An impedance immunosensor based on O-phenylenediamine modified gold electrode for the determination of phytohormone abscisic acid(ABA) was proposed.The operating pH,absorption time,absorption temperature and concentra...An impedance immunosensor based on O-phenylenediamine modified gold electrode for the determination of phytohormone abscisic acid(ABA) was proposed.The operating pH,absorption time,absorption temperature and concentration of anti-ABA antibody were investigated to optimize the analytical performance.The calibration curve for the determination of ABA was obtained from this impedance immunosensor under optimal conditions.The results showed that the detection limit at about 1 ng/mL in the range of 10-5000 ng/mL...展开更多
Ionic liquid like 1-ethyl-3-methylimidazolium bromine ([EMIM]Br) has been used as electrolyte for the electropolymerization of O-phenylenediamine at glassy carbon electrode by cyclic voltammetry. It is found that poly...Ionic liquid like 1-ethyl-3-methylimidazolium bromine ([EMIM]Br) has been used as electrolyte for the electropolymerization of O-phenylenediamine at glassy carbon electrode by cyclic voltammetry. It is found that poly (O-phenylenediamine) film modified electrode has favorable electrochemical activity in acid solution.展开更多
Hemeproteins encapsulated in reversed micelle formulated with di-2-ethylhexyl sulfosuccinate(AOT) was found to catalyze the polymerization of o-phenylenediamine(o-PDA) with hydrogen peroxide, whereas o-PDA catalyzed...Hemeproteins encapsulated in reversed micelle formulated with di-2-ethylhexyl sulfosuccinate(AOT) was found to catalyze the polymerization of o-phenylenediamine(o-PDA) with hydrogen peroxide, whereas o-PDA catalyzed by hemeproteins dissolved in water could only form its trimers. As the nanostructural environment in reversed micelle acts as a certain orientation surrounding medium, it offers a strong electrostatic field that alters the reductive potential of Fe 3+/Fe 2+(E m7) in the heme of hemeproteins and thus increases the catalytic activity of peroxidase accordingly. According to the results of UV-Vis, 1H NMR and FTIR, the polymer catalyzed by hemoglobin(Hb) in reversed micelle was presumed to be constructed of lines and trapeziforms alternatively.展开更多
,3-Disubstituted quinoxalines were synthesized from α-acetylthioformanilide and ophenylenediamine. Further studies sliowed that there existed competitive re- actions. One was a condensation reaction which produced su...,3-Disubstituted quinoxalines were synthesized from α-acetylthioformanilide and ophenylenediamine. Further studies sliowed that there existed competitive re- actions. One was a condensation reaction which produced substituted quinoxaline and the other was a substitution reaction which produced substituted quinoxaline-2- thione.展开更多
Instead of 2-(aroylmethylene)benzimidazolines 3 or 2-(aroyl-methyl)benzimidazoles 4, 4-aryl-2, 3-dihydro-1H-1, 5-benzodiazepin-2-ones 5 were obtained exclusively from the reaction of o-phenylenediamine (1) and ethyl a...Instead of 2-(aroylmethylene)benzimidazolines 3 or 2-(aroyl-methyl)benzimidazoles 4, 4-aryl-2, 3-dihydro-1H-1, 5-benzodiazepin-2-ones 5 were obtained exclusively from the reaction of o-phenylenediamine (1) and ethyl aroylacetates 2 in the presence of a catalytic amount of potassium hydroxide.展开更多
The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in ab...The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in absence of photosensitizers. Herein, we report the systematic study of the interaction between the oxidized form bqdi ligand, tris-(o-benzoquinonediimine) with divalent first-row transition metal series using DFT calculations. The lowest energy structures, bond length, binding energies, frontier molecular orbital analysis, natural bond orbitals, and global reactivity descriptor were calculated using B3LYP/6-311G(d,P) level of theory. The time dependent-DFT at the CAM-B3LYP/6-311+G(d,p) level of theory was applied to determine the electronic structures and the optical spectra. The theoretical binding trend of the divalent first-row transition metal series is