荧光增白剂检测方法研究进展

介绍荧光增白剂的主要应用,对荧光增白剂常用的检测方法紫外灯法、紫外分光光度法、分子荧光光谱法、液相色谱法、高效液相色谱–质谱联用法的应用进行综述,并分析了各检测方法的优缺点,展望了未来的发展方向。     

六价铬测定方法研究进展

综述了近年来六价铬的测定方法,包括分光光度法、离子色谱法、高效液相色谱-电感耦合等离子体质谱联用法和离子色谱-电感耦合等离子体质谱联用法的研究进展,并对六价铬测定方法的发展前景进行了展望(引用文献51篇)。     

离子抑制色谱法测定棘豆属植物提取物中的苦马豆素

苦马豆素（swainsonine,SW）属吲哚兹定生物碱,是植物引起疯草中毒特征症状的唯一毒素。研究发现,SW除有毒性外,还具有很强的抗癌活性和免疫增强功能。目前其测定方法有α-甘露糖苷酶抑制分光光度法、薄层色潜扫描法、气相色谱法、液相色谱／质谱联用法等。但分光光度法样品基体干扰大,线性范围窄;薄层色谱扫描法、气相色谱法需经衍生化处理,操作繁琐。难以准确测定;液相色谱／质谱联用法仪器价格高,不易推广使用。本文建立的离子抑制色谱法分析SW,样品不经过衍生化,紫外检测器直接检测。操作简便,通用性强,为进一步研究动物疯草中毒和SW的抗癌作用奠定了基础。     

乳清酸分析方法的研究进展

综述了近年来乳清酸分析方法的研究进展,内容包括紫外-可见分光光度法、荧光分析法、电化学分析法、色谱分析法、色谱-质谱联用法和量热法等几个方面,展望了乳清酸分析方法的发展方向.     

孔雀石绿探针共振瑞利散射法测定安乃近

<正>安乃近是治疗各种急、慢性疼痛性疾病的首选药,属吡唑酮类药物,在临床上应用广泛。目前,测定安乃近的方法主要有滴定法[1]、高效液相色谱法[2-3]、液相色谱-质谱联用法[4]、化学发光法[5]、荧光分析法[6]、紫外分光光度法[7]、红外光谱法[8]和电化学分析法[9-10]等,未见用共振瑞利散射法的报道。本工作以孔雀石绿为探针,用共振瑞利散射法测定痕量安乃近。试验发现:在浓度较低的氢氧化钠溶     

离子色谱法测定草甘膦原药中的杂质成分

草甘膦(glyphosate)学名N-(邻酰基甲基)甘氨酸,是一种灭生性慢性内吸有机磷除草剂,具有高效、低毒、广谱性的特点,目前尚无替代品种,是国际上广泛采用的除草剂之一.根据GB 12686-2004草甘膦原药规定,草甘膦质量分数不低于95.0%,杂质总含量不高于5.0%.已经建立的测定草甘膦含量的方法有:分光光度法~([1])、薄层层析法~([2])、气相色谱法~([3])、高效液相色谱法~([4,5])、色谱-质谱联用法~([6,7]),但对于草甘膦主成分及5种杂质含量的测定却鲜见报道.     

现代仪器分析技术在荧光增白剂检测中的应用

综述了近10年光谱(包括紫外分光光度法、荧光分光光度法等)、色谱(包括高效液相色谱法、超高效液相色谱法、超高效合相色谱法)、质谱(包括液相色谱-串联质谱法、液相色谱-串联高分辨飞行时间质谱法)等现代仪器分析技术在荧光增白剂检测中的应用,并对其发展趋势进行了展望。     

药物中磺酸酯类基因毒性杂质测定方法研究进展

介绍磺酸酯类基因毒性杂质的分析方法,包括高效液相色谱法、液相色谱-质谱联用法、气相色谱法和气相色谱-质谱联用法等。高效液相色谱法操作简单,应用广泛,能实现绝大多数化合物的分离、分析;液相色谱-质谱联用法具有灵敏度高、准度高、特异性高等特点;气相色谱应用于易分离气体和易挥发的成分的检测,灵敏度高,专属性强;气相色谱-质谱联用法具有分析速度快、分离效能好、灵敏度高、选择性强的特点。开发通用、简便、灵敏度高的分析检测方法,为更好地监测磺酸酯类基因毒性杂质提供理论参考。     

