOF (PCN-134). The PCN-134@Zr-BTB composites combine the advantages of 2D and 3D MOFs with extensive mesoporous structures and large surface area for effective removal and enrichment of bisphenols (BPs). In comparison with pristine PCN-134 and Zr-BTB materials, the PCN-134@Zr-BTB hybrid material presented excellent adsorption performance for BPs. The adsorption isotherms are consistent with the Langmuir model, and the maximum adsorption capacity of four bisphenols (BPs) ranged from 135.1 mg/g to 628.9 mg/g. The adsorption kinetics are in accordance with the pseudo-second-order model. The recoveries ranged from 72.8% to 108%. The limits of detection were calculated at 0.02–0.03 ng/mL. The enrichment factors were calculated in the range of 310–374. According to FT-IR and XPS analysis, the main adsorption mechanisms are hydrogen bonding and π-π stacking. Nevertheless, this work provides a new and convenient strategy for the preparation of new hierarchical mixed-dimensional MOF@MOF (PCN-134@Zr-BTB) hybrid material for extraction and enrichment of BPs from aqueous matrix.
2023, 34(12): 108629
doi: 10.1016/j.cclet.2023.108629
Abstract:
The mitigation of under-coordinated Pb2+ (halide vacancy) defect remains an imperative challenge in the perovskite solar cells, especially printable mesoscopic perovskite solar cells (FP-PSCs). Here we report a commercial-available polyazin anticancer drug Sapanisertib as coordination passivator of halide vacancies in FP-PSCs, thereby achieving the photoelectric conversion efficiency (PCE) to 18.46%, along with a record certified PCE of 18.27%. In polazin Sapanisertib (Sap), there exists two kinds of nitrogen atoms: in-aromatic ring (in purine and oxazole rings, IAR-Ns) and out-aromatic ring (substituted amino groups, OAR-Ns). Through multiple characterizations, and DFT calculations show that substituted amino groups OAR-Ns hardly get interaction with the halide vacancy due to the distribution of charge density in Sapanisertib. Our work suggests that the selective coordination is of great significance for the design of high-performance passivators for printable mesoscopic perovskite solar cells.
The mitigation of under-coordinated Pb2+ (halide vacancy) defect remains an imperative challenge in the perovskite solar cells, especially printable mesoscopic perovskite solar cells (FP-PSCs). Here we report a commercial-available polyazin anticancer drug Sapanisertib as coordination passivator of halide vacancies in FP-PSCs, thereby achieving the photoelectric conversion efficiency (PCE) to 18.46%, along with a record certified PCE of 18.27%. In polazin Sapanisertib (Sap), there exists two kinds of nitrogen atoms: in-aromatic ring (in purine and oxazole rings, IAR-Ns) and out-aromatic ring (substituted amino groups, OAR-Ns). Through multiple characterizations, and DFT calculations show that substituted amino groups OAR-Ns hardly get interaction with the halide vacancy due to the distribution of charge density in Sapanisertib. Our work suggests that the selective coordination is of great significance for the design of high-performance passivators for printable mesoscopic perovskite solar cells.
2023, 34(12): 108630
doi: 10.1016/j.cclet.2023.108630
Abstract:
Ring-opening copolymerization of CO2 and epoxides is a promising way to manufacture high value-added materials. Despite a variety of catalyst systems have been reported, the reaction is still limited by low activity and polymer selectivity. Herein, a strategy of polymerization-enhanced Lewis acidity is reported to construct a series of highly efficient polymeric aluminum porphyrin catalysts (PAPCs). The characterization of the coordination equilibrium constant (Keq) showed significantly enhanced Lewis acidity of PAPC (Keq = 18.2 L/mol) compared to the monomeric counterpart (Keq = 6.4 L/mol), accompanied with increased turnover frequency (TOF) from 136 h−1 to 5500 h−1. Through detailed regulation of Lewis acidity, the highly Lewis acidic PAPC-OTs displayed a record high TOF of 30,200 h−1 with polymer selectivity of up to 99%.
Ring-opening copolymerization of CO2 and epoxides is a promising way to manufacture high value-added materials. Despite a variety of catalyst systems have been reported, the reaction is still limited by low activity and polymer selectivity. Herein, a strategy of polymerization-enhanced Lewis acidity is reported to construct a series of highly efficient polymeric aluminum porphyrin catalysts (PAPCs). The characterization of the coordination equilibrium constant (Keq) showed significantly enhanced Lewis acidity of PAPC (Keq = 18.2 L/mol) compared to the monomeric counterpart (Keq = 6.4 L/mol), accompanied with increased turnover frequency (TOF) from 136 h−1 to 5500 h−1. Through detailed regulation of Lewis acidity, the highly Lewis acidic PAPC-OTs displayed a record high TOF of 30,200 h−1 with polymer selectivity of up to 99%.