decreasing as follows: Cu >Ti > V > Co > Ni > Fe > Cr > Zn >Mn. Among them, the binding potency of iron (II) by the bqdi ligand was not predominantly sturdy as compared to other first-row divalent transition metal ions. The origin of strong coordination with Fe(II) is attributed to its extra capability to induce covalent coordination of bqdi ligands. The complex exhibited two strong peaks at 370 nm and 452 nm, due to the HOMO-3 to LUMO+1 and HOMO-1 to LUMO transitions, respectively. Natural bond orbital analysis showed that the major interaction happens between the N lone pair electrons of the ligand with an anti-bonding orbital of metal ions, in which Ti showed the highest interaction energy than other metal ions. The present systemic DFT study of bqdi ligands with the first-row transition metals strongly encourages the future establishment of photochemical hydrogen production in absence of photosensitizers.展开更多
Glyoxylic acid （5 mol%） performs as a novel highly water-soluble catalyst for the synthesis of 2-aryl-l-arylmethyl-lH- benzimidazoles from a wide range of substituted o-phenylenediamines and various substituted alde...Glyoxylic acid （5 mol%） performs as a novel highly water-soluble catalyst for the synthesis of 2-aryl-l-arylmethyl-lH- benzimidazoles from a wide range of substituted o-phenylenediamines and various substituted aldehydes in good to excellent isolated yields （85-95%） using water as solvent at ambient temperature. The remarkable advantages offered by this method are easily and inexpensive available catalyst, simple procedure, mild conditions, much faster （20--40 rain） reactions and excellent yields of products.展开更多
1,5-Benzodiazepine derivatives have been synthesized by the condensation of o-phenylenediamines and ketones in the presence of boric acid as catalyst under mild conditions. This method is simple, environmentally benig...1,5-Benzodiazepine derivatives have been synthesized by the condensation of o-phenylenediamines and ketones in the presence of boric acid as catalyst under mild conditions. This method is simple, environmentally benign and high yielding. ？2009 Chun Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
MgBr2 performs as a novel catalyst for the synthesis of various 1,5-benzodiazepine derivatives from wide range of substituted o- phenylenediamines and various ketones in good to excellent isolated yields （93-98%） us...MgBr2 performs as a novel catalyst for the synthesis of various 1,5-benzodiazepine derivatives from wide range of substituted o- phenylenediamines and various ketones in good to excellent isolated yields （93-98%） using water as solvent at ambient temperature. Several solvents were examined for this reaction; however, in terms of reaction yield and time, water was found to be the optimum solvent. The remarkable advantages offered by this method are easily and inexpensive available catalyst, simple procedure, mild conditions, much faster （40-60 man） reactions and good to excellent yields of products.展开更多
Under visible light illumination, 2,3-diaminophenazine （DAPN） was generated from the oxidation of o-phenylenediamine （OPDA） in Fe^3＋/H2O2 solution. Hydroxyl radical （＊OH） produced in this system was determined...Under visible light illumination, 2,3-diaminophenazine （DAPN） was generated from the oxidation of o-phenylenediamine （OPDA） in Fe^3＋/H2O2 solution. Hydroxyl radical （＊OH） produced in this system was determined by directly measuring the concentration of DAPN. In comparison with the traditional methods, the determination is more accurate and simple.展开更多
A simple and versatile method for the synthesis of 1,5-benzodiazepines from o-phenylenediamine and ketones in the presence of solvents and under solvent-free conditions that used an amorphous mesoporous iron aluminoph...A simple and versatile method for the synthesis of 1,5-benzodiazepines from o-phenylenediamine and ketones in the presence of solvents and under solvent-free conditions that used an amorphous mesoporous iron aluminophosphate as catalyst was developed.High yields with excellent selectivity were obtained with a wide variety of ketones under mild reaction conditions.The catalyst had the advantages of ease of preparation,ease of handling,simple recovery,reusability,non toxicity,and being inexpensive.展开更多