场放大样品进样-压力辅助毛细管区带电泳测定饮用水中的百草枯

1 引 言 百草枯属有机杂环类季铵盐除草剂,由于它具有优良的除草效果,已广泛应用于多种作物的杂草防治.百草枯具有极强的水溶性,极易迁移至水体环境中,从而对饮用水的质量安全构成潜在威胁.目前,百草枯的残留检测方法主要有分光光度法[1]、液相色谱-质谱联用法[2]、气相色谱质谱联用法[3]和毛细管电泳法(CE) [4～6].采用分光光度法测定百草枯,不仅操作繁琐费时,而且灵敏度低.采用气相色谱法测定百草枯,通常需要衍生化,应用较少[3].采用液相色谱法测定百草枯,通常需要在流动相中添加离子对试剂[2].毛细管电泳具有分离效率高,分析速度快等优点,已被广泛用于水样中百草枯残留的测定.然而,毛细管电泳灵敏度不高,极大地限制了其在实际样品分析中的应用.场放大样品进样(FASI)是一种简单有效的在线富集方法,其富集倍数可达1000倍[7],可有效提高毛细管电泳技术的灵敏度,因此应用较为广泛.本实验建立了场放大样品进样-压力辅助毛细管区带电泳法(CZE),用于测定饮用水中百草枯的残留量.     

不同生长期忍冬叶中活性成分的动态变化及抗菌作用研究

研究了不同生长期忍冬叶中活性成分的差异性及动态变化和抑菌活性.分别采用紫外分光光度法(UVVis)对不同生长期忍冬叶中总黄酮含量进行测定;采用气相色谱-质谱(GC-MS)联用法对不同生长期忍冬叶中的挥发性成分进行测定;采用高效液相色谱法(HPLC)对不同生长期忍冬叶中的绿原酸、新绿原酸、异绿原酸C、咖啡酸、木犀草素、木犀草苷、金丝桃苷、芦丁、槲皮素9种化合物的含量进行测定;采用平板打孔法测定不同生长期忍冬叶的抗菌活性.结果表明不同生长期忍冬叶中活性成分的含量差异较大,6月份所测各种活性成分含量均较高,且抑菌效果最好.综合不同生长期忍冬叶中各活性成分的含量,确定忍冬叶的最佳采摘期为6月份,为忍冬叶的综合开发利用提供理论依据.     

Determination of melatonin and its precursors and metabolites using capillary electrophoresis with UV and fluorometric detection

A micellar electrokinetic chromatography method has been developed for simultaneous determination of melatonin and its precursors and metabolites. A 20 mM borate buffer pH 9.5 with 50 mM SDS served as the electrolyte. Tryptophan, 5-methoxyindoleacetic acid, 6-hydroxymelatonin, melatonin, serotonin, and 5-methoxytryptamine were baseline separated in less than 13 min. The limits of detection for UV detection and fluorometric detection based on native fluorescence of analytes were at the sub-ppm level. The proposed method with UV detection was applied to melatonin content control in pharmaceutical tablets with a precision expressed as RSD (n = 7) = 1.6%. For biological samples extraction with chloroform and ethyl acetate was examined. With ethyl acetate and chloroform recoveries of 87.2% and 82.1% melatonin, respectively, were obtained from plasma samples. The recovery of melatonin from spiked urine samples was 80.0% for ethyl acetate and 82.5% for chloroform. Fluorometric detection provides about two-fold improvement over UV in the detection of melatonin and minor improvements for three other analytes, but is much poorer than UV for tryptophan and 6-hydroxymelatonin in applied conditions.     

Analysis of melatonin using a pH- and temperature-responsive aqueous chromatography system

A new method for the qualitative and quantitative analysis of an intracerebral hormone, such as melatonin, has been proposed, utilizing newly designed copolymers that include ion-exchange groups. These copolymers responded to both the temperature and the pH, and the copolymers were modified with cross-linked hydrogel applied onto aminopropyl silica beads. The products were evaluated as HPLC packing materials for a pH- and temperature-responsive chromatography. The property of the surface of the stationary phase was altered from hydrophilic to hydrophobic, and from charged to non-charged by changes in both the temperature and the pH. In the chromatographic system, we investigated how to change the retention of melatonin by varying the temperature. A pH- and temperature-responsive chromatography is expected to be useful for the separation of pharmaceuticals and biomolecules.     

