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2023 Volume 39 Issue 8
2023, 39(8): 1441-1462
doi: 10.11862/CJIC.2023.103
Abstract:
Cancer is the second health-threatening risk for humans. Accurate screening and diagnosis technology as well as efficient treatment approaches are the key factors to cure cancer. The rapid development of nanotechnology has brought new ideas and fresh perspectives to cancer diagnosis and treatment. MXene, as a new two-dimensional material, possesses a large specific surface area, high conductivity, good hydrophilicity, and excellent biocompatibility. It can be used as an excellent substrate material to construct a biosensor platform with high compatibility and catalytic performance by combining it with other nanomaterials for the accurate detection of cancer biomarkers. In addition, MXene is an ideal tumor photothermal therapy (PTT) reagent with adjustable components, strong absorption, and high photothermal conversion efficiency in the visible-to-infrared region. To date, few reviews regarding the application of MXene in cancer diagnosis and treatment are reported. In view of this, we summarize the recent advances of Mxene-based biosensing platforms for the detection of different cancer markers, and also conclude the latest research progress of different MXene materials in PTT, and then put forward the challenges and development trends of MXene in cancer diagnosis and treatment.
Cancer is the second health-threatening risk for humans. Accurate screening and diagnosis technology as well as efficient treatment approaches are the key factors to cure cancer. The rapid development of nanotechnology has brought new ideas and fresh perspectives to cancer diagnosis and treatment. MXene, as a new two-dimensional material, possesses a large specific surface area, high conductivity, good hydrophilicity, and excellent biocompatibility. It can be used as an excellent substrate material to construct a biosensor platform with high compatibility and catalytic performance by combining it with other nanomaterials for the accurate detection of cancer biomarkers. In addition, MXene is an ideal tumor photothermal therapy (PTT) reagent with adjustable components, strong absorption, and high photothermal conversion efficiency in the visible-to-infrared region. To date, few reviews regarding the application of MXene in cancer diagnosis and treatment are reported. In view of this, we summarize the recent advances of Mxene-based biosensing platforms for the detection of different cancer markers, and also conclude the latest research progress of different MXene materials in PTT, and then put forward the challenges and development trends of MXene in cancer diagnosis and treatment.
2023, 39(8): 1463-1470
doi: 10.11862/CJIC.2023.124
Abstract:
Nucleus probes for real-time imaging of DNA in live cells are very rare. Herein, the combined use of Ru(N^N)3, Ir(C^N)2(N^N), Re(CO)3Cl(N^N), and Pt(C^N)(N^N) produced four heterobimetallic complexes. Two different functional metal sites are arranged at both ends of linear bis-chelating linkers (N^N)-(N^N), leading to asymmetric dumbbell-like molecules M1-M2, namely, Ru-Re, Ru-Pt, Ir-Re, and Ir-Pt. The red emissive probes of Ru-Re and Ru-Pt offer the benefits of large Stokes shift, excellent nucleus membrane penetration, and DNA binding ability with good photostability. Moreover, DNA imaging of Ru-Re and Ru-Pt probes was comparable to the commercial dye of Hoechst 33342 which is specially used for staining DNA in the nucleus of live cells. However, the Ir-based probes of Ir-Re and Ir-Pt directly targeted mitochondria. The emission properties and selective intracellular localizations of different probes are highly dependent on the metal species used in the heterobimetallic complexes.
Nucleus probes for real-time imaging of DNA in live cells are very rare. Herein, the combined use of Ru(N^N)3, Ir(C^N)2(N^N), Re(CO)3Cl(N^N), and Pt(C^N)(N^N) produced four heterobimetallic complexes. Two different functional metal sites are arranged at both ends of linear bis-chelating linkers (N^N)-(N^N), leading to asymmetric dumbbell-like molecules M1-M2, namely, Ru-Re, Ru-Pt, Ir-Re, and Ir-Pt. The red emissive probes of Ru-Re and Ru-Pt offer the benefits of large Stokes shift, excellent nucleus membrane penetration, and DNA binding ability with good photostability. Moreover, DNA imaging of Ru-Re and Ru-Pt probes was comparable to the commercial dye of Hoechst 33342 which is specially used for staining DNA in the nucleus of live cells. However, the Ir-based probes of Ir-Re and Ir-Pt directly targeted mitochondria. The emission properties and selective intracellular localizations of different probes are highly dependent on the metal species used in the heterobimetallic complexes.
2023, 39(8): 1564-1570
doi: 10.11862/CJIC.2023.119
Abstract:
A cyanide-bridged Fe4ⅢNi2Ⅱ hexa-nuclear complex [Fe4Ni2(Tp)4(CN)12(dpzpen)2]·12H2O·3CH3OH (1) (Tp=hydrotris(pyrazolyl)borate, dpzpen=2, 9-di(pyrazo-1-yl)-1, 10-phenanthroline) was prepared by the reaction of tricyanideferrate(Ⅲ) (Bu4N)[FeⅢ(Tp)(CN)3] with ligand dpzpen and NiⅡ salt. Structural analysis indicates that two [FeⅢ(Tp)(CN)3]- units bridge two [NiⅡ(dpzpen)]2+ fragments forming an approximately rhombic Fe2ⅢNi2Ⅱ skeleton with another two [FeⅢ(Tp)(CN)3]- hanging outside the rhombus through cyanide bridges. Magnetic studies show that complex 1 exhibits ferromagnetic interaction between FeⅢ and NiⅡ through cyanide groups. More significantly, the magnetic-structural relationship of complex 1 was established by fitting the temperature dependence of magnetic susceptibility based on its structural model. The best-fitting parameters J3d (15.73 cm-1) > J2d (3.53 cm-1) ≈ J1d (3.50 cm-1) were in good agreement with the variation tendency of corresponding Ni—N bond lengths and Ni—N≡C angles (J3d: 0.206 5 nm, 169.8°; J2d: 0.206 2 nm, 163.1°; J1d: 0.198 7 nm, 161.6°), indicating a shorter Ni—N bond length and a larger Ni—N≡C angle in favor of ferromagnetic interaction for cyanide-bridged FeⅢ-NiⅡ system.