A facile method of preparation of benzimidazoles by microwave irradiation was described. The mixtures of o-phenylenediamine and carboxylic acids were heated by microwave irradiation, to give 2-substituted benzimidazol...A facile method of preparation of benzimidazoles by microwave irradiation was described. The mixtures of o-phenylenediamine and carboxylic acids were heated by microwave irradiation, to give 2-substituted benzimidazoles with yields of 49%～93%. The reaction time was shortened to 3～6 min. However, the reaction of ethylenediamine with carboxylic acids did not give imidazoles but the N,N-diacyl ethylenediamines. The alphatic diamines lacked the activity to form imidazole ring. With adipic acid, intermolecular acylation took place to afford poly(ethylene adipamide).展开更多
The title compound 2 was synthesized by the reaction of 3-keto-D-xylose with O-C6H4NH2NH2 and characterized by IR, NMR and HRMS, and its crystal structure was determined by X-ray diffraction analysis. The crystal is o...The title compound 2 was synthesized by the reaction of 3-keto-D-xylose with O-C6H4NH2NH2 and characterized by IR, NMR and HRMS, and its crystal structure was determined by X-ray diffraction analysis. The crystal is of orthorhombic system （C21H22N2O5, Mr = 382.41）, space group P2 1 2 1 2 1 with α = 10.140（2）, b = 10.802（2）, c = 17.840（4） A, β = 90°, V = 1954.1（7）A^3, Z = 4, Dc = 1.300 g/cm^3, F（000） = 808, μ = 0.094 mm^-1, the final R = 0.0354 and wR = 0.0514 for 1924 observed reflections （I 〉 2σ（I））. One intermolecular and one intramolecular hydrogen bonds were found. The absolute configuration of this molecule was confirmed by comparison with that of the original material.展开更多
The in situ ultraviolet-visible (UV-Vis) spectroelectrochemical study on the copolymerization of diphenylamine (DPA) and o-phenylenediamine (OPD) has been performed at a constant potential of 0.8 V using indium tin ox...The in situ ultraviolet-visible (UV-Vis) spectroelectrochemical study on the copolymerization of diphenylamine (DPA) and o-phenylenediamine (OPD) has been performed at a constant potential of 0.8 V using indium tin oxide (ITO)-coated glass electrodes as working electrode. And also, as a comparison, the electrochemical homopolymerizations of DPA and OPD have been investigated by using the in situ spectroelectrochemical technique. The intermediate species generated during the electrochemical homopoly-merization of DPA and OPD, and the copolymerization of DPA with OPD have been identified by using the in situ spectroelectrochemical procedure. The results reveal the formation of an intermediate in the initial stage of copolymerization through the cross-reaction of the cation radicals of DPA and OPD, and the absorption peak located at 538 nm in the UV–Vis spectra is assigned to this intermediate. To further investigate the copolymerization of DPA with OPD, cyclic voltammetry (CV) has been used to study the electrochemical homopolymerization of DPA and OPD and also the copolymerization of DPA and OPD with different concentration ratios in solution. The different voltammetric characteristics between the homopolymerization and copolymerization processes exhibit the occurrence of the copolymerization, and the difference between the copolymerization of DPA and OPD with different concentration ratios shows the dependence of the copoly-merization on the concentrations of DPA and OPD. The copolymer has also been characterized by Fourier transform infrared spectroscopy (FT-IR).展开更多
Here we demonstrate the synthesis of multifunctionalised benzimidazoles through the coupling of o-phenylenediamine with aldehydes by using Copper (II) hydroxide as an efficient solid catalyst in methanol at room tempe...Here we demonstrate the synthesis of multifunctionalised benzimidazoles through the coupling of o-phenylenediamine with aldehydes by using Copper (II) hydroxide as an efficient solid catalyst in methanol at room temperature. The Copper (II) hydroxide solid catalyst gave better yields (80%-99%) in short reaction time (4-8 h). These commercially available cheap catalysts are more active than many reported expensive heterogeneous catalysts. Using the Copper hydroxide fresh catalyst, the yield of product 3a was 98%, while the recovered catalyst in the three subsequent cycles gave the yield of 94%, 90% and 88% respectively.展开更多
