盐酸乙胺丁醇-Cu(Ⅱ)配合物的紫外光谱特征及含量测定

建立了一种间接测定盐酸乙胺丁醇含量的紫外-可见分光光度法。在pH 5.0介质中,盐酸乙胺丁醇与Cu~(2+)能以1:1的配比形成络合物,且在256 nm波长处有最大吸收,稳定常数为3.4×10~7。结果表明:在55.60～333.6μg/mL范围内,盐酸乙胺丁醇的浓度c与络合物的吸光度A之间呈现良好的线性关系,A=0.0005c+0.3003,r=0.9996,检出限为6.6μg/mL。将该方法应用于实际样品制剂的含量测定,得到加标回收率为95.2%～103.5%,RSDs为1.6%～2.8%。该方法可用于盐酸乙胺丁醇的含量测定。     

毛细管气相色谱法测定复方盐酸金刚乙胺胶囊中的盐酸金刚乙胺

复方盐酸金刚乙胺胶囊为一新的复方制剂,其主要成分为盐酸金刚乙胺、对乙酰氨基酚、盐酸伪麻黄碱和马来酸氯苯那敏,国内外均未上市,其生产工艺及处方正在申请专利。盐酸金刚乙胺是盐酸金刚烷胺的类似物,抗A型流感病毒活性比后者强,而中枢神经毒性比后者小。本文以盐酸金刚烷胺为内标,对样品先碱化后提取,然后采用气相色谱法（GC）测定其中的盐酸金刚乙胺含量。     

反向流动注射化学发光法测定盐酸乙胺丁醇

基于盐酸乙胺丁醇与高碘酸钾～鲁米诺反应产生很强的化学发光,结合反向流动注射技术,建立了流动注射化学发光法测定盐酸乙胺丁醇的新方法。在优化的实验条件下,该法的线性范围为4.0×10-8～2×10-5g/mL,检出限为8×10-9g/mL,对6.0×10-7g/mL盐酸乙胺丁醇进行11次平行测定,方法的相对标准偏差为1.9%。该法可用于片剂中盐酸乙胺丁醇的测定。     

阿司匹林双嘧达莫片溶出度及含量测定方法研究

建立了阿司匹林双嘧达莫片溶出度和含量的测定方法。采用Amethyst C18-H色谱柱(4.6 mm×250 mm, 5μm),以磷酸盐缓冲液-甲醇-乙腈为流动相，梯度洗脱，流速1.0 mL/min,检测波长235 nm。溶出度实验采用篮法，以0.1 mol/L盐酸溶液和磷酸盐缓冲液(pH 6.8)为溶出介质。结果表明：溶出度实验中双嘧达莫、阿司匹林和水杨酸质量浓度分别在0.5508～49.57、1.668～150.1和0.2004～18.04μg/mL范围内线性关系良好(r²≥0.9998),回收率在97.7%～102.0%之间(RSD≤1.0%,n=6)。含量测定实验中阿司匹林和双嘧达莫质量浓度分别在29.71～267.4μg/mL和10.42～93.78μg/mL范围内线性关系良好(r²≥0.9999),回收率在98.1%～101.0%之间(RSD<1.0%,n=9)。本方法准确性好、精密度高、操作简单，适用于阿司匹林双嘧达莫片溶出度和含量测定。     

基于标准制剂控制模式和定量指纹图谱评价复方甘草片的质量一致性

通过建立复方甘草片标准制剂（SP）控制模式和定量高效液相色谱指纹图谱,结合5个质量标志物的精准定量评价了9个厂家共145批复方甘草片质量一致性。首先建立了复方甘草片标准制剂的标准指纹图谱（SP-RFP）,然后以SP-RFP作为评价标准,采用系统指纹定量法对145批复方甘草片进行整体定性和整体定量评价。用双标校正法校正定量指纹图谱的系统误差,结果表明所检样品质量均合格。此外,在统一化色谱条件下测定各原料药和模拟样品,对制剂指纹进行归属相关度和准确度评判,得到原料指纹与制剂指纹的相关性,从而实现智能预测制剂或原料药质量和阻止低劣原料入药。同时用紫外全指纹溶出度法测定5个厂家的复方甘草片的溶出度曲线,用以评价制剂工艺的合理性。以上方法可行且准确度高,实现了对复方甘草片质量和工艺的一致性评价。该文为中药质量一致性评价提供了基础评价模式和基本操作思路以及具体实例。     

测量复方药物溶出度的全自动药物溶出度测定仪

自行设计组装了一套可以同时测定复方药剂的全自动药物溶出度测定仪.该仪器由光学检测系统(由光源、流动型吸收池,小型光谱仪组成)、自动进样系统、控制与数据处理系统和机械搅拌系统4部分组成.光学系统的检测器是线阵电荷耦合器件(CCD),故可进行同时全光谱采集.数据处理部分采用了自行设计的基于径向基函数的人工神经网络进行浓度预测.用本装置对市售复方药剂鲁南贝特进行的溶出度测量表明,测量的精密度高,准确度较高,分析速度快,样品无需前处理.     

近红外光谱法在琥乙红霉素片定量分析中的应用

运用近红外光谱法对14个厂家22个批次的琥乙红霉素片进行定量分析,包括琥乙红霉素片含量及溶出度的测定。通过偏最小二乘回归方法建立的含量均匀度和溶出度模型相关系数分别达0.99601和0.98189,校正均方根误差分别为0.670和0.575,预测均方根误差为0.646和0.514,与交叉验证均方根误差相近(分别为0.822和0.683)。基于准确性轮廓外部验证的95%的公差区间,样品相对误差低于5%,含量均匀度和溶出度模型的可预测性得到进一步的验证。本研究表明,近红外光谱法能用于琥乙红霉素片含量的测定,同时也能实现对不同厂家琥乙红霉素片溶出度的预测。     

关于召开2007年全国药物溶出度专题学术研讨会的通知

近年来,随着药学科技事业的不断发展,新型药物固体制剂不断涌现,药物溶出度已成为评价药物固体制剂的重要指标之一。为引导药物分析工作者及时了解国内外药物溶出度发展的最新动态,准确掌握相关信息和相关方法。经研究决定,拟定于2007年下半年在上海市召开全国药物溶出度专题学     

反相高效液相色谱-蒸发光散射检测法测定复方中的盐酸葡萄糖胺

建立了应用反相高效液相色谱-蒸发光散射检测器(RP-HPLC-ELSD)测定复方产品中盐酸葡萄糖胺含量的方法。该方法以C18色谱柱为固定相,甲醇-0.3%五氟丙酸为流动相,采用蒸发光检测器,测定了复方中盐酸葡萄糖胺的含量。结果表明,盐酸葡萄糖胺在0.2～1.0 mg/mL的质量浓度范围内二次回归的相关系数为0.9999,精密度(以相对标准偏差表示)为0.50%。该方法具有简便、快速、准确、重现性较好的特点。     

水杨酸片溶出度测定测量审核结果分析与常见问题探讨

通过对2015—2020年开展的水杨酸片溶出度测定测量审核工作的回顾和梳理,阐述了水杨酸片溶出度测量审核工作的实施模式,分析了可能影响溶出度测定结果的因素,并就参与实验室存在的问题和相关的改进措施进行了探讨。水杨酸片溶出度测定测量审核是相关实验室提升溶出度测定检测能力的一种有效方法,在加强组织方质量管理体系的改进和建设方面也有积极的促进作用。     

Liquid chromatographic determination of ethambutol in serum samples based on intramolecular excimer-forming fluorescence derivatization.

A selective liquid chromatographic method has been developed for the assay of ethambutol in serum samples. The assay involves intramolecular excimer-forming derivatization with 4-(1-pyrene)butanoyl chloride (PBC) and isocratic reversed-phase chromatography with fluorescence detection. After acetonitrile-deproteinization of the serum sample, the derivatization reaction of ethambutol with PBC was completed within 30 min at 50 degrees C. N,N'-Diethylethylenediamine was used as an internal standard. The detection limit of ethambutol was 23 ng/ml serum, corresponding to 180 fmol on column at a signal-to-noise ratio of 3. The present method was selective enough to analyze ethambutol in rabbit serum without any tedious sample clean-up procedure because biogenic monoamines gave no peak in the chromatogram. The method was applicable to drug monitoring in rabbit serum.     

