The cathodic wave of vitamin C has not been reported in the literature so far.Its E_(1/2)was found at-1.85 volt vs.Ag/AgCl(25℃)in the base solution of 0.1mol/L Bu_4NI.Various electrochemical and spectral techniques w...The cathodic wave of vitamin C has not been reported in the literature so far.Its E_(1/2)was found at-1.85 volt vs.Ag/AgCl(25℃)in the base solution of 0.1mol/L Bu_4NI.Various electrochemical and spectral techniques were used for studying the electrode reaction. They all showed that the electrode reaction was quasi-reversible while C was more than 1.0×10^(-6)mol/L and mainly adsorptive while C was less than 1.0×10^(-6)mol/L at a mercury electrode.The electron transfer number was 2 and the electron transfer coefficient 0.57. Using DPP techniques,the linear response range was 5.0×10^(-7)-2.0×10^(-3)mol/L and the detection limit 1×10^(-7)mol/L.展开更多
This paper reports a polarographic catalytic wave of lysozyme (LE) in the presence of KIO3. The mechanism of the catalytic wave was discussed. It is illustrated by the catalytic wave of LE that, besides the Brdicka cu...This paper reports a polarographic catalytic wave of lysozyme (LE) in the presence of KIO3. The mechanism of the catalytic wave was discussed. It is illustrated by the catalytic wave of LE that, besides the Brdicka current, there exists a new kind of catalytic wave of protein.展开更多
It is reported in this paper a polarographic catalytic double wave of oxygen reduction caused by diphenylamine compounds(diphs).The electrochemical process of the wave includes the polarographic generation of the supe...It is reported in this paper a polarographic catalytic double wave of oxygen reduction caused by diphenylamine compounds(diphs).The electrochemical process of the wave includes the polarographic generation of the superoxide anion O_2^- and the dismutation of O_2^- catalyzed by diphs with redox pseudoreversibility.展开更多
The sensitive second derivative waves of Cu(Ⅱ),Pb(Ⅱ),Cd(Ⅱ),Ni(Ⅱ),Zn(Ⅱ),Fe(Ⅱ)and Mn(Ⅱ),forming in the substrate solution(pH=9.26)consisting of ammonia,ammonium chlorid,gelatin and ascorbic acid were researched.T...The sensitive second derivative waves of Cu(Ⅱ),Pb(Ⅱ),Cd(Ⅱ),Ni(Ⅱ),Zn(Ⅱ),Fe(Ⅱ)and Mn(Ⅱ),forming in the substrate solution(pH=9.26)consisting of ammonia,ammonium chlorid,gelatin and ascorbic acid were researched.The peak potentials of the polarographic waves of the seven ions are at about 0.48,0.63,0.79,1.04,1.28,1.44 and 1.60 V respectively.Combining with microwave technique,a new method for the simultaneous determination of the seven trace elements in Chinese traditional medicine was developed.The method is easy to operate,rapid,simple and convenient.When the signal-to-noise rate equals 3,the detection limits of Cu,Pb,Cd,Ni,Zn,Fe and Mn are 4.2×10 3,5.3×10 3,2.1×10 3,5.8×10 4,3.0×10 3,7.7×10 4 and 1.1×10 3 μg/mL respectively.Well linear relationships exist between the concentrations and the peak currents when Cu,Pb,Cd,Ni,Zn,Fe and Mn concentrations are within 8.5×10 3 10,9.7×10 3 10,4.5×10 3 10,1.2×10 3 10,6.4×10 3 10,1.5×10 3 10 and 2.8×10 3 10 μg/mL,respectively.The method has been used to the simultaneous determination of the seven trace elements in Salvia Miltiorrhiza Root and compound Salvia Miltiorrhiza Root injection,the relative standard deviations(RSDs)of the Cu,Pb,Cd,Ni,Zn,Fe and Mn in the two medicines are 3.9% and 5.8%,4.0% and 4.1%,4.3% and 5.7%,4.9% and 5.3%,4.4% and 4.7%,3.5% and 4.0%,0.51% and 2.8%,respectively;the comparisons of the determination results with the values obtained by the standard method indicate that the presented method has very well veracity.展开更多
In the present paper, linear sweep polarography (LPS) was employed to study Yb 3+ KMnO 4 system. Results show that this system is characterized as a catalytic wave. The first step of Yb 3+ reduction was th...In the present paper, linear sweep polarography (LPS) was employed to study Yb 3+ KMnO 4 system. Results show that this system is characterized as a catalytic wave. The first step of Yb 3+ reduction was the one electron reduction to Yb 2+ , and improvement in the sensitivity of Yb 3+ was studied. Convolution voltammetry and cyclic voltammetry were employed to determine the rate constant and to confirm the process of electrode. The effects of various parameters, including pH, electrolyte, catalyst concentration and surface active substance on the reduction process were examined.展开更多
