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2019 Volume 36 Issue 4
2019, 36(4): 367-378
doi: 10.11944/j.issn.1000-0518.2019.04.180412
Abstract:
bBladder cancer is a kind of malignant tumor with high morbidity and mortality. Usually, it only can be diagnosed at the middle or late stage, causing serious physical and mental harm to patients. Cystoscopy is the gold standard for the diagnosis of bladder cancer. However, cystoscopy is invasive to some extent. The limited sensitivity and specificity of cystoscopy are also main barriers for achieving the required early and precise diagnosis of bladder cancer. The occurrence of bladder cancer would have a significant impact on the components of blood and urine. In this regard, non-invasive liquid biopsy shows great potential for realizing early bladder cancer diagnosis. This review describes the development of liquid biopsy-based diagnostic methods for bladder cancer. The main biomarkers of bladder cancer are briefly introduced. The diagnostic methods and mechanisms of bladder cancer with liquid(such as urine and blood) as the detection objects are comprehensively discussed. In addition, the opportunities and challenges of liquid biopsy for bladder cancer diagnosis are recommended. We hope this review will provide guidance for bladder cancer-based liquid biopsy techniques.
bBladder cancer is a kind of malignant tumor with high morbidity and mortality. Usually, it only can be diagnosed at the middle or late stage, causing serious physical and mental harm to patients. Cystoscopy is the gold standard for the diagnosis of bladder cancer. However, cystoscopy is invasive to some extent. The limited sensitivity and specificity of cystoscopy are also main barriers for achieving the required early and precise diagnosis of bladder cancer. The occurrence of bladder cancer would have a significant impact on the components of blood and urine. In this regard, non-invasive liquid biopsy shows great potential for realizing early bladder cancer diagnosis. This review describes the development of liquid biopsy-based diagnostic methods for bladder cancer. The main biomarkers of bladder cancer are briefly introduced. The diagnostic methods and mechanisms of bladder cancer with liquid(such as urine and blood) as the detection objects are comprehensively discussed. In addition, the opportunities and challenges of liquid biopsy for bladder cancer diagnosis are recommended. We hope this review will provide guidance for bladder cancer-based liquid biopsy techniques.
2019, 36(4): 379-391
doi: 10.11944/j.issn.1000-0518.2019.04.180417
Abstract:
Electrochemiluminescence sensors own the advantage of high sensitivity, low background signal and simple operation, therefore, they have wide application in agriculture, industry, environment, clinic, food and so on. In this review, the application and analytical performance of electrochemiluminescence sensors in the detection of pesticide residues and mycotoxins are disucssed. The present situation of electrochemiluminescence sensors in the field of agriculture sensing is reviewed, and the development trend of the sensors in the future is described.
Electrochemiluminescence sensors own the advantage of high sensitivity, low background signal and simple operation, therefore, they have wide application in agriculture, industry, environment, clinic, food and so on. In this review, the application and analytical performance of electrochemiluminescence sensors in the detection of pesticide residues and mycotoxins are disucssed. The present situation of electrochemiluminescence sensors in the field of agriculture sensing is reviewed, and the development trend of the sensors in the future is described.
2019, 36(4): 392-401
doi: 10.11944/j.issn.1000-0518.2019.04.180369
Abstract:
Functionalization of fullerenes is an important part of fullerene chemistry. Many novel fullerene derivatives have been synthesized during recent years, and the compounds have exhibited promising potentials in biomedical chemistry and organic solar cells. Compared with the rapid development of fullerene chemistry, progress on the fullerene thiolation is slow, which has attracted more attention recently. Herein, the latest progress on the thiolation reactions of fullerenes is reviewed, which includes the recent result from our group.
Functionalization of fullerenes is an important part of fullerene chemistry. Many novel fullerene derivatives have been synthesized during recent years, and the compounds have exhibited promising potentials in biomedical chemistry and organic solar cells. Compared with the rapid development of fullerene chemistry, progress on the fullerene thiolation is slow, which has attracted more attention recently. Herein, the latest progress on the thiolation reactions of fullerenes is reviewed, which includes the recent result from our group.
2019, 36(4): 402-413
doi: 10.11944/j.issn.1000-0518.2019.04.180269
Abstract:
To develop a platform for the site-selective immobilization of proteins and the screening of mixture-based ligand libraries through magnetic separation of complexes of ligands and targets, a bivalent affinity labeling reagent(Br-Ⅱ) against fusion tag glutathione S-transferase(GST) was designed and characterized. The use of two flexible benzenes as the moiety to occupy the hydrophobic site in one active site of GST, bromoacetyl as the group for covalent modification of sulfhydryl group nearby and carboxyl as the linking group yielded a monovalent affinity labeling reagent; the linkage of the monovalent affinity labeling reagent to the primary amines on diethylenetriamine gave Br-Ⅱ as the bivalent affinity labeling reagent that contained a secondary amino group for further conjugation with carboxyl group on magnetic beads. The kinetics and ratios for irreversible and reversible labeling of GST tag, before and after conjugation with reduced glutathione(GSH), respectively, was characterized for the designed bivalent affinity labeling reagent. Using alkaline phosphatase as the unwanted protein and the fluorescent ligand 8-anilino-1-naphthalenesulfonic acid as the small molecule model, the immobilization specificity for GST tag, and also the nonspecific adsorption for hydrophobic small molecules of the resultant GST-immobilized magnetic beads were checked. The designed compound showed half inhibitory concentration of (22±0.2) μmol/L, and its GSH adduct gave half inhibitory concentration of (0.41±0.06) μmol/L; the reversible and irreversible labeling of GST tag dimer showed both binding ratios close to 1:1; the Br-Ⅱ-functionalized magnetic beads showed selective immobilization of GST tag in the presence of alkaline phosphatase, and the immobilization capacity of about 25 mg/g for GST via either reversible or irreversible immobilization. After the immobilization of GST and further treatment with the GSH adduct of the monovalent affinity labeling reagent, magnetic beads showed no significant nonspecific binding of 8-anilino-1-naphthalenesulfonic acid. Therefore, magnetic beads after being functionalized with the titled compound are suitable for the immobilization of GST-fused proteins.
To develop a platform for the site-selective immobilization of proteins and the screening of mixture-based ligand libraries through magnetic separation of complexes of ligands and targets, a bivalent affinity labeling reagent(Br-Ⅱ) against fusion tag glutathione S-transferase(GST) was designed and characterized. The use of two flexible benzenes as the moiety to occupy the hydrophobic site in one active site of GST, bromoacetyl as the group for covalent modification of sulfhydryl group nearby and carboxyl as the linking group yielded a monovalent affinity labeling reagent; the linkage of the monovalent affinity labeling reagent to the primary amines on diethylenetriamine gave Br-Ⅱ as the bivalent affinity labeling reagent that contained a secondary amino group for further conjugation with carboxyl group on magnetic beads. The kinetics and ratios for irreversible and reversible labeling of GST tag, before and after conjugation with reduced glutathione(GSH), respectively, was characterized for the designed bivalent affinity labeling reagent. Using alkaline phosphatase as the unwanted protein and the fluorescent ligand 8-anilino-1-naphthalenesulfonic acid as the small molecule model, the immobilization specificity for GST tag, and also the nonspecific adsorption for hydrophobic small molecules of the resultant GST-immobilized magnetic beads were checked. The designed compound showed half inhibitory concentration of (22±0.2) μmol/L, and its GSH adduct gave half inhibitory concentration of (0.41±0.06) μmol/L; the reversible and irreversible labeling of GST tag dimer showed both binding ratios close to 1:1; the Br-Ⅱ-functionalized magnetic beads showed selective immobilization of GST tag in the presence of alkaline phosphatase, and the immobilization capacity of about 25 mg/g for GST via either reversible or irreversible immobilization. After the immobilization of GST and further treatment with the GSH adduct of the monovalent affinity labeling reagent, magnetic beads showed no significant nonspecific binding of 8-anilino-1-naphthalenesulfonic acid. Therefore, magnetic beads after being functionalized with the titled compound are suitable for the immobilization of GST-fused proteins.
Zeolitic Imidazolate Framework-67 Efficiently Catalyzes the Ring-Opening Polymerization of L-Lactide
2019, 36(4): 414-422
doi: 10.11944/j.issn.1000-0518.2019.04.180398
Abstract:
To explore the metal effecting in structure of zeolitic imidazolate frameworks(ZIFs) influenced to its catalytic activity, we have synthesized ZIF-8, Zn/Co-ZIF and ZIF-67 by room temperature method and applied them as catalysts for the bulk ring-opening polymerization of L-lactide. Under the same reaction condition, ZIF-67 shows the highest catalytic activity. Compared to 2-methylimidazolate(linker) as a catalyst under the same reaction condition, the poly(lactic acid) obtained with ZIF-67 has highly isotactic structure. In addition, the matrix assisted laser desorption ionization-time of flight(MALDI-TOF) mass spectrum indicate that the poly(lactic acid) obtained with ZIF-67 has an almost linear structure. ZIF-67 can be reused for three times without significantly loss of catalytic activity.
