倒数示波计时电位法在药物分析中的应用

倒数示波计时电位法在药物分析中的应用胡娟，朱俊杰，郑建斌，高鸿（南京大学化学系，南京，２１０００８）关键词：倒数示波计时电位法，吡哌酸，盐酸普萘洛尔，盐酸氯丙嗪，盐酸普鲁卡因，直接测定。目前，大部份药物测定均采用药典法￣［１］，但由于药典法分析某些药...     

甲氧氯普胺的流动注射光度分析

基于在盐酸介质中,利用甲氧氯普胺－亚硝酸钠－α－萘胺的重氮化－偶合反应,建立了流动注射光度法测定甲氯普胺的新方法,利用单纯形优化法选择了最佳实验条件。方法的线性范围为0.0-30mg/L,进样频率为160／h。11次重复测定的相对标准偏差小于0.6％,该方法已成功用于药物中甲氧氯普胺含量的测定,测定结果与药典法对照,并经统计学处理,结果满意。     

碳糊电极法测定普鲁卡因注射液中普鲁卡因的含量

制备了一种以普鲁卡因与单质碘形成的缔合物为电活性物的全固态碳糊普鲁卡因电极,利用该电极对普鲁卡因的响应测定普鲁卡因注射液中普鲁卡因的含量。电极的线性响应范围为3．5×10^-5～0．1mol／L,线性回归方程为E=57．01gc＋102．2,相关系数r=0．999,检出限为2．5×10^-5mol／L。盐酸普鲁卡因的回收率在96．1％～104.3％之间,测定结果的相对标准偏差为1．86％-2.30％（n=5）。该电极响应迅速,重现性好。用该电极测定了盐酸普鲁卡因注射液中普鲁卡因的含量,测定结果与药典法测定结果相符。     

水杨基荧光酮—Tween—80荧光熄灭法直接测定水样中镍

在硼砂－盐酸缓冲液中，Ｔｗｅｅｎ－８０存在下，水杨基荧光酮与镍具有荧光熄灭的特性．利用该特性拟定了镍的测定方法．该法灵敏度高，选择性好，可直接用于水样中镍的测定，取得了满意的结果．     

电化学发光法测定盐酸普鲁卡因

基于盐酸普鲁卡因对鲁米诺在中性介质中铂电极上电化学发光的催化增敏作用 ,建立了测定盐酸普鲁卡因电化学发光新方法。电化学发光强度与盐酸普鲁卡因质量浓度在 4 .0× 1 0 -7～6 .0× 1 0 -6g mL范围内有良好的线性关系 ,检测限为 2 .0× 1 0 -7g mL,相对标准偏差为 4 .4 %。该方法已用于针剂中盐酸普鲁卡因的测定     

原子发射光谱法间接测定黄连素片剂中盐酸小檗碱的研究

本文提出了离子对-原子发射光谱间接测定黄连素片剂中盐酸小檗碱的新方法。发现用1,2-二氯乙烷作萃取剂效果最佳。用此怯测定实际样品的结果与药典法一致,相对误差为0.61％,单一测定的相对标准偏差为0.67％。本法还可在盐酸普鲁卡因共存下单独测定盐酸小檗碱。方法可靠、适用,选择性较好。     

基于SERRS法检测盐酸普鲁卡因

结合偶氮衍生反应,建立了盐酸普鲁卡因的表面增强共振拉曼散射(SERRS)检测方法。将对巯基苯胺(PATP)重氮化,得到的重氮盐离子与盐酸普鲁卡因发生偶氮衍生反应,生成相应偶氮产物,再与银纳米粒子混合并立即进行拉曼测试,最后利用偶氮产物的SERRS响应检测盐酸普鲁卡因含量。优化实验条件为：最大吸收峰波长为442 nm的银溶胶作为增强基底,532 nm作为激发波长,偶氮衍生的最佳时间为20 min,偶氮衍生过程中最佳Na₂CO₃质量浓度为8%。在10 ng/mL～10μg/mL范围内,得到SERRS强度比值I₁₄₃₅/I₃₈₄(y)与盐酸普鲁卡因浓度负对数(x)间的线性方程为y=78.97421-8.66853x,线性相关系数R²为0.9774,检出限(LOD)为8.196 ng/mL。方法对盐酸普鲁卡因注射液测定结果与标准值基本一致,采用标准加入法测得回收率在96.4%～103.3%之间,相对标准偏差(RSD)在3.4%～6.4%之间。将方法用于大鼠血清模拟样品测定,回收率在96...     