Variation of melatonin and serotonin content in rat pineal gland with sex and oestrous phase difference determined by high-performance liquid chromatography with fluorimetric detection

Simultaneous determination of melatonin and serotonin in rat pineal gland is described using reversed-phase high-performance liquid chromatography with fluorimetric detection. These indoles were analysed isocratically within 15 min. In this work, veratric acid (3,4-dimethoxybenzoic acid), which has fluorescence characteristics (lambda ex = 290 nm, lambda em = 350 nm) around the wavelength of native fluorescence of melatonin (lambda ex = 285 nm, lambda em = 345 nm), was used as an internal standard. This method was applied to the determination of melatonin and serotonin in male and female rat pineal gland. No significant differences between the two groups were observed in the pineal melatonin and serotonin contents. The pineal melatonin and serotonin contents were compared with the oestrous and the di-oestrous phases of female rats. They were not widely different from each other.     

Concurrent on-line sampling of melatonin in pineal microdialysates from conscious rat and its analysis by high-performance liquid chromatography with electrochemical detection

Dynamic changes of melatonin in microdialysates from the pineal gland of a freely moving rat were repeatedly determined by using on-line high-performance liquid chromatography with electrochemical detection. The detection limit for melatonin, ca. 5 pg, was well below that achieved with other systems. We observed a drastic increase of extracellular pineal melatonin during the transitional phase from the light period to the dark period. This application of microdialysis is a useful tool in the study of the physiological role of the mammalian pineal body.     

Sensitive Adsorptive Stripping Voltammetric Methodologies for the Determination of Melatonin in Biological Fluids

The reversible redox process that melatonin presented on carbon paste electrodes was the basis of a sensitive methodology for the determination of this hormone. From all the processes presented by this hormone, this was never used before as the basis of voltammetric measurements for melatonin determination. Therefore, parameters that affected the cyclic voltammetric signal were studied. A limit of detection as low as 9×10^?11 M was obtained when optimized alternating current voltammetry was employed. The reproducibility was excellent due to an adequate pretreatment of the solid electrode (RSD=2.7%, n=10). A comparison with methodologies that employ different electrochemical techniques from the point of view of their analytical characteristics was made. This methodology has proved to be suitable for the determination of melatonin in biological fluids.     

三维荧光光谱结合二阶校正法测定保健品中的褪黑素

采用三维荧光光谱结合基于交替三线性分解算法(ATLD)的二阶校正方法测定了2种保健品中褪黑素的含量. 当组分数取2时, 测得美益天褪黑素维生素B6胶囊(MYT)和纽斯葆牌褪黑素片(NSB)中褪黑素的含量分别为(3.074±0.019) mg/capsule和(1.649±0.059) mg/tablet, 平均加标回收率分别为(97.9±4.0)%和(103.4±2.7)%, 检出限为1.4 ng/mL. 结果表明, 该方法准确可靠. 该方法具有"二阶优势", 即使样品中存在干扰, 仍可获得较好的结果, 且灵敏度较高. 采用高效液相色谱(HPLC)法对该方法进行了验证, 用t-test对2种方法获得的结果进行比较发现, 2种方法的结果之间无显著性差异, 具有良好的一致性, 但本文方法更环保、 简单. 因此, 三维荧光光谱结合二阶校正方法可作为测定褪黑素含量的新方法, 用于对含褪黑素的保健类产品进行质量监控.     

Simultaneous analysis of serotonin, melatonin, piceid and resveratrol in fruits using liquid chromatography tandem mass spectrometry

