脱镁叶绿酸的制备及其光敏抗菌活性

以初步纯化的叶绿素为原料,利用叶绿素酶水解、选择性酸降解两种方法制备脱镁叶绿酸。高效液相色谱分析显示两种方法得到的产物图谱相似,酸降解产物中脱镁叶绿酸A的含量较高。抗菌实验表明脱镁叶绿酸对革兰阳性菌具有光敏抑菌效果,对革兰阴性菌和酵母无明显作用。     

Novel applications of multichannel spectroscopy in pharmaceutical analysis

Multichannel detectors based on the linear photodiode array, the silicon vidicon tube and charge coupled (or injection) devices are reviewed with reference to their applications in analytical spectroscopy and high-performance liquid chromatography (HPLC). The use of computer-aided techniques, including second derivative spectroscopy and spectral deconvolution methods, for the multichannel spectroscopic analysis of pharmaceuticals is discussed, and applications are reviewed in clinical chemistry, enzyme analysis and studies on aromatic amino acids in proteins. In HPLC, the principles and applications of digital algorithms for validation of peak homogeneity are considered, with reference to spectral suppression, spectral deconvolution, absorbance ratio and the second derivative of the elution profile. The isometric projections of (A, λ, t) data, and their cartographically equivalent contour plots, are discussed and the impact of multicolour graphics is assessed. The implications of two-dimensional multichannel detectors for detection of luminescence radiation are considered in the context of analytical spectroscopy, and detection in both HPLC and thin-layer chromatography. The potential contribution of charge coupled and charge injection devices as the next generation of multichannel detectors is considered.     

离子色谱法分析氨基糖苷类抗菌药物的质量标准研究进展

目的：综述各国药典中离子色谱法分析氨基糖苷类抗菌药物的质量标准进展情况。方法：介绍了氨基糖苷类抗菌药物的发展历程及离子色谱原理,概述了各国药典中氨基糖苷类抗菌药物的质量标准变迁,分析了各国药典离子色谱法在该类药物中的应用与质量标准沿革,并探讨了离子色谱法测定该类药物的发展趋势。结果与结论：氨基糖苷类抗菌药物的分析方法逐渐从薄层色谱法、高效液相色谱衍生化法、高效液相色谱-蒸发光散射法向离子色谱法发展,并日益成为该类抗菌药物较理想的质量控制方法,为今后氨基糖苷类抗菌药物的标准提高及质量控制提供了参考。     

Specificity of pepsin-catalyzed peptide bond synthesis

The rates of the pepsin-catalyzed synthesis of oligopeptides of the general type A-Phe-Leu-B by the condensation of A-Phe-OH with H-Leu-B have been determined by means of analytical high performance liquid chromatography. Variation of the A group led to large changes in the initial rates of the condensation reaction, and the effect of such changes was found to be similar to that previously found for the secondary specificity of pepsin in the hydrolysis of oligopeptide substrates. Replacement of the Phe and Leu residues of A-Phe-OH or H-Leu-B by other amino acid residues gave relative rates of synthesis in accord with the known primary specificity of the hydrolytic action of pepsin. Partially-acetylated pepsin, which exhibits enhanced hydrolytic activity, also catalyzed the condensation reaction more effectively. The results are discussed in relation to the potential utility and limitations of pepsin as a catalyst in the preparative synthesis of oligopeptides and to the problem of the mechanism of its action.     

头孢菌素类抗生素的质量分析方法

本文对头孢菌素类抗生素分析方法的应用现状作一简单概述,并分别对目前常用的分析方法(高效液相色谱法、高效毛细管电泳法、化学发光法、荧光分析法、电化学分析法)以及极具推广价值的分析方法(近红外光谱法等)在头孢菌素类抗生素含量测定中的应用作一评述.     

Biochemical and environmental applications of microcolumn liquid and supercritical fluid chromatography

Recent trends in microcolumn liquid chromatography and capillary supercritical fluid chromatography are reviewed, emphasizing research carried out in the author's laboratory. Current and potential applications of these methods in biochemistry, medicine and environmental science are stressed.     

