现时金银花与山银花比较鉴别分析

目的对市售金银花与山银花真伪与种类鉴别的方法进行研究同时考察商品质量。方法采用体视显微、薄层色谱、液-质联用、标识成分(绿原酸、木犀草苷、灰毡毛忍冬皂苷乙、川续断皂苷乙)含量测定等方法对获得的27批样品进行了比较检定。结果花表面腺毛非腺毛的有无及形态、花萼特征、是否检出灰毡毛忍冬皂苷乙可作为鉴别金银花与山银花的依据;27批样品中,16批为金银花,其中1批掺有加重粉;11批为山银花,其中7批灰毡毛忍冬、2批红腺忍冬、1批华南忍冬、1批黄褐毛忍冬。结论体视显微特征和薄层色谱法可鉴别金银花与山银花,结合高效液相测定结果实现了对27批样品的质量考察与比较鉴别研究。     

金银花药材中重金属铅、镉含量分析

目的测定五批金银花药材中重金属铅、镉含量。方法采用高压消解法处理样品,石墨炉原子吸收分光光度法测定了其铅、镉含量。结果五批药材均检出一定量的铅、镉,但含量较低,未超出国家限量标准,符合《中华人民共和国药典2005年版一部》金银花项下有关规定。结论该方法简便快速,灵敏度高,能够用来分析金银花药材中重金属铅、镉含量。     

指数方程法快速测定金银花提取液中绿原酸的含量

目的：建立金银花提取液中绿原酸的快速稳定的定量方法。方法：采用反相高效液相色谱法测定金银花提取液中绿原酸的含量，同时测定对应样品的紫外光谱，选取指数方程：Y=a＋bX^c＋ε。依据紫外吸收度和HPLC法测得的绿原酸含量相关性最佳的原则，建立预测绿原酸含量的指数方程，并对预测结果进行检验。结果：以HPLC法测得的绿原酸含量和金银花提取液在200～400nm范围内201个波长点吸收度值的平均值进行相关分析，所得绿原酸含量的预测方程为C=-0．0424＋2．9712A^1.15（r=0．9816，n=19），固定指数参数C=1．15，以HPLC法测得的绿原酸含量与相关性最佳的波长点进行相关分析，所得绿原酸含量的预测方程为C=0．0317＋2．4286（A304nm）^1.15（r=0．9566，n=19）；2个方程所得到的绿原酸含量的预测值与测定值之间均具有良好的相关性，其相关系数分别为0．9888（n=10）和0．9908（n=10）。结论：本方法所建立的指数方程预测金银花提取液中绿原酸含量准确、快速，可为制药过程中金银花提取液的快速质量控制提供方法。     

原子吸收分光光度法测定骨碎补药材中的重金属

目的建立原子吸收分光光度法,测定骨碎补药材中的铅、镉、砷、汞、铜重金属含量。方法以原子吸收分光光度法在324.8 nm波长处检测铜含量,在283.3 nm波长处检测铅含量,在228.8 nm波长处检测镉含量;另采用原子荧光光谱法测定砷、汞的含量。结果 10批骨碎补药材中的重金属含量,铜为2.687 5～8.521 7 mg/kg,镉为0.200 6～0.270 8 mg/kg,铅为0.250 4～1.000 mg/kg,汞为0.003 4～0.029 4 mg/kg,砷0.006 6～0.053 3 mg/kg。结论 10批骨碎补样品中重金属含量均符合2005年版《中国药典(一部)》和香港《中成药注册申请手册》中有关重金属标准的规定。     