A cyanide-bridged Fe4ⅢNi2Ⅱ hexa-nuclear complex [Fe4Ni2(Tp)4(CN)12(dpzpen)2]·12H2O·3CH3OH (1) (Tp=hydrotris(pyrazolyl)borate, dpzpen=2, 9-di(pyrazo-1-yl)-1, 10-phenanthroline) was prepared by the reaction of tricyanideferrate(Ⅲ) (Bu4N)[FeⅢ(Tp)(CN)3] with ligand dpzpen and NiⅡ salt. Structural analysis indicates that two [FeⅢ(Tp)(CN)3]- units bridge two [NiⅡ(dpzpen)]2+ fragments forming an approximately rhombic Fe2ⅢNi2Ⅱ skeleton with another two [FeⅢ(Tp)(CN)3]- hanging outside the rhombus through cyanide bridges. Magnetic studies show that complex 1 exhibits ferromagnetic interaction between FeⅢ and NiⅡ through cyanide groups. More significantly, the magnetic-structural relationship of complex 1 was established by fitting the temperature dependence of magnetic susceptibility based on its structural model. The best-fitting parameters J3d (15.73 cm-1) > J2d (3.53 cm-1) ≈ J1d (3.50 cm-1) were in good agreement with the variation tendency of corresponding Ni—N bond lengths and Ni—N≡C angles (J3d: 0.206 5 nm, 169.8°; J2d: 0.206 2 nm, 163.1°; J1d: 0.198 7 nm, 161.6°), indicating a shorter Ni—N bond length and a larger Ni—N≡C angle in favor of ferromagnetic interaction for cyanide-bridged FeⅢ-NiⅡ system.
2023, 39(8): 1571-1578
doi: 10.11862/CJIC.2023.118
Abstract:
A new organic compound 3-(5, 7-dioxoimidazo[4, 5-f]isoindol-6(1H, 5H, 7H)-yl) benzenesulfonic acid (DIBS) was synthesized by condensation of benzimidazo-5, 6-dicarboxylic acid and m-aminobenzene sulfonic acid. Then two solid phases, DIBS(10℃) and DIBS(60℃), were obtained by recrystallization at different temperatures. DIBS(10℃) had green room temperature phosphorescence with a lifetime of 721.6 ms, while the yellow-green afterglow of DIBS(60℃) consisted of delayed fluorescence and room temperature phosphorescence with lifetimes of 259.8 and 336.3 ms, respectively. The different luminescence behaviors of the two phases can be attributed to the different conformations and stacking structures of DIBS molecules in the two phases. Interestingly, DIBS(10℃) could be transformed into DIBS(60℃) under grinding or heating stimulation, showing rare afterglow stimulus - response behavior.
A new organic compound 3-(5, 7-dioxoimidazo[4, 5-f]isoindol-6(1H, 5H, 7H)-yl) benzenesulfonic acid (DIBS) was synthesized by condensation of benzimidazo-5, 6-dicarboxylic acid and m-aminobenzene sulfonic acid. Then two solid phases, DIBS(10℃) and DIBS(60℃), were obtained by recrystallization at different temperatures. DIBS(10℃) had green room temperature phosphorescence with a lifetime of 721.6 ms, while the yellow-green afterglow of DIBS(60℃) consisted of delayed fluorescence and room temperature phosphorescence with lifetimes of 259.8 and 336.3 ms, respectively. The different luminescence behaviors of the two phases can be attributed to the different conformations and stacking structures of DIBS molecules in the two phases. Interestingly, DIBS(10℃) could be transformed into DIBS(60℃) under grinding or heating stimulation, showing rare afterglow stimulus - response behavior.
2023, 39(8): 1579-1586
doi: 10.11862/CJIC.2023.121
Abstract:
Using tris(acetylacetonato)cobalt(Ⅲ) (Co(acac)3) and zinc(Ⅱ) acetylacetonate (Zn(acac)2) as precursors and 2-nitrobenzoic acid (2-nbaH) as ligand, three 1D complexes [Co(H2O)(2-nba)2]n (Co-1), [Co3(2-nba)4(acac)2]n (Co-2), and [Zn2(2-nba)4]n (Zn-3) were obtained by solvothermal reaction in toluene. The complexes were characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, and UV-Vis diffuse reflectance spectroscopy. In complex Co-1, each Co2+ ion is coordinated by two bridged water molecules and four 2-nba- ions to form an octahedron geometry. When 2-nba- was not sufficient, the acac- ligands from the precursor were involved in the bonding with Co2+, leading to another 1D complex Co-2 with a different local structure. Most prominent is that two-thirds of the Co2+ ions in Co-2 are pentagonal triangular-dipyramid, while the other one-third is similar to that of Co-1. The synthetic method for Co was also successfully applied to Zn(acac)2 to give a 1D zigzag-shaped Zn-3. In complex Zn-3, the Zn2+ ions exhibited the {ZnO4} tetrahedral geometry protected only by 2-nba- ions. The results show that the competitive coordination between 2-nba- and acac- can significantly affect the coordination environment of Co2+ ions.
Using tris(acetylacetonato)cobalt(Ⅲ) (Co(acac)3) and zinc(Ⅱ) acetylacetonate (Zn(acac)2) as precursors and 2-nitrobenzoic acid (2-nbaH) as ligand, three 1D complexes [Co(H2O)(2-nba)2]n (Co-1), [Co3(2-nba)4(acac)2]n (Co-2), and [Zn2(2-nba)4]n (Zn-3) were obtained by solvothermal reaction in toluene. The complexes were characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, and UV-Vis diffuse reflectance spectroscopy. In complex Co-1, each Co2+ ion is coordinated by two bridged water molecules and four 2-nba- ions to form an octahedron geometry. When 2-nba- was not sufficient, the acac- ligands from the precursor were involved in the bonding with Co2+, leading to another 1D complex Co-2 with a different local structure. Most prominent is that two-thirds of the Co2+ ions in Co-2 are pentagonal triangular-dipyramid, while the other one-third is similar to that of Co-1. The synthetic method for Co was also successfully applied to Zn(acac)2 to give a 1D zigzag-shaped Zn-3. In complex Zn-3, the Zn2+ ions exhibited the {ZnO4} tetrahedral geometry protected only by 2-nba- ions. The results show that the competitive coordination between 2-nba- and acac- can significantly affect the coordination environment of Co2+ ions.