An analytical method was developed for the simultaneous quantification of serotonin, melatonin, trans- and cis-piceid, and trans- and cis-resveratrol using reversed-phase high performance liquid chromatography coupled to mass spectrometry (HPLC-MS) with electrospray ionization (ESI) in both positive and negative ionization modes. HPLC optimal analytical separation was achieved using a mixture of acetonitrile and water with 0.1% formic acid as the mobile phase in linear gradient elution. The mass spectrometry parameters were optimized for reliable quantification and the enhanced selectivity and sensitivity selected reaction monitoring mode (SRM) was applied. For extraction, the direct analysis of initial methanol extracts was compared with further ethyl acetate extraction. In order to demonstrate the applicability of this analytical method, serotonin, melatonin, trans- and cis-piceid, and trans- and cis-resveratrol from 24 kinds of commonly consumed fruits were quantified. The highest serotonin content was found in plantain, while orange bell peppers had the highest melatonin content. Grape samples possessed higher trans- and cis-piceid, and trans- and cis-resveratrol contents than the other fruits. The results indicate that the combination of HPLC-MS detection and simple sample preparation allows the rapid and accurate quantification of serotonin, melatonin, trans- and cis-piceid, and trans- and cis-resveratrol in fruits.     

In vivo microdialysis/liquid chromatography/tandem mass spectrometry for the on-line monitoring of melatonin in rat

Liquid chromatography/tandem mass spectrometry (LC/MS/MS) has been coupled to in vivo microdialysis for on-line monitoring of melatonin in a freely moving rat for a period of 15 hours. A microdialysis probe was surgically implanted into the jugular vein of the rat, and deionized water was used as the perfusion medium at a flow rate of 1.0 microL/min. Microdialysis samples were collected in an on-line injector with sample injection every 30 minutes. Melatonin was dosed by intraperitoneal (i.p.) injection and then monitored by microdialysis/LC/MS/MS. The whole experiment, including the microdialysis sampling and sample injection into the LC/MS system, was fully automated. Metabolites of melatonin were identified off-line by LC/MSn experiments. Two metabolites were identified as 6-hydroxymelatonin and cyclic 2-hydroxymelatonin, consistent with ones found previously in the literature.     

Quantification of the neurotransmitters melatonin and N-acetyl-serotonin in human serum by supercritical fluid chromatography coupled with tandem mass spectrometry

The aim of this study was developing a supercritical fluid chromatography tandem mass spectrometry (SFC-MS/MS) method and an ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) method, for the analysis of N-acetyl-serotonin (NAS) and melatonin (Mel) in human serum, and to compare the performance of these methods. Deuterated isotopologues of the neurotransmitters were synthesized and evaluated for suitability as internal standards in sample preparation. Liquid-liquid extraction was selected as sample preparation procedure. With chloroform, the best extraction solvent tested, an extraction yield of 48 ± 2% for N-acetyl-serotonin and 101 ± 10% for melatonin was achieved. SFC separation was accomplished within 3 min on a BEH stationary phase, employing isocratic elution with 90% carbon dioxide and 0.1% formic acid as well as 0.05% ammonium formate in methanol. For the 4 min UHPLC gradient separation with 0.1% formic acid in water and methanol, respectively, a Kinetex XB-C18 was used as stationary phase. Both chromatographic techniques were optimized regarding mobile phase composition, additives to the mobile phase and column temperature. Multiple reaction monitoring (MRM) analysis was used for quantification of the metabolites. Both methods were validated regarding retention time stability, LOD, LOQ, repeatability and reproducibility of quantification, process efficiency, extraction recovery and matrix effects. LOD and LOQ were 0.017 and 0.05 pg μL⁻¹ for NAS and 0.006 and 0.018 pg μL⁻¹ for Mel in SFC-MS/MS compared to 0.028 and 0.1 pg μL⁻¹ for NAS and 0.006 and 0.017 pg μL⁻¹ for Mel in UHPLC-MS/MS.     

Design of experiment techniques for the optimization of chromatographic analysis conditions: A review

Design of experiment (DoE) techniques have been widely used in the field of chromatographic parameters optimization as a valuable tool. A systematic literature review of the available DoE techniques applied to the development of a chromatographic analysis method is presented in this paper. First, the most common available designs and the implementation steps of DoE are comprehensively introduced. Then the studies in recent 10 years for the application of DoE techniques in various chromatographic techniques are discussed, such as capillary electrophoresis, liquid chromatography, gas chromatography, thin-layer chromatography, and high-speed countercurrent chromatography. Current problems and future outlooks are finally given to provide a certain inspiration of research in the application of DoE techniques to the different chromatographic techniques field. This review contributes to a better understanding of the DoE techniques for the efficient optimization of chromatographic analysis conditions, especially for the analysis of complex systems, such as multicomponent drugs and natural products.