LC-MS/MS法快速测定吡罗昔康制剂中吡罗昔康含量

建立了快速液相色谱-质谱/质谱联用法测定吡罗昔康制剂中吡罗昔康含量的方法。样品以0.1 mol/L盐酸甲醇溶液提取、微孔滤膜过滤、离心后,通过电喷雾离子化(ESI),采用多反应检测(MRM)方式进行正离子检测,用于定量分析的检测离子为m/z 332.2→94.8。采用Shim-pack XR-ODS(3.0 mm×75mm,2.0μm)柱分离,以乙腈-水-甲酸(60:40:0.1,V/V/V)为流动相,流速为0.40 mL/min,在3 min内完成吡罗昔康定量分析。线性范围为2.5～1000.0ng/mL,最低检测限为2.5 ng/mL;日内测定的相对标准偏差小于3.2%,日间测定的相对标准偏差小于3.8%。方法可作为吡罗昔康制剂的质量中吡罗昔康控制方法,并可用于少量血浆样品的测定,也适用于药物代谢动力学研究。     

Liquid chromatographic method for the simultaneous determination of captopril,piroxicam, and amlodipine in bulk drug,pharmaceutical formulation,and human serum by programming the detector

A highly sensitive LC method with UV detection has been developed for the simultaneous determination of coadministered drugs captopril, piroxicam, and amlodipine in bulk drug, pharmaceutical formulations, and human serum at the isosbestic point (235 nm) and at individual λ_max (220, 255, and 238 nm, respectively) by programming the detector with time to match the individual analyte's chromophore, which enhanced the sensitivity with linear range. The assay involved an isocratic elution of analytes on a Bondapak C₁₈ (10 μm, 25 × 0.46 cm) column at ambient temperature using a mobile phase of methanol/water 80:20 at pH 2.9 and a flow rate of 1.0 mL/min. Linearity was found to be 0.25–25, 0.10–6.0, and 0.20–13.0 μg/mL with correlation coefficient >0.998 and detection limits of 7.39, 3.90, and 9.38 ng/mL, respectively, whereas calibration curves for wavelength‐programmed analysis were 0.10–6.0, 0.04–2.56, and 0.10–10.0 μg/mL with correlation coefficient >0.998 and detection limits of 5.79, 2.68, and 3.87 ng/mL, respectively. All the validated parameters were in the acceptable range. The recovery of drugs was 99.32–100.39 and 98.65–101.96% in pharmaceutical formulation and human serum, respectively, at the isosbestic point and at individual λ_max. This method is applicable for the analysis of drugs in bulk drug, tablets, serum, and in clinical samples without interference of excipients or endogenous serum components.     

Template occluded SBA-15: An effective dissolution enhancer for poorly water-soluble drug

The aim of the present work was to improve the dissolution rate of piroxicam by inclusion into template occluded SBA-15. Our strategy involves directly introducing piroxicam into as-prepared SBA-15 occluded with P123 (EO₂₀PO₇₀EO₂₀) by self assembling method in acetonitrile/methylene chloride mixture solution. Ultraviolet spectrometry experiment and thermogravimetric analysis-differential scanning calorimetry (TG-DSC) profiles show that the piroxicam and P123 contents in the inclusion compound are 12 wt% and 28 wt%, respectively. X-ray powder diffraction and DSC analysis reveal that the included piroxicam is arranged in amorphous form. N₂ adsorption-desorption experiment indicates that the piroxicam has been introduced to the mesopores instead of precipitating at the outside of the silica material. The inclusion compound was submitted to in vitro dissolution tests, the results show that the piroxicam dissolve from template occluded inclusion compound more rapidly, than these from the piroxicam crystalline and template removed samples in all tested conditions. Thus a facile method to improve the dissolution rate of poorly water-soluble drug was established, and this discovery opens a new avenue for the utilization of templates used for the synthesis of mesoporous materials.     

吡罗昔康凝胶有效成分的紫外分光光度法测定

吡罗昔康凝胶是吡罗昔康加适量的基质的透明的透皮吸收制剂。本文提出了对其有效成分吡罗昔康进行紫外光光度测定的方法，该方法简便、快速，能用于纯度较高的样品分析，可作为吡罗昔康凝胶药品质量标准控制方法。     

吡罗昔康凝胶有效成分的高效液相色谱研究

本文提出了采用内标法 ,将 HPLC用于吡罗昔康凝胶有效成分测定的新方法。讨论了流动相及内标的选择 ,进样量和空白基质的影响等。在优化的实验条件下 ,吡罗昔康浓度在 0 .0 2～ 0 .2 mg/m L范围内 ,其浓度与吡罗昔康和内标的峰面积之比呈线性关系。应用于实际样品分析 ,其结果与紫外分光光度法一致 ,平均回收率为 99.6% ,相对标准偏差为 1 .0 %。方法简单 ,准确度高 ,专属性强 ,可用于吡罗昔康凝胶样品的稳定性考察和质量控制     

流动注射化学发光抑制法测定吡罗昔康

基于吖啶橙在氢氧化钠介质中能被高锰酸钾氧化产生较强的化学发光,吡罗昔康能强烈抑制其化学发光,建立了高锰酸钾-吖啶橙-吡罗昔康化学发光抑制测定吡罗昔康的新方法。吡罗昔康在1.0×10-5~7.0×10-4g/mL范围内与化学发光强度呈良好线性关系,方法的检出限为4.5×10-6g/mL,对1.0×10-5g/mL吡罗昔康连续进行6次测定的相对标准偏差为3.6%。     

Deviation from van't Hoff dependence in RP-LC induced by tautomeric interconversion observed for four compounds

The most encountered situations in reversed-phase liquid chromatography for temperature dependence of retention are those obeying the linear equation known as the van't Hoff plot. When studying compounds that are involved in structural modifications, it is likely that the temperature dependences of their retention factors do not follow this rule. It is the aim of this paper to report some particular cases when compounds involved in tautomeric interconversion have a different retention behavior with temperature: a deviation from the linearity of ln k on 1/T, or, in certain temperature ranges, temperature increase leading to a retention increase. Examples of compounds exhibiting deviation from the van't Hoff temperature dependence are piroxicam, drotaverine, vincamine, and epivincamine. A simple thermodynamic model relying on tautomeric equilibria in mobile phase is proposed for these compounds, which gives a polynomial dependence between ln k and 1/T.