金银花提取物中5种有机酸含量测定的紫外光谱法

目的:建立应用紫外光谱快速测定金银花提取物中5种有机酸含量的方法。方法:以HPLC法为参照,测定金银花提取物中绿原酸、咖啡酸、3,4-二咖啡酰奎宁酸、3,5-二咖啡酰奎宁酸、4,5-二咖啡酰奎宁酸的含量。在220～400 nm范围内扫描金银花提取物溶液的紫外吸收光谱,采用偏最小二乘法分别建立样品紫外吸收光谱与5种有机酸含量之间的校正模型,并对模型的预测能力进行考察。结果:5个校正模型对预测集样本的预测值与对照值的相关系数都在0.90以上,相对预测误差分别为1.46%,-2.13%,0.42%,6.40%,3.83%,预测结果准确。结论:本方法操作简便、快速准确,可作为金银花提取物中有机酸含量测定的一种快速分析方法。     

火焰原子吸收分光光度法测定雷奈酸锶干混悬剂中的锶含量

目的：建立测定雷奈酸锶干混悬剂中锶含量的火焰原子吸收分光光度法。方法：使用含有0．1g·L-1铯离子和5．0g·L-1镧离子的0．1％硝酸溶液对样品进行溶解和稀释,采用空气一乙炔火焰原子吸收光谱法在460．7nm波长处进行测定。结果：当锶的质量浓度在6．30～25．20mg·L-1范围内时,其吸光度和质量浓度线性关系良好,相关系数为0．9997;平均加样回收率为101．4％,RSD为1．8％;测得3批雷奈酸锶干混悬剂中锶含量分别为制剂中锶标示含量的98．7％、99．3％和99．8％。结论：该方法便捷、准确、灵敏度高,适用于雷奈酸锶干混悬剂中锶含量的测定。     

注射用苦参碱的稳定性研究

目的考察注射用苦参碱的稳定性。方法采用高效液相色谱法测定其中苦参碱及有关物质的含量。以乙腈-0．1％磷酸（7：93）作为流动相，检测波长为202nm，理论塔板数按苦参碱计算应不低于1500。结果与放置0d时比较，放置6个月后3批样品的各项指标均无明显变化。结论注射用苦参碱在避光、阴凉处保存时稳定性良好。     

金银花中3种有机酸的反相高效液相色谱法定量分析

目的 :建立用反相高效液相色谱内标法梯度洗脱同时测定金银花中绿原酸、咖啡酸、 3,5 -二咖啡酰奎尼酸含量的方法 ,并对 4个产地 3种金银花中上述 3种化合物进行定量分析。方法 :采用岛津CLC -ODS柱 (6 0mm× 15 0mm) ,甲醇 - 10 %的磷酸氢二钠和醋酸缓冲液流动相不同比例进行梯度洗脱 ,内标物为水杨酸 ,检测波长 30 4nm。结果 :西南地区金银花药材主流商品灰毡毛忍冬、细毡毛忍冬干燥花蕾中绿原酸、咖啡酸、 3,5 -二咖啡酰奎尼酸含量高于山东、河南产金银花。结论 :本法灵敏快速 ,准确可靠     

新疆桃仁中苦杏仁苷含量测定新方法研究

目的：建立桃仁中苦杏仁苷灵敏度高、适用性强的高效液相色谱测定新方法,并对收集于新疆地区的41批代表性药材进行含量测定。方法：样品采用索氏提取器脱脂、加入70％甲醇回流的方法灭酶和提取,色谱柱为SymmetryC18（4．6mm×150mm,5μm）,以水-乙腈为流动相梯度洗脱,流量1mL·min^-1,柱温35℃,检测波长210nm。结果：方法学验证各项指标均符合要求,41批新疆桃仁中苦杏仁苷含量在2．05％-3．62％范围内,平均含量为3．04％±0．29％。结论：所建立测定方法简便、稳定、易行,可用于新疆桃仁中苦杏仁苷含量测定和质量控制。     

