A new approach for assembling amperometric mushroom pulp tissue based membrane electrode for determination of L tyrosine analysis is proposed. Ferrocene is used as a mediator of electron transfer between tyrosinase ...A new approach for assembling amperometric mushroom pulp tissue based membrane electrode for determination of L tyrosine analysis is proposed. Ferrocene is used as a mediator of electron transfer between tyrosinase in mushroom tissue and a graphite electrode. The optimal operation conditions are studied. The linear response range of the biosensor is 2 0×10 -4 to 4 5×10 -3 mol·L -1 with response time of less than 5 min and lifetime of at least 30 d. The biosensor can be applied to practical sample analysis.展开更多
Nation-membrane-based proton exchange fuel cells （PEMFCs） typically operate at below 100 ℃. However, H3PO4-doped polybenzimidazole （PBI）-based PEMFCs can operate at 100-200 ℃. This is advantageous because of acc...Nation-membrane-based proton exchange fuel cells （PEMFCs） typically operate at below 100 ℃. However, H3PO4-doped polybenzimidazole （PBI）-based PEMFCs can operate at 100-200 ℃. This is advantageous because of accelerated reaction rates and enhanced tolerance to poisons such as CO and S02, which can arise from reformed gas or the atmosphere. However, the strong adsorption of phosphoric anions on the Pt surface dramatically decreases the electrocatalytic activity. This study exploits the ＂third-body effect＂, in which a small amount of organic molecules are pre-adsorbed on the Pt surface to inhibit the adsorption of phosphoric anions. Pre-adsorbate species inhibit the ad- sorption of phosphoric anions, but can also partially occlude active sites. Thus, the optimum pre-adsorbate coverage is studied by correlating the oxygen reduction reaction （ORR） activity of Pt with pre-adsorbate coverage on the Pt surface. The influence of the pre-adsorbate molecule length is investigated using the organic amines, butylamine, octylamine, and dodecylamine, in both 0.1 mol/L HCI04 and 0.1 mol/L H3P04. Such amines readily bond to the Pt surface. In aqueous HCI04 electrolyte, the ORR activity of Pt decreases monotonically with increasing pre-adsorbate coverage. In aqueous H3P04 electrolyte, the ORR activity of Pt initially increases and then decreases with in- creasing pre-adsorbate coverage. The maximum ORR activity in H3P04 occurs at a pre-adsorbate coverage of around 20%. The effect of molecular length of the pre-adsorbate is negligible, but its coverage strongly affects the degree to which phosphoric anion adsorption is inhibited. Butylamine adsorbs to Pt at partial active sites, which decreases the electrochemically active surface area. Ad- sorbed butylamine may also modify the electronic structure of the Pt surface. The ORR activity in the phosphoric acid electrolyte remains relatively low, even when using the pre-adsorbate modified Pt/C catalysts. Further development of the catalyst and electrolyte is required before the commercialization of H3PO4-PBl-based PEMFCs can be realized.展开更多
A magnetic bar carbon paste electrode （MBCPE） modified with Fe3O4 magnetic nanoparticles （Fe3O4NPs） and 2‐（3,4‐dihydroxyphenyl） benzothiazole （DPB） for the electrochemical determina‐tion of hydrazine was de...A magnetic bar carbon paste electrode （MBCPE） modified with Fe3O4 magnetic nanoparticles （Fe3O4NPs） and 2‐（3,4‐dihydroxyphenyl） benzothiazole （DPB） for the electrochemical determina‐tion of hydrazine was developed. The DPB was firstly self‐assembled on the Fe3O4NPs, and the re‐sulting Fe3O4NPs/DPB composite was then absorbed on the designed MBCPE. The MBCPE was used to attract the magnetic nanoparticles to the electrode surface. Owing to its high conductivity and large effective surface area, the novel electrode had a very large current response for the electrocat‐alytic oxidation of hydrazine. The modified electrode was characterized by voltammetry, scanning electron