2023, 39(8): 1587-1596
doi: 10.11862/CJIC.2023.125
Abstract:
A new 2D coordination polymer (CP) [Cd2(L)(dbpy)2(HCOO)(H2O)]•3H2O (1), where H3L=5-((4-carboxybenzyl)amino)isophthalic acid and dbpy=5, 5′-dimethyl-2, 2′-bipyridine, was successfully synthesized by solvothermal method. The structure of CP 1 was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR, thermogravimetric analysis, and solid fluorescence spectroscopy. The structure of CP 1 can be simplified into a 3-connected 2D hcb layer with the point symbol of (63). More importantly, CP 1 could selectively and sensitively recognize antibiotic nitrofurantoin in an aqueous medium by fluorescence quenching effect and had a low detection limit (LOD=0.19 μmol•L-1). In addition, the fluorescence quenching mechanism may be caused by the fluorescence resonance energy transfer.
A new 2D coordination polymer (CP) [Cd2(L)(dbpy)2(HCOO)(H2O)]•3H2O (1), where H3L=5-((4-carboxybenzyl)amino)isophthalic acid and dbpy=5, 5′-dimethyl-2, 2′-bipyridine, was successfully synthesized by solvothermal method. The structure of CP 1 was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analysis, IR, thermogravimetric analysis, and solid fluorescence spectroscopy. The structure of CP 1 can be simplified into a 3-connected 2D hcb layer with the point symbol of (63). More importantly, CP 1 could selectively and sensitively recognize antibiotic nitrofurantoin in an aqueous medium by fluorescence quenching effect and had a low detection limit (LOD=0.19 μmol•L-1). In addition, the fluorescence quenching mechanism may be caused by the fluorescence resonance energy transfer.
2023, 39(8): 1597-1609
doi: 10.11862/CJIC.2023.088
Abstract:
A novel nitrogen-rich doped carbon hollow nanocage (NC) supported binary metal sulfide nanoparticle (CoNixSy) composite CoNixSy/NC was successfully prepared by a simple pyrolysis-vulcanization two-step method. In this strategy, dimethylglyoxime nickel was used as the nickel source to increase the active site, and the core-shell structure of the precursor ZIF-8@Ni-ZIF-67 provided the possibility for the construction of hollow carbon nanocages. More importantly, this unique hollow structure loaded with binary metal sulfide nanoparticles made the CoNixSy/NC possess more active sites, high conductivity, and structural stability when used as an electrode material, thereby providing a higher specific capacity (629.2 F·g-1 at 1 A·g-1) and excellent cycle stability (93.4% capacity retention after 1 000 cycles at 1 A·g-1). When further assembled into a symmetrical supercapacitor, a specific capacitance of 207.2 F·g-1 can be provided at 1 A·g-1, and the retention rate was 85.36% after 1 000 cycles of stabilization.
A novel nitrogen-rich doped carbon hollow nanocage (NC) supported binary metal sulfide nanoparticle (CoNixSy) composite CoNixSy/NC was successfully prepared by a simple pyrolysis-vulcanization two-step method. In this strategy, dimethylglyoxime nickel was used as the nickel source to increase the active site, and the core-shell structure of the precursor ZIF-8@Ni-ZIF-67 provided the possibility for the construction of hollow carbon nanocages. More importantly, this unique hollow structure loaded with binary metal sulfide nanoparticles made the CoNixSy/NC possess more active sites, high conductivity, and structural stability when used as an electrode material, thereby providing a higher specific capacity (629.2 F·g-1 at 1 A·g-1) and excellent cycle stability (93.4% capacity retention after 1 000 cycles at 1 A·g-1). When further assembled into a symmetrical supercapacitor, a specific capacitance of 207.2 F·g-1 can be provided at 1 A·g-1, and the retention rate was 85.36% after 1 000 cycles of stabilization.
2023, 39(8): 1610-1618
doi: 10.11862/CJIC.2023.120
Abstract:
Two 2D zinc(Ⅱ) coordination polymers (CPs), named as [Zn4(3-CIA)2(OH)2(3-bibz)2] (1) and [Zn2(4-CIA)(OH)(3-bibz)]·H2O (2), where 3-H3CIA=5-((3-carboxyphenoxy) methyl) isophthalic acid, 4-H3CIA=5-((4-carboxyphenoxy) methyl) isophthalic acid, and 3-bibz=3-bis(imidazole-1-ylmethyl) benzene, have been prepared hydrothermally and characterized using techniques such as single crystal X-ray diffraction, IR, thermogravimetry, and powder X-ray diffraction. Structural analyses show 1 possesses 2D based on tetra-nuclear building units and 2 exhibits a 2D network from tri-nuclear units due to the different coordination fashions of organic ligands. The fluorescence sensing tests of CPs 1 and 2 on organic solvents showed that their fluorescence exhibited complete quenching by nitrobenzene in water, and the limits of detection were 0.248 and 0.309 μmol·L-1, respectively. Through theoretical calculation, it is found that the sensing mechanism of the two CPs on nitrobenzene can be mainly attributed to the photoinduced electron transfer (PET) effect.
Two 2D zinc(Ⅱ) coordination polymers (CPs), named as [Zn4(3-CIA)2(OH)2(3-bibz)2] (1) and [Zn2(4-CIA)(OH)(3-bibz)]·H2O (2), where 3-H3CIA=5-((3-carboxyphenoxy) methyl) isophthalic acid, 4-H3CIA=5-((4-carboxyphenoxy) methyl) isophthalic acid, and 3-bibz=3-bis(imidazole-1-ylmethyl) benzene, have been prepared hydrothermally and characterized using techniques such as single crystal X-ray diffraction, IR, thermogravimetry, and powder X-ray diffraction. Structural analyses show 1 possesses 2D based on tetra-nuclear building units and 2 exhibits a 2D network from tri-nuclear units due to the different coordination fashions of organic ligands. The fluorescence sensing tests of CPs 1 and 2 on organic solvents showed that their fluorescence exhibited complete quenching by nitrobenzene in water, and the limits of detection were 0.248 and 0.309 μmol·L-1, respectively. Through theoretical calculation, it is found that the sensing mechanism of the two CPs on nitrobenzene can be mainly attributed to the photoinduced electron transfer (PET) effect.