Analytical applications of enhanced drug luminescence

Luminescence emission from drugs is strongly dependent on their physicochemical environment. Several biomedically and environmentally important compounds and pharmaceuticals exhibit sufficient intrinsic luminescence properties to allow their determination by high-performance liquid chromatography (HPLC) with fluorimetric, chemiluminescence or room temperature phosphorimetric detection. In the case of weakly fluorescing compounds it is possible to use the dependence of the emitted radiation on the molecular environment at the moment of measurement.

The composition of the eluent, i.e. solvents, added salts and buffers, pH and ionic strength, oxygen content and temperature, are of the highest importance for the luminescence detection of drugs in solution (e.g. in liquid chromatography) or adsorbed onto solid surfaces (e.g. in thin-layer chromatography). Post-column or post-plate acid—base manipulation and the use of specific reagents may remarkably enhance the observed luminescence of several molecules.

The term “enhancement” of luminescence comprises various sample treatments leading to an increase of the emitted radiation. These treatments include the addition of non-fluorescent compounds to, or the creation of organized media (surfactants, cyclodextrins, heavy atoms) in, the sample to be measured. They may also involve changes in molecular environment, pH, the application of excessive drying conditions, the removal of oxygen, the protection of adsorbed compounds against non-radiative decay mechanisms by means of specific spraying or dipping conditions, amongst others. The use of organized media in luminescence spectroscopy is growing. Many of the recent studies have involved micelles for enhancing the fluorescence, room temperature phosphorescence and chemiluminescence of several chemicals. Cyclodextrins are increasingly used for various analytical applications. Liquid paraffin, triethanolamine, dodecane, Triton X-100 and Fomblin Y-Vac are commonly used fluorescence enhancers in chromatographic assays. Examples of these systems in drug analysis are presented.     

色谱-质谱联用技术用于遗传毒性杂质检测的研究进展

遗传毒性杂质种类繁多且通常痕量存在于药物中,而色谱-质谱联用技术具有相对更高的灵敏度和选择性,极适用于分析药物中的遗传毒性杂质。主要介绍了如何根据遗传毒性杂质的极性、挥发性、热不稳定性等理化性质建立合适的色谱-质谱联用技术,并综述了气相色谱、液相色谱、超高液相色谱、亲水性相互作用色谱、超临界流体色谱、毛细管电泳色谱6种色谱技术与质谱联用在遗传毒性杂质（如亚硝胺类、磺酸酯类、卤代烷烃类等）检测中的研究进展,从而为建立科学合理的遗传毒性杂质检测方法提供参考。     

Enantiomeric separations and their application in pharmaceutical analysis using chiral eluents

The most important problems of enantiomeric separations using chiral eluents are discussed. The methods have been compared with respect to enantiomeric purity of reagents, reagent selection and separation variables. The most important considerations for methods based on inclusion-complexation with different CDs and on using chiral counter ions are summarised and compared. A new possibility for the separation of enantiomeric compounds with the aid of a combination of ion-pair and inclusion-complex formation has been introduced. As a consequence of this investigation, the selectivity of the separation can be significantly improved; those ionic isomers and enantiomers which cannot be separated or are unsatisfactorily separated by ion-pair chromatography or by inclusion-complex formation, can be separated by the combined technique. Comparison of methods applicable for enantiomeric separations is also given with respect to solving specific analytical tasks in the field of pharmaceutical analysis.     

色谱技术在药物定性分析应用中的研究进展

色谱分析是1种利用混合物中组分在两相间的分配以获得分离的分析方法.综述HPLC法、指纹图谱法以及其他分析技术在药物定性分析中应用的文献资料,讨论了应色谱技术的进步对未来药物、生物样品分析的意义,并对其应用的研究进展作一分析.     