microscopy, electrochemical impedance spectroscopy, infrared spectroscopy, and UV‐visible spectroscopy. Voltammetric methods were used to study the electrochemical behaviour of hydrazine on MBCPE/Fe3O4NPs/DPB in phosphate buffer solution （pH = 7.0）. The MBCPE/Fe3O4NPs/DPB, acting as an electrochemical sensor, exhibited very high electrocatalytic activity for the oxidation of hydrazine. The presence of DPB was found to reduce the oxidation potential of hydrazine and increase the catalytic current. The dependence of the electrocatalytic current on the hydrazine concentration exhibited two linear ranges, 0.1–0.4 μmol/L and 0.7–12.0 μmol/L, with a detection limit of 18.0 nmol/L. Additionally, the simultaneous determination of hydrazine and phe‐nol was investigated using the MBCPE/Fe3O4NPs/DPB electrode. Voltammetric experiments showed a linear range of 100–470 μmol/L and a detection limit of 24.3 μmol/L for phenol, and the proposed electrode was applied to the determination of hydrazine and phenol in water samples.展开更多
The electrocatalytic oxidation of methanol was studied over Ni, Co and Cu binary or ternary alloys on graphite electrodes in a NaOH solution （0.1 mol/L）. The catalysts were prepared by cycling the graphite electrode...The electrocatalytic oxidation of methanol was studied over Ni, Co and Cu binary or ternary alloys on graphite electrodes in a NaOH solution （0.1 mol/L）. The catalysts were prepared by cycling the graphite electrode in solutions containing Ni, Cu and Co ions at cathodic potentials. The synergistic effects and catalytic activity of the modified electrodes were investigated by cyclic voltammetry （CV）, chronoamperometry CCA） and electrochemical impedance spectroscopy （EIS）. It was found that, in the presence of methanol, the modified Ni-based ternary alloy electrode （G/NiCuCo） exhibited a significantly higher response for methanol oxidation compared to the other samples. The anodic peak currents showed a linear dependency on the square root of the scan rate, which is a characteristic of a diffusion controlled process. During CA studies, the reaction exhibited Cottrellin behavior and the diffusion coefficient of methanol was determined to be 6.25× 10-6 cm2/s and the catalytic rate constant, K, for methanol oxidation was found to be 40×107 cm3/Cmol.s）. EIS was used to investigate the catalytic oxidation of methanol on the surface of the modified electrode.展开更多
Carboxyl graphene modified CuxO/Cu electrode was fabricated. The bare copper electrode was firstly anodic polarized in 1.0 mol/L NaOH solution in order to get CuxO nanoparticles, then the carboxyl graphene （CG） was ...Carboxyl graphene modified CuxO/Cu electrode was fabricated. The bare copper electrode was firstly anodic polarized in 1.0 mol/L NaOH solution in order to get CuxO nanoparticles, then the carboxyl graphene （CG） was electrodeposited on the CuxO/Cu electrode by cyclic potential sweeping. The electrocatalytic oxidation behaviors of calcium folinate （CF） at the graphene modified CuxO/Cu electrode were investigated by cyclic voltammetry. A positive scan polarization reverse catalytic voltammetry was used to obtain the pure catalytic oxidation current. The graphene modified CuxO/Cu electrode was served as the electrochemical sensor of CF, a highly sensitivity of 22.0μA.（μmol/μL）^-1cm^-2 was achieved, and the current response was linear with increasing CF concentration in the range of 2.0×10^-7 mol/L to 2.0×10^-5 mol/L, which crossed three orders of magnitude, and the detection limit was found 7.6×10^-5 mol/L （S/N=3）. In addition, the proposed sensor was successfully applied in determination of CF in drug sample.展开更多