一测多评法测定8个银翘解毒系列制剂中的7种酚酸类成分的含量

建立8个银翘解毒系列制剂中君药金银花所含的7种酚酸类成分(新绿原酸、绿原酸、隐绿原酸、咖啡酸、异绿原酸B、异绿原酸A、异绿原酸C)的一测多评统一方法。首先,采用HPLC以绿原酸为内参物,建立绿原酸与其他6种酚酸类成分的相对校正因子(RCF),并用不同浓度、不同色谱柱、不同HPLC验证其耐用性,利用金银花提取物作随行对照定位各待测色谱峰。然后利用RCF计算8个不同银翘解毒系列制剂样品中其他6种酚酸类成分的含量,并与外标法的测定结果进行比较,对该方法进行可行性验证。结果表明,所建立的平均相对校正因子的耐用性良好(RSD在0.80%~2.56%),一测多评法测定样品中的酚酸类成分的含量与外标法的含量测定结果一致(相对平均偏差<0.93%)。因此,一测多评法可以成功应用于8个银翘解毒系列制剂中金银花的酚酸类成分的定量控制。     

Pharmaceutical gel analysis by NIR spectroscopy: Determination of the active principle and low concentration of preservatives

Near infrared spectroscopy has proved highly suitable for the analysis of pharmaceutical formulations. However, its limited sensitivity can severely restrict its scope of application. In this work, we determine the active principle and two preservatives in a pharmaceutical preparation available as a hydrogel. The matrix of the pharmaceutical preparation exhibits strong absorption in the NIR spectral region; also, the two preservatives (parabens) are very similar in chemical and spectral terms, and present at low concentrations in the pharmaceutical. These complications make it rather difficult to accurately quantify the active principle and the preservatives, which can only be accomplished by using an effective design in order to prepare the samples to be included in the calibration set and select the optimum spectral range for measuring each analyte. The evaporation of solvents during the measurement process produces increasing errors related with sample's air exposition; the introductions of new samples with a wider range of the volatile components correct this effect. An ANOVA of the predictions obtained with the new models shows that correct the error due to evaporation. The proposed method was validated for the analytical control of the studied preparation.     

High performance liquid chromatographic determination of ambroxol in the presence of different preservatives in pharmaceutical formulations

A high-performance chromatographic method is described for simultaneous determination of ambroxol in the presence of different preservatives in syrups. The method separates ambroxol from methyl- ethyl-, propyl- and butyl paraben and from other multi-component mixtures. The retention behaviour of ambroxol and parabens as a function of both pH and mobile phase composition was investigated. The eluents were monitored with a UV detector at 247 nm. Linear relationships between the amount of pharmaceutical compounds and peak heights were confirmed at the concentrations of 0.74-14.08 microg ml(-1). The high recovery (no extraction of the samples is required) and the low %RSD confirm the suitability of the proposed method for the determination of ambroxol in different pharmaceutical preparations.     

A new validated method for the simultaneous determination of benzocaine, propylparaben and benzyl alcohol in a bioadhesive gel by HPLC

A new HPLC-RP method has been developed and validated for the simultaneous determination of benzocaine, two preservatives (propylparaben (nipasol) and benzyl alcohol) and degradation products of benzocaine in a semisolid pharmaceutical dosage form (benzocaine gel). The method uses a Nucleosil 120 C18 column and gradient elution. The mobile phase consisted of a mixture of methanol and glacial acetic acid (10%, v/v) at different proportion according to a time-schedule programme, pumped at a flow rate of 2.0 ml min⁻¹. The DAD detector was set at 258 nm. The validation study was carried out fulfilling the ICH guidelines in order to prove that the new analytical method, meets the reliability characteristics, and these characteristics showed the capacity of analytical method to keep, throughout the time, the fundamental criteria for validation: selectivity, linearity, precision, accuracy and sensitivity. The method was applied during the quality control of benzocaine gel in order to quantify the drug (benzocaine), preservatives and degraded products and proved to be suitable for rapid and reliable quality control method.     

