SPME-HPLC法测定水中的酚类化合物

采用固相微萃取(SPME)高效液相色谱法(HPLC)同时测定了水中苯酚、4-硝基酚、3-甲基酚、2,4-二氯酚、2,4,6-三氯酚、五氯酚等六种酚类化合物的含量.采用ZORBOX SB-C18柱,以甲醇-1%乙酸水溶液为流动相进行梯度洗脱,流速为1.0 mL/min.紫外检测波长为254、280 nm.六种酚类化合物的检出限为0.31～1.90μg/L,加标回收率为88%～103%.该方法操作简单,能快速、准确地检测水中的酚类化合物.

武汉东湖光合色素与叶绿素a代谢产物的HPLC研究

用高效液相色谱 (HPLC)法研究了武汉东湖周年及围隔实验水柱颗粒物色素的组成及变化。共检测到约 2 0种色素 ,类胡萝卜素含量较高的有硅藻的标志色素岩藻黄素 ,隐藻的异黄素 ,蓝、绿藻的黄体素、玉米黄素及胡萝卜素。东湖叶绿素a的代谢产物主要为脱植基叶绿素a(全湖年均约占叶绿素a的 5 % ) ,而非脱镁叶绿素a或脱镁叶绿酸a。围隔实验结果表明 :叶绿素a与总浮游植物 (r =0 .84) ,叶绿素b与绿藻 (r=0 .77) ,岩藻黄素与硅藻 (r =0 6 8) ,异黄素与隐藻生物量 (r=0 .83

Determinations of residual furazolidone and its metabolite, 3-amino-2-oxazolidinone (AOZ), in fish feeds by HPLC-UV and LC-MS/MS, respectively

The antibacterial drug furazolidone belonging to the group of nitