A new type of polarographic catalytic wave of organic compound——Studies on the polarographic catalytic wave of medroprogesterone acetate in the presence of KIO_3

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, 1H~ process is simultaneous with the dimerization reaction between HMPA(?) and neutral molecular MPA. In DMF media containing 0.1 mol/L tetrabutylammonium tetrafluoborate (TBA·BF_4), 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 KIO_3, a polarographic catalytic wave of MPA is observable due to a chemical reaction between HMPA(?) or MPA(?) and KIO_3 as well as its intermediate species to regenerate MPA. The catalytic wave, which is caused by the reduction of organic com     

维生素B2的极谱催化波研究及应用

维生素B2是人和动物维持机体正常结构与功能的必需营养物质,具有广泛的生理功能。目前,测定维生素B2的方法有高效液相色谱法、荧光分析法、化学发光分析法、紫外分光光度法及电化学分析法等,而其中电化学分析法大都需要采用化学修饰电极,对电极需特殊处理,比较麻烦和费时。本文发现在KH2PO4-Na2HPO4缓冲介质中,维生素B2在-0．43V（vs．SCE）电位附近产生的还原波可被H2O2催化,产生一新的极谱催化波。通过伏安分析并结合光谱分析,本文研究并推导了该极谱催化波的产生机理,并建立了测定维生素B2的新方法。该方法简单,操作简便快速,无需对电极进行特殊处理,而灵敏度与其他电化学测定方法相当。     

Study and Application of Polarographic Catalytic Wave of Chlordiazepoxide in the Presence of Persulfate

ＩｎｔｒｏｄｕｃｔｉｏｎＣｈｌｏｒｄｉａｚｅｐｏｘｉｄｅ (7 ｃｈｌｏｒｏ 2 ｍｅｔｈｙｌａｍｉｎｏ 5 ｐｈｅｎｙｌ 3Ｈ 1,4 ｂｅｎｚｏｄｉａｚｅｐｉｎｅ 4 ｏｘｉｄｅ)ｓｈｏｗｉｎｇｐｏｗｅｒｆｕｌａｎ ｔｉａｎｘｉｅｔｙｅｆｆｅｃｔｈａｓｂｅｅｎｗｉｄｅｌｙｕｓｅｄａｓａｐｓｙｃｈｏｔｈｅｒａｐｅｕ ｔｉｃｄｒｕｇ .Ｃｏｎｓｅｑｕｅｎｔｌｙ ,ｔｈｅｎｅｅｄａｒｏｓｅｆｏｒｓｅｎｓｉｔｉｖｅａｎｄｒａｐｉｄｄｅｔｅｒｍｉｎａｔｉｏｎｏｆｃｈｌｏｒｄｉａｚｅｐｏｘｉｄｅｉｎｂｌｏｏｄ ,ｕｒｉｎｅａｎ…     

Study and Application on Polarographic Catalytic Wave of Human Serum Albumin in the Presence of Kio3

ABSTRACT

A polarographic catalytic wave of human serum albumin (HSA) in the presence of KIO³ was reported. In 0.1 M NaAc～HAc buffer (pH4.7) solution, a reduction wave of HSA with peak potential ?0.60 V (vs., Ag/AgCl) resulted from the reduction of five disulfide linkages to sulfhydryl group. In the presence of KIO³, HSA yielded a polarographic catalytic wave at the original potential due to reduction and regeneration of these disulfide linkages. The catalytic wave can be used to determine trace of HSA. In the 0.1 M HAc～NaAc (pH4.7±0.2) ～1×10^?3 M KIO³ solution, the peak current was linearly proportional to HSA concentration in the range of 1.5×10^?7～7.5×10^?7 M. The catalytic wave improved two orders of magnitude in sensitivity compared with corresponding reduction wave.     

Adsorption-parallel catalytic waves of cinnamic acid in hydrogen peroxide-tetra-n-butylammonium bromide-acetate system

The mechanism of the adsorption-parallel catalytic wave of cinnamic acid (C6H5—CH = CH—COOH) in acetate buffer (pH = 4.0)-H2O2-tetra-n-butylammonium bromide (Bu4N · Br) solution was studied by the linear-sweep polarography, cyclic voltammetry and digital simulation approach. Experimental results indicate that the reduction mechanism of cinnamic acid is ECdimE' process, in which the C = C double bond of cinnamic acid first undergoes 1 e, 1H reduction to produce an intermediate free radical C6H5—CH—CH2—COOH(E), then the further reduction of the free radical in 1e,1H addition (E') occurs simultaneously with a dimerization reaction between two free radicals (Cdim). Bu4N · Br enhances the polarographic current of cinnamic acid and shifts the peak potential to positive direction. The enhancement action of Bu4N · Br is due to the adsorption of cinnamic acid induced by Bu4N species. In addition, H2O2 causes the parallel catalytic wave of cinnamic acid. The mechanism of the catalytic wave is EC' proce     

极谱催化波法测定土霉素

H2 O2 存在时 ,产生土霉素的极谱催化波 ,该催化波的灵敏度比相应土霉素的还原波高 8倍 ,据此拟定了测定土霉素的新方法。在 0 .1 0mol LKH2 PO4 Na2 HPO4(pH 7.4± 0 .2 ) - 1 .6× 1 0 -3 mol LH2 O2 底液中 ,催化波峰电流与土霉素浓度在 5 .0× 1 0 -7～ 9.0× 1 0 -6mol L范围内呈线性关系 (n =1 0 ,r=0 9996)。检出限为 1 .0× 1 0 -7mol L。     

苯甲醛-过二硫酸盐体系中苯甲醛的极谱催化波

Both polarographic reduction wave and catalytic wave of benzaldehyde were studied in 0 1 mol/L NH 4Cl NH 3·H 2O (pH 9 8) buffer solution. The results show that benzaldehyde is reduced in 1e, 1H + process to an intermediate free radical ArCHOH ·. ArCHOH · reacts with neutral molecule ArCHO to form a dimer (ArCHO ArCHOH) ·. The dimer is further reduced in 1e, 1H + process. In the presence of oxidant K 2S 2O 8, a polarographic catalytic wave of benzaldehyde is produced due to the oxidation of ArCHOH · by both K 2S 2O 8 and its intermediate SO - 4 · to regenerate benzaldehyde. The apparent rate constant of the oxidization reaction is 316 mol/(L·s).     

极谱催化波法测定中草药中的芦丁

基于芦丁在K2S2O8存在下产生的极谱催化波,拟定了测定中草药中芦丁的方法。在0.1 mol/L HAc-NaAc(pH 3.60±0.05),8×10-3mol/L K2S2O8支持电解质中,芦丁催化波峰电位为-1.37 V(vs.SCE),它的二阶导数峰电流与其浓度在1.6×10-6~1.6×10-5mol/L范围内呈线性关系(r=0.9960,n=6)。检出限为9.013×10-11mol/L,回收率为96.18%~102.66%。样品可不经分离,直接测定。采用该方法测得山楂和川明参中芦丁的质量分数分别为1.78%和1.60%。     

Study and application of parallel catalytic hydrogen wave of lincomycin in the presence of persulfate

The polarographic currents of lincomycin in the absence and the presence of persulfate are studied by linear potential scan polarography and cyclic voltammetry. The reduction wave of lincomycin in phosphate buffer is a catalytic hydrogen wave, which is the reduction of the proton combined with lincomycin in nature. When S₂O₈²⁻ is present, the atomic hydrogen as intermediate product from the reduction of the combined proton is oxidized by both S₂O₈²⁻ and its reduction intermediate, sulfate radical anion SO₄⁻, to regenerate the original proton, producing the parallel catalytic hydrogen wave. Based on the parallel catalytic hydrogen wave, a novel method for the determination of lincomycin is proposed. In 0.48 mol l⁻¹ KH₂PO₄-Na₂HPO₄ (pH 7.4)-8.0×10⁻³ mol l⁻¹ K₂S₂O₈ supporting electrolyte, the peak potential of the parallel catalytic hydrogen wave is −1.82 V (vs. SCE). The second-order derivative peak current is rectilinear to the lincomycin concentration in the range of 8.5×10⁻⁸-9.0×10⁻⁵ mol l⁻¹ and the detection limit is 4×10⁻⁸ mol l⁻¹. The parallel catalytic hydrogen wave is three orders in magnitude higher than that of the corresponding catalytic hydrogen wave in analytical sensitivity. The proposed method is applied to the rapid determination of lincomycin hydrochloride in eye drops without previous separation.     