In order to enhance the power output of microbial fuel cell as well as its stability, the development of a new type of anode is essential. The purpose of this work is to modify a stainless steel foam, using the layer-...In order to enhance the power output of microbial fuel cell as well as its stability, the development of a new type of anode is essential. The purpose of this work is to modify a stainless steel foam, using the layer-by-layer self-assembly technique, with rGO （reduced grapbene oxide） and PEI （polyethyleneimine）. The efficiency of this kind of modification has been investigated to determine the supply of graphene in term of electricity generation and stability. Under an applied voltage, which is used to form an electroactive biofilm, the modified stainless steel foam （SSF/（PE1/rGO）5） exhibited a current 50 times higher than the blank anode. The roughness of the SSF/（PEI/rGO）5 observed by SEM （scanning electron microscopy） is more favorable to attach more bacteria on it. Also, graphene improved the stability of the electrode as no response where observed for the blank anode after 18 days meanwhile the SSF/（PEI/rGO）5 was still running after 54 days.展开更多
Development of uric acid sensor based on molecularly imprinted polymer （MIP） was studi ed. The sensor was developed by coating the imprinted polymethacrylic acid on the surface of a hanging mercury drop ele, ctrode ...Development of uric acid sensor based on molecularly imprinted polymer （MIP） was studi ed. The sensor was developed by coating the imprinted polymethacrylic acid on the surface of a hanging mercury drop ele, ctrode （HMDE） at -1 V （vs. Ag/AgCI） during 60 s. Uric acid was accumulated on the modified electrode at -1 V （vs. Ag/AgC1） during 60 s in acetate buffer pH = 5 and stripped at scan rate of 59 mV/s. Oxidation of uric acid on the surface of modified electrode is irreversible through the diffusion controlled process and polymethacrylic acid is a non-electrical conducting polymer. The current signal obtained from Ehe analysis of uric acid by using HMDE is higher than that of the HMD-palymethacrylic acid （polyMAA）, HMD-MIP and HMD-non imprinted polymer （NIP） electrode. The HMD-MIP has demonstrated its performance as a sensitive voltammetric sensor for uric acid. The modified electrode has been tested for the determination of uric acid in the serum sample with recovery percentage of 95.7% （n = 2）. The limit of detection obtained was 6.0 x 10-10 M.展开更多
Nanomaterials have been used increasingly in a wide variety of applications, and some of them have shown toxic effects on experimental animals and cells. In this study, a previously established photoelectrochemical DN...Nanomaterials have been used increasingly in a wide variety of applications, and some of them have shown toxic effects on experimental animals and cells. In this study, a previously established photoelectrochemical DNA sensor was employed to rapidly detect DNA damage induced by polystyrene nanosphere （PSNS） suspensions. In the sensor, a double-stranded DNA film was assembled on a semiconductor electrode, and a DNA intercalator, Ru（bpy）2（dppz）2＋ （bpy = 2,2＇-bipyridine, dppz = dipyrido[3,2-a：2＇,3＇-c]phenazine） was used as the photoelectrochemical signal indicator. After the DNA-modified electrode was exposed to 2.0 mg/mL PSNS suspension, photocurrent of DNA-bound Ru（bpy）2（dppz）2＋ decreased by about 20%. The decrease is attributed to the chemical damage of DNA and consequently less binding of Ru（bpy）2（dppz）2＋ molecules to the electrode. Gel electrophoresis of DNA samples incubated with PSNS suspension confirmed DNA damage after the chemical exposure. However, in both photoelectrochemical and gel electrophoresis experiments, extensively washed PSNS did not induce any DNA damage, and the supernatant of PSNS suspension exhibited comparable DNA damage as the unwashed PSNS suspension. Furthermore, UV-visible absorption spectrum of the supematant displayed a pattern very similar to that of styrene oxide （SO）, a compound which has been shown to induce DNA damage by forming covalent DNA adducts. It is therefore suggested that styrene oxide and other residual chemicals in the PSNS may be responsible for the observed DNA damage. The results highlight the importance of full characterization of nanomaterials before their toxicity study, and demonstrate the utility of photoelectrochemical DNA sensors in the rapid assessment of DNA damage induced by chemicals and nanomaterials.展开更多