To explore the metal effecting in structure of zeolitic imidazolate frameworks(ZIFs) influenced to its catalytic activity, we have synthesized ZIF-8, Zn/Co-ZIF and ZIF-67 by room temperature method and applied them as catalysts for the bulk ring-opening polymerization of L-lactide. Under the same reaction condition, ZIF-67 shows the highest catalytic activity. Compared to 2-methylimidazolate(linker) as a catalyst under the same reaction condition, the poly(lactic acid) obtained with ZIF-67 has highly isotactic structure. In addition, the matrix assisted laser desorption ionization-time of flight(MALDI-TOF) mass spectrum indicate that the poly(lactic acid) obtained with ZIF-67 has an almost linear structure. ZIF-67 can be reused for three times without significantly loss of catalytic activity.
2019, 36(4): 423-430
doi: 10.11944/j.issn.1000-0518.2019.04.180404
Abstract:
The ordered aggregation of non-fullerene small molecular acceptors(SMAs) is critical in determining the charge transport and bimolecular recombination in polymer/SMAs solar cells. However, due to the asymmetric phase separation, the polymers prefer to form crystalline networks, which inhibits the molecular diffusion of SMAs and results in weak crystallinity of SMAs. In poly[(2, 6-(4, 8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1, 2-b:4, 5-b']dithiophene))-alt-(5, 5-(1', 3'-di-2-thienyl-5', 7'bis(2-ethylhexyl)benzo[1', 2'-c:4', 5'-c']dithiophene-4, 8-dione))](PBDB-T)/9-bis(2-methylene-((3-(1, 1-dicyanomethylene)-6, 7-difluoro)-indanone))-5, 5, 11, 11-tetrakis(4-hexylphenyl)-dithieno[2, 3-d:2', 3'-d']-s-indaceno[1, 2-b:5, 6-b']dithiophene(IT-4F) blends, crystallization of IT-4F could be improved by tetrahydrofuran solvent vapor annealing, while crystallization of PBDB-T could be enhanced by thermal annealing at 150℃. Hence, the prior crystallization of IT-4F could be realized by regulating the sequence of two post annealing methods, which facilitates the diffusion of IT-4F and is benefit for the formation of interpenetrating network. The optimization of the film morphology reduced the bimolecular recombination and resulted in an improved device performance from 5.95% to 7.18%.
The ordered aggregation of non-fullerene small molecular acceptors(SMAs) is critical in determining the charge transport and bimolecular recombination in polymer/SMAs solar cells. However, due to the asymmetric phase separation, the polymers prefer to form crystalline networks, which inhibits the molecular diffusion of SMAs and results in weak crystallinity of SMAs. In poly[(2, 6-(4, 8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1, 2-b:4, 5-b']dithiophene))-alt-(5, 5-(1', 3'-di-2-thienyl-5', 7'bis(2-ethylhexyl)benzo[1', 2'-c:4', 5'-c']dithiophene-4, 8-dione))](PBDB-T)/9-bis(2-methylene-((3-(1, 1-dicyanomethylene)-6, 7-difluoro)-indanone))-5, 5, 11, 11-tetrakis(4-hexylphenyl)-dithieno[2, 3-d:2', 3'-d']-s-indaceno[1, 2-b:5, 6-b']dithiophene(IT-4F) blends, crystallization of IT-4F could be improved by tetrahydrofuran solvent vapor annealing, while crystallization of PBDB-T could be enhanced by thermal annealing at 150℃. Hence, the prior crystallization of IT-4F could be realized by regulating the sequence of two post annealing methods, which facilitates the diffusion of IT-4F and is benefit for the formation of interpenetrating network. The optimization of the film morphology reduced the bimolecular recombination and resulted in an improved device performance from 5.95% to 7.18%.