A simple, environmental-friendly, and practical method for the synthesis of benzodiazepine derivatives through a reaction of substituted o-phenylenediamines with alkyl propiolates has been developed. The reactions gen...A simple, environmental-friendly, and practical method for the synthesis of benzodiazepine derivatives through a reaction of substituted o-phenylenediamines with alkyl propiolates has been developed. The reactions generated the 1,5-benzodiazepines in good to excellent yields in the presence of catalytic amount of In（OTf）3 under sol- vent-free reaction conditions.展开更多
In this study, we report a novel magnetic biomimetic nanozyme(Fe3O4@Cu/GMP(guanosine5′-monophosphate)) with high laccase-like activity, which could oxidize toxic ophenylenediamine(OPD) and remove phenolic compounds.T...In this study, we report a novel magnetic biomimetic nanozyme(Fe3O4@Cu/GMP(guanosine5′-monophosphate)) with high laccase-like activity, which could oxidize toxic ophenylenediamine(OPD) and remove phenolic compounds.The magnetic laccase-like nanozyme was readily obtained via complexed Cu2+and GMP that grew on the surface of magnetic Fe3O4 nanoparticles.The prepared Fe3O4@Cu/GMP catalyst could be magnetically recycled for at least five cycles while still retaining above 70% activity.As a laccase mimic,Fe3O4@Cu/GMP had more activity and robust stability than natural laccase for the oxidization of OPD.Fe3O4@Cu/GMP retained about 90% residual activity at 90℃ and showed little change at pH 3–9, and the nanozyme kept its excellent activity after long-term storage.Meanwhile, Fe3O4@Cu/GMP had better activity for removing phenolic compounds, and the removal of naphthol was more than 95%.Consequently, the proposed Fe3O4@Cu/GMP nanozyme shows potential for use as a robust catalyst for applications in environmental remediation.展开更多
Vanadyl acetylacetonate,VO（acac）_2,has been found to be very effective catalyst for synthesis of a variety of benzimidazoles under solvent-free condition.The methodology involves the exposure of a mixture of o-pheny...Vanadyl acetylacetonate,VO（acac）_2,has been found to be very effective catalyst for synthesis of a variety of benzimidazoles under solvent-free condition.The methodology involves the exposure of a mixture of o-phenylenediamine and a selected aromatic carboxylic acid/aldehyde to microwave radiation without the use of any solvent or supporting agents.The benzimidazoles were obtained in quick time with high yields.展开更多
Alkali-ion batteries,including potassium-ion batter-ies,lithium-ion batteries,and sodium-ion batteries are important energy storage devices;however,with the cation size increased,there exists a great challenge for an ...Alkali-ion batteries,including potassium-ion batter-ies,lithium-ion batteries,and sodium-ion batteries are important energy storage devices;however,with the cation size increased,there exists a great challenge for an inorganic electrode material to accommodate the different properties of the alkali-ion.Herein,as a proof-of-concept experiment,an imine-rich poly(o-phenylenediamine)(PoPD)is syn-thesized through a rational controllable oxidization.Due to the abundance of active sites and ladder-conjugated structure,PoPD in the optimized oxida-tion state endows alkali-ion batteries with a stable cyclability at high capacity.The highly reversible redox performance of PoPD with alkali-ions is verified by theoretical calculations and demonstrat-ed as a trifunctional electrode material(537 and 307 mAh·g^(−1) for Li and Na storage capacity after 300 cycles,respectively),especially for successful application in potassium storage(450 mAh·g^(−1) after 205 cycles),and provides compelling evidence for the wide application of organic electrode materials.展开更多