Determination of phenolic preservatives in gelatin and vacant capsules for medicine use by ion-suppression reversed-phase high performance liquid chromatography

A reliable method for the simultaneous determination of phenolic preservatives parahydroxybenzoic acid, methyl, ethyl, propyl, butyl and pentyl parahydroxybenzoates in gelatin and vacant capsules for medical use has been developed by ion-suppression reversed-phase high performance liquid chromatography. Separation was carried out on a Kromasil C(18) column by isocratic elution using methanol-perchloric acid (pH 2.0; 10 mM) (60:40, v/v) at a flow-rate of 1.0 ml min(-1), and detection by UV absorbance at a wavelength of 254 nm. This method has been successfully applied to the routine analyses of these preservatives in the real samples.     

Sorption of benzoic acid, sorbic acid, benzyl alcohol, and benzalkonium chloride by flexible tubing

Earlier studies using methylparaben, propylparaben, and several types of flexible tubing showed that the parabens are sorbed by a number of commonly used tubing. The sorption increased with increase in time of contact and the tubing surface area. The temperature and pH ranges tested did not affect sorption. Current studies evaluated other commonly used antimicrobial preservatives used in oral, parenteral, opthalmic, nasal, and other pharmaceutical products. These preservatives include benzoic acid, sorbic acid, benzyl alcohol, and benzalkonium chloride. Results show that all preservatives, except benzalkonium chloride, are sorbed by several types of flexible tubing. After 24 hr, some types of tubing sorbed over 40% of benzoic acid, benzyl alcohol, and about 30% of sorbic acid. Significant losses were observed within a few hours. No sorption of benzalkonium chloride occurred in the tubing tested. Three different types of fluoropolymer resin tubing, Teflon (flourinated ethylene propylene (FEP), Teflon perfluoroalkoxy) (PFA) and Teflon polytetrafluoroethylene (PTFE, NXT), fluoropolymer FEP laminated Tygon tubing, and Zelite do not sorb any of the preservatives. Silicone tubing shows the highest sorption of preservatives. After 120 hr, as much as 64% of the preservative is sorbed by some tubing. Detailed studies using silicone tubing show that the sorption increases with increase in surface area at 25 degrees C, and increasing the temperature to 40 degrees C shows little change in sorption. At the concentration range generally used in formulations, the concentration of the preservative has no significant effect on sorption. Refilling the tubing with fresh preservative solution after contact with preservative solution for 168 hr still causes extensive sorption of the preservative. Desorption studies indicate that the sorbed preservatives are desorbed in water to a limited extent over 120 hr. Results are important in situations where short or extended interruptions occur in the processing and filling of products. This can lead to decreased and variable results due to residence of the solution in the tubing.     

胶束电动毛细管电泳法同时测定麻杏止咳糖浆中的6种防腐剂

目的建立胶束电动毛细管色谱二极管阵列检测法(MEKC-DAD)同时测定不同厂家的麻杏止咳糖浆中苯甲酸、山梨酸、对羟基苯甲酸甲酯、对羟基苯甲酸乙酯、对羟基苯甲酸丙酯、对羟基苯甲酸丁酯等6种防腐剂的含量。方法采用胶束电动毛细管分离模式,用未涂渍的标准熔融石英毛细管柱(75μm×64 cm,有效长度56 cm)为分离通道;背景电解质溶液:15 mmol·L^-1硼砂-60 mmol·L^-1硼酸-50 mmol·L^-1 SDS;检测波长195 nm;运行电压:15 kV;运行温度:20℃;压力进样:50 mbar,5 s。结果各化合物的浓度与峰面积的线性关系良好(r≥0.9993);精密度、稳定性试验的RSD<2.0%;加样回收率范围为98.7%~101.2%(n=9)。5家企业共10批样品均未检出山梨酸和对羟基苯甲酸酯类;5家企业样品的苯甲酸含量与处方相符。结论本方法可用于麻杏止咳糖浆中防腐剂的检测,为其生产工艺和质量控制提供有意义的实验数据和参考依据。     

Determination of ambroxol hydrochloride, methylparaben and benzoic acid in pharmaceutical preparations based on sequential injection technique coupled with monolithic column