2023, 39(8): 1619-1627
doi: 10.11862/CJIC.2023.117
Abstract:
In this work, four diiron dithiolato pentacarbonyl complexes with phosphine ligands were synthesized and structurally characterized. The starting complex [Fe2(CO)6(μ-SCH2CH(CH2OOCH)S)] (1) reacted with triphenylphosphine, tricyclohexylphosphine, tris(2-methoxyphenyl)phosphine, or tris(4-(trifluoromethyl)phenyl)phosphine and Me3NO·2H2O as the decarbonylation agent to produce the target products [Fe2(CO)5(L)(μ-SCH2CH(CH2OOCH)S)] (L=PPh3 (2), PCy3 (3), P(2-C6H4OCH3)3 (4), P(4-C6H4CF3)3 (5)) in 59%-88% yields. Complexes 2-5 have been characterized by elemental analysis, IR, and NMR spectroscopy, together with single-crystal X-ray diffraction analysis. Electrochemical studies have revealed that complexes 1-5 could electro-catalyze the reduction of proton to hydrogen and complex 1 had better catalytic efficiency than other complexes.
In this work, four diiron dithiolato pentacarbonyl complexes with phosphine ligands were synthesized and structurally characterized. The starting complex [Fe2(CO)6(μ-SCH2CH(CH2OOCH)S)] (1) reacted with triphenylphosphine, tricyclohexylphosphine, tris(2-methoxyphenyl)phosphine, or tris(4-(trifluoromethyl)phenyl)phosphine and Me3NO·2H2O as the decarbonylation agent to produce the target products [Fe2(CO)5(L)(μ-SCH2CH(CH2OOCH)S)] (L=PPh3 (2), PCy3 (3), P(2-C6H4OCH3)3 (4), P(4-C6H4CF3)3 (5)) in 59%-88% yields. Complexes 2-5 have been characterized by elemental analysis, IR, and NMR spectroscopy, together with single-crystal X-ray diffraction analysis. Electrochemical studies have revealed that complexes 1-5 could electro-catalyze the reduction of proton to hydrogen and complex 1 had better catalytic efficiency than other complexes.
2023, 39(8): 1628-1636
doi: 10.11862/CJIC.2023.126
Abstract:
Two new trinuclear complexes consisting of MnⅢ-Schiff base (SB) building block bridged by O—P—O units, namely [Mn3(salen)3(L)]ClO4·H2O (1) and [Mn3(salpn)3(L)]ClO4 (2), where salen2-=N, N′-(ethylene)bis(salicylideneiminato), salpn2-=N, N′-(propylene)bis(salicylideneiminato), H2L=5-(ethoxycarbonyl)-naphthalen-1-yl)phosphonic acid, were synthesized by using solvent evaporation and characterized by using single-crystal X-ray diffraction, IR, and powder X-ray diffraction. Complexes 1 and 2 are isostructural and show similar trinuclear [Mn3(SB)3(L)]+, in which O—P—O groups among the phosphonate ligand bridge three Mn(Ⅲ) ion centers, and an additional disordered ClO4- as a balance anion. These [Mn3(SB)3(L)]+ trimers are assembled by π-π interaction from the neighboring complexes, giving rise to a supramolecular 1D wave chain. Magnetic measurements of 1 and 2 indicate that the three Mn(Ⅲ) ions in the asymmetric structure are two with high spin and one with low spin, while dominant antiferromagnetic interactions are mediated between the Mn(Ⅲ) ions.
Two new trinuclear complexes consisting of MnⅢ-Schiff base (SB) building block bridged by O—P—O units, namely [Mn3(salen)3(L)]ClO4·H2O (1) and [Mn3(salpn)3(L)]ClO4 (2), where salen2-=N, N′-(ethylene)bis(salicylideneiminato), salpn2-=N, N′-(propylene)bis(salicylideneiminato), H2L=5-(ethoxycarbonyl)-naphthalen-1-yl)phosphonic acid, were synthesized by using solvent evaporation and characterized by using single-crystal X-ray diffraction, IR, and powder X-ray diffraction. Complexes 1 and 2 are isostructural and show similar trinuclear [Mn3(SB)3(L)]+, in which O—P—O groups among the phosphonate ligand bridge three Mn(Ⅲ) ion centers, and an additional disordered ClO4- as a balance anion. These [Mn3(SB)3(L)]+ trimers are assembled by π-π interaction from the neighboring complexes, giving rise to a supramolecular 1D wave chain. Magnetic measurements of 1 and 2 indicate that the three Mn(Ⅲ) ions in the asymmetric structure are two with high spin and one with low spin, while dominant antiferromagnetic interactions are mediated between the Mn(Ⅲ) ions.
2023, 39(8): 1637-1648
doi: 10.11862/CJIC.2023.127
Abstract:
The double shell hollow cube structural ZnSnO3 (ZSO) was prepared by high-temperature calcination with ZnSn(OH)6 as a precursor. Then, the CdIn2S4 (CIS) nanocrystalline was wrapped on the surface of ZSO by a hydrothermal method. Thus CdIn2S4/ZnSnO3 (CIS/ZSO) heterostructures were successfully prepared. The photocatalytic hydrogen evolution reaction (HER) result indicated that the as-prepared 12% CIS/ZSO heterostructure obtained with the molar ratio of CIS to ZSO of 12% exhibited excellent photocatalytic H2-production activity with the hydrogen yield of 1 676.48 μmol·g-1 for 3 h, about 12 times and 8 times of original ZSO and CIS, respectively. The enhanced activity of the ZSO photocatalytic HER was attributed to the successful construction of the CIS/ZSO heterostructure. The formation of the CIS/ZSO heterostructural interface significantly improved the separation efficiency of photogenerated electron/hole pairs and reduced their recombination rate. Furthermore, the possible reaction mechanism was proposed by analyzing the charge transfer pathway.
The double shell hollow cube structural ZnSnO3 (ZSO) was prepared by high-temperature calcination with ZnSn(OH)6 as a precursor. Then, the CdIn2S4 (CIS) nanocrystalline was wrapped on the surface of ZSO by a hydrothermal method. Thus CdIn2S4/ZnSnO3 (CIS/ZSO) heterostructures were successfully prepared. The photocatalytic hydrogen evolution reaction (HER) result indicated that the as-prepared 12% CIS/ZSO heterostructure obtained with the molar ratio of CIS to ZSO of 12% exhibited excellent photocatalytic H2-production activity with the hydrogen yield of 1 676.48 μmol·g-1 for 3 h, about 12 times and 8 times of original ZSO and CIS, respectively. The enhanced activity of the ZSO photocatalytic HER was attributed to the successful construction of the CIS/ZSO heterostructure. The formation of the CIS/ZSO heterostructural interface significantly improved the separation efficiency of photogenerated electron/hole pairs and reduced their recombination rate. Furthermore, the possible reaction mechanism was proposed by analyzing the charge transfer pathway.
2023, 39(8): 1471-1480
doi: 10.11862/CJIC.2023.133
Abstract:
For the first time, nitrogen-doped carbon dots (N-CDs) with excellent properties were synthesized by hydrothermal method using honeysuckle as a carbon source and ethylenediamine as a nitrogen source. The prepared N-CDs have abundant functional groups, small particle sizes, good water solubility, excellent fluorescence performance, and high chemical stability. They can emit bright blue fluorescence under ultraviolet light. Using quinine sulfate as a reference, the fluorescence quantum yield of N-CDs was measured to be as high as 15.6%. Under optimal conditions, N-CDs could selectively detect Co2+, and the fluorescence intensity of N-CDs was linearly quenched by Co2+ in a range of 0.5 to 3.6 nmol·L-1, with a detection limit as low as 1.38 nmol·L-1. The quenching mechanism belongs to the internal filtering effect and static quenching. Therefore, an ultra-sensitive Co2+ detection method has been established. To further confirm the feasibility of this sensor, we have also successfully applied it to the precise analysis of Co2+ in tap water samples. In addition, N-CDs have been successfully used for cell imaging and intracellular Co2+ sensing due to their low cytotoxicity and good biocompatibility.
For the first time, nitrogen-doped carbon dots (N-CDs) with excellent properties were synthesized by hydrothermal method using honeysuckle as a carbon source and ethylenediamine as a nitrogen source. The prepared N-CDs have abundant functional groups, small particle sizes, good water solubility, excellent fluorescence performance, and high chemical stability. They can emit bright blue fluorescence under ultraviolet light. Using quinine sulfate as a reference, the fluorescence quantum yield of N-CDs was measured to be as high as 15.6%. Under optimal conditions, N-CDs could selectively detect Co2+, and the fluorescence intensity of N-CDs was linearly quenched by Co2+ in a range of 0.5 to 3.6 nmol·L-1, with a detection limit as low as 1.38 nmol·L-1. The quenching mechanism belongs to the internal filtering effect and static quenching. Therefore, an ultra-sensitive Co2+ detection method has been established. To further confirm the feasibility of this sensor, we have also successfully applied it to the precise analysis of Co2+ in tap water samples. In addition, N-CDs have been successfully used for cell imaging and intracellular Co2+ sensing due to their low cytotoxicity and good biocompatibility.
2023, 39(8): 1481-1488
doi: 10.11862/CJIC.2023.099
Abstract:
A two-dimensional cobalt-based coordination polymer ([KCo(pa)(OH)]n, Co-pa, H2pa=phthalic acid) was synthesized by a simple solvothermal reaction of Co(Ac)2·4H2O and phthalic acid, and characterized by FT-IR spectrum, thermogravimetric analysis, powder X-ray diffraction, X-ray photoelectron spectrum, scanning electron microscope, and N2 adsorption-desorption isotherm. When Co-pa was used as the electrode material for supercapacitors, the Co-pa electrode presented a higher specific capacitance, better rate performance, and cycle stability. At the current densities of 1 and 10 A·g-1, the specific capacitances were 910 and 400 F·g-1, respectively. After 2 000 cycles at 2 A·g-1, the capacitance retention remains 81%. The better pseudo-capacitance performance is attributed to Co-pa nanorods with small size, Co(Ⅱ) ions included in Co-pa, phthalate anions, and their layered structure.
A two-dimensional cobalt-based coordination polymer ([KCo(pa)(OH)]n, Co-pa, H2pa=phthalic acid) was synthesized by a simple solvothermal reaction of Co(Ac)2·4H2O and phthalic acid, and characterized by FT-IR spectrum, thermogravimetric analysis, powder X-ray diffraction, X-ray photoelectron spectrum, scanning electron microscope, and N2 adsorption-desorption isotherm. When Co-pa was used as the electrode material for supercapacitors, the Co-pa electrode presented a higher specific capacitance, better rate performance, and cycle stability. At the current densities of 1 and 10 A·g-1, the specific capacitances were 910 and 400 F·g-1, respectively. After 2 000 cycles at 2 A·g-1, the capacitance retention remains 81%. The better pseudo-capacitance performance is attributed to Co-pa nanorods with small size, Co(Ⅱ) ions included in Co-pa, phthalate anions, and their layered structure.
2023, 39(8): 1489-1500
doi: 10.11862/CJIC.2023.115
Abstract:
TiO2 nanoparticles anchored on hollow carbon spheres (HCS) composites (HCS@TiO2) were prepared via a facile wet-chemistry and controllable pyrolysis using polystyrene@polypyrrole derived HCS as substrates and titanium oxide acetylacetone (TOAC) as Ti source, respectively. The crystalline structures, micro morphologies, and optical properties of HCS@TiO2 composites were characterized by powder X-ray diffraction, ultraviolet-visible spectra, X-ray photoelectron spectra, thermogravimetric analysis, scanning electron microscope, transmission electron microscope, photoluminescence spectra, and Mott-Schottky curves. The structural optimization of HCS@TiO2 composites was investigated by tuning the loading mass of TiO2 and pyrolysis temperatures. Antibacterial performances for E. Coli and S. aureus were evaluated by using HCS@TiO2 with different loading masses and control group (HCS and TiO2) under simulated sunlight irradiation conditions as well as different irradiation times. It was found that the optimized HCS@TiO2-15 (the mass ratio of TOAC to HCS was 15∶1, the pyrolysis temperature was 650 ℃) showed a high antibacterial efficiency (above 99%) which was far superior to that of HCS and TiO2. Moreover, the irradiation time was determined to 90 min having best antibacterial activity (the survival rate was less than 1%).