The electrochemical behavior of nanodiamond （ND） film functionalized with carboxylic acid groups was studied systemati- cally on a glassy carbon （GC） electrode. One stable redox couple corresponding to the carboxy...The electrochemical behavior of nanodiamond （ND） film functionalized with carboxylic acid groups was studied systemati- cally on a glassy carbon （GC） electrode. One stable redox couple corresponding to the carboxylic acid group was observed. At the scan rate of 0.1 V/s, the cathodic and anodic peak potentials were -0.093 V and 0.088 V （vs. Ag/AgCI）, respectively. The carboxylic acid groups on the ND surface were reduced to CH2OH via a four electron redox process. The ND film modified electrode showed favorable electrocatalytic behavior toward the oxidation as well as the reduction of biomolecules, such as tryptophan and nicotinamide adenine dinucleotide.展开更多
文摘A new approach for assembling amperometric mushroom pulp tissue based membrane electrode for determination of L tyrosine analysis is proposed. Ferrocene is used as a mediator of electron transfer between tyrosinase in mushroom tissue and a graphite electrode. The optimal operation conditions are studied. The linear response range of the biosensor is 2 0×10 -4 to 4 5×10 -3 mol·L -1 with response time of less than 5 min and lifetime of at least 30 d. The biosensor can be applied to practical sample analysis.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA09030104)the National Basic Research Program of China(973 Program,2012CB215500)the Key Program of the Chinese Academy of Sciences(KGZD-EW-T08)
文摘Nation-membrane-based proton exchange fuel cells （PEMFCs） typically operate at below 100 ℃. However, H3PO4-doped polybenzimidazole （PBI）-based PEMFCs can operate at 100-200 ℃. This is advantageous because of accelerated reaction rates and enhanced tolerance to poisons such as CO and S02, which can arise from reformed gas or the atmosphere. However, the strong adsorption of phosphoric anions on the Pt surface dramatically decreases the electrocatalytic activity. This study exploits the ＂third-body effect＂, in which a small amount of organic molecules are pre-adsorbed on the Pt surface to inhibit the adsorption of phosphoric anions. Pre-adsorbate species inhibit the ad- sorption of phosphoric anions, but can also partially occlude active sites. Thus, the optimum pre-adsorbate coverage is studied by correlating the oxygen reduction reaction （ORR） activity of Pt with pre-adsorbate coverage on the Pt surface. The influence of the pre-adsorbate molecule length is investigated using the organic amines, butylamine, octylamine, and dodecylamine, in both 0.1 mol/L HCI04 and 0.1 mol/L H3P04. Such amines readily bond to the Pt surface. In aqueous HCI04 electrolyte, the ORR activity of Pt decreases monotonically with increasing pre-adsorbate coverage. In aqueous H3P04 electrolyte, the ORR activity of Pt initially increases and then decreases with in- creasing pre-adsorbate coverage. The maximum ORR activity in H3P04 occurs at a pre-adsorbate coverage of around 20%. The effect of molecular length of the pre-adsorbate is negligible, but its coverage strongly affects the degree to which phosphoric anion adsorption is inhibited. Butylamine adsorbs to Pt at partial active sites, which decreases the electrochemically active surface area. Ad- sorbed butylamine may also modify the electronic structure of the Pt surface. The ORR activity in the phosphoric acid electrolyte remains relatively low, even when using the pre-adsorbate modified Pt/C catalysts. Further development of the catalyst and electrolyte is required before the commercialization of H3PO4-PBl-based PEMFCs can be realized.