The porous monolithic columns show high performance at relatively low pressure. The coupling of short monoliths with sequential injection technique (SIA) results in a new approach to implementation of separation step to non-separation low-pressure method. In this contribution, a new separation method for simultaneous determination of ambroxol, methylparaben and benzoic acid was developed based on a novel reversed-phase sequential injection chromatography (SIC) technique with UV detection. A Chromolith SpeedROD RP-18e, 50-4.6 mm column with 10 mm precolumn and a FIAlab 3000 system with a six-port selection valve and 5 ml syringe were used for sequential injection chromatographic separations in our study. The mobile phase used was acetonitrile-tetrahydrofuran-0.05M acetic acid (10:10:90, v/v/v), pH 3.75 adjusted with triethylamine, flow rate 0.48 mlmin(-1), UV-detection was at 245 nm. The analysis time was <11 min. A new SIC method was validated and compared with HPLC. The method was found to be useful for the routine analysis of the active compounds ambroxol and preservatives (methylparaben or benzoic acid) in various pharmaceutical syrups and drops.     

Simultaneous analysis of dehydroacetic acid, benzoic acid, sorbic acid and salicylic acid in cosmetic products by solid-phase extraction and high-performance liquid chromatography

A high-performance liquid chromatographic (HPLC) method for simultaneous determination of dehydroacetic acid (DHA), benzoic acid (BA), sorbic acid (SOA) and salicylic acid (SA) was developed for application to cosmetic products. Isocratic reversed-phase HPLC was employed for quantitative analysis using tetra-n-butylammonium (TBA) hydroxide as an ion-pair reagent. Cosmetic samples were purified by solid-phase extraction using Bond-Elut SI cartridges. Four acidic preservatives were eluted with methanol from cartridges. The HPLC assay was carried out using TSK gel ODS-80TM column (5 microm, 150 x 4.6 mm I.D.). The mobile phase consisted of a mixture of water and methanol (65:35, v/v) containing 2.5 mM TBA hydroxide adjusted with phosphoric acid to pH 7.0. The calibration curves of these preservatives showed good linearity with UV detection (235 nm). The correlation coefficients were better than 0.999 in all cases. The lower limits of detection (defined as a signal-to-noise ratio of about 3) were approximately 2.5 ng for DHA, 4.0 ng for BA, 2.0 ng for SOA and 5.5 ng for SA. The procedure described here is simple, selective and is suitable for quality control of finished cosmetic products.     

Validation of an HPLC method for the quantification of ambroxol hydrochloride and benzoic acid in a syrup as pharmaceutical form stress test for stability evaluation

A method is described for ambroxol, trans-4-(2-amino-3,5-dibromobenzylamino) cyclohexanol hydrochloride, and benzoic acid separation by HPLC with UV detection at 247 nm in a syrup as pharmaceutical presentation. Optimal conditions were: Column Symmetry Shield RPC8, 5 μm 250×4.6 mm, and methanol/(H₃PO₄ 8.5 mM/triethylamine pH=2.8) 40:60 v/v. Validation was performed using standards and the pharmaceutical preparation which contains the compounds described above. Results from both standards and samples show suitable validation parameters. The pharmaceutical grade substances were tested by factors that could influence the chemical stability. These reaction mixtures were analysed to evaluate the capability of the method to separate degradation products. Degradation products did not interfere with the determination of the substances tested by the assay.     

Determination of imipramine in presence of iminodibenzyl and in pharmaceutical dosage form

Two spectrophotometric methods for the determination of imipramine in presence of iminodibenzyl as an impurity are described. The first method is a ratio-spectra first derivative spectrophotometry, the signals were measured at 240.2 nm for imipramine. Calibration graph was found linear in the range 5-30 microg ml(-1). The second method is based on the reaction of imipramine base, being an electron donor, with p-chloranilic acid, being pi acceptor, to form a purple colored charge transfer complex. The absorbance was measured at 520.5 nm without interference with iminodibenzyl. Both methods are rapid, simple and do not require any preliminary separation or treatment of the samples. Furthermore, the two methods were applied to pharmaceutical dosage form.