盐酸去氯羟嗪和盐酸氯丙那林的毛细管电泳-电致化学发光法同时测定

基于盐酸去氯羟嗪和盐酸氯丙那林都能增强联吡啶钌的电致化学发光信号,建立了一种分离检测海珠喘息定片中盐酸去氯羟嗪和盐酸氯丙那林的毛细管电泳-电致化学发光新方法.考察了联吡啶钌浓度、检测电位、磷酸盐缓冲液(PBS)浓度及其pH值、进样电压和进样时间等实验条件对分离、检测体系的影响.在优化的实验条件下,海珠喘息定片中的盐酸去氯羟嗪和盐酸氯丙那林在4 min内可实现分离检测.其线性范围均为5×107～1 × 10-5mol/L(相关系数分别为0.998 4和0.999 0),检出限分别为1.05×10-7mol/L和6.98×10-8mol/L(S/N=3).     

QuEChERS-高效液相色谱/质谱联用法测定猪肉中氯丙那林

利用QuEChERS-高效液相色谱/质谱联用法建立了猪肉中氯丙那林的定性定量分析方法。猪肉样品用乙酸乙酯和K2CO3超声提取,加入C18、PSA和中性Al2O3粉离心净化样品;采用Aglient XDB-C18色谱柱(150×4.6mm,3.5μm),流动相为0.1%甲酸-甲醇上机监测;采用电喷雾离子源正离子模式(ESI+)和多反应监测模式(MRM)进行质谱分析。结果表明,氯丙那林在0.005~5μg/L之间呈线性关系,相关系数(r)为1.0000;检出限和定量限分别为0.15μg/kg和2.50μg/kg。在2.5、5.0和10.0μg/kg添加水平下,氯丙那林的回收率(n=12)范围为70.32%~92.13%,相对标准偏差均小于10%(n=12)。该方法快捷,简单,成本低且安全有效,适用于猪肉中氯丙那林的痕量检测。     

手性流动相添加剂法拆分盐酸氯丙那林对映体

盐酸氯丙那林(Clorprenaline hydrochloride)其化学名为α-[[(1-甲基乙基)氨基]甲基]-2-氯-苯甲醇盐酸盐,分子中含有一个手性碳原子,分子式见图1.临床上使用的是盐酸氯丙那林外消旋体,可用于支气管哮喘、哮喘型支气管炎、慢性支气管炎合并肺气肿,可止喘并改善肺功能.     

超高效液相色谱-四极杆-飞行时间质谱检测和鉴定猪尿中氯丙那林的主要代谢产物北大核心CSCD

采用超高效液相色谱-四极杆-飞行时间质谱(UPLC/Q-TOF MS)检测和鉴定了猪尿中氯丙那林的主要代谢产物,并讨论了氯丙那林在猪体内的主要代谢途径。按10 mg/kg(b.w.)的剂量口服灌食氯丙那林,分别采集给药前及给药后的猪尿液样品。采用UPLC/Q-TOF MS对样品进行分析,并应用质量亏损过滤和离子色谱峰提取等数据处理技术,在给药后24 h内的猪尿中检测和鉴定了9种氯丙那林的代谢产物,其中,Ⅰ相代谢产物2种,Ⅱ相代谢产物7种。然后,根据氯丙那林原形和代谢产物的碎片离子特征,对代谢产物的结构进行鉴定。最后,根据所鉴定的代谢产物,推测氯丙那林在猪体内的代谢途径包括苯环羟基化、β-羟基和仲氨基的葡萄糖醛酸轭合、羟基化后的葡萄糖醛酸和硫酸轭合等。研究结果表明,羟基化氯丙那林及其轭合产物的相对含量大于60%,明显高于氯丙那林原形及其轭合产物,是尿液中的主要代谢产物。本研究将为确定氯丙那林在动物体内的残留标示物及加强对氯丙那林非法使用的监控提供科学依据。     

超高效液相色谱-四极杆-飞行时间质谱检测和鉴定猪尿中氯丙那林的主要代谢产物

采用超高效液相色谱-四极杆-飞行时间质谱(UPLC/Q-TOF MS)检测和鉴定了猪尿中氯丙那林的主要代谢产物,并讨论了氯丙那林在猪体内的主要代谢途径。按10 mg/kg(b. w.)的剂量口服灌食氯丙那林,分别采集给药前及给药后的猪尿液样品。采用UPLC/Q-TOF MS对样品进行分析,并应用质量亏损过滤和离子色谱峰提取等数据处理技术,在给药后24 h内的猪尿中检测和鉴定了9种氯丙那林的代谢产物,其中,Ⅰ相代谢产物2种,Ⅱ相代谢产物7种。然后,根据氯丙那林原形和代谢产物的碎片离子特征,对代谢产物的结构进行鉴定。最后,根据所鉴定的代谢产物,推测氯丙那林在猪体内的代谢途径包括苯环羟基化、β -羟基和仲氨基的葡萄糖醛酸轭合、羟基化后的葡萄糖醛酸和硫酸轭合等。研究结果表明,羟基化氯丙那林及其轭合产物的相对含量大于60%,明显高于氯丙那林原形及其轭合产物,是尿液中的主要代谢产物。本研究将为确定氯丙那林在动物体内的残留标示物及加强对氯丙那林非法使用的监控提供科学依据。     

超高效液相色谱-串联质谱法同时测定饲料中3种氯丙那林异构体和巴氯芬

以溶剂提取-固相萃取为前处理方式,建立了超高效液相色谱-串联质谱法检测饲料中3种氯丙那林异构体和巴氯芬的新方法。试样用0.1 mol/L HCl-甲醇(4∶1,V/V)溶剂振荡提取20 min,离心去杂质后由MCX柱净化、浓缩,经Waters BEH C18色谱柱梯度洗脱分离,串联质谱法测定,正离子扫描,并以外标法计算结果。方法检出限为20μg/kg,定量限为50μg/kg。4种目标化合物在3个添加水平上进行回收实验,回收率均在80%~110%之间;相对标准偏差均小于或等于10.2%。     

毛细管电色谱-电喷雾-飞行时间/质谱联用分离分析混合手性药物

建立了一种毛细管电色谱-电喷雾-飞行时间/质谱(CEC-ESI-TOF/MS)联用分离分析盐酸异丙肾上腺素和盐酸氯丙那林混合手性药物的方法。利用实验室自制有机-无机杂化开管柱作为色谱分离柱,考察了缓冲溶液的浓度、p H值、运行电压、分离温度、鞘液的种类、鞘液添加剂、鞘液的流速等分离检测条件对分离度和电离强度的影响。结果表明,在优化的分离检测条件下,两种混合手性药物的4个组分在18.5min内实现基线分离。     

反相高效液相色谱/电喷雾质谱法测定血浆中盐酸舍曲林

采用反相高效液相色谱-电喷雾质谱法(LC-ESI/MS)测定人体血浆中盐酸舍曲林。以盐酸丙咪嗪为内标,按内标法定量。血浆样品经pH 10.00碳酸钠溶液碱化,加入甲基叔丁基醚萃取,离心分离,取上清液吹干,用流动相溶解进样。色谱柱:RP-Extend-C18(150 mm×4.6 mm,5μm),柱温:40℃;流动相:pH 3.00的三氟乙酸溶液-甲醇(40∶60,V/V),流速0.6 mL/m in。质谱采用选择离子监控模式,检测离子的核质比(m/z)分别是281(丙咪嗪)和159(舍曲林)。舍曲林和丙咪嗪的保留时间分别是5.4 m in和3.8 m in;舍曲林标准曲线线性范围为1~80μg/L;检出限为1.0μg/L(S/N>10);日间、日内相对标准差均小于6.0%,相对回收率为90%~106%;提取回收率在75%~93%范围内。此法适合人体药代动力学的血浆样品的分析,结果准确、可靠。     

流动注射时间扫描荧光分析法测定盐酸二氧丙嗪

研究了硫酸颜色反应用于盐酸二氧丙嗪荧光测定的方法.盐酸二氧丙嗪与浓硫酸反应后,诱发产生强荧光.结合流动注射进样技术,借助时间扫描荧光方式,提出了流动注射时间扫描荧光分析法测定盐酸二氧丙嗪的新方法.体系最大激发和发射波长分别为274.0 nm和376.0 nm.盐酸二氧丙嗪浓度在2.8×10-7～4.0×10-5g/mL...     