2023, 34(12): 108634
doi: 10.1016/j.cclet.2023.108634
Abstract:
Transition metal and nitrogen co-doped carbons (M-N-C) have proven to be promising catalysts for CO2 electroreduction into CO because of the high activity and selectivity. Effective enrichment of the active transition metal coordinated nitrogen sites is desirable but is challenging for a practical volumetric productivity. Herein, we report four kinds of model electrocatalysts to unveil this issue, which include the NC structures with surface N-functionalities, Ni-N-C_I with one layer of surface Ni-N3C sites, NC@Ni-N-C_I with surface N-functionalities and underneath Ni-N3C sites as well as Ni-N-C_II with doubled surface Ni-N3C sites. The X-ray absorption spectroscopy indicates the coordination configuration of Ni-N3C. For NC catalysts, when N-doping level increased from 3.5 at% to 8.4 at%, the CO partial current density increased from below 0.1 mA/cm2 to 3 mA/cm2. Introducing one layer of Ni-N3C onto the NC structures leads to a 54 times higher CO partial current density than that of NC, in the meantime the FECO is 66 times higher. Furthermore, doubling the density of surface Ni-N3C sites by a layer-by-layer method doubles the CO partial current density (jCO), indicating its potential to achieve a high density of active coordinated sites and current densities.
Transition metal and nitrogen co-doped carbons (M-N-C) have proven to be promising catalysts for CO2 electroreduction into CO because of the high activity and selectivity. Effective enrichment of the active transition metal coordinated nitrogen sites is desirable but is challenging for a practical volumetric productivity. Herein, we report four kinds of model electrocatalysts to unveil this issue, which include the NC structures with surface N-functionalities, Ni-N-C_I with one layer of surface Ni-N3C sites, NC@Ni-N-C_I with surface N-functionalities and underneath Ni-N3C sites as well as Ni-N-C_II with doubled surface Ni-N3C sites. The X-ray absorption spectroscopy indicates the coordination configuration of Ni-N3C. For NC catalysts, when N-doping level increased from 3.5 at% to 8.4 at%, the CO partial current density increased from below 0.1 mA/cm2 to 3 mA/cm2. Introducing one layer of Ni-N3C onto the NC structures leads to a 54 times higher CO partial current density than that of NC, in the meantime the FECO is 66 times higher. Furthermore, doubling the density of surface Ni-N3C sites by a layer-by-layer method doubles the CO partial current density (jCO), indicating its potential to achieve a high density of active coordinated sites and current densities.
2023, 34(12): 108640
doi: 10.1016/j.cclet.2023.108640
Abstract:
Lithium metal batteries (LMBs) are considered to be one of the most promising high-energy-density battery systems. However, their practical application in carbonate electrolytes is hampered by lithium dendrite growth, resulting in short cycle life. Herein, an electrolyte regulation strategy is developed to improve the cyclability of LMBs in carbonate electrolytes by introducing LiNO3 using trimethyl phosphate with a slightly higher donor number compared to NO3− as a solubilizer. This not only allows the formaion of Li+-coordinated NO3− but also achieves the regulation of electrolyte solvation structures, leading to the formation of robust and ion-conductive solid-electrolyte interphase films with inorganic-rich inner and organic-rich outer layers on the Li metal anodes. As a result, high Coulombic efficiency of 99.1% and stable plating/stripping cycling of Li metal anode in Li||Cu cells were realized. Furthermore, excellent performance was also demonstrated in Li||LiNi0.83Co0.11Mn0.06O2 (NCM83) full cells and Cu||NCM83 anode-free cells using high mass-loading cathodes. This work provides a simple interphase engineering strategy through regulating the electrolyte solvation structures for high-energy-density LMBs.
Lithium metal batteries (LMBs) are considered to be one of the most promising high-energy-density battery systems. However, their practical application in carbonate electrolytes is hampered by lithium dendrite growth, resulting in short cycle life. Herein, an electrolyte regulation strategy is developed to improve the cyclability of LMBs in carbonate electrolytes by introducing LiNO3 using trimethyl phosphate with a slightly higher donor number compared to NO3− as a solubilizer. This not only allows the formaion of Li+-coordinated NO3− but also achieves the regulation of electrolyte solvation structures, leading to the formation of robust and ion-conductive solid-electrolyte interphase films with inorganic-rich inner and organic-rich outer layers on the Li metal anodes. As a result, high Coulombic efficiency of 99.1% and stable plating/stripping cycling of Li metal anode in Li||Cu cells were realized. Furthermore, excellent performance was also demonstrated in Li||LiNi0.83Co0.11Mn0.06O2 (NCM83) full cells and Cu||NCM83 anode-free cells using high mass-loading cathodes. This work provides a simple interphase engineering strategy through regulating the electrolyte solvation structures for high-energy-density LMBs.
2023, 34(12): 108699
doi: 10.1016/j.cclet.2023.108699
Abstract:
A facile and efficient electrochemical method for sustainable constructing both selanyl phenanthrenes and selanyl polycyclic heteroaromatics (32 examples, 71%-97% yields) through the radical annulation of 2-alkynyl biaryls and 2-heteroaryl-substituted alkynyl benzenes with diselenides at ambient temperature under additive-, chemical oxidant-, catalyst-free and mild conditions was established.
A facile and efficient electrochemical method for sustainable constructing both selanyl phenanthrenes and selanyl polycyclic heteroaromatics (32 examples, 71%-97% yields) through the radical annulation of 2-alkynyl biaryls and 2-heteroaryl-substituted alkynyl benzenes with diselenides at ambient temperature under additive-, chemical oxidant-, catalyst-free and mild conditions was established.