Normalizing inflamed soils including reactive oxygen species(ROS),nitric oxide(NO),cellfree DNA,and regulating infammation-related seeds such as macrophages,neutrophils,fibroblasts,represent a promising strategy to ma...Normalizing inflamed soils including reactive oxygen species(ROS),nitric oxide(NO),cellfree DNA,and regulating infammation-related seeds such as macrophages,neutrophils,fibroblasts,represent a promising strategy to maintain synovial tissue homeostasis for rheumatoid arthritis(RA)treatment.Herein,ROS scavenging amphiphilic block copolymer PEGylated bilirubin and NO-scavenging PEGylated o-phenylenediamine were fabricated to self-assemble into a dually responsive nanoparticle loaded with JAK inhibitor notopterol(Not@BR/oPDA-PEG,NBOP NPs).The simultaneous ROS and NO depletion combined with JAK-STAT pathway inhibition could not only promote M2 polarization to reduce further ROS and NO generation,but also decrease cytokines and chemokines to prevent immune cell recruitment.Specifically,NBOP NPs responded to high level ROS and NO,and disintegrated to release notopterol in inflamed joints as the hydrophobic heads BR and oPDA were transformed into hydrophilic ones.The released notopterol could inhibit the JAK-STAT pathway of infammatory cells to reduce the secretion of pro-inflammatory cytokines and chemokines.This strategy represented an effective way to regulate RA soils and seeds through breaking the positive feedback loop of inflammation aggravation,achieving an excellent anti-RA efficacy in a collagen-induced arthritis rat model.Taken together,our work offered a reference to adjust RA soils and seeds for enhanced RA treatment.展开更多
基金supported by the National Natural Science Foundation of China(No.90817101,30670190 and 3060049)
文摘An impedance immunosensor based on O-phenylenediamine modified gold electrode for the determination of phytohormone abscisic acid(ABA) was proposed.The operating pH,absorption time,absorption temperature and concentration of anti-ABA antibody were investigated to optimize the analytical performance.The calibration curve for the determination of ABA was obtained from this impedance immunosensor under optimal conditions.The results showed that the detection limit at about 1 ng/mL in the range of 10-5000 ng/mL...
文摘Ionic liquid like 1-ethyl-3-methylimidazolium bromine ([EMIM]Br) has been used as electrolyte for the electropolymerization of O-phenylenediamine at glassy carbon electrode by cyclic voltammetry. It is found that poly (O-phenylenediamine) film modified electrode has favorable electrochemical activity in acid solution.
文摘Hemeproteins encapsulated in reversed micelle formulated with di-2-ethylhexyl sulfosuccinate(AOT) was found to catalyze the polymerization of o-phenylenediamine(o-PDA) with hydrogen peroxide, whereas o-PDA catalyzed by hemeproteins dissolved in water could only form its trimers. As the nanostructural environment in reversed micelle acts as a certain orientation surrounding medium, it offers a strong electrostatic field that alters the reductive potential of Fe 3+/Fe 2+(E m7) in the heme of hemeproteins and thus increases the catalytic activity of peroxidase accordingly. According to the results of UV-Vis, 1H NMR and FTIR, the polymer catalyzed by hemoglobin(Hb) in reversed micelle was presumed to be constructed of lines and trapeziforms alternatively.
文摘,3-Disubstituted quinoxalines were synthesized from α-acetylthioformanilide and ophenylenediamine. Further studies sliowed that there existed competitive re- actions. One was a condensation reaction which produced substituted quinoxaline and the other was a substitution reaction which produced substituted quinoxaline-2- thione.
基金This work was supported by the National Natural Science Foundation of China.
文摘Instead of 2-(aroylmethylene)benzimidazolines 3 or 2-(aroyl-methyl)benzimidazoles 4, 4-aryl-2, 3-dihydro-1H-1, 5-benzodiazepin-2-ones 5 were obtained exclusively from the reaction of o-phenylenediamine (1) and ethyl aroylacetates 2 in the presence of a catalytic amount of potassium hydroxide.