文摘A magnetic bar carbon paste electrode （MBCPE） modified with Fe3O4 magnetic nanoparticles （Fe3O4NPs） and 2‐（3,4‐dihydroxyphenyl） benzothiazole （DPB） for the electrochemical determina‐tion of hydrazine was developed. The DPB was firstly self‐assembled on the Fe3O4NPs, and the re‐sulting Fe3O4NPs/DPB composite was then absorbed on the designed MBCPE. The MBCPE was used to attract the magnetic nanoparticles to the electrode surface. Owing to its high conductivity and large effective surface area, the novel electrode had a very large current response for the electrocat‐alytic oxidation of hydrazine. The modified electrode was characterized by voltammetry, scanning electron microscopy, electrochemical impedance spectroscopy, infrared spectroscopy, and UV‐visible spectroscopy. Voltammetric methods were used to study the electrochemical behaviour of hydrazine on MBCPE/Fe3O4NPs/DPB in phosphate buffer solution （pH = 7.0）. The MBCPE/Fe3O4NPs/DPB, acting as an electrochemical sensor, exhibited very high electrocatalytic activity for the oxidation of hydrazine. The presence of DPB was found to reduce the oxidation potential of hydrazine and increase the catalytic current. The dependence of the electrocatalytic current on the hydrazine concentration exhibited two linear ranges, 0.1–0.4 μmol/L and 0.7–12.0 μmol/L, with a detection limit of 18.0 nmol/L. Additionally, the simultaneous determination of hydrazine and phe‐nol was investigated using the MBCPE/Fe3O4NPs/DPB electrode. Voltammetric experiments showed a linear range of 100–470 μmol/L and a detection limit of 24.3 μmol/L for phenol, and the proposed electrode was applied to the determination of hydrazine and phenol in water samples.
基金provided by K.N.Toosi University of Technology Research Council to conduct this research
文摘The electrocatalytic oxidation of methanol was studied over Ni, Co and Cu binary or ternary alloys on graphite electrodes in a NaOH solution （0.1 mol/L）. The catalysts were prepared by cycling the graphite electrode in solutions containing Ni, Cu and Co ions at cathodic potentials. The synergistic effects and catalytic activity of the modified electrodes were investigated by cyclic voltammetry （CV）, chronoamperometry CCA） and electrochemical impedance spectroscopy （EIS）. It was found that, in the presence of methanol, the modified Ni-based ternary alloy electrode （G/NiCuCo） exhibited a significantly higher response for methanol oxidation compared to the other samples. The anodic peak currents showed a linear dependency on the square root of the scan rate, which is a characteristic of a diffusion controlled process. During CA studies, the reaction exhibited Cottrellin behavior and the diffusion coefficient of methanol was determined to be 6.25× 10-6 cm2/s and the catalytic rate constant, K, for methanol oxidation was found to be 40×107 cm3/Cmol.s）. EIS was used to investigate the catalytic oxidation of methanol on the surface of the modified electrode.
文摘Carboxyl graphene modified CuxO/Cu electrode was fabricated. The bare copper electrode was firstly anodic polarized in 1.0 mol/L NaOH solution in order to get CuxO nanoparticles, then the carboxyl graphene （CG） was electrodeposited on the CuxO/Cu electrode by cyclic potential sweeping. The electrocatalytic oxidation behaviors of calcium folinate （CF） at the graphene modified CuxO/Cu electrode were investigated by cyclic voltammetry. A positive scan polarization reverse catalytic voltammetry was used to obtain the pure catalytic oxidation current. The graphene modified CuxO/Cu electrode was served as the electrochemical sensor of CF, a highly sensitivity of 22.0μA.（μmol/μL）^-1cm^-2 was achieved, and the current response was linear with increasing CF concentration in the range of 2.0×10^-7 mol/L to 2.0×10^-5 mol/L, which crossed three orders of magnitude, and the detection limit was found 7.6×10^-5 mol/L （S/N=3）. In addition, the proposed sensor was successfully applied in determination of CF in drug sample.
文摘In order to enhance the power output of microbial fuel cell as well as its stability, the development of a new type of anode is essential. The purpose of this work is to modify a stainless steel foam, using the layer-by-layer self-assembly technique, with rGO （reduced grapbene oxide） and PEI （polyethyleneimine）. The efficiency of this kind of modification has been investigated to determine the supply of graphene in term of electricity generation and stability. Under an applied voltage, which is used to form an electroactive biofilm, the modified stainless steel foam （SSF/（PE1/rGO）5） exhibited a current 50 times higher than the blank anode. The roughness of the SSF/（PEI/rGO）5 observed by SEM （scanning electron microscopy） is more favorable to attach more bacteria on it. Also, graphene improved the stability of the electrode as no response where observed for the blank anode after 18 days meanwhile the SSF/（PEI/rGO）5 was still running after 54 days.