High-performance liquid chromatographic determination of memantine hydrochloride in rat plasma using sensitive fluorometric derivatization

In this study, we investigated a simple, sensitive and reliable liquid chromatography‐fluorescence detection method for the determination of memantine hydrochloride in rat plasma which was based on derivatization with 9‐fluorenylmethyl chloroformate (FMOC‐Cl). For the first time, FMOC‐Cl was introduced into derivatization of memantine hydrochloride in rat plasma. The amino groups of memantine hydrochloride and amantadine hydrochloride (internal standard) were trapped with FMOC‐Cl to form memantine hydrochloride‐FMOC‐Cl and amantadine hydrochloride‐FMOC‐Cl compositions, which can be very compatible for LC‐FLD. Precipitation of plasma proteins by acetonitrile was followed by vortex mixing and centrifugation. Chromatographic separation was performed on a C₁₈ column (DIAMONSIL 150×4.6 mm, id 5 μm) with a mobile phase consisting of acetonitrile and water at a flow rate of 1.0 mL/min. The retention times of memantine hydrochloride‐FMOC‐Cl and amantadine hydrochloride‐FMOC‐Cl compositions were 23.69 and 40.27 min, respectively. Optimal conditions for the derivatization of memantine hydrochloride were also described. The limit of quantification (LOQ) was 25 ng/mL for memantine hydrochloride in plasma, the linear range was 0.025–5.0 μg/mL in plasma with a correlation coefficient (r) of 0.9999. The relative standard deviations (RSDs) of intra‐day and inter‐day assays were 4.46–12.19 and 5.23–11.50%, respectively. The validated method was successfully applied to the determination of memantine hydrochloride in rat plasma samples.     

Determination of ethambutol hydrochloride in the combination tablets by precolumn derivatization

A new high-performance liquid chromatography method for the quantitative determination of ethambutol hydrochloride in combination tablets is presented. Ethambutol is derivatized with phenylethylisocyanatate at room temperature (22 +/- 2 degrees C) for 5 min. Separation is performed by a C(18) column using methanol-water-glacial acetic acid (70:30:0.2, v/v/v) as the mobile phase. The method is linear for drug concentrations in the range of 20-120 microg/mL (r=0.9995). The intra- and inter-day precisions are lower than 1.46% and 2.22%, respectively. The average recovery of the samples at three levels is 99.8%. The results show that derivatization of ethambutol is stable at 30 degrees C for 24 h. This method is simple, rapid, and stable in the presence of common excipients and antituberculosis drugs in the tablets.     

Derivatization of secondary amines with 2-naphthalene-sulfonyl chloride for high-performance liquid chromatographic analysis of spectinomycin

A normal-phase high-performance liquid chromatographic (HPLC) method has been developed for the assay of spectinomycin hydrochloride and spectinomycin sulfate for detection at 254 nm. The method involves pre-column derivatization of secondary amines of spectinomycin with 2-naphthalenesulfonyl chloride (NSCl) using a catalyst. Lincomycin, 1-methylpyrrole, 2-acetyl-1-methylpyrrole, and 2-acetyl-pyrrole act as catalysts for sulfonylation of spectinomycin. Without a catalyst, the derivatization reaction forms a considerable amount of actinospectinoic acid, a degradation compound of spectinomycin, and peak area:weight ratio of the derivative is approximately 15% lower than those with the catalyst. Following derivatization the sample is extracted and chromatographed on a normal-phase silica column with detection at 254 nm. The method is applicable for the analysis of both the hydrochloride and sulfate salt forms of spectinomycin. All the known degradation compounds of spectinomycin such as actinamine, actinospectinoic acid and the biosynthesis intermediates, dihydrospectinomycin diastereoisomers, are completely separated with this method. Mass spectrometric data confirms that spectinomycin is derivatized with NSCl at the secondary amines located at positions 6 and 8 of the ring structure. The standard curves for the HPLC assay of spectinomycin hydrochloride and sulfate are linear with correlation coefficients of 0.9997 and 0.9999, respectively over the range of 0.05 mg/ml to 0.3 mg/ml. The relative standard deviations (R.S.D.) of the HPLC assay methods for spectinomycin hydrochloride and sulfate are 0.67% and 0.86%, respectively. Spectinomycin hydrochloride and sulfate bulk drugs were assayed by the HPLC method and compared to gas-liquid chromatography and microbiological assay results. The HPLC method was used to assay spectinomycin in a veterinary formulation, Linco-Spectin soluble powder. The sensitivity of the HPLC assay was determined to be approximately 4 ng sample load on the column, which suggests applicability in serum and residue level studies.     