乳癖消现代制剂及其质量控制方法的研究进展

目的 对目前国内销售的乳癖消现代剂型,质量控制方法进行探讨.方法 查阅文献,分类整理,归纳总结.结果 乳癖消现代制剂多为片剂、胶囊剂、贴膏剂等,质量控制方法研究多采用高效液相色谱法,薄层扫描法和气相色谱法.结论 乳癖消现代制剂的研制需以质量稳定、安全、有效为原则,采用现代分析方法,不断完善制剂质量控制的研究.     

Optimization of detectors for modern liquid chromatography

The development of modern liquid chromatographic methods depends strongly on the development of suitable measuring systems for the separated compounds. This is the case as generally an on-line coupling of separation and detection is preferred because of ease of operation, reliability and more efficient data handling. Unfortunately, the best conditions for the separation are often not optimal from the detection point of view. Conflicts arise in various respects and compromises have to be made. Depending on the complexity, cost and performance of each, either the chromatographic separation, or the detection process, has to be adapted, the one to the other. A number of contemporary developments in the techniques of liquid chromatography tend to sharpen these conflicts. Further reduction in particle size, reduction of the column diameter, introduction of multicolumn operation and the exploration of open tubular liquid chromatography can be mentioned in this respect. From this point of view a broad discussion of the role of detection techniques in the development and performance of liquid chromatographic analytical procedures is given.     

分子印迹液相色谱整体柱制备及最新应用

分子印迹整体柱是结合分子印迹聚合物(MIP)和整体柱而形成的,具有选择性高、成本低、理化性质稳定、传质快速和通透性高等多种优点,近年来被认为是制备高性能色谱固定相材料最有前途的方法之一,尤其是制备MIP液相色谱整体柱.本文重点论述了印迹整体柱材料作为液相色谱固定相的各种制备方法及在药物分离检测中的最新研究应用.另外也表述了一些关于印迹整体柱未来发展趋势的观点.     

Reaction monitoring of tocopherols with active nitrogen oxides by ultra high-speed liquid chromatography

Ultra high-speed liquid chromatography (LC) has become increasingly popular in analytical research fields. This analytical system provides fast and efficient chromatographic separation over a wide range of flow rate and pressure. In this study, we applied an ultra high-speed LC system to monitor the reaction of α-, γ-, and δ-tocopherols with active nitrogen species. By using an ultra high-speed LC system equipped with a photo-diode array detector, short time analysis and detection of a wide range of reaction products were accomplished efficiently. The analysis time of tocopherol and its major oxidation products were greatly shortened compared to conventional HPLC methods (more than 10 times). The ultra reversed-phase LC was demonstrated to be as a powerful tool for monitoring rapid oxidation reactions of tocopherols with active nitrogen species.     

氨基酸分析新技术在药学研究中的应用

氨基酸分析技术是药物研究领域的重要课题,广泛应用于蛋白多肽类药物、中草药和生物样品中氨基酸的研究。液相色谱法、毛细管电泳法等以其独特的优势在氨基酸分析领域有着重要的作用,近红外光谱法也已被成功应用于氨基酸分析。综述近年来国内外氨基酸分析新技术在药学研究中的应用。     

Harmonization of strategies for the validation of quantitative analytical procedures: a SFSTP proposal part IV. Examples of application

A harmonized approach for the validation of analytical methods based on accuracy profile was introduced by a SFSTP commission on the validation of analytical procedure. This fourth and last document aims at illustrating this methodology and the statistics used. Therefore the validation of real case methods are proposed such as methods for the quality control of drugs, for the quantitation of impurities in drug substances, for bioanalysis or for the determination of nutriments. Furthermore, different types of analytical methods are used in order to demonstrate the applicability of the proposed approach to a wide range of methods such as liquid chromatography (LC-UV, LC-MS), spectrophotometry or ELISA.     