文摘The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in absence of photosensitizers. Herein, we report the systematic study of the interaction between the oxidized form bqdi ligand, tris-(o-benzoquinonediimine) with divalent first-row transition metal series using DFT calculations. The lowest energy structures, bond length, binding energies, frontier molecular orbital analysis, natural bond orbitals, and global reactivity descriptor were calculated using B3LYP/6-311G(d,P) level of theory. The time dependent-DFT at the CAM-B3LYP/6-311+G(d,p) level of theory was applied to determine the electronic structures and the optical spectra. The theoretical binding trend of the divalent first-row transition metal series is decreasing as follows: Cu >Ti > V > Co > Ni > Fe > Cr > Zn >Mn. Among them, the binding potency of iron (II) by the bqdi ligand was not predominantly sturdy as compared to other first-row divalent transition metal ions. The origin of strong coordination with Fe(II) is attributed to its extra capability to induce covalent coordination of bqdi ligands. The complex exhibited two strong peaks at 370 nm and 452 nm, due to the HOMO-3 to LUMO+1 and HOMO-1 to LUMO transitions, respectively. Natural bond orbital analysis showed that the major interaction happens between the N lone pair electrons of the ligand with an anti-bonding orbital of metal ions, in which Ti showed the highest interaction energy than other metal ions. The present systemic DFT study of bqdi ligands with the first-row transition metals strongly encourages the future establishment of photochemical hydrogen production in absence of photosensitizers.
基金Head,Department of Chemistry,Vinayakrao Patil Mahavidyala Vaijapur 423701(M.S.),India,for partial support of this work.
文摘Glyoxylic acid （5 mol%） performs as a novel highly water-soluble catalyst for the synthesis of 2-aryl-l-arylmethyl-lH- benzimidazoles from a wide range of substituted o-phenylenediamines and various substituted aldehydes in good to excellent isolated yields （85-95%） using water as solvent at ambient temperature. The remarkable advantages offered by this method are easily and inexpensive available catalyst, simple procedure, mild conditions, much faster （20--40 rain） reactions and excellent yields of products.
文摘1,5-Benzodiazepine derivatives have been synthesized by the condensation of o-phenylenediamines and ketones in the presence of boric acid as catalyst under mild conditions. This method is simple, environmentally benign and high yielding. ？2009 Chun Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
文摘MgBr2 performs as a novel catalyst for the synthesis of various 1,5-benzodiazepine derivatives from wide range of substituted o- phenylenediamines and various ketones in good to excellent isolated yields （93-98%） using water as solvent at ambient temperature. Several solvents were examined for this reaction; however, in terms of reaction yield and time, water was found to be the optimum solvent. The remarkable advantages offered by this method are easily and inexpensive available catalyst, simple procedure, mild conditions, much faster （40-60 man） reactions and good to excellent yields of products.
基金supported by the National Basic Research Program of China(No. 2008CB417206)the National Natural Science Foundation of China(No.20877048)
文摘Under visible light illumination, 2,3-diaminophenazine （DAPN） was generated from the oxidation of o-phenylenediamine （OPDA） in Fe^3＋/H2O2 solution. Hydroxyl radical （＊OH） produced in this system was determined by directly measuring the concentration of DAPN. In comparison with the traditional methods, the determination is more accurate and simple.
文摘A simple and versatile method for the synthesis of 1,5-benzodiazepines from o-phenylenediamine and ketones in the presence of solvents and under solvent-free conditions that used an amorphous mesoporous iron aluminophosphate as catalyst was developed.High yields with excellent selectivity were obtained with a wide variety of ketones under mild reaction conditions.The catalyst had the advantages of ease of preparation,ease of handling,simple recovery,reusability,non toxicity,and being inexpensive.
文摘A facile method of preparation of benzimidazoles by microwave irradiation was described. The mixtures of o-phenylenediamine and carboxylic acids were heated by microwave irradiation, to give 2-substituted benzimidazoles with yields of 49%～93%. The reaction time was shortened to 3～6 min. However, the reaction of ethylenediamine with carboxylic acids did not give imidazoles but the N,N-diacyl ethylenediamines. The alphatic diamines lacked the activity to form imidazole ring. With adipic acid, intermolecular acylation took place to afford poly(ethylene adipamide).