1,2-萘醌-4-磺酸钠为显色剂吸光度差值法测定盐酸普鲁卡因

1,2-萘醌-4-磺酸钠与盐酸普鲁卡因在pH 4.70的条件下反应,产物在300和483 nm处有两个吸收峰,可用两波长下吸光度差值测定盐酸普鲁卡因,本文对吸光度差值与分析物浓度之间的关系作了理论推导。吸光度差值(ΔA)与盐酸普鲁卡因质量浓度在2.0~36.0 mg/L范围内具有良好线性关系,线性回归方程为:ρ=37.092 0ΔA-0.332 3,线性相关系数为0.999 1,相对标准偏差为1.49%,回收率为97%~105%。试验了pH值、放置时间及干扰离子对测定的影响。此法简便、快速、准确,可用于注射液中盐酸普鲁卡因含量的测定,与药典方法对照,结果满意。     

流动注射化学发光法测定盐酸异丙嗪

在酸性溶液中，高锰酸钾能氧化盐酸异丙嗪产生化学发光反应，乙二醛的存在可使发光强度增强。据此，采用流动注射技术，建立了一种测定盐酸异丙嗪的化学发光分析分析。方法的检出限为３．５×１０＾－８ｇ／ｍＬ，相对标准偏差为２．８％（１．０×１０＾－６ｇ／ｍＬ盐酸异丙嗪，ｎ＝１１），线性范围为１．０×１０＾－７￣６．０×１０＾－５ｇ／ｍＬ。该法已用于盐酸异丙嗪针剂和片剂中盐酸异丙嗪含量的测定，并与药典标准方法进     

纳米金探针瑞利共振散射法测定针剂中盐酸普鲁卡因

采用葡萄糖还原氯金酸的方法制得粒径约15nm的纳米金,在pH3.54酸性介质中它可以与盐酸普鲁卡因作用形成体积更大的纳米金聚集体。这种聚集体的形成可以使纳米金的瑞利共振散射强度急剧增强,其最大散射峰位于354nm左右。在适当的条件下,相对散射强度(ΔI)与盐酸普鲁卡因的浓度成正比。采用标准加入法,对针剂中的普鲁卡因进行测定,得到满意结果。线性范围0～40μg/L(r=0.9996);对含盐酸普鲁卡因30μg/L的溶液平行测定的相对标准偏差为2.51%(n=11);检出限(3σ)为16ng/L;测定限(10σ)为54ng/L。     

Spectrophotometric determination of procaine hydrochloride in pharmaceutical products using 1,2-naphthoquinone-4-sulfonic acid as the chromogenic reagent

Spectrophotometric determination of procaine hydrochloride is described. The procaine hydrochloride reacts with 1,2-naphthoquinone-4-sulfonic acid in pH 3.60 buffer solution to form a salmon pink compound, and its maximum absorption wavelength is at 484 nm, epsilon(484)=5.22 x 10(3).The absorbance for procaine hydrochloride from 0.30 to 100 microg ml(-1) obeys Beer's law. The linear regression equation of the calibration graph is C=19.23A-0.03, with a linear regression correlative coefficient is 0.9996, the detection limit is 0.28 microg ml(-1); recovery is from 98.0 to 105.2%. Effects of pH, surfactant, organic solvent, foreign ions, and standing time on the determination of procaine hydrochloride have been examined. This method is rapid and simple, and can be used for the determination of procaine hydrochloride in injection solution of procaine hydrochloride. The results obtained by this method agreed with those by the official method (dead-stop titration).     