Simultaneous detection of 93 synthetic cannabinoids by liquid chromatography‐tandem mass spectrometry and retrospective application to real forensic samples

The Internet is flooded with steadily changing synthetic cannabinoids in `Spice` products. In routine forensic work, it is difficult to keep the analytical methods for the detection of these analytes up to date. We describe a liquid chromatography‐tandem mass spectrometry method after liquid‐liquid extraction for the detection of 93 synthetic cannabinoids in human serum. The method was validated for selectivity and specificity, matrix effects, and analytical limits (<1 ng/mL for 81 substances) for qualitative analysis. A short quantitative validation regarding linearity and precision data was also conducted. The method was applied to 189 serum samples provided by police authorities. Sixty‐four samples (33.8%) were found positive for at least one synthetic cannabinoid, whereby MDMB‐CHMICA, AB‐CHMINACA, and 5 F‐PB‐22 were the substances most frequently detected. Consumption of these substances and plasma concentrations are linked to symptoms documented by the police. Six case reports are presented. Copyright © 2016 John Wiley & Sons, Ltd.     

ENANTIOSELECTIVE DRUG ANALYSIS: PROBLEMS AND RESOLUTIONS

1. With the increasing appreciation that the enantiomers of a chiral drug can differ pharmacokinetically and/or pharmacodynamically, there is considerable interest in methods for the resolution and quantification of enantiomers. 2. Enantiomers possess identical physical and chemical properties in a symmetrical environment and, therefore, their resolution requires the introduction of an asymmetric or chiral environment allowing diastereomeric interactions. This can be achieved using a number of chromatographic techniques, of which the most developed and widely used is high-performance liquid chromatography (HPLC). 3. Resolution and quantification of enantiomers can be performed using HPLC by either converting the enantiomers to covalent diastereomers prior to chromatography or introducing a chiral environment to the chromatographic system, thereby allowing temporary diastereomeric interactions. 4. Antibodies are chiral molecules which can bind the enantiomers of a chiral drug in a differential manner. This is the basis of enantioselective immunoassay, which is a promising technique for the enantioselective analysis of drugs in biological fluids. 5. Each of the methods available has its limitations, advantages and potential applications in the pharmaceutical industry.     

Comparison of fast liquid chromatography/tandem mass spectrometric methods for simultaneous determination of cladribine and clofarabine in mouse plasma

Several fast high performance liquid chromatography/atmospheric pressure ionization/tandem mass spectrometric (HPLC-API/MS/MS) methods were evaluated for the simultaneous determination of cladribine and clofarabine in mouse plasma samples. The chemical separation for analytes under reversed-phase conditions were achieved by using either ultra-performance liquid chromatography (UPLC) or micro-column HPLC coupled to either a quadrupole linear ion trap mass spectrometer (QTrap MS) or a triple quadrupole mass spectrometer. Atmospheric pressure chemical ionization (APCI) or atmospheric pressure photoionization (APPI) interfaces in the positive mode were employed prior to mass spectrometric detection. The effects of various dopant solvents on the APPI sensitivities of analytes and the internal standard were investigated. The matrix ionization suppression potential for the test compounds in plasma samples on fast HPLC-MS/MS methods was examined by a post-column infusion technique. In this work, these proposed approaches were successfully employed to determine the concentrations of cladribine and clofarabine in mouse plasma in the low ng/ml region. The mouse plasma levels of all analytes obtained by these fast HPLC-MS/MS methods were compared and found to be well correlated in terms of analytical accuracy.     

反相离子对色谱法测定人血浆盐酸伪麻黄碱浓度

目的建立反相高效液相色谱法检测人血浆中盐酸伪麻黄碱浓度的方法。方法采用SupELCO discoveryC18(250mm×4.6mm,5μm)色谱柱,乙腈-水为流动相,流速1.0ml/min,检测波长190nm,柱温25℃。结果盐酸伪麻黄碱浓度在10-1000μg/L范围内线性良好(r=0.9991),最低检测限为10μg/L。批内相对标准偏差(RSD)<10%,批间RSD<12%;提取回收率为84.85%。结论反相高效液相色谱法简便、快速、准确,可用于人体内伪麻黄碱的血药浓度测定及药动学研究。