Rapid determination of telmisartan in pharmaceuticals and serum by the parallel catalytic hydrogen wave method

The polarographic characteristics of telmisartan have been investigated in 0.8 mol L^–1 NH₃.H₂O–NH₄Cl (pH 8.9)–0.01 mol L^–1 H₂O₂ as supporting electrolyte. The results demonstrate that the polarographic reduction wave at ca. –1.30 V in the absence of H₂O₂ is a catalytic hydrogen wave, and the reduction wave enhanced by H₂O₂ is a so-called parallel catalytic hydrogen wave. The analytical sensitivity of the parallel catalytic hydrogen wave is ca. 60 times higher than that of the corresponding catalytic hydrogen wave. Based on the parallel catalytic hydrogen wave a novel method has been developed for determination of telmisartan by linear sweep polarography. The calibration curve is linear in the range 2.0×10^–8–2.0×10^–6 mol L^–1 and the detection limit is 1.0×10^–8 mol L^–1. The precision is excellent with relative standard deviations of 2.6% at a concentration of 1.0×10^–7 mol L^–1 telmisartan. The proposed method has been applied to the direct determination of the telmisartan in capsule forms and biological samples. The proposed method has been proved to be advantageous over existing CZE and MEKC methods in simplicity, rapidity, and reproducibility.     

Polarographic catalytic wave of hydrogen

A polarographic catalytic hydrogen wave of bovine serum albumin (BSA) at about-1.80 V (vs. SCE) in NH₄Cl-NH₃ · H₂O buffer is further catalyzed by such oxidants as iodate, persulfate and hydrogen peroxide, producing a kinetic wave. Studies show that the kinetic wave is a parallel catalytic wave of hydrogen, which resulted from that hydrogen ion is electrochemically reduced and chemically regenerated through oxidation of its reduction product, atomic hydrogen, by oxidants mentioned above. It is a new type of poralographic catalytic wave of protein, which is suggested to be named as a parallel catalytic hydrogen wave.     

有机化合物极谱催化波研究的进展

评述有机化合物极谱催化波研究的进展．建议有机化合物极谱催化波的主要类型及其命名分别为：(1)平行催化波,包括平行催化波、诱导吸附-平行催化波和缔合-平行催化波;(2)平行催化氢波,包括平行催化氢波和缔合-平行催化氢波．简要介绍蛋白质、黄酮类化合物、甾族类化合物、醌类化合物、α,β-不饱和羰基化合物、含氮化合物和荷电表面活性剂等不同种类有机化合物的极谱催化波及其应用．     

Polarographic catalytic wave of hydrogen——Parallel catalytic hydrogen wave of bovine serum albumin in the presence of oxidants

A polarographic catalytic hydrogen wave of bovine serum albumin (BSA) at about -1.80 V (vs. SCE) in NH4CI-NH3 · H2O buffer is further catalyzed by such oxidants as iodate, per-sulfate and hydrogen peroxide, producing a kinetic wave. Studies show that the kinetic wave is a parallel catalytic wave of hydrogen, which resulted from that hydrogen ion is electrochemically reduced and chemically regenerated through oxidation of its reduction product, atomic hydrogen, by oxidants mentioned above. It is a new type of poralographic catalytic wave of protein, which is suggested to be named as a parallel catalytic hydrogen wave.     

过硫酸钾存在下曲匹布通极谱平行催化波的研究及其应用

采用平行催化波法、循环伏安法等手段研究了在KH2PO4-Na2HPO4介质中过二硫酸钾存在下曲匹布通平行催化波产生的机理。曲匹布通的羰基官能团C=O在KH2PO4-Na2HPO4介质中以2e-,2H+方式极谱还原,产生了单个还原波。加入氧化剂过二硫酸钾时,曲匹布通还原中间体自由基在电极表面上能被过二硫酸钾及其中间还原体硫酸根阴离子自由基氧化,再生为原可还原基团C=O,从而产生了曲匹布通的平行催化波。基于此,提出了一种测定曲匹布通的新方法。     