Use of p-dimethylaminobenzalhyde as a colored reagent for determination of procaine hydrochloride by spectrophotometry

Spectrophotometric determination of procaine hydrochloride is described. The procaine hydrochloride reacts with p-dimethylaminobenzalhyde in glacial acetic acid to form an Schiff base which is a yellow compound, and its maximum absorption wavelength is at 455nm, ₄₅₅=3.46×10⁴. The absorbance for procaine hydrochloride from 0.2 to 15 μg ml⁻¹ obeys Beer's law. The linear regression equation of the calibration graph is C=5.866A−0.02, with a linear regression correlative coefficient is 0.9994 and relative standard deviation (RSD) of 1.7%; the detection limit is 0.1 μg ml⁻¹; recovery is from 92.0 to 110.0%. Effects of reaction medium, temperature, gentamycin, beneylpenicillin, kanamycin, streptomycin, foreign ions, and stand for time on the determination of procaine hydrochloride have been examined. The results obtained by this method agreed with those by the official method (dead-stop titration). This method is rapid and simple, and can be used for the determination of procaine hydrochloride in injection solution of procaine hydrochloride.     

Determination of trace procaine hydrochloride by differential pulse adsorptive stripping voltammetry with a Nafion modified glassy carbon electrode.

A sensitive and selective method for the determination of procaine hydrochloride with a Nafion-modified glassy carbon electrode has been developed. The voltammetric behavior of procaine hydrochloride on the Nafion-modified electrode indicated that the modified electrode not only increased the sensitivity of the determination of procaine hydrochloride, but also catalyzed the electrode process. Procaine hydrochloride was accumulated in Britton-Robinson buffer (pH 2.09) at a potential of -0.2 V (vs. SCE) for 180 s, and was then determined by differential pulse adsorptive stripping voltammetry. The effect of various parameters, such as the pH of the medium, the mass of drop-coated Nafion, the accumulation potential, the accumulation time and the scan rate, were investigated. Under the optimum conditions, a linear calibration graph was obtained in the concentration range of 6.0 x 10(-8) to 6.0 x 10(-6) mol l(-1) with a correlation coefficient of 0.9987. The relative standard deviation was 4.18% for eight successive determinations of 1.0 x 10(-7) mol l(-1) procaine hydrochloride, and the detection limit (three times signal to noise) was 7.0 x 10(-9) mol l(-1). A study of interfering substances was also performed, and the method was applied to the direct determinations of procaine hydrochloride in the injection solution of procaine hydrochloride and in rabbit serum.     

Spectrophotometric determination of procaine hydrochloride with hemoglobin as catalyst

A highly sensitive and simple spectrophotometric method for the determination of procaine hydrochloride based on its inhibitory effect on the hemoglobin-catalyzed reaction of H₂O₂ and acid chrome blue K(ACBK) was developed. The concentration of procaine hydrochloride is in linear relationship with the percentage inhibition (I%) of system under the optimal experimental conditions. The calibration graph is linear in the range from 1.50 × 10⁻⁷ to 4.15 × 10⁻⁶ M with the detection limit of 3.80 × 10⁻⁸ M. This method can be used for the determination of procaine hydrochloride in injection solution of procaine hydrochloride with satisfactory results. The article is published in the original. The article is published in the original.     

Electrochemistry and voltammetry of procaine using a carbon nanotube film coated electrode

A new rapid, convenient and sensitive electrochemical method is described for the determination of procaine in pharmaceutical preparations, based on the unique properties of a multi-wall carbon nanotube (MWNT) thin film. The electrochemical behavior of procaine at the MWNT film-coated glassy carbon electrode (GCE) was investigated in detail, showing that the MWNT-coated GCE exhibits electrocatalytic activity to the oxidation of procaine because of the significant peak current enhancement and the lowering of oxidation overpotential. Furthermore, the mechanism for the oxidation of procaine at the MWNT-coated GCE was also studied. Finally, various experimental parameters such as solution pH value, the amount of MWNT, accumulation conditions and scan rate were optimized for the determination of procaine, and a new method with detection limit of 2 x 10(-7) mol/L was developed for procaine determination. This newly proposed method was successfully demonstrated with procaine hydrochloride injection.     

A Sensitive Electrochemical Sensor Based on Solution Polymerized Molecularly Imprinted Polymers for Procaine Detection

A sensitive and selective method for the determination of procaine hydrochloride using molecularly imprinted polymers (MIPs) modified glassy carbon electrodes was developed. The MIPs were prepared by solution polymerization using procaine hydrochloride as the template molecules and acrylic acid (AA) and vinyltriethoxysilane (WD‐20) as the functional monomer and cross‐linking agent, respectively. A film was formed on the surface of the glassy carbon electrodes and later cross‐linked with ethanol as solvent. Next, these electrodes were employed to detect procaine hydrochloride by differential pulse voltammetry (DPV). Under the optimized conditions, good linearity (correlation coefficient of 0.9986) was observed between the oxidation peak current and the concentration of procaine hydrochloride in the range of 4.0×10^?8 to 2.4×10^?5 M in a pH 7.0 0.04 M phosphate buffer solution, and the detection limit (S/N=3) was 1.02×10^?8 M. In addition, the stability and reproducibility of the sensors were satisfactory. Moreover, the concentration of procaine hydrochloride in human blood serum samples was detected, and its recoveries ranged from 97.5 % to 106.4 % with RSD less than 2.15 %. These results suggest that the prepared molecularly imprinted electrochemical sensors can be used for the determination of procaine in clinical studies.     

Determination of the binding constant for the inclusion complex between procaine hydrochloride and beta-cyclodextrin by capillary electrophoresis

The apparent electrophoretic mobilities of procaine hydrochloride (μ_i) in a series of concentration of β-cyclodextrin were measured directly by capillary electrophoresis technology. A new mathematical treatment method is proposed, which based on the fact that the molar ratio of the inclusion complex was 1:1 established by spectrophotometry. Using the proposed method, the binding constant of the inclusion complex of procaine hydrochloride with β-cyclodextrin can be obtained easily. The determination result was in correspondence with those of the spectrophotometric and fluorescence methods.     

Determination of procaine hydrochloride by ion-pairing flow injection analysis with piezoelectric detection

A fast and simple method for the determination of procaine hydrochloride by ion-pairing flow injection analysis has been developed. It is based on the formation of an ion-pair with sodium dodecyl phenylsulphonate and piezoelectric detection. The calibration curve was linear between 0.02 and 2.00 mg/mL, with a detection limit of 0.01 mg/mL, a relative standard deviation of 0.3% (10 replicates) and a sampling frequency of 120/h. The proposed method has been satisfactorily applied to the determination of procaine hydrochloride in pharmaceutical preparations. Received: 19 August 1996 / Revised: 6 November 1996 / Accepted: 12 December 1996     

Resonance Rayleigh scattering technology as a new method for the determination of the inclusion constant of beta-cyclodextrin

The interaction of procaine hydrochloride and beta-cyclodextrin in aqueous solution was studied using resonance Rayleigh scattering technology. The molar ratio of the inclusion complex was 1:1 established by spectrophotometry. The resonance Rayleigh scattering technology was first applied in the determination of the beta-cyclodextrin inclusion constant. The inclusion constant of procaine hydrochloride beta-cyclodextrin complex Kf is 1.23 x 10(2) and 1.27 x 10(2) l mol(-1) for method I and 1.15 x 10(2) and 1.21 x 10(2) l mol(-1) for method II. These determination results were in correspondence with the results of the spectrophotometric and fluorescence methods. Therefore, the resonance Rayleigh scattering method can be used as a new technology for the determination of the inclusion constant.     

共振非线性散射技术测定盐酸普鲁卡因与β-环湖精包结常数的新方法

盐酸普鲁卡因水溶液的共振非线性散射较弱，当β环糊精加人溶液中并与盐酸 普鲁片因形成包合物时，共振非线散射强度明显增强，且随着β-环糊精的浓度增 加，体系的共振非线性散射逐渐增强，利用共振非线性散射技术研究糊精与盐酸普 鲁卡因的相互作用，并发展了一种用二级散射、二倍频散射、三倍频散射和3／2倍 频散射技术测定β-包合物包结常数的新方法，测定结果与用分光光度法、荧光法 和共振瑞利散射法测得结果一致，从而建立起测定环糊精包结常数的新方法．