文摘Development of uric acid sensor based on molecularly imprinted polymer （MIP） was studi ed. The sensor was developed by coating the imprinted polymethacrylic acid on the surface of a hanging mercury drop ele, ctrode （HMDE） at -1 V （vs. Ag/AgCI） during 60 s. Uric acid was accumulated on the modified electrode at -1 V （vs. Ag/AgC1） during 60 s in acetate buffer pH = 5 and stripped at scan rate of 59 mV/s. Oxidation of uric acid on the surface of modified electrode is irreversible through the diffusion controlled process and polymethacrylic acid is a non-electrical conducting polymer. The current signal obtained from Ehe analysis of uric acid by using HMDE is higher than that of the HMD-palymethacrylic acid （polyMAA）, HMD-MIP and HMD-non imprinted polymer （NIP） electrode. The HMD-MIP has demonstrated its performance as a sensitive voltammetric sensor for uric acid. The modified electrode has been tested for the determination of uric acid in the serum sample with recovery percentage of 95.7% （n = 2）. The limit of detection obtained was 6.0 x 10-10 M.
基金supported by the National Basic Research Program of China (2011CB936001)the National Natural Science Foundation of China (20825519, 20890112 & 20921063)Beijing Municipal Education Committee (KZ201110005006)
文摘Nanomaterials have been used increasingly in a wide variety of applications, and some of them have shown toxic effects on experimental animals and cells. In this study, a previously established photoelectrochemical DNA sensor was employed to rapidly detect DNA damage induced by polystyrene nanosphere （PSNS） suspensions. In the sensor, a double-stranded DNA film was assembled on a semiconductor electrode, and a DNA intercalator, Ru（bpy）2（dppz）2＋ （bpy = 2,2＇-bipyridine, dppz = dipyrido[3,2-a：2＇,3＇-c]phenazine） was used as the photoelectrochemical signal indicator. After the DNA-modified electrode was exposed to 2.0 mg/mL PSNS suspension, photocurrent of DNA-bound Ru（bpy）2（dppz）2＋ decreased by about 20%. The decrease is attributed to the chemical damage of DNA and consequently less binding of Ru（bpy）2（dppz）2＋ molecules to the electrode. Gel electrophoresis of DNA samples incubated with PSNS suspension confirmed DNA damage after the chemical exposure. However, in both photoelectrochemical and gel electrophoresis experiments, extensively washed PSNS did not induce any DNA damage, and the supernatant of PSNS suspension exhibited comparable DNA damage as the unwashed PSNS suspension. Furthermore, UV-visible absorption spectrum of the supematant displayed a pattern very similar to that of styrene oxide （SO）, a compound which has been shown to induce DNA damage by forming covalent DNA adducts. It is therefore suggested that styrene oxide and other residual chemicals in the PSNS may be responsible for the observed DNA damage. The results highlight the importance of full characterization of nanomaterials before their toxicity study, and demonstrate the utility of photoelectrochemical DNA sensors in the rapid assessment of DNA damage induced by chemicals and nanomaterials.
基金sponsored by the National Natural Science Foundation of China (21075136)
文摘The electrochemical behavior of nanodiamond （ND） film functionalized with carboxylic acid groups was studied systemati- cally on a glassy carbon （GC） electrode. One stable redox couple corresponding to the carboxylic acid group was observed. At the scan rate of 0.1 V/s, the cathodic and anodic peak potentials were -0.093 V and 0.088 V （vs. Ag/AgCI）, respectively. The carboxylic acid groups on the ND surface were reduced to CH2OH via a four electron redox process. The ND film modified electrode showed favorable electrocatalytic behavior toward the oxidation as well as the reduction of biomolecules, such as tryptophan and nicotinamide adenine dinucleotide.