2019, 36(4): 431-439
doi: 10.11944/j.issn.1000-0518.2019.04.180360
Abstract:
As a classical model of confined polymer systems, polymer brushes have potential applications in colloid stability, polymer self-assembly, tribology, and so on. We present herein a combination of atom transfer radical polymerization(ATRP) and click chemistry method to synthesize pH-responsive poly(4-vinylpyridine-b-polyethylene glycol)(P4VP-b-PEG) block polymer brushes on gold(Au) substrates. The changes of the morphologies, surface chemical composition and surface roughness of the as-prepared Au/P4VP-b-PEG polymer brushes treated by different pH solutions were further studied by frequency-dissipation quartz microbalance(QCM-D), X-ray photoelectron spectroscopy(XPS) and atomic force microscopy(AFM), respectively. The results showed that P4VP-b-PEG block polymer brushes treated with different pH solutions exhibited stimuli-response behaviors. At pH=1.5, the P4VP segment was protonated, and the P4VP-b-PEG chain exhibited stretching conformation due to electrostatic repulsion. At pH=11.5, the P4VP segment was deprotonated, and the P4VP-b-PEG segment collapsed due to the loss of partial binding water.
As a classical model of confined polymer systems, polymer brushes have potential applications in colloid stability, polymer self-assembly, tribology, and so on. We present herein a combination of atom transfer radical polymerization(ATRP) and click chemistry method to synthesize pH-responsive poly(4-vinylpyridine-b-polyethylene glycol)(P4VP-b-PEG) block polymer brushes on gold(Au) substrates. The changes of the morphologies, surface chemical composition and surface roughness of the as-prepared Au/P4VP-b-PEG polymer brushes treated by different pH solutions were further studied by frequency-dissipation quartz microbalance(QCM-D), X-ray photoelectron spectroscopy(XPS) and atomic force microscopy(AFM), respectively. The results showed that P4VP-b-PEG block polymer brushes treated with different pH solutions exhibited stimuli-response behaviors. At pH=1.5, the P4VP segment was protonated, and the P4VP-b-PEG chain exhibited stretching conformation due to electrostatic repulsion. At pH=11.5, the P4VP segment was deprotonated, and the P4VP-b-PEG segment collapsed due to the loss of partial binding water.
2019, 36(4): 440-450
doi: 10.11944/j.issn.1000-0518.2019.04.180207
Abstract:
Poly(N-isopropylacrylamide)(PNIPAM) is an amphiphilic thermosensitive polymer with the hydrophilic amide group and the hydrophobic isopropyl group in the side chain. A reversible phase change occurs due to intermolecular interaction with the change of outside temperature. Tetraphenylethene derivatives have advantages of easy-to-synthesize, highly efficient chemical modification feasibility, aggregation-induced emission(AIE) characteristic and high quantum yield. Therefore, a macromolecular initiator F was prepared by the polymerization of N-isopropylacrylamide through single electron transfer-living free radical polymerization with tetraphenylethene derivative as the initiator. Then styrene was used as comonomer to convert the active PNIPAM initiator to an amphiphilic block polymer G, which was characterized by gel permeation chromatography and Fourier transform infrared spectra. Using tetraphenylethene-based AIE-active initiator as the research object of reference, the photophysical properties of amphiphilic block polymer at different temperatures and concentrations were studied to correlate the AIE activity with the amphiphilic nature of the block polymer in detail. It was found that the fluorescence intensity of AIE-active initiators decreased with the increase of temperature at the same concentration of dispersion, while the fluorescence intensity of the block polymer increased firstly, and then decreased after the temperature exceeded 37℃. Under the same conditions, by changing the concentrations of AIE-active initiators and block polymer in tetrahydrofuran/water mixed solvents, we found that the fluorescence intensity of AIE-active initiator decreased with the decrease of concentration, while the change tendency of fluorescence intensity for block polymer was similar as those obtained from the temperature changes. It is feasible to investigate the self-assembly behaviors of the amphiphilic block polymer by grafting the AIE active moiety to the terminal of polymer.