Simple,Rapid, and Sensitive Determination of Thiols by Liquid Chromatography with Fluorescence Detection

Thiol compounds are important for protecting cells from oxidative stress. One common method of quantifying thiols is liquid chromatographic separation with fluorescence detection of their derivatives. The pH and the concentration of tris (2-carboxyethyl) phosphine hydrochloride in the reaction medium were shown to have significant effects on the fluorescence intensity of five thiol compounds: cysteine, glutathione, and three phytochelatins. The optimal pH range for derivatization, as indicated by the maximum fluorescence intensities, was 7.75–8.0 for all of the evaluated thiols. The thiol derivative fluorescence increased and then decreased with the tris (2-carboxyethyl) phosphine hydrochloride concentration. In particular, the fluorescence intensities of all of the derivatives decreased by 96.5–99.9% when tris (2-carboxyethyl) phosphine hydrochloride levels were increased from 0.1 to 1?mmol L^?1. We attributed these changes to preferential interactions between tris (2-carboxyethyl) phosphine hydrochloride and the thiol-specific fluorophore, monobromobimane. We describe herein a method, based on our optimized solution pH and tris (2-carboxyethyl) phosphine hydrochloride concentration, that is rapid (12?min) and boasts excellent recovery (91.3–102%), sensitivity (limit of detections, 17.8–75.2?pmol L^?1) and precision (relative standard deviation values ≤1.03%) for the quantification of these thiol compounds in microalgal samples.     

衍生化气相色谱法测定盐酸芬氟拉明片的纯度

 应用衍生化气相色谱法测定盐酸芬氟拉明片的纯度。样品溶解后经碱化乙酸乙酯提取 ,以盐酸美西律作内标 ,提取液用三氟乙酸酐进行酰化衍生化 ,衍生化产物在 5 %SE 30的色谱柱上分析 ,用氢火焰离子化检测器 (FID)检测。实验结果表明 ,芬氟拉明的质量浓度在 0 1g/L～ 0 5 g/L范围内线性良好 (r =0 9996 ) ;芬氟拉明与内标美西律的分离度大于 4;理论塔板数以芬氟拉明峰计大于 2 0 0 0 ;方法的精密度好 ,相对标准偏差 (RSD)为 1 4% (n=7) ;平均回收率为 (10 0 2± 2 2 ) % (n =6 ) ;检测限为 8ng。用该方法得到的结果灵敏、准确、重复性好。     

Determination of the DNA methylation level in tumor cells by capillary electrophoresis and laser-induced fluorescence detection

An analytical method to determine the genome-wide DNA methylation in only 100 ng DNA is presented. The analysis is based on DNA isolation and hydrolysis followed by derivatization of the 2'-desoxyribonucleoside-3'-monophosphates with a fluorescence dye (4,4-difluoro-5,7-dimethyl-4-bora-3a,4a-diaza-s-indacene-3-propionyl ethylene diamine hydrochloride, Bodipy FL EDA). The separation of the derivatives was carried out by micellar electrokinetic chromatography, and laser-induced fluorescence was used for detection. To calculate the methylation level, the derivatization factor and the quantum yields of the Bodipy conjugates of 2'-desoxycytidine-3'-monophosphate (dCMP) and 2'-desoxy-5-methylcytidine-3'-monophosphate (5m-dCMP) were determined by measurement of methylated Lambda DNA. The assignment was made by cochromatography with the synthesized and characterized standard compound 5m-dCMP. After optimization of the method it was possible to determine the methylation level in 100-ng DNA samples with a standard deviation of less than 5%.     