TiO2 nanoparticles anchored on hollow carbon spheres (HCS) composites (HCS@TiO2) were prepared via a facile wet-chemistry and controllable pyrolysis using polystyrene@polypyrrole derived HCS as substrates and titanium oxide acetylacetone (TOAC) as Ti source, respectively. The crystalline structures, micro morphologies, and optical properties of HCS@TiO2 composites were characterized by powder X-ray diffraction, ultraviolet-visible spectra, X-ray photoelectron spectra, thermogravimetric analysis, scanning electron microscope, transmission electron microscope, photoluminescence spectra, and Mott-Schottky curves. The structural optimization of HCS@TiO2 composites was investigated by tuning the loading mass of TiO2 and pyrolysis temperatures. Antibacterial performances for E. Coli and S. aureus were evaluated by using HCS@TiO2 with different loading masses and control group (HCS and TiO2) under simulated sunlight irradiation conditions as well as different irradiation times. It was found that the optimized HCS@TiO2-15 (the mass ratio of TOAC to HCS was 15∶1, the pyrolysis temperature was 650 ℃) showed a high antibacterial efficiency (above 99%) which was far superior to that of HCS and TiO2. Moreover, the irradiation time was determined to 90 min having best antibacterial activity (the survival rate was less than 1%).
2023, 39(8): 1501-1509
doi: 10.11862/CJIC.2023.128
Abstract:
Aqueous zinc-ion batteries (AZIBs) using the Zn metal anode have been considered one of the next-generation commercial batteries with high security, robust capacity, and low price. However, side reactions, Zn dendrites, and limited lifespan still constrain their practical applications. Herein, the electrolyte additive (glycine, Gly) was introduced into the conventional ZnSO4 electrolyte (denoted as ZnSO4-Gly). The abundant polar groups (—COOH and —NH2) on the Gly can regulate the solvation structure of Zn2+ and thus redistribute Zn2+ deposition to avoid dendrites and side reactions. As a result, the excellent cycle life (3 000 h, at 1 mA·cm-2 and 1 mAh·cm-2) of the Zn||Zn symmetric cell was realized in typical ZnSO4 electrolytes with only 50 mmol·L-1 of Gly additive, overwhelmingly larger than bare ZnSO4 (300 h). The Zn||MnO2 battery with ZnSO4-Gly electrolyte displayed much better than the additive-free device in terms of specific capacity and capacity retention.
Aqueous zinc-ion batteries (AZIBs) using the Zn metal anode have been considered one of the next-generation commercial batteries with high security, robust capacity, and low price. However, side reactions, Zn dendrites, and limited lifespan still constrain their practical applications. Herein, the electrolyte additive (glycine, Gly) was introduced into the conventional ZnSO4 electrolyte (denoted as ZnSO4-Gly). The abundant polar groups (—COOH and —NH2) on the Gly can regulate the solvation structure of Zn2+ and thus redistribute Zn2+ deposition to avoid dendrites and side reactions. As a result, the excellent cycle life (3 000 h, at 1 mA·cm-2 and 1 mAh·cm-2) of the Zn||Zn symmetric cell was realized in typical ZnSO4 electrolytes with only 50 mmol·L-1 of Gly additive, overwhelmingly larger than bare ZnSO4 (300 h). The Zn||MnO2 battery with ZnSO4-Gly electrolyte displayed much better than the additive-free device in terms of specific capacity and capacity retention.
2023, 39(8): 1510-1518
doi: 10.11862/CJIC.2023.079
Abstract:
Herein, a representative metal-organic framework (MOF), UiO-66, with a microporous structure and hydrothermal stability, has been chosen as porous support. Photo-responsive adsorbents were prepared by introducing the spiropyran derivative SP-CH3 into the non-polar pore cage of UiO-66 as photo-regulated active sites. The framework structure of the support material was maintained after SP-CH3 functionalization. An anionic dye, methyl orange, was adopted as a probe to explore the adsorption and desorption performance of the adsorbent in different light conditions. The experimental results showed that the adsorption amount of methyl orange by the sample after UV irradiation was 41.99 mg·g-1, which increased by 57.56% in comparison to that after visible light irradiation. In addition, the desorption of methyl orange of the adsorbent after visible light irradiation was up to 81.6%. Changes in the electric surface charge and polarity of the adsorbents, owing to efficient photo-isomerization of spiropyran in the non-polar environment of UiO-66 cage, have great effects on the adsorption/desorption behaviors of methyl orange on the adsorbents. The resultant adsorbents with photo-regulated active sites exhibit enhanced adsorptive performance and effective desorption.
Herein, a representative metal-organic framework (MOF), UiO-66, with a microporous structure and hydrothermal stability, has been chosen as porous support. Photo-responsive adsorbents were prepared by introducing the spiropyran derivative SP-CH3 into the non-polar pore cage of UiO-66 as photo-regulated active sites. The framework structure of the support material was maintained after SP-CH3 functionalization. An anionic dye, methyl orange, was adopted as a probe to explore the adsorption and desorption performance of the adsorbent in different light conditions. The experimental results showed that the adsorption amount of methyl orange by the sample after UV irradiation was 41.99 mg·g-1, which increased by 57.56% in comparison to that after visible light irradiation. In addition, the desorption of methyl orange of the adsorbent after visible light irradiation was up to 81.6%. Changes in the electric surface charge and polarity of the adsorbents, owing to efficient photo-isomerization of spiropyran in the non-polar environment of UiO-66 cage, have great effects on the adsorption/desorption behaviors of methyl orange on the adsorbents. The resultant adsorbents with photo-regulated active sites exhibit enhanced adsorptive performance and effective desorption.
2023, 39(8): 1519-1526
doi: 10.11862/CJIC.2023.094
Abstract:
CuGa2O4 nanomaterials were synthesized by the co-precipitation method, and a series of WS2/CuGa2O4 composite materials were prepared by the hydrothermal method. The crystal phase, morphology, and chemical state of the as-prepared materials were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and so on. The effect of the doped amount of WS2 on the gas-sensing sensitivity of CuGa2O4 materials to ethanol gas was studied. The results showed that when the mass ratio of WS2 to CuGa2O4 was 1%, the response of this gas sensor to 100 μL·L-1 ethanol gas at room temperature was 345.3, and the response and recovery times were 184 and 69 s, the detection limit reached 0.1 μL·L-1.