Poly(N-isopropylacrylamide)(PNIPAM) is an amphiphilic thermosensitive polymer with the hydrophilic amide group and the hydrophobic isopropyl group in the side chain. A reversible phase change occurs due to intermolecular interaction with the change of outside temperature. Tetraphenylethene derivatives have advantages of easy-to-synthesize, highly efficient chemical modification feasibility, aggregation-induced emission(AIE) characteristic and high quantum yield. Therefore, a macromolecular initiator F was prepared by the polymerization of N-isopropylacrylamide through single electron transfer-living free radical polymerization with tetraphenylethene derivative as the initiator. Then styrene was used as comonomer to convert the active PNIPAM initiator to an amphiphilic block polymer G, which was characterized by gel permeation chromatography and Fourier transform infrared spectra. Using tetraphenylethene-based AIE-active initiator as the research object of reference, the photophysical properties of amphiphilic block polymer at different temperatures and concentrations were studied to correlate the AIE activity with the amphiphilic nature of the block polymer in detail. It was found that the fluorescence intensity of AIE-active initiators decreased with the increase of temperature at the same concentration of dispersion, while the fluorescence intensity of the block polymer increased firstly, and then decreased after the temperature exceeded 37℃. Under the same conditions, by changing the concentrations of AIE-active initiators and block polymer in tetrahydrofuran/water mixed solvents, we found that the fluorescence intensity of AIE-active initiator decreased with the decrease of concentration, while the change tendency of fluorescence intensity for block polymer was similar as those obtained from the temperature changes. It is feasible to investigate the self-assembly behaviors of the amphiphilic block polymer by grafting the AIE active moiety to the terminal of polymer.
2019, 36(4): 451-458
doi: 10.11944/j.issn.1000-0518.2019.04.180300
Abstract:
The compatibilization of immiscible poly(n-butyl methacrylate)(PBMA)/polystyrene(PS) blends was realized by the reaction of furan and maleimide groups. The furan-functionalized poly(n-butyl methacrylate)(P(BMA-co-FMA)) and maleimide-functionalized polystyrene(MPS) was synthesized by copolymerization and post-polymerization modification, respectively. The Diels-Alder reaction of the functionalized polymers and their blend were confirmed by nuclear magnetic resonance spectroscopy(NMR). The reaction of furan and maleimide dramatically promoted the compatibility of two components, confirmed by a homogeneous microstructure evidenced by transmission electron microscopy(TEM) observation and by the presence of a single glass transition temperature in the (P(BMA-co-FMA)/MPS blends. The properties of the blend materials could be controlled conveniently by adjusting the reaction time, and the blends transformed from tough material to brittle material gradually as the reaction processed, which was confirmed by the three point bending test.
The compatibilization of immiscible poly(n-butyl methacrylate)(PBMA)/polystyrene(PS) blends was realized by the reaction of furan and maleimide groups. The furan-functionalized poly(n-butyl methacrylate)(P(BMA-co-FMA)) and maleimide-functionalized polystyrene(MPS) was synthesized by copolymerization and post-polymerization modification, respectively. The Diels-Alder reaction of the functionalized polymers and their blend were confirmed by nuclear magnetic resonance spectroscopy(NMR). The reaction of furan and maleimide dramatically promoted the compatibility of two components, confirmed by a homogeneous microstructure evidenced by transmission electron microscopy(TEM) observation and by the presence of a single glass transition temperature in the (P(BMA-co-FMA)/MPS blends. The properties of the blend materials could be controlled conveniently by adjusting the reaction time, and the blends transformed from tough material to brittle material gradually as the reaction processed, which was confirmed by the three point bending test.
2019, 36(4): 459-464
doi: 10.11944/j.issn.1000-0518.2019.04.180264
Abstract:
By reaction of an aryl substituted imidazole dicarboxylate ligand 2-(4-cyanophenyl)-1H-imidazole-4, 5-dicarboxylic acid(p-CNPhH3IDC) with cadmium nitrate, in the presence of N-containing chelate ligand, 2, 2'-bipyridine(2, 2'-bipy), a one-dimensional chain-like coordination polymer, [Cd(p-CNPhHIDC)(2, 2'-bipy)]n(1) with mixed ligands was prepared hydrothermally. The structure and properties of the coordination polymer were studied by elemental analysis, Fourier transform infrared spectrometer and single crystal X-ray diffraction. The results show that the coordination polymer has good thermal stability under 231.6℃. After being soaked in acetonitrile, methanol, acetaldehyde and other solvents, the fluorescence intensity of coordination polymer 1 was weakened(aldehyde, CH2Cl2) or enhanced(DMF, nitrobenzene and acetone) to a certain extent. A 60 nm blue shift in its fluorescence emission, in pyridine indicated a good identification effect on pyridine by this polymer.