Polarographic catalytic wave of chlordiazepoxide in the presence of K 2S 2O 8 was studied in aqueous and DMF/H 2O mixed solutions. The results showed that a single reduction wave in alkaline medium was the reducti...Polarographic catalytic wave of chlordiazepoxide in the presence of K 2S 2O 8 was studied in aqueous and DMF/H 2O mixed solutions. The results showed that a single reduction wave in alkaline medium was the reduction of the N=C bond in 1,2 position of chlordiazepoxide via an intermediate free radical in two one electron successive additions. When K 2S 2O 8 was present, the free radical of the N=C bond was oxidized to regenerate the original, producing a parallel catalytic wave of chlordiazepoxide. It was determined that the apparent rate constant k f of the oxidation reaction was 3.2×10 3 mol -1 ·L·s -1 . Using the catalytic wave the trace of chlordiazepoxide can be determined by linear potential scan polarography. In NH 3/NH 4Cl (pH 10.2±0.1, 0.12 mol/L)/K 2S 2O 8 (0.016 mol/L) supporting electrolyte, the second order derivative peak current of the catalytic wave was rectilinear to chlordiazepoxide concentration in the range of 3.20×10 -8 -1.60×10 -7 , 1.60×10 -7 -1.44×10 -6 and 1.44 ×10 -6 -1.44×10 -5 mol/L, respectively. The limit of detection was 9.0×10 -9 mol/L.展开更多
The polarographic behavior and catalytic wave mechanism of medroprogesterone acetate ( MPA) were studied in both aqueous and DMF media. In 0.2 mol/L acetic acid-sodium acetate ( pH 5 .0 ) buffer solution, the C=C bond...The polarographic behavior and catalytic wave mechanism of medroprogesterone acetate ( MPA) were studied in both aqueous and DMF media. In 0.2 mol/L acetic acid-sodium acetate ( pH 5 .0 ) buffer solution, the C=C bond of MPA first undergoes le,lH+ reduction to form protonated free radical HMPA , the further reduction of HMPA in le,lH + process is simultaneous with the dimerization reaction between HMPA and neutral molecular MPA. In DMF media containing 0.1 mol/ L tetrabutylammonium tetrafluoborate ( TBA ·BF4 ) , the C=C bond of MPA shows two le, 1H+ reduction waves, which are ascribed to the reduction of MPA and free radical MPA' , respectively. Here, no dimerization reaction occurs. These processes produce the reduction wave of MPA. In the presence of oxidant KIO3, a polarographic catalytic wave of MPA is observable due to a chemical reaction between HMPA or MPA ~ and KIO3 as well as its intermediate species to regenerate MPA. The catalytic wave, which is caused by the reduction of organic compound itself and the chemical reaction between oxidant and organic intermediate free radical to regenerate original organic compound, is a new-type wave of organic compound. Under optimum experimental conditions, the sensitivity of MPA catalytic wave in the presence of KIO3 is an order of magnitude higher than that of its reduction wave. The catalytic wave can be used for analytical purpose. The calculated rate constant of catalytic reaction is 1.7 X103mol·-1·S-1 .展开更多
The polarographic catalytic wave of oxygen reduction caused by mefenamic acid (MA) with redox properties was reported in this paper. The electrochemical process of the catalytic wave was proposed that the superoxide a...The polarographic catalytic wave of oxygen reduction caused by mefenamic acid (MA) with redox properties was reported in this paper. The electrochemical process of the catalytic wave was proposed that the superoxide anion O(?) was generated polarographically and the dismutation of the O(?) was catalyzed by MA to reproduce O_2 and H_2O_2. This explained chemically the scavenging of the O_2^- by MA im biomedical area. Based on the catalytic wave, a new method for the determination of MA by single-sweep polarography was developed.展开更多
In our previous papers, the isonuclear complexes of RE (Ⅲ)-Ni (Ⅱ) (or Co(Ⅱ))-ALC had been studied by single-sweep polarograph. In the present note, the polarographic adsorptive complex wave of RE (Ⅲ)-Cu (Ⅱ)-ALC i...In our previous papers, the isonuclear complexes of RE (Ⅲ)-Ni (Ⅱ) (or Co(Ⅱ))-ALC had been studied by single-sweep polarograph. In the present note, the polarographic adsorptive complex wave of RE (Ⅲ)-Cu (Ⅱ)-ALC is reported. The mechanisms of the two are different, the former being the reduced wave of ligand (ALC),展开更多
The rare earth ions form complexes with ECAB in 0.1 mol/L NaAc-HAc supporting electrolyte at pH 6. The composition of the complex was determined by spectrophotometric method to be 1: 2. The decrease of SAC peak height...The rare earth ions form complexes with ECAB in 0.1 mol/L NaAc-HAc supporting electrolyte at pH 6. The composition of the complex was determined by spectrophotometric method to be 1: 2. The decrease of SAC peak height of ECAB is proportional to the concentration of rare earth ions in the range of 1×10^(-6)-2×10^(-5) mol/L. The reduction mechanism of ECAB and RE-ECAB is proposed based on the experimental evidence. The complexing group of ECAB with RE ions iust is the redox group, so when RE ions are added, there is no new peak appearing in the polarograms:, the only phenomenon observed is that the peak current of ECAB decreases. The fast protonation of EGAB carbanion formed after the second electron transfer results in the formation of colourless tetrahedral molecules.展开更多
基金Project supported by National Natural Science Foundation of P.R.China and by Foundation of Lab of Electroanalytical Chemistry,Changchun Institute of Applied Chemistry,Academia Sinica
文摘The cathodic wave of vitamin C has not been reported in the literature so far.Its E_(1/2)was found at-1.85 volt vs.Ag/AgCl(25℃)in the base solution of 0.1mol/L Bu_4NI.Various electrochemical and spectral techniques were used for studying the electrode reaction. They all showed that the electrode reaction was quasi-reversible while C was more than 1.0×10^(-6)mol/L and mainly adsorptive while C was less than 1.0×10^(-6)mol/L at a mercury electrode.The electron transfer number was 2 and the electron transfer coefficient 0.57. Using DPP techniques,the linear response range was 5.0×10^(-7)-2.0×10^(-3)mol/L and the detection limit 1×10^(-7)mol/L.
文摘This paper reports a polarographic catalytic wave of lysozyme (LE) in the presence of KIO3. The mechanism of the catalytic wave was discussed. It is illustrated by the catalytic wave of LE that, besides the Brdicka current, there exists a new kind of catalytic wave of protein.
文摘It is reported in this paper a polarographic catalytic double wave of oxygen reduction caused by diphenylamine compounds(diphs).The electrochemical process of the wave includes the polarographic generation of the superoxide anion O_2^- and the dismutation of O_2^- catalyzed by diphs with redox pseudoreversibility.
基金Proejcr(20235020) supported by the National Natural Science Foundation of China
文摘The sensitive second derivative waves of Cu(Ⅱ),Pb(Ⅱ),Cd(Ⅱ),Ni(Ⅱ),Zn(Ⅱ),Fe(Ⅱ)and Mn(Ⅱ),forming in the substrate solution(pH=9.26)consisting of ammonia,ammonium chlorid,gelatin and ascorbic acid were researched.The peak potentials of the polarographic waves of the seven ions are at about 0.48,0.63,0.79,1.04,1.28,1.44 and 1.60 V respectively.Combining with microwave technique,a new method for the simultaneous determination of the seven trace elements in Chinese traditional medicine was developed.The method is easy to operate,rapid,simple and convenient.When the signal-to-noise rate equals 3,the detection limits of Cu,Pb,Cd,Ni,Zn,Fe and Mn are 4.2×10 3,5.3×10 3,2.1×10 3,5.8×10 4,3.0×10 3,7.7×10 4 and 1.1×10 3 μg/mL respectively.Well linear relationships exist between the concentrations and the peak currents when Cu,Pb,Cd,Ni,Zn,Fe and Mn concentrations are within 8.5×10 3 10,9.7×10 3 10,4.5×10 3 10,1.2×10 3 10,6.4×10 3 10,1.5×10 3 10 and 2.8×10 3 10 μg/mL,respectively.The method has been used to the simultaneous determination of the seven trace elements in Salvia Miltiorrhiza Root and compound Salvia Miltiorrhiza Root injection,the relative standard deviations(RSDs)of the Cu,Pb,Cd,Ni,Zn,Fe and Mn in the two medicines are 3.9% and 5.8%,4.0% and 4.1%,4.3% and 5.7%,4.9% and 5.3%,4.4% and 4.7%,3.5% and 4.0%,0.51% and 2.8%,respectively;the comparisons of the determination results with the values obtained by the standard method indicate that the presented method has very well veracity.
文摘In the present paper, linear sweep polarography (LPS) was employed to study Yb 3+ KMnO 4 system. Results show that this system is characterized as a catalytic wave. The first step of Yb 3+ reduction was the one electron reduction to Yb 2+ , and improvement in the sensitivity of Yb 3+ was studied. Convolution voltammetry and cyclic voltammetry were employed to determine the rate constant and to confirm the process of electrode. The effects of various parameters, including pH, electrolyte, catalyst concentration and surface active substance on the reduction process were examined.
文摘Polarographic catalytic wave of chlordiazepoxide in the presence of K 2S 2O 8 was studied in aqueous and DMF/H 2O mixed solutions. The results showed that a single reduction wave in alkaline medium was the reduction of the N=C bond in 1,2 position of chlordiazepoxide via an intermediate free radical in two one electron successive additions. When K 2S 2O 8 was present, the free radical of the N=C bond was oxidized to regenerate the original, producing a parallel catalytic wave of chlordiazepoxide. It was determined that the apparent rate constant k f of the oxidation reaction was 3.2×10 3 mol -1 ·L·s -1 . Using the catalytic wave the trace of chlordiazepoxide can be determined by linear potential scan polarography. In NH 3/NH 4Cl (pH 10.2±0.1, 0.12 mol/L)/K 2S 2O 8 (0.016 mol/L) supporting electrolyte, the second order derivative peak current of the catalytic wave was rectilinear to chlordiazepoxide concentration in the range of 3.20×10 -8 -1.60×10 -7 , 1.60×10 -7 -1.44×10 -6 and 1.44 ×10 -6 -1.44×10 -5 mol/L, respectively. The limit of detection was 9.0×10 -9 mol/L.
基金Project supported by the National Natural Science Foundation of China (Grant No. 29875017).
文摘The polarographic behavior and catalytic wave mechanism of medroprogesterone acetate ( MPA) were studied in both aqueous and DMF media. In 0.2 mol/L acetic acid-sodium acetate ( pH 5 .0 ) buffer solution, the C=C bond of MPA first undergoes le,lH+ reduction to form protonated free radical HMPA , the further reduction of HMPA in le,lH + process is simultaneous with the dimerization reaction between HMPA and neutral molecular MPA. In DMF media containing 0.1 mol/ L tetrabutylammonium tetrafluoborate ( TBA ·BF4 ) , the C=C bond of MPA shows two le, 1H+ reduction waves, which are ascribed to the reduction of MPA and free radical MPA' , respectively. Here, no dimerization reaction occurs. These processes produce the reduction wave of MPA. In the presence of oxidant KIO3, a polarographic catalytic wave of MPA is observable due to a chemical reaction between HMPA or MPA ~ and KIO3 as well as its intermediate species to regenerate MPA. The catalytic wave, which is caused by the reduction of organic compound itself and the chemical reaction between oxidant and organic intermediate free radical to regenerate original organic compound, is a new-type wave of organic compound. Under optimum experimental conditions, the sensitivity of MPA catalytic wave in the presence of KIO3 is an order of magnitude higher than that of its reduction wave. The catalytic wave can be used for analytical purpose. The calculated rate constant of catalytic reaction is 1.7 X103mol·-1·S-1 .
文摘The polarographic catalytic wave of oxygen reduction caused by mefenamic acid (MA) with redox properties was reported in this paper. The electrochemical process of the catalytic wave was proposed that the superoxide anion O(?) was generated polarographically and the dismutation of the O(?) was catalyzed by MA to reproduce O_2 and H_2O_2. This explained chemically the scavenging of the O_2^- by MA im biomedical area. Based on the catalytic wave, a new method for the determination of MA by single-sweep polarography was developed.
基金Project supported by the National Natural Science Foundation of China
文摘In our previous papers, the isonuclear complexes of RE (Ⅲ)-Ni (Ⅱ) (or Co(Ⅱ))-ALC had been studied by single-sweep polarograph. In the present note, the polarographic adsorptive complex wave of RE (Ⅲ)-Cu (Ⅱ)-ALC is reported. The mechanisms of the two are different, the former being the reduced wave of ligand (ALC),
基金Project supported by the National Natural Science Foundation of China
文摘The rare earth ions form complexes with ECAB in 0.1 mol/L NaAc-HAc supporting electrolyte at pH 6. The composition of the complex was determined by spectrophotometric method to be 1: 2. The decrease of SAC peak height of ECAB is proportional to the concentration of rare earth ions in the range of 1×10^(-6)-2×10^(-5) mol/L. The reduction mechanism of ECAB and RE-ECAB is proposed based on the experimental evidence. The complexing group of ECAB with RE ions iust is the redox group, so when RE ions are added, there is no new peak appearing in the polarograms:, the only phenomenon observed is that the peak current of ECAB decreases. The fast protonation of EGAB carbanion formed after the second electron transfer results in the formation of colourless tetrahedral molecules.