基金supported by the National Natural Science Foundation of China (No. 20472075)
文摘The title compound 2 was synthesized by the reaction of 3-keto-D-xylose with O-C6H4NH2NH2 and characterized by IR, NMR and HRMS, and its crystal structure was determined by X-ray diffraction analysis. The crystal is of orthorhombic system （C21H22N2O5, Mr = 382.41）, space group P2 1 2 1 2 1 with α = 10.140（2）, b = 10.802（2）, c = 17.840（4） A, β = 90°, V = 1954.1（7）A^3, Z = 4, Dc = 1.300 g/cm^3, F（000） = 808, μ = 0.094 mm^-1, the final R = 0.0354 and wR = 0.0514 for 1924 observed reflections （I 〉 2σ（I））. One intermolecular and one intramolecular hydrogen bonds were found. The absolute configuration of this molecule was confirmed by comparison with that of the original material.
文摘The in situ ultraviolet-visible (UV-Vis) spectroelectrochemical study on the copolymerization of diphenylamine (DPA) and o-phenylenediamine (OPD) has been performed at a constant potential of 0.8 V using indium tin oxide (ITO)-coated glass electrodes as working electrode. And also, as a comparison, the electrochemical homopolymerizations of DPA and OPD have been investigated by using the in situ spectroelectrochemical technique. The intermediate species generated during the electrochemical homopoly-merization of DPA and OPD, and the copolymerization of DPA with OPD have been identified by using the in situ spectroelectrochemical procedure. The results reveal the formation of an intermediate in the initial stage of copolymerization through the cross-reaction of the cation radicals of DPA and OPD, and the absorption peak located at 538 nm in the UV–Vis spectra is assigned to this intermediate. To further investigate the copolymerization of DPA with OPD, cyclic voltammetry (CV) has been used to study the electrochemical homopolymerization of DPA and OPD and also the copolymerization of DPA and OPD with different concentration ratios in solution. The different voltammetric characteristics between the homopolymerization and copolymerization processes exhibit the occurrence of the copolymerization, and the difference between the copolymerization of DPA and OPD with different concentration ratios shows the dependence of the copoly-merization on the concentrations of DPA and OPD. The copolymer has also been characterized by Fourier transform infrared spectroscopy (FT-IR).
文摘Here we demonstrate the synthesis of multifunctionalised benzimidazoles through the coupling of o-phenylenediamine with aldehydes by using Copper (II) hydroxide as an efficient solid catalyst in methanol at room temperature. The Copper (II) hydroxide solid catalyst gave better yields (80%-99%) in short reaction time (4-8 h). These commercially available cheap catalysts are more active than many reported expensive heterogeneous catalysts. Using the Copper hydroxide fresh catalyst, the yield of product 3a was 98%, while the recovered catalyst in the three subsequent cycles gave the yield of 94%, 90% and 88% respectively.
基金Project supported bythe National Natural Science Foundation of China（Nol 20972057）.
文摘A simple, environmental-friendly, and practical method for the synthesis of benzodiazepine derivatives through a reaction of substituted o-phenylenediamines with alkyl propiolates has been developed. The reactions generated the 1,5-benzodiazepines in good to excellent yields in the presence of catalytic amount of In（OTf）3 under sol- vent-free reaction conditions.
基金financial support from the National Natural Science Foundation of China (No.21878014)the Beijing Municipal Natural Science Foundation (No.2182019)+2 种基金the Beijing Natural Science Foundation–Beijing Municipal Education Commission Joint Funding project (No.KZ201710020014)the Double First-rate Program (No.ylkxj03)the Overseas Expertise Introduction Project for Discipline Innovation (No.B13005).
文摘In this study, we report a novel magnetic biomimetic nanozyme(Fe3O4@Cu/GMP(guanosine5′-monophosphate)) with high laccase-like activity, which could oxidize toxic ophenylenediamine(OPD) and remove phenolic compounds.The magnetic laccase-like nanozyme was readily obtained via complexed Cu2+and GMP that grew on the surface of magnetic Fe3O4 nanoparticles.The prepared Fe3O4@Cu/GMP catalyst could be magnetically recycled for at least five cycles while still retaining above 70% activity.As a laccase mimic,Fe3O4@Cu/GMP had more activity and robust stability than natural laccase for the oxidization of OPD.Fe3O4@Cu/GMP retained about 90% residual activity at 90℃ and showed little change at pH 3–9, and the nanozyme kept its excellent activity after long-term storage.Meanwhile, Fe3O4@Cu/GMP had better activity for removing phenolic compounds, and the removal of naphthol was more than 95%.Consequently, the proposed Fe3O4@Cu/GMP nanozyme shows potential for use as a robust catalyst for applications in environmental remediation.
基金the Department of Science and Technology(DST),New Delhi,Government of India for providing financial support(SR/FTP/CS-100/2007)
文摘Vanadyl acetylacetonate,VO（acac）_2,has been found to be very effective catalyst for synthesis of a variety of benzimidazoles under solvent-free condition.The methodology involves the exposure of a mixture of o-phenylenediamine and a selected aromatic carboxylic acid/aldehyde to microwave radiation without the use of any solvent or supporting agents.The benzimidazoles were obtained in quick time with high yields.
基金This work was financially supported by the National Natural Science Foundation of China(21725103and51472232),JCKY2016130B010,Jilin Province Science and Technolo-gy Development Plan Funding Project(20180101203JC and 20160101289JC)Changchun Science and Tech-nologyDevelopmentPlanFundingProject(18DY012).
文摘Alkali-ion batteries,including potassium-ion batter-ies,lithium-ion batteries,and sodium-ion batteries are important energy storage devices;however,with the cation size increased,there exists a great challenge for an inorganic electrode material to accommodate the different properties of the alkali-ion.Herein,as a proof-of-concept experiment,an imine-rich poly(o-phenylenediamine)(PoPD)is syn-thesized through a rational controllable oxidization.Due to the abundance of active sites and ladder-conjugated structure,PoPD in the optimized oxida-tion state endows alkali-ion batteries with a stable cyclability at high capacity.The highly reversible redox performance of PoPD with alkali-ions is verified by theoretical calculations and demonstrat-ed as a trifunctional electrode material(537 and 307 mAh·g^(−1) for Li and Na storage capacity after 300 cycles,respectively),especially for successful application in potassium storage(450 mAh·g^(−1) after 205 cycles),and provides compelling evidence for the wide application of organic electrode materials.
基金supported by the National Natural Science Foundation of China(51922111,82204724)the Science and Technology Development Fund,Macao SAR(File no.0124/2019/A3 and SKL-QRCM(UM)-2023-2025,China)the University of Macao(File no.MYRG2022-00203-ICMS,China).
文摘Normalizing inflamed soils including reactive oxygen species(ROS),nitric oxide(NO),cellfree DNA,and regulating infammation-related seeds such as macrophages,neutrophils,fibroblasts,represent a promising strategy to maintain synovial tissue homeostasis for rheumatoid arthritis(RA)treatment.Herein,ROS scavenging amphiphilic block copolymer PEGylated bilirubin and NO-scavenging PEGylated o-phenylenediamine were fabricated to self-assemble into a dually responsive nanoparticle loaded with JAK inhibitor notopterol(Not@BR/oPDA-PEG,NBOP NPs).The simultaneous ROS and NO depletion combined with JAK-STAT pathway inhibition could not only promote M2 polarization to reduce further ROS and NO generation,but also decrease cytokines and chemokines to prevent immune cell recruitment.Specifically,NBOP NPs responded to high level ROS and NO,and disintegrated to release notopterol in inflamed joints as the hydrophobic heads BR and oPDA were transformed into hydrophilic ones.The released notopterol could inhibit the JAK-STAT pathway of infammatory cells to reduce the secretion of pro-inflammatory cytokines and chemokines.This strategy represented an effective way to regulate RA soils and seeds through breaking the positive feedback loop of inflammation aggravation,achieving an excellent anti-RA efficacy in a collagen-induced arthritis rat model.Taken together,our work offered a reference to adjust RA soils and seeds for enhanced RA treatment.