CuGa2O4 nanomaterials were synthesized by the co-precipitation method, and a series of WS2/CuGa2O4 composite materials were prepared by the hydrothermal method. The crystal phase, morphology, and chemical state of the as-prepared materials were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and so on. The effect of the doped amount of WS2 on the gas-sensing sensitivity of CuGa2O4 materials to ethanol gas was studied. The results showed that when the mass ratio of WS2 to CuGa2O4 was 1%, the response of this gas sensor to 100 μL·L-1 ethanol gas at room temperature was 345.3, and the response and recovery times were 184 and 69 s, the detection limit reached 0.1 μL·L-1.
2023, 39(8): 1527-1535
doi: 10.11862/CJIC.2023.098
Abstract:
In this work, fluorescent carbon dots (CDs) solution was prepared via a hydrothermal method with ethylenediamine, phosphoric acid, and boric acid as starting materials. Subsequently, the obtained solution was heated at 180 ℃ for 5 h to get phosphorescent CDs powder. The structure, morphology and size, surface groups and chemical compositions, and optical properties of as-prepared CDs were then characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible absorption spectroscopy, and photoluminescence spectra. The results showed the synthesized CDs were amorphous carbon structure, well-dispersed, and sphere-like in shape with a diameter of 3.78-7.64 nm. CDs were rich in heteroatom groups containing N, P, and B on the surface. Under 365 nm UV light irradiation, the CDs powder exhibited bright blue fluorescence, and green room-temperature phosphorescence (RTP) was observed for up to 10 s after switching off the 365 nm light irradiation. The as-obtained CDs powder as an efficient fingerprint reagent was successfully used for developing latent fingerprints (LFPs) on substrates with complex background patterns and strong background fluorescence. After turning off the 365 nm UV light, the clear whole fingerprint shapes with well-defined details can be observed. The background patterns and background fluorescence interference were efficiently eliminated by capturing the phosphorescent latent fingerprint images. Meanwhile, the developed 7-day-old LFPs on various substrates with strong background interference showed well-resolved green ridge flow phosphorescence fingerprint patterns.
In this work, fluorescent carbon dots (CDs) solution was prepared via a hydrothermal method with ethylenediamine, phosphoric acid, and boric acid as starting materials. Subsequently, the obtained solution was heated at 180 ℃ for 5 h to get phosphorescent CDs powder. The structure, morphology and size, surface groups and chemical compositions, and optical properties of as-prepared CDs were then characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible absorption spectroscopy, and photoluminescence spectra. The results showed the synthesized CDs were amorphous carbon structure, well-dispersed, and sphere-like in shape with a diameter of 3.78-7.64 nm. CDs were rich in heteroatom groups containing N, P, and B on the surface. Under 365 nm UV light irradiation, the CDs powder exhibited bright blue fluorescence, and green room-temperature phosphorescence (RTP) was observed for up to 10 s after switching off the 365 nm light irradiation. The as-obtained CDs powder as an efficient fingerprint reagent was successfully used for developing latent fingerprints (LFPs) on substrates with complex background patterns and strong background fluorescence. After turning off the 365 nm UV light, the clear whole fingerprint shapes with well-defined details can be observed. The background patterns and background fluorescence interference were efficiently eliminated by capturing the phosphorescent latent fingerprint images. Meanwhile, the developed 7-day-old LFPs on various substrates with strong background interference showed well-resolved green ridge flow phosphorescence fingerprint patterns.
2023, 39(8): 1536-1544
doi: 10.11862/CJIC.2023.093
Abstract:
The less solvent solid-state reaction (LSR) between CuCl2·2H2O and NH4Cl in a little water produced only (NH4)2[CuCl4(H2O)2] since NH4[CuCl3] was not stable in water; however, in a little absolute ethanol at 60 ℃, the LSR produced NH4[CuCl3], or (NH4)2[CuCl4] according to the mixed stoichiometric ratio. The LSR of CuCl2 and NH4Cl in a 1∶2 molar ratio proceeds in two steps: the formation of NH4[CuCl3] at an early stage and a further reaction between NH4[CuCl3] and remaining NH4Cl to form the final product (NH4)2[CuCl4]. In contrast, the LSR of CuCl2·2H2O and 2, 2′-bipyridine (bipy) in 1∶1 molar ratio in a little water produced solely [Cu(bipy)Cl2], but the 1∶2 product, [Cu(bipy)2Cl2]·2H2O did appear in its early stage. The reason may be that the structure of the solid CuCl2·2H2O, which is polymerized planer trans-[CuCl2(H2O)2], converts to molecular trans-[CuCl2(H2O)4] in water, and the latter makes the activation energy of successive substitution of two H2O molecules by bipy closer. Thus, bipy rapidly and successively replaces four water molecules in trans-[CuCl2(H2O)4] to form a 1∶2 product. This surprising result indicates that the LSR of [Cu(bipy)2Cl2]·2H2O and CuCl2·2H2O is also spontaneous, and according to thermodynamics, it is possible if the ΔrG⊖ of the second reaction is bigger than that of the first one of the consecutive reactions. Therefore, the LSR could also proceed stepwise, which is hard to find in solution reactions.
The less solvent solid-state reaction (LSR) between CuCl2·2H2O and NH4Cl in a little water produced only (NH4)2[CuCl4(H2O)2] since NH4[CuCl3] was not stable in water; however, in a little absolute ethanol at 60 ℃, the LSR produced NH4[CuCl3], or (NH4)2[CuCl4] according to the mixed stoichiometric ratio. The LSR of CuCl2 and NH4Cl in a 1∶2 molar ratio proceeds in two steps: the formation of NH4[CuCl3] at an early stage and a further reaction between NH4[CuCl3] and remaining NH4Cl to form the final product (NH4)2[CuCl4]. In contrast, the LSR of CuCl2·2H2O and 2, 2′-bipyridine (bipy) in 1∶1 molar ratio in a little water produced solely [Cu(bipy)Cl2], but the 1∶2 product, [Cu(bipy)2Cl2]·2H2O did appear in its early stage. The reason may be that the structure of the solid CuCl2·2H2O, which is polymerized planer trans-[CuCl2(H2O)2], converts to molecular trans-[CuCl2(H2O)4] in water, and the latter makes the activation energy of successive substitution of two H2O molecules by bipy closer. Thus, bipy rapidly and successively replaces four water molecules in trans-[CuCl2(H2O)4] to form a 1∶2 product. This surprising result indicates that the LSR of [Cu(bipy)2Cl2]·2H2O and CuCl2·2H2O is also spontaneous, and according to thermodynamics, it is possible if the ΔrG⊖ of the second reaction is bigger than that of the first one of the consecutive reactions. Therefore, the LSR could also proceed stepwise, which is hard to find in solution reactions.
2023, 39(8): 1545-1552
doi: 10.11862/CJIC.2023.087
Abstract:
A novel tri-branched structure organoboron complex based on triphenylamine (TPAB) was designed and synthesized by Suzuki coupling reaction, condensation reaction, and complexation reaction using tris(4-bromophenyl)amine, 4-aminophenyl boronic acid pinacol ester, 4-(diethylamino)salicylaldehyde and boron trifluoride etherate. The structures of the compounds were characterized by 1H and 13C NMR. The photophysical properties of TPAB in solution and solid state were investigated by UV-Vis absorption and fluorescence spectra. TPAB was a dual-state emission active compound that showed strong fluorescence in both solution and solid state. The absorption peak of TPAB in tetrahydrofuran solution was located at 417 nm and the emission peak was located at 548 nm with a fluorescence quantum yield of 40.49% and a fluorescence lifetime of 1.72 ns. The fluorescence emission peak of the TPAB solid was located at 582 nm with a fluorescence quantum yield of 11.43% and a fluorescence lifetime of 0.72 ns. In addition, the fluorescence property of the compound was stable and was not affected by pH, metal ions, amino acids, and pressure. Based on the excellent fluorescence property, TPAB was applied for cell imaging that performed bright fluorescence in HepG2 cells under one- and two-photon excitation.
A novel tri-branched structure organoboron complex based on triphenylamine (TPAB) was designed and synthesized by Suzuki coupling reaction, condensation reaction, and complexation reaction using tris(4-bromophenyl)amine, 4-aminophenyl boronic acid pinacol ester, 4-(diethylamino)salicylaldehyde and boron trifluoride etherate. The structures of the compounds were characterized by 1H and 13C NMR. The photophysical properties of TPAB in solution and solid state were investigated by UV-Vis absorption and fluorescence spectra. TPAB was a dual-state emission active compound that showed strong fluorescence in both solution and solid state. The absorption peak of TPAB in tetrahydrofuran solution was located at 417 nm and the emission peak was located at 548 nm with a fluorescence quantum yield of 40.49% and a fluorescence lifetime of 1.72 ns. The fluorescence emission peak of the TPAB solid was located at 582 nm with a fluorescence quantum yield of 11.43% and a fluorescence lifetime of 0.72 ns. In addition, the fluorescence property of the compound was stable and was not affected by pH, metal ions, amino acids, and pressure. Based on the excellent fluorescence property, TPAB was applied for cell imaging that performed bright fluorescence in HepG2 cells under one- and two-photon excitation.
2023, 39(8): 1553-1563
doi: 10.11862/CJIC.2023.114
Abstract:
A novel MOF-808/BiOCl composite heterojunction material was prepared by combining highly stable MOF-808 with BiOCl by simple hydrothermal method. The photocatalytic performance of composite MOF-808/BiOCl on ciprofloxacin (CIP) was investigated using CIP as a contaminant. Compared with pure BiOCl, the performance of composite materials has been improved. Among them, composites containing 10% MOF-808 (MOF-808/BiOCl-10%) showed the best photocatalytic activity. Within 20 min of UV light irradiation, the photocatalytic degradation efficiency of CIP by MOF-808/BiOCl-10% was as high as 94.7%. X-ray powder diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), fluorescence spectroscopy, ultraviolet-visible diffuse reflection spectroscopy (UV-Vis DRS), photocurrent, electrochemical impedance, and other characterization techniques were performed to analyze the phase composition, morphology and photoelectrochemical properties of materials. The formation of MOF-808 and BiOCl heterojunctions is beneficial to suppress the compounding efficiency of photogenerated carriers and improving photocatalytic activity. The UV-Vis diffuse reflectance spectroscopy results show that the light absorption range of MOF-808/BiOCl-10% material is improved. At the same time, radical trapping experiments were carried out. It indicates that ·O2- and h+ are the active species that play a major role in the degradation of CIP by MOF-808/BiOCl-10%. Based on the above experimental data, the possible photocatalytic mechanism of MOF-808/BiOCl composites was proposed.
A novel MOF-808/BiOCl composite heterojunction material was prepared by combining highly stable MOF-808 with BiOCl by simple hydrothermal method. The photocatalytic performance of composite MOF-808/BiOCl on ciprofloxacin (CIP) was investigated using CIP as a contaminant. Compared with pure BiOCl, the performance of composite materials has been improved. Among them, composites containing 10% MOF-808 (MOF-808/BiOCl-10%) showed the best photocatalytic activity. Within 20 min of UV light irradiation, the photocatalytic degradation efficiency of CIP by MOF-808/BiOCl-10% was as high as 94.7%. X-ray powder diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), fluorescence spectroscopy, ultraviolet-visible diffuse reflection spectroscopy (UV-Vis DRS), photocurrent, electrochemical impedance, and other characterization techniques were performed to analyze the phase composition, morphology and photoelectrochemical properties of materials. The formation of MOF-808 and BiOCl heterojunctions is beneficial to suppress the compounding efficiency of photogenerated carriers and improving photocatalytic activity. The UV-Vis diffuse reflectance spectroscopy results show that the light absorption range of MOF-808/BiOCl-10% material is improved. At the same time, radical trapping experiments were carried out. It indicates that ·O2- and h+ are the active species that play a major role in the degradation of CIP by MOF-808/BiOCl-10%. Based on the above experimental data, the possible photocatalytic mechanism of MOF-808/BiOCl composites was proposed.