By reaction of an aryl substituted imidazole dicarboxylate ligand 2-(4-cyanophenyl)-1H-imidazole-4, 5-dicarboxylic acid(p-CNPhH3IDC) with cadmium nitrate, in the presence of N-containing chelate ligand, 2, 2'-bipyridine(2, 2'-bipy), a one-dimensional chain-like coordination polymer, [Cd(p-CNPhHIDC)(2, 2'-bipy)]n(1) with mixed ligands was prepared hydrothermally. The structure and properties of the coordination polymer were studied by elemental analysis, Fourier transform infrared spectrometer and single crystal X-ray diffraction. The results show that the coordination polymer has good thermal stability under 231.6℃. After being soaked in acetonitrile, methanol, acetaldehyde and other solvents, the fluorescence intensity of coordination polymer 1 was weakened(aldehyde, CH2Cl2) or enhanced(DMF, nitrobenzene and acetone) to a certain extent. A 60 nm blue shift in its fluorescence emission, in pyridine indicated a good identification effect on pyridine by this polymer.
2019, 36(4): 465-473
doi: 10.11944/j.issn.1000-0518.2019.04.180265
Abstract:
A highly dispersible nanosilver catalyst of ZnO modified Ag/SiO2 was successfully applied to the one-pot efficient synthesis of 3-methylindole from aniline and biomass-derived glycerol for the first time. The catalyst exhibited an excellent catalytic performance. The investigations of Ag-based catalysts via X-ray diffraction(XRD), transmission electron microscopy(TEM), temperature programmed reduction of H2(H2-TPR), temperature programmed desorption(TPD) of NH3 or CO2, thermogravimetric(TG) analysis and inductively coupled plasma(ICP) emission spectroscopy indicate that ZnO can enhance the interaction between silver and the support and make Ag particles be firmly anchored on the support of SiO2-ZnO. As a result, not only the dispersion of silver is increased obviously, but also the aggregation or sintering of silver nanoparticles is inhibited effectively. In addition, ZnO can also increase the acid and base sites of the Ag-based catalyst significantly, which is very beneficial to the hydrogenolysis of glycerol to 1, 2-propanediol and promoted the synthesis of 3-methylindole greatly. The yield of 3-methylindole is up to 64% at the reaction time of 16 h and is only decreased by 4% after Ag/SiO2-ZnO is reused four times. Furthermore, the synthesis mechanism of 3-methylindole from glycerol and aniline over Ag/SiO2-ZnO catalyst was proposed, in which 1, 2-propanediol is the intermediate to produce 3-methylindole.
A highly dispersible nanosilver catalyst of ZnO modified Ag/SiO2 was successfully applied to the one-pot efficient synthesis of 3-methylindole from aniline and biomass-derived glycerol for the first time. The catalyst exhibited an excellent catalytic performance. The investigations of Ag-based catalysts via X-ray diffraction(XRD), transmission electron microscopy(TEM), temperature programmed reduction of H2(H2-TPR), temperature programmed desorption(TPD) of NH3 or CO2, thermogravimetric(TG) analysis and inductively coupled plasma(ICP) emission spectroscopy indicate that ZnO can enhance the interaction between silver and the support and make Ag particles be firmly anchored on the support of SiO2-ZnO. As a result, not only the dispersion of silver is increased obviously, but also the aggregation or sintering of silver nanoparticles is inhibited effectively. In addition, ZnO can also increase the acid and base sites of the Ag-based catalyst significantly, which is very beneficial to the hydrogenolysis of glycerol to 1, 2-propanediol and promoted the synthesis of 3-methylindole greatly. The yield of 3-methylindole is up to 64% at the reaction time of 16 h and is only decreased by 4% after Ag/SiO2-ZnO is reused four times. Furthermore, the synthesis mechanism of 3-methylindole from glycerol and aniline over Ag/SiO2-ZnO catalyst was proposed, in which 1, 2-propanediol is the intermediate to produce 3-methylindole.