盐酸二氧丙嗪分子印迹电极的制备与性能研究

以邻苯二胺为功能单体,盐酸二氧丙嗪为模板分子,对盐酸二氧丙嗪分子印迹电极制备与性能进行了研究。建立了一种新的测定盐酸二氧丙嗪的电化学分析方法。用循环伏安法和差分脉冲伏安法法研究了该电极的选择性和灵敏度。该分子印迹电极对盐酸二氧丙嗪分子具有显著的催化还原和选择作用。在p H5.6的乙酸-乙酸钠缓冲溶液中,还原峰电流与盐酸二氧丙嗪浓度在0.01~1.0 mg/m L范围内呈良好的线性关系,检出限为0.005 mg/m L。方法可用于药剂中盐酸二氧丙嗪含量的测定。     

近红外光谱快速测定复方磺胺甲噁唑药效成分

基于近红外漫反射光谱技术,利用偏最小二乘多元校正方法建立了复方磺胺甲噁唑片中的两个有效成分磺胺甲噁唑(SMZ)和甲氧苄啶(TMP)含量的快速同时测定方法。对于SMZ和TMP定量分析模型,相关系数分别为99.969%与99.938%,校正集残差分别为0.217与0.159,而预测根均方差分别为0.310和0.418。该方法具有简单、快捷、两组分同时准确测定以及样品不经任何预处理等特点。     

近红外光谱测定复方对乙酰氨基酚片的有效成分

复方对乙酰氨基酚是临床上常用的解热镇痛药,常用剂型有片剂和注射剂,其片剂含有对乙酰氨基酚、阿司匹林和咖啡因等三种有效成分。对于该制剂的质量控制,《中国药典》[1]利用分光光度法测定对乙酰氨基酚的含量,用氢氧化钠标准溶液、高氯酸标准溶液分别滴定阿司匹林和咖啡因从而     

近红外光谱法同时测定通天口服液中天麻素和芍药苷的含量

本文应用近红外光谱结合偏最小二乘法建立了同时测定通天口服液中天麻素与芍药苷含量的方法。以高效液相色谱(HPLC)法测定通天口服液样品中天麻素和芍药苷的化学参考值,随机抽取60个样本作校正集,20个样本作预测集。用偏最小二乘法(PLS)将校正集样本的近红外光谱与相应样本的天麻素和芍药苷含量分别相关联建立模型。结果表明,天麻素和芍药苷校正模型的决定系数分别为96.28%、94.55%,模型的交叉验证均方差分别为0.0336、0.00908,预测集的决定系数分别为94.23%、92.86%,预测集均方差分别为0.0453、0.00839。同时还做了模型的精密度实验,该方法能用于大批量样品的快速分析。     

偏最小二乘紫外分光光度法同时测定丁烯二酸的顺反异构体

将偏最小二乘法用于紫外分光光度分析,在pH=1.4的磷酸溶液中,同时测定了丁烯二酸的顺、反异构体。确定了测定的最佳波长范围为190～268nm;测得23个混合标样的吸光度值用于建立模型,顺、反丁烯二酸的浓度范围为3.0～14.0mg/L和1.0～13.0mg/L。所建立的测定二者模型的相关系数分别为0.9951和0.9983;平均回收率分别为100.8%和100.7%;均方根误差(RMSE)分别为0.3667和0.2233;预测相对误差(REP)分别为5.05%和3.49%。对3个批次反丁烯二酸样品的测定结果与高效液相色谱法的测定结果进行比较,经成对t检验表明,两种方法的测定结果无显著性差异。     

Direct Kinetic Determination of Bromhexine Hydrochloride in Pharmaceutical Formulations

Abstract

A very simple, automatic, fast method for the photometric determination of bromhexine hydrochloride based on the application of kinetic methodology and the stopped-flow mixing technique to the coupling reaction between the diazotized bromhexine derivative and N-(1-naphthyl)ethylenediamine is proposed. The high initial rate of this reaction allows analytical measurements to be made within only 0.5–1 s, which makes the method applicable to automatic routine analyses. The calibration graph is linear over the range 1.5–65.0 μg mL^?1 and the precision (as %RSD) is less than 2%. The presence of antibiotics such as penicillins and cephalosporins in a 100-fold excess has no effect on the analyte determination. The proposed method was satisfactorily used for direct analysis of pharmaceutical formulations containing these antibiotics.     