2023, 34(12): 108711
doi: 10.1016/j.cclet.2023.108711
Abstract:
Aprotic lithium-air batteries (LABs) have been known as the holy grail of energy storage systems due to their extremely high energy density. However, their real-world application is still hindered by the great challenges from the Li anode side, like dendrite growth and corrosion reactions, thus a pure oxygen atmosphere is usually adopted to prolong the lifetime of LABs, which is a major obstacle to fully liberate the energy density advantages of LABs. Here, a gel polymer electrolyte has been designed through in-situ polymerization of 1,3-dioxolane (DOL) by utilizing the unique semi-open nature of LABs to protect the Li anode to conquer its shortcomings, enabling the high-performance running of LABs in the ambient air. Unlike common liquid electrolytes, the in-situ formed gel polymer electrolyte could facilitate constructing a gradient SEI film with the gradual decrease of organic components from top to bottom, preventing the Li anode from dendrite growth and air-induced corrosion reactions and thus realizing durable Li repeated plating/stripping (2000 h). Benefiting from the anode protection effects of the gradient SEI film, the LABs display a long lifetime of 170 cycles, paving an avenue for practical, long-term, and high-efficiency operation of LABs.
Aprotic lithium-air batteries (LABs) have been known as the holy grail of energy storage systems due to their extremely high energy density. However, their real-world application is still hindered by the great challenges from the Li anode side, like dendrite growth and corrosion reactions, thus a pure oxygen atmosphere is usually adopted to prolong the lifetime of LABs, which is a major obstacle to fully liberate the energy density advantages of LABs. Here, a gel polymer electrolyte has been designed through in-situ polymerization of 1,3-dioxolane (DOL) by utilizing the unique semi-open nature of LABs to protect the Li anode to conquer its shortcomings, enabling the high-performance running of LABs in the ambient air. Unlike common liquid electrolytes, the in-situ formed gel polymer electrolyte could facilitate constructing a gradient SEI film with the gradual decrease of organic components from top to bottom, preventing the Li anode from dendrite growth and air-induced corrosion reactions and thus realizing durable Li repeated plating/stripping (2000 h). Benefiting from the anode protection effects of the gradient SEI film, the LABs display a long lifetime of 170 cycles, paving an avenue for practical, long-term, and high-efficiency operation of LABs.
2023, 34(12): 108745
doi: 10.1016/j.cclet.2023.108745
Abstract:
Single-atomic catalysts (SACs) caught considerable attention due to their unique structural properties, complete exposed active site, and 100% atom utilization efficiency with remarkable catalytic activity. Mesoporous single-atomic cobalt catalyst with Co-N4 active sites was synthesized by using nitrogen-doped graphene derived from acrylonitrile. Single-atomic cobalt was observed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) in Co@Nx-C-800. Notably, the density functional theory (DFT) calculation and the extended X-ray absorption fine structures (EXAFS) fitting results indicate that the coordination structure of Co-N is four-coordinated. In this work, the practical hydrogenation of nitroarenes to anilines enabled by Co@Nx-C-800 was established with excellent yields and selectivity, which proved its advantages and potential applications.
Single-atomic catalysts (SACs) caught considerable attention due to their unique structural properties, complete exposed active site, and 100% atom utilization efficiency with remarkable catalytic activity. Mesoporous single-atomic cobalt catalyst with Co-N4 active sites was synthesized by using nitrogen-doped graphene derived from acrylonitrile. Single-atomic cobalt was observed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) in Co@Nx-C-800. Notably, the density functional theory (DFT) calculation and the extended X-ray absorption fine structures (EXAFS) fitting results indicate that the coordination structure of Co-N is four-coordinated. In this work, the practical hydrogenation of nitroarenes to anilines enabled by Co@Nx-C-800 was established with excellent yields and selectivity, which proved its advantages and potential applications.
2023, 34(12): 108791
doi: 10.1016/j.cclet.2023.108791
Abstract:
The detection of cytokines plays an important role in clinical diagnosis and immune mechanism research of chicken diseases. In this work, a novel and ultrasensitive chemiluminescent (CL) imaging array immunosensor was proposed to detect multiple chicken cytokines based on DNAzyme@CuS nanoparticles (DNAzyme@CuSNPs) dual mimic enzyme signal amplification strategy. DNAzyme@CuSNPs owns excellent peroxidase property, which was modified with second antibody (Ab2) to prepare DNAzyme@CuSNPs detection probe, and demonstrated high catalysis CL imaging signal due to synergistic catalysis. Chicken interleukin-4 (ChIL-4) and chicken interferon-γ (ChIFN-γ) were used as model analysis samples, the DNAzyme@CuSNPs-based CL imaging immunosensor achieved simultaneous and high-throughput detection of ChIL-4 and ChIFN-γ with wide linear range of 10−3–102 ng/mL, and the detection limits are 0.41 pg/mL and 0.36 pg/mL, respectively. The multiplex chicken cytokines CL imaging array immunosensor shows a high sensitivity, wide linear range, excellent specificity and acceptable stability. This research opens dual mimic enzyme signal-amplified strategy to develop sensitive CL imaging immunoassay for chicken diseases detection application.