2019, 36(4): 474-481
doi: 10.11944/j.issn.1000-0518.2019.04.180236
Abstract:
In order to optimize the structure of BiOCl photocatalyst, improve its adsorption performance to organic pollutants, and enhance photocatalytic activity, BiOCl/montmorillonite(MMT) composite photocatalyst was prepared by ultrasonic assisted chemical precipitation method. The influence of composite mass fraction of montmorillonite(w(MMT)) on its photoactivity was investigated. The characterization results of XRD, SEM, FTIR and DRS show that the obtained composite catalyst has a microsphere structure with a band gap of 3.24 eV. With the increase of w(MMT), the microsphere structure of the composite catalyst is gradually destroyed, but the band gap energy does not change significantly. The adsorption and photocatalytic activity of the composite catalyst were investigated with 8-hydroxyquinoline as the target. The results show that with increase of w(MMT), the adsorption and photocatalytic oxidation activity of 8-hydroxyquinoline is gradually increased, which can be attributed to the increased specific surface area and reduced photo-generated carriers' recombination efficiency due to the composite of montmorillonite. When w(MMT) is 15%, the adsorption and photocatalytic performance of the catalyst are optimal. After 50 min of illumination, the degradation rate of 8-hydroxyquinoline reaches 85.6%, and the mineralization rate reaches 51.0%. Photogenerated holes and superoxide radical anions are the main oxidation active species. The composite catalyst also efficiently degrades catechol and p-aminobenzoic acid. At the same time, the composite photocatalyst exhibits strong chemical stability, indicating that it has strong practical application value and can be used for treating industrial wastewater containing organic phenolic pollutants.
In order to optimize the structure of BiOCl photocatalyst, improve its adsorption performance to organic pollutants, and enhance photocatalytic activity, BiOCl/montmorillonite(MMT) composite photocatalyst was prepared by ultrasonic assisted chemical precipitation method. The influence of composite mass fraction of montmorillonite(w(MMT)) on its photoactivity was investigated. The characterization results of XRD, SEM, FTIR and DRS show that the obtained composite catalyst has a microsphere structure with a band gap of 3.24 eV. With the increase of w(MMT), the microsphere structure of the composite catalyst is gradually destroyed, but the band gap energy does not change significantly. The adsorption and photocatalytic activity of the composite catalyst were investigated with 8-hydroxyquinoline as the target. The results show that with increase of w(MMT), the adsorption and photocatalytic oxidation activity of 8-hydroxyquinoline is gradually increased, which can be attributed to the increased specific surface area and reduced photo-generated carriers' recombination efficiency due to the composite of montmorillonite. When w(MMT) is 15%, the adsorption and photocatalytic performance of the catalyst are optimal. After 50 min of illumination, the degradation rate of 8-hydroxyquinoline reaches 85.6%, and the mineralization rate reaches 51.0%. Photogenerated holes and superoxide radical anions are the main oxidation active species. The composite catalyst also efficiently degrades catechol and p-aminobenzoic acid. At the same time, the composite photocatalyst exhibits strong chemical stability, indicating that it has strong practical application value and can be used for treating industrial wastewater containing organic phenolic pollutants.
2019, 36(4): 482-488
doi: 10.11944/j.issn.1000-0518.2019.04.180294
Abstract:
A novel class of lignin-based porous carbon(PC) for supercapacitor electrode was successfully fabricated using lignin as the carbon precursor and NaCl as the template by reflux at low temperature and calcination at high temperature. The results indicate that the porous structures of the obtained samples can be regulated by varying the calcination temperature, where the surface area and pore volume of samples firstly increases then decreases with the increase of the temperature. As a result, the specific surface area of the obtained sample can be tailored in the range of 548~600 m2/g. PC calcinated at 700℃ has the largest surface area and exhibits the highest specific capacitance of 252 F/g and an effective areal capacitance of 31.2 μF/cm2 in 6 mol/L KOH solution. NaCl template can be cycled by washing from the products. This paper proposes a green method for synthesis of high value-added porous carbon from waste materials.
A novel class of lignin-based porous carbon(PC) for supercapacitor electrode was successfully fabricated using lignin as the carbon precursor and NaCl as the template by reflux at low temperature and calcination at high temperature. The results indicate that the porous structures of the obtained samples can be regulated by varying the calcination temperature, where the surface area and pore volume of samples firstly increases then decreases with the increase of the temperature. As a result, the specific surface area of the obtained sample can be tailored in the range of 548~600 m2/g. PC calcinated at 700℃ has the largest surface area and exhibits the highest specific capacitance of 252 F/g and an effective areal capacitance of 31.2 μF/cm2 in 6 mol/L KOH solution. NaCl template can be cycled by washing from the products. This paper proposes a green method for synthesis of high value-added porous carbon from waste materials.