Headspace solid-phase microextraction with on-fiber derivatization for the determination of aldehydes in algae by gas chromatography-mass spectrometry

A simple, fast, sensitive and cost-effective method based on headspace solid-phase microextraction (HS-SPME) with on-fiber derivatization coupled with gas chromatography-mass spectrometry was developed for the determination of six typical aldehydes, 2E-hexenal, heptanal, 2E-heptenal, 2E,4E-heptadienal, 2E-decenal and 2E,4E-decadienal in laboratory algae cultures. As derivatization reagent, O-2,3,4,5,6-(pentafluorobenzyl) hydroxylamine hydrochloride, was loaded onto the poly(dimethylsiloxane)/divinylbenzene fiber for aldehydes on-fiber derivatization prior to HS-SPME. Various influence factors of extraction efficiency were systematically investigated. Under optimized extraction conditions, excellent method performances for all the six aldehydes were attained, such as satisfactory extraction recoveries ranging from 67.1 to 117%, with the precision (relative standard deviation) within 5.3-11.1%, and low detection limits in the range of 0.026-0.044 μg/L. The validated method was successfully applied for the analysis of the aldehydes in two diatoms (Skeletonema costatum and Chaetoceros muelleri), two pyrrophytas (Prorocentrum micans and Scrippsiella trochoidea) and Calanus sinicus eggs (feeding on the two diatoms above).     

基于巯基化衍生的气相色谱-质谱法测定有机相及水相中氯化氰

氯化氰(ClCN)是常用的化工中间体,也是《禁止化学武器公约》附表颁布的化学毒剂之一。采用传统的比色法或气相色谱法对ClCN进行分析时,稳定性差且检出限高。研究建立了有机相及水相中ClCN的巯基化衍生过程及气相色谱-质谱(GC-MS)的检测方法。经比较后选择1-丁基硫醇作为衍生试剂,有机相中ClCN的衍生条件为衍生温度40 ℃,体系pH=9,反应时间10 min,反应结束后直接进行GC-MS分析。水相中ClCN的衍生条件与有机相相同,衍生完毕后进行顶空-固相微萃取(HS-SPME)。实验考察了萃取温度对萃取吸附效果的影响,确定最佳萃取温度为55 ℃。通过GC-EI/MS确认ClCN的巯基化衍生产物为硫氰酸丁酯,并对质谱图中主要的离子碎片进行结构确认。采用气相色谱-串联质谱法(GC-MS/MS)对硫氰酸丁酯裂解规律进行了分析。采用GC-MS/SIM对有机相及水相中的ClCN进行分析。方法学考察结果表明,ClCN在有机相(20~2000 μg/L)及水相(20~1200 μg/L)中相应的范围内线性关系良好(相关系数(R ²)>0.99);在3个添加水平下有机相中CICN的回收率为87.3%~98.8%,不同的水相基质中CICN的回收率为97.6%~102.2%, RSD分别为2.1%~4.7%和2.8%~4.2%,衍生过程具有良好的专属性。采用禁止化学武器公约组织(OPCW)的水平考试空白有机样品(样品基质为正己烷)对研究方法进行验证,该方法能够成功检出目标物。该研究建立的巯基化衍生-气相色谱-质谱法灵敏度高,精密度好,能够为环境中ClCN的定性定量分析提供技术支持。     

微流控芯片毛细管电泳激光诱导荧光检测法测定片剂中盐酸美西律的含量

建立了微流控芯片毛细管电泳激光诱导荧光检测法测定片剂中盐酸美西律含量的方法,对衍生条件和电泳条件进行了系统的考察。盐酸美西律经异硫氰酸荧光素(FITC)40℃衍生6h,以20 mmol/L硼砂为电泳缓冲溶液,进样30s后,分离电压2000V,可在1 min内完成一次检测。方法的检出限为0.022 mg/L、线性范围0.108～1.079 mg/L、相关系数0.994,加标回收率为99.7%～102.3%,方法适用于盐酸美西律的检测和质量控制。