The detection of cytokines plays an important role in clinical diagnosis and immune mechanism research of chicken diseases. In this work, a novel and ultrasensitive chemiluminescent (CL) imaging array immunosensor was proposed to detect multiple chicken cytokines based on DNAzyme@CuS nanoparticles (DNAzyme@CuSNPs) dual mimic enzyme signal amplification strategy. DNAzyme@CuSNPs owns excellent peroxidase property, which was modified with second antibody (Ab2) to prepare DNAzyme@CuSNPs detection probe, and demonstrated high catalysis CL imaging signal due to synergistic catalysis. Chicken interleukin-4 (ChIL-4) and chicken interferon-γ (ChIFN-γ) were used as model analysis samples, the DNAzyme@CuSNPs-based CL imaging immunosensor achieved simultaneous and high-throughput detection of ChIL-4 and ChIFN-γ with wide linear range of 10−3–102 ng/mL, and the detection limits are 0.41 pg/mL and 0.36 pg/mL, respectively. The multiplex chicken cytokines CL imaging array immunosensor shows a high sensitivity, wide linear range, excellent specificity and acceptable stability. This research opens dual mimic enzyme signal-amplified strategy to develop sensitive CL imaging immunoassay for chicken diseases detection application.
2023, 34(12): 108801
doi: 10.1016/j.cclet.2023.108801
Abstract:
Photosynthesis [6CO2 + 12H2O → (CH2O)6 + 6O2 + 6H2O] in nature contains a light reaction process for oxygen evolution and a dark reaction process for carbon dioxide (CO2) reduction to carbohydrates, which is of great significance for the survival of living matter. Therefore, for simulating photosynthesis, it is desirable to design and fabricate a bifunctional catalyst for promoting photocatalytic water oxidation and CO2 reduction performances. Herein, a molecular confined synthesis strategy is reasonably proposed and applied, that is the bifunctional CoOx/Co/C-T (T = 700, 800 and 900 ℃) photocatalysts prepared by the pyrolysis of molecular Co-EDTA under N2 and air atmosphere in turn. Among the prepared photocatalysts, the CoOx/Co/C-800 shows the best photocatalytic water oxidation activity with an oxygen yield of 51.2%. In addition, for CO2 reduction reaction, the CO evolution rate of 12.6 µmol/h and selectivity of 75% can be achieved over this catalyst. The improved photocatalytic activities are attributed to the rapid electron transfer between the photosensitizer and the catalyst, which is strongly supported by the current density-voltage (j-V), steady-state and time-resolved photoluminescence spectra (PL). Overall, this work provides a reference for the preparation and optimization of photocatalysts with the capacity for water oxidation and CO2 reduction reactions.
Photosynthesis [6CO2 + 12H2O → (CH2O)6 + 6O2 + 6H2O] in nature contains a light reaction process for oxygen evolution and a dark reaction process for carbon dioxide (CO2) reduction to carbohydrates, which is of great significance for the survival of living matter. Therefore, for simulating photosynthesis, it is desirable to design and fabricate a bifunctional catalyst for promoting photocatalytic water oxidation and CO2 reduction performances. Herein, a molecular confined synthesis strategy is reasonably proposed and applied, that is the bifunctional CoOx/Co/C-T (T = 700, 800 and 900 ℃) photocatalysts prepared by the pyrolysis of molecular Co-EDTA under N2 and air atmosphere in turn. Among the prepared photocatalysts, the CoOx/Co/C-800 shows the best photocatalytic water oxidation activity with an oxygen yield of 51.2%. In addition, for CO2 reduction reaction, the CO evolution rate of 12.6 µmol/h and selectivity of 75% can be achieved over this catalyst. The improved photocatalytic activities are attributed to the rapid electron transfer between the photosensitizer and the catalyst, which is strongly supported by the current density-voltage (j-V), steady-state and time-resolved photoluminescence spectra (PL). Overall, this work provides a reference for the preparation and optimization of photocatalysts with the capacity for water oxidation and CO2 reduction reactions.
2023, 34(12): 108810
doi: 10.1016/j.cclet.2023.108810
Abstract:
P2-type layered oxides are receiving significant interest due to their superior structure and intrinsic performances. There are strenuous attempts to balance the structure stability, phase transition as well as desirable electrochemical performances by inducing anion/cation ions, changing morphology, adjusting valence, etc. In this work, several same-period elements of Sc, Ti, V, Cr, Fe, Cu and Zn are doped into Na0.50Li0.08Mn0.60Co0.16Ni0.16O2 cathodes, which are manipulated by ions radii and valence state, further studied by operando X-ray powder diffraction patterns (XRD). As a result, the Cu2+ doped cathode performed higher rate capacities (as high as 86 mAh/g even at 10 C) and more stable structures (capacity retention of ~89.4% for 100 cycles), which owing to the synergistic effect among the tightened TMO2 layer, enlarged d-spacing, reduce OO electrostatic repulsion, ameliorate lattice distortion as well as mitigate ordering of Na+/vacancy.
P2-type layered oxides are receiving significant interest due to their superior structure and intrinsic performances. There are strenuous attempts to balance the structure stability, phase transition as well as desirable electrochemical performances by inducing anion/cation ions, changing morphology, adjusting valence, etc. In this work, several same-period elements of Sc, Ti, V, Cr, Fe, Cu and Zn are doped into Na0.50Li0.08Mn0.60Co0.16Ni0.16O2 cathodes, which are manipulated by ions radii and valence state, further studied by operando X-ray powder diffraction patterns (XRD). As a result, the Cu2+ doped cathode performed higher rate capacities (as high as 86 mAh/g even at 10 C) and more stable structures (capacity retention of ~89.4% for 100 cycles), which owing to the synergistic effect among the tightened TMO2 layer, enlarged d-spacing, reduce OO electrostatic repulsion, ameliorate lattice distortion as well as mitigate ordering of Na+/vacancy.
2023, 34(12): 108194
doi: 10.1016/j.cclet.2023.108194
Abstract:
Because of abundant redox activity, broad tunability, and specific atomic structure, polyoxometalates (POMs or POM) clusters have attracted burgeoning interests in electrochemical especially energy storage fields. Nevertheless, due to the high solubility and fully oxidized state, they often suffer from electrically insulation as well as chemical and electrochemical instability. Traditional noncovalent loading or covalent grafting of POMs on conductive substrates have been successfully performed to overcome this problem. However, severe shedding or agglomeration of POMs arising from weak interactions with substrates or excessive entrapment or weak destruction in conductive supports cause significantly reduced availability and stability. To this end, precise confinement of POMs into conductive supports has been tried to improve their dispersibility and stability. Herein, recent progress of POMs from surface loading to precise confinement in the electrochemistry energy storage field is reviewed. Firstly, we illustrate the typical non-confinement methods (viz. covalent and non-covalent) for supported POMs in energy storage applications. Secondly, different strategies for precise confinement of POMs in organic and inorganic materials for related applications are also discussed. Finally, future research directions and opportunities for confined POMs, and derived ultrafine nanostructures are also proposed. This review seeks to point out future research directions of supported POMs in the electrochemistry-related fields.
Because of abundant redox activity, broad tunability, and specific atomic structure, polyoxometalates (POMs or POM) clusters have attracted burgeoning interests in electrochemical especially energy storage fields. Nevertheless, due to the high solubility and fully oxidized state, they often suffer from electrically insulation as well as chemical and electrochemical instability. Traditional noncovalent loading or covalent grafting of POMs on conductive substrates have been successfully performed to overcome this problem. However, severe shedding or agglomeration of POMs arising from weak interactions with substrates or excessive entrapment or weak destruction in conductive supports cause significantly reduced availability and stability. To this end, precise confinement of POMs into conductive supports has been tried to improve their dispersibility and stability. Herein, recent progress of POMs from surface loading to precise confinement in the electrochemistry energy storage field is reviewed. Firstly, we illustrate the typical non-confinement methods (viz. covalent and non-covalent) for supported POMs in energy storage applications. Secondly, different strategies for precise confinement of POMs in organic and inorganic materials for related applications are also discussed. Finally, future research directions and opportunities for confined POMs, and derived ultrafine nanostructures are also proposed. This review seeks to point out future research directions of supported POMs in the electrochemistry-related fields.
2023, 34(12): 108280
doi: 10.1016/j.cclet.2023.108280
Abstract:
Ammonia borane (NH3BH3, AB) is an ideal raw material of hydrogen production with higher hydrogen storage capacity. In this paper, the catalytic processes of AB dehydrogenation were described from different ways, including thermal dehydrogenation, hydrolysis, methanolysis, photocatalysis and photo-piezoelectric synergy catalysis with experimental research and theoretical calculations. Catalyst models include bulk materials, two-dimensional materials, nanocluster particles and single/diatomic structures. Among them, the proportion of H2 released is different, and the reaction conditions are also different, which are suitable for different application scenarios. Through this review, we could have a preliminary comprehensive understanding of AB dehydrogenation reaction.
Ammonia borane (NH3BH3, AB) is an ideal raw material of hydrogen production with higher hydrogen storage capacity. In this paper, the catalytic processes of AB dehydrogenation were described from different ways, including thermal dehydrogenation, hydrolysis, methanolysis, photocatalysis and photo-piezoelectric synergy catalysis with experimental research and theoretical calculations. Catalyst models include bulk materials, two-dimensional materials, nanocluster particles and single/diatomic structures. Among them, the proportion of H2 released is different, and the reaction conditions are also different, which are suitable for different application scenarios. Through this review, we could have a preliminary comprehensive understanding of AB dehydrogenation reaction.
2023, 34(12): 108307
doi: 10.1016/j.cclet.2023.108307
Abstract:
“Rocking chair” type lithium-ion batteries with lithium metal-free anodes have been successfully commercialized over the past few decades. Zinc-ion batteries (ZIBs) have gained increasing attention in recent years given their safety, greenness, ease of manufacture, and cost-efficiency. Nevertheless, the practical application of ZIBs is largely hindered by the dendritic growth of the Zn metal anode, low Coulombic efficiency, great harm, and existence of various side reactions. Herein, this review provides a systematic overview of emerging “rocking chair” type ZIBs with zinc metal-free anodes. Firstly, the basic fundamentals, advantages, and challenges of “rocking chair” type ZIBs are introduced. Subsequently, an overview of the design principles and recent progress of “rocking chair” type ZIBs with zinc metal-free anodes are presented. Finally, the key challenges and perspectives for future advancement of “rocking chair” type ZIBs with zinc metal-free anodes are proposed. This review is anticipated to attracted increased focus to metal-free anodes “rocking chair” type metal-ion battery and provide new inspirations for the development of high-energy metal-ion batteries.
“Rocking chair” type lithium-ion batteries with lithium metal-free anodes have been successfully commercialized over the past few decades. Zinc-ion batteries (ZIBs) have gained increasing attention in recent years given their safety, greenness, ease of manufacture, and cost-efficiency. Nevertheless, the practical application of ZIBs is largely hindered by the dendritic growth of the Zn metal anode, low Coulombic efficiency, great harm, and existence of various side reactions. Herein, this review provides a systematic overview of emerging “rocking chair” type ZIBs with zinc metal-free anodes. Firstly, the basic fundamentals, advantages, and challenges of “rocking chair” type ZIBs are introduced. Subsequently, an overview of the design principles and recent progress of “rocking chair” type ZIBs with zinc metal-free anodes are presented. Finally, the key challenges and perspectives for future advancement of “rocking chair” type ZIBs with zinc metal-free anodes are proposed. This review is anticipated to attracted increased focus to metal-free anodes “rocking chair” type metal-ion battery and provide new inspirations for the development of high-energy metal-ion batteries.
2023, 34(12): 108336
doi: 10.1016/j.cclet.2023.108336
Abstract:
Rho-associated coiled-coil-containing protein kinase (ROCK) belongs to the serine-threonine family, and ROCK is involved in a variety of biological processes including cell migration, adhesion, proliferation and differentiation through phosphorylation of different downstream substrates. The aberrant activation of ROCK is associated with the pathological conditions in different systems including various diseases, including cancer, neurological diseases, inflammation, cardiovascular diseases and glaucoma. Therefore, the ROCK inhibitors have potential applicability for treating the aforementioned diseases. Four small molecule ROCK inhibitors have been approved for clinical use: fasudil, ripasudil, netarsudil and belumosudil. In recent years, more small molecule ROCK inhibitors have been identified. This paper reviews the ROCK inhibitors reported in past seven years. We mainly focused on the summarization of the structure–activity relationships, inhibitory efficacy, pharmacological mechanisms and the relevant clinical studies of the reported ROCK inhibitors. Besides the small molecular inhibitors, the peptides and biological extracts which exhibit ROCK inhibitory effects are also included. We also provide suggestions for the future development of the potent ROCK inhibitors.
Rho-associated coiled-coil-containing protein kinase (ROCK) belongs to the serine-threonine family, and ROCK is involved in a variety of biological processes including cell migration, adhesion, proliferation and differentiation through phosphorylation of different downstream substrates. The aberrant activation of ROCK is associated with the pathological conditions in different systems including various diseases, including cancer, neurological diseases, inflammation, cardiovascular diseases and glaucoma. Therefore, the ROCK inhibitors have potential applicability for treating the aforementioned diseases. Four small molecule ROCK inhibitors have been approved for clinical use: fasudil, ripasudil, netarsudil and belumosudil. In recent years, more small molecule ROCK inhibitors have been identified. This paper reviews the ROCK inhibitors reported in past seven years. We mainly focused on the summarization of the structure–activity relationships, inhibitory efficacy, pharmacological mechanisms and the relevant clinical studies of the reported ROCK inhibitors. Besides the small molecular inhibitors, the peptides and biological extracts which exhibit ROCK inhibitory effects are also included. We also provide suggestions for the future development of the potent ROCK inhibitors.
2023, 34(12): 108417
doi: 10.1016/j.cclet.2023.108417
Abstract:
Herein, we review the significant of ordered macroporous (OM) TiO2-based catalysts for boosting photocatalytic CO2 reduction. Based on the need to improve the three key factors of photogenerated charge separation efficiency, solar energy utilization and CO2 adsorption rate during the conversion of CO2 to H2O, we summarized five modification measures: including doping ions into OM TiO2, introducing second semiconductor coupling and noble metal nanoparticles for fabricating multiple Z-scheme heterojunctions, constructing hierarchical pore and carbon-loaded OM TiO2 materials, which effectively enhance the absorption rate of visible light, the separation rate of electrons-hole pairs and the selection of multiple active sites. The OM structured TiO2-based photocatalysts solve the single or multiple key factors for enhancing photocatalytic performances during CO2 conversion. The catalytic mechanism and pathways of OM structured TiO2-based photocatalysts for CO2 reduction are discussed and summarized. It provides new insights on the development of high-efficient catalyst for photocatalytic CO2 conversion to solar fuels.
Herein, we review the significant of ordered macroporous (OM) TiO2-based catalysts for boosting photocatalytic CO2 reduction. Based on the need to improve the three key factors of photogenerated charge separation efficiency, solar energy utilization and CO2 adsorption rate during the conversion of CO2 to H2O, we summarized five modification measures: including doping ions into OM TiO2, introducing second semiconductor coupling and noble metal nanoparticles for fabricating multiple Z-scheme heterojunctions, constructing hierarchical pore and carbon-loaded OM TiO2 materials, which effectively enhance the absorption rate of visible light, the separation rate of electrons-hole pairs and the selection of multiple active sites. The OM structured TiO2-based photocatalysts solve the single or multiple key factors for enhancing photocatalytic performances during CO2 conversion. The catalytic mechanism and pathways of OM structured TiO2-based photocatalysts for CO2 reduction are discussed and summarized. It provides new insights on the development of high-efficient catalyst for photocatalytic CO2 conversion to solar fuels.
2023, 34(12): 108441
doi: 10.1016/j.cclet.2023.108441
Abstract:
Büchner reaction, as a unique type of expansive dearomatization, has become a practical strategy for the straightforward assembly of valuable functionalized cycloheptatrienes from ubiquitous aromatic precursors. Although the asymmetric version has been investigated since the early 1990s, enantioselective Büchner reaction is still limited by the catalyst type and substrate scope. This review aims to propose the limitation and possible development direction of this field by summarizing the evolution of catalytic asymmetric Büchner reaction, which is organized on the basis of intra- and intermolecular reactions. Considering the different metal carbene precursors, the reactions are further classified by carbene sources.
Büchner reaction, as a unique type of expansive dearomatization, has become a practical strategy for the straightforward assembly of valuable functionalized cycloheptatrienes from ubiquitous aromatic precursors. Although the asymmetric version has been investigated since the early 1990s, enantioselective Büchner reaction is still limited by the catalyst type and substrate scope. This review aims to propose the limitation and possible development direction of this field by summarizing the evolution of catalytic asymmetric Büchner reaction, which is organized on the basis of intra- and intermolecular reactions. Considering the different metal carbene precursors, the reactions are further classified by carbene sources.
2023, 34(12): 108627
doi: 10.1016/j.cclet.2023.108627
Abstract:
DNA-based supramolecular hydrogels are important and promising biomaterials for various applications due to their inherent biocompatibility and tunable physicochemical properties. The three-dimensional supramolecular matrix of DNA formed by non-covalently dynamic cross-linking provides exceptional adaptability, self-healing, injectable and responsive properties for hydrogels. In addition, DNA hydrogels are also ideal bio-scaffold materials owing to their tissue-like mechanics and intrinsic biological functions. Technically, DNA can assemble into supramolecular networks by pure complementary base pairing; it can also be combined with other building blocks to construct hybrid hydrogels. This review focuses on the development and construction strategies of DNA hydrogels. Assembly and synthesis methods, diverse responsiveness and biomedical applications are summarized. Finally, the challenges and prospects of DNA-based supramolecular hydrogels are discussed.
DNA-based supramolecular hydrogels are important and promising biomaterials for various applications due to their inherent biocompatibility and tunable physicochemical properties. The three-dimensional supramolecular matrix of DNA formed by non-covalently dynamic cross-linking provides exceptional adaptability, self-healing, injectable and responsive properties for hydrogels. In addition, DNA hydrogels are also ideal bio-scaffold materials owing to their tissue-like mechanics and intrinsic biological functions. Technically, DNA can assemble into supramolecular networks by pure complementary base pairing; it can also be combined with other building blocks to construct hybrid hydrogels. This review focuses on the development and construction strategies of DNA hydrogels. Assembly and synthesis methods, diverse responsiveness and biomedical applications are summarized. Finally, the challenges and prospects of DNA-based supramolecular hydrogels are discussed.
2023, 34(12): 108657
doi: 10.1016/j.cclet.2023.108657
Abstract:
Tetrahydro-γ-carbolines (THγCs) constitute one of the most important subtypes of indole alkaloids. In addition to being substructures of natural products, these structural motifs and moieties can often be found in pharmaceuticals due to their diverse bioactivities such as antiviral, antibacterial, antifungal, antiparasitic, antitumor, anti-inflammatory, and neuropharmacological activities. Beyond the pharmacological and biological aspects of these scaffolds, they have considerable synthetic applications for the construction of further bioactive compounds, too. The aim of this review is to summarize recent developments in the synthesis of this compound class.
Tetrahydro-γ-carbolines (THγCs) constitute one of the most important subtypes of indole alkaloids. In addition to being substructures of natural products, these structural motifs and moieties can often be found in pharmaceuticals due to their diverse bioactivities such as antiviral, antibacterial, antifungal, antiparasitic, antitumor, anti-inflammatory, and neuropharmacological activities. Beyond the pharmacological and biological aspects of these scaffolds, they have considerable synthetic applications for the construction of further bioactive compounds, too. The aim of this review is to summarize recent developments in the synthesis of this compound class.