Rapid and Nondestructive Analysis of Bacillus Calmette–Guerin Polysaccharide Nucleic Acid Injection by near-Infrared Spectroscopy with Chemometrics

A novel quantitative analytical method using near-infrared (NIR) spectroscopy combined with chemometrics has been developed to determine the polysaccharides and nucleic acids for routine quality analysis of Bacillus Calmette–Guerin polysaccharide and nucleic acid injections. A Monte-Carlo method was used to detect and discard outliers and to improve the predictive ability of the model. Various other spectral preprocessing methods such as smoothing, derivative, multiplicative scattering correction, standard normal variables, and orthogonal signal correction methods were used to remove noise and other irrelevant information from the spectra. Sample-set partitioning based on joint x–y distance method was utilized to divide the sample measurements into calibration and validation datasets. The optimal wavelength variables were determined by competitive adaptive weighted sampling. The model was established and cross-validated using partial least square regression. The root mean square errors of cross-validation for polysaccharides and nucleic acids were determined to be 0.0382 and 5.218, and the root mean square errors of prediction were 0.0229 and 6.282. The overall results show that NIR spectroscopy combined with chemometry is effective for the quantitative analysis of Bacillus Calmette–Guerin polysaccharide and nucleic acid injections.     

Determination of Fipronil in Acetamiprid Formulation by Attenuated Total Reflectance-Mid-Infrared Spectroscopy Combined with Partial Least Squares Regression

There is a high demand for rapid determination of fipronil in pesticide preparations because it has been restricted and even prohibited in many countries. An infrared-based methodology was developed for this analyte in acetamiprid formulations by attenuated total reflectance mid-infrared spectroscopy. The quantitative calibration models of fipronil were established by partial least squares regression. The determination coefficients (R²) of the model were above 0.99 while both the root mean square error of prediction and root mean square error of calibration were below 0.0011, which showed the partial least squares model accurately predicted fipronil concentrations in acetamiprid. The accuracy was further demonstrated by comparison with another two models' results of low (<1.0%, w/w) and high concentration sample sets (1.0%–4.5%, w/w). These results demonstrate the potential of infrared spectroscopy to quickly detect fipronil in acetamiprid.     

Noncontact analysis of the fiber weight per unit area in prepreg by near-infrared spectroscopy

The fiber weight per unit area in prepreg is an important factor to ensure the quality of the composite products. Near-infrared spectroscopy (NIRS) technology together with a noncontact reflectance sources has been applied for quality analysis of the fiber weight per unit area. The range of the unit area fiber weight was 13.39–14.14 mg cm⁻². The regression method was employed by partial least squares (PLS) and principal components regression (PCR). The calibration model was developed by 55 samples to determine the fiber weight per unit area in prepreg. The determination coefficient (R²), root mean square error of calibration (RMSEC) and root mean square error of prediction (RMSEP) were 0.82, 0.092, 0.099, respectively. The predicted values of the fiber weight per unit area in prepreg measured by NIRS technology were comparable to the values obtained by the reference method. For this technology, the noncontact reflectance sources focused directly on the sample with neither previous treatment nor manipulation. The results of the paired t-test revealed that there was no significant difference between the NIR method and the reference method. Besides, the prepreg could be analyzed one time within 20 s without sample destruction.     

傅里叶变换近红外光谱法快速检测人血清生化成分

应用傅里叶变换近红外光谱透射技术结合偏最小二乘法(PLS)建立了人血清中7种生化成分的定标模型,利用内部交叉验证和自动优化功能对定标模型进行了优化,确定了最优建模参数。模型对人血清中总胆固醇、甘油三酯、总蛋白、白蛋白、载脂蛋白B、低密度脂蛋白胆固醇、葡萄糖定标样品集的预测值与化学值的相关系数r分别为0.9011、0.9593、0.9249、0.761、0.8831、0.5191、0 9148,预测校正标准误差RMSECV分别为15mg/dL,21.6mg/dL,2 66g/L,3 96g/L,0.091g/L,16.2mg/dL,0.49mmol/L。     

用局部拟合主成分回归计算光度分析法测定黄连生物碱

针对具有样本数据非无匀分布和非线性特点的光度分析问题，提聘种局部拟合 主成分回归法，用于中药多组分计算测定。该方法根据待测样本与各已知样本光度 分析数据的欧式距离确定相应的权值，将部分权值较大的样本组成校正集，并用分 段线性拟合算法建立待测样本的校正预测模型，将其用于分析黄连的药根碱、巴巴 亭和小檗碱等三种生物碱，所得预测均方根误差分别为0.023,0.0400和0.052，优 于主成分回归法、偏最小二乘法以及人工神经元网络法所得结果。这表明，本方法 用于中药光度分析能获得较为准确的计算分析结果。