黄芩甙的极谱催化波研究及应用

在 0 .2 4mol/L混合酸 NaOH(Britton Robinson) (pH 2 .0 ) -8× 1 0 -3 mol/LKIO3 支持电解质中 ,黄芩甙产生一极谱催化波 ,峰电位为 -1 .2 0V(vs.SCE)。该波的一阶导数峰峰电流与黄芩甙浓度在 1×1 0 -7～ 3× 1 0 -6mol/L范围内呈线性关系 (r=0 .9988)。用该法测定了三黄片中黄芩甙的含量。该催化波是有机化合物极谱催化波的一种新类型—缔合 /平行催化波。IO-3 有双重作用 :( 1 )IO-3 作为配位体与吸附在电极表面的质子化黄芩甙形成离子对缔合物 ,引起峰电位的负移 ;( 2 )IO-3 及其还原中间体作为氧化剂氧化黄芩甙羰基经单电子单质子还原产生的自由基 ,产生了极谱催化波     

Polarographic Catalytic Wave of Prednisone in the Presence of Persulfate and its Application

 A polarographic catalytic wave of prednisone in the presence of K₂S₂O₈ was observed. The polarographic catalytic wave of prednisone as catalyst was attributed to such chemical reaction parallel to electrode reaction as oxidized the free radical from one electron reduction of the Δ^1,4-3 keto group of prednisone to regenerate the original keto group. The catalytic wave can be used for the determination of prednisone with the help of conventional polarographic equipment, such as linear-potential scan polarograph. In 0.12 mol l⁻¹ HAc-0.08 mol l⁻¹ NaAc-0.014 mol l⁻¹ K₂S₂O₈ (pH 4.6) supporting electrolyte, the second-order derivative peak current of the catalytic wave was rectilinear to prednisone concentration in the range of 3.2 × 10⁻⁷∼1.6 × 10⁻⁵ mol l⁻¹. The detection limit was 8.0 × 10⁻⁸ mol l⁻¹. Received August 6, 2001; accepted April 17, 2002; published online July 22, 2002     

A polarographic study of the pre-sodium type catalytic hydrogen wave exhibited by selenocystine

Selenocysteine, formed by reduction of selenocystine at the DME at about -0.6 V in an ammoniacal buffer, produces a pre-sodium catalytic hydrogen wave. The effects on this wave of variation of several physico-chemical parameters such as selenocystine concentration, mercury column height, buffer capacity and concentration, and ionic strength, have been studied. The results obtained all support the conclusion that the wave is of pre-sodium type. The partially protonated species of selenocysteine seem to be catalytically active. An analytical determination of selenocystine in the presence of selenocysteine, based on this study, is proposed.     

A new type of boronic acid fluorescent reporter compound for sugar recognition

Fluorescent boronic acids that change fluorescent properties upon carbohydrate binding are very useful for the preparation of fluorescent sensors for sugars. Herein we report 5-quinolineboronic acid (5-QBA) that shows significant fluorescent property changes through a unique pK_a-switching mechanism upon binding a diol in aqueous solution.     

叶酸的平行催化波及其分析应用

在Britton-Robinson(pH 4.1)的缓冲溶液中叶酸于-0.56 V(vs.SCE)产生一还原波,该波能被氧化剂过硫酸钾催化形成平行催化波.催化波峰电位不变,峰电流增加10倍,二阶导数波波高与叶酸的浓度在5.0×10-9～3.5×10-7 mol/L范围内呈线性关系(r=0.999),检出限可达3.0×10-9mol/L.方法简便灵敏,运用该法测定了叶酸片剂中的叶酸.     

Investigation of CF2 carbene on the surface of activated charcoal in the synthesis of trifluoroiodomethane via vapor-phase catalytic reaction

This paper investigates the synthetic mechanism of trifluoroiodomethane (CF₃I) in the reaction of trifluoromethane and iodine via vapor-phase catalytic reaction. It is suggested that CF₂ carbene is the key intermediate and is formed in the pyrolysis process of CHF₃ at high temperature. However, in pyrolysis of CHF₃ under activated charcoal (AC) existing conditions, no C₂F₄ was detected. H₂ and 2-methyl-2-butene could not trap the CF₂ carbene. When treating the remained compounds on the used AC with H₂, CH₄ is formed on the process. It is proposed that CF₂ carbene combines with AC strongly and transfers into CF₃ radical on heat. In addition, it is found that the AC is not only the catalyst supporter to form CF₃I, but also a co-catalyst to promote the formation of CF₂ carbene and CF₃ radical.