2023, 34(12): 108722
doi: 10.1016/j.cclet.2023.108722
Abstract:
Persulfate-based advanced oxidation processes (AOPs) have obtained increasing attention due to the generation of sulfate radical (SO4•‒) with high reactivity for organic contaminants degradation. Numerous activation methods have been used to activate two common persulfates: peroxymonosulfate (PMS) and peroxydisulfate (PDS). However, the comparisons of activation methods and two oxidants in the comprehensive degradation performance of the target contaminant are still limited. Thus, taking norfloxacin (NOR) as the target contaminant, we proposed five key parameters (the observed pseudo-first-order rate constant, kobs; average mineralization rate, rm; utilization efficiency of catalyst, Ucat; utilization efficiency of oxidant, Uox; and net utilization efficiency of oxidant, Uox') to quantify the comprehensive degradation performance of NOR. The irradiation affected target pollutants, catalysts, and oxidants, leading to an improved degradation performance of NOR. Various heterogeneous catalysts were compared in terms of the key elements contained. Fe, Co, and Mn-based materials performed better, while carbon-based catalysts performed poorly on NOR degradation. The overall degradation performance of NOR was different for PMS and PDS, which can be ascribed to their varied reaction pathways towards NOR, but stemmed from different properties of PMS and PDS. Besides, the effect of pH on the degradation efficiency of NOR was investigated. A neutral solution was optimal for PMS system, while an acidic solution worked better for PDS system. Finally, we analyzed the molecule structure of NOR by density functional theory (DFT) calculation to study the sites easy to attack. Then, we summarized four typical degradation pathways of NOR in SO4•‒-based AOP systems, including defluorination, piperazine ring cleavage, piperazine ring oxidation, and quinoline group transformation.
Persulfate-based advanced oxidation processes (AOPs) have obtained increasing attention due to the generation of sulfate radical (SO4•‒) with high reactivity for organic contaminants degradation. Numerous activation methods have been used to activate two common persulfates: peroxymonosulfate (PMS) and peroxydisulfate (PDS). However, the comparisons of activation methods and two oxidants in the comprehensive degradation performance of the target contaminant are still limited. Thus, taking norfloxacin (NOR) as the target contaminant, we proposed five key parameters (the observed pseudo-first-order rate constant, kobs; average mineralization rate, rm; utilization efficiency of catalyst, Ucat; utilization efficiency of oxidant, Uox; and net utilization efficiency of oxidant, Uox') to quantify the comprehensive degradation performance of NOR. The irradiation affected target pollutants, catalysts, and oxidants, leading to an improved degradation performance of NOR. Various heterogeneous catalysts were compared in terms of the key elements contained. Fe, Co, and Mn-based materials performed better, while carbon-based catalysts performed poorly on NOR degradation. The overall degradation performance of NOR was different for PMS and PDS, which can be ascribed to their varied reaction pathways towards NOR, but stemmed from different properties of PMS and PDS. Besides, the effect of pH on the degradation efficiency of NOR was investigated. A neutral solution was optimal for PMS system, while an acidic solution worked better for PDS system. Finally, we analyzed the molecule structure of NOR by density functional theory (DFT) calculation to study the sites easy to attack. Then, we summarized four typical degradation pathways of NOR in SO4•‒-based AOP systems, including defluorination, piperazine ring cleavage, piperazine ring oxidation, and quinoline group transformation.
2023, 34(12): 108456
doi: 10.1016/j.cclet.2023.108456
Abstract:
2023, 34(12): 108754
doi: 10.1016/j.cclet.2023.108754
Abstract:
2023, 34(12): 108625
doi: 10.1016/j.cclet.2023.108625
Abstract:
Three-dimensional (3D) histology has exhibited tremendous potential in fundamental research and clinical disease grading, but compatible labeling techniques are still lacking. Recently in Science Advances, Pac et al. report a new histological technique termed 3DNFC, which realizes 3D fluorescence imaging of thick tissues via citrate-based in situ fluorophore formation.
Three-dimensional (3D) histology has exhibited tremendous potential in fundamental research and clinical disease grading, but compatible labeling techniques are still lacking. Recently in Science Advances, Pac et al. report a new histological technique termed 3DNFC, which realizes 3D fluorescence imaging of thick tissues via citrate-based in situ fluorophore formation.
2023, 34(12): 108784
doi: 10.1016/j.cclet.2023.108784
Abstract:
Artificial photocatalysis offers a promising strategy to sustainably produce hydrogen peroxide (H2O2) that is one of the most valuable multifunctional chemicals. Among various photocatalysts, polymeric carbon nitride (pCN) has drawn continuous attention in non-sacrificial H2O2 production. However, the poor activity of half reactions, i.e., the oxygen reduction reaction (ORR) and water oxidation reaction (WOR), greatly restricts the efficiency of photocatalytic H2O2 production. In this highlight, we discuss the significant advances in molecular engineering of carbon nitrides for H2O2 photosynthesis and the importance of the deep understanding of the photocatalysis process for rational design and reaction pathways of organic conjugated polymers to address the growing H2O2 demand. Furthermore, we summarize the emerging applications of photocatalytic H2O2 productions beyond energy and environment.
Artificial photocatalysis offers a promising strategy to sustainably produce hydrogen peroxide (H2O2) that is one of the most valuable multifunctional chemicals. Among various photocatalysts, polymeric carbon nitride (pCN) has drawn continuous attention in non-sacrificial H2O2 production. However, the poor activity of half reactions, i.e., the oxygen reduction reaction (ORR) and water oxidation reaction (WOR), greatly restricts the efficiency of photocatalytic H2O2 production. In this highlight, we discuss the significant advances in molecular engineering of carbon nitrides for H2O2 photosynthesis and the importance of the deep understanding of the photocatalysis process for rational design and reaction pathways of organic conjugated polymers to address the growing H2O2 demand. Furthermore, we summarize the emerging applications of photocatalytic H2O2 productions beyond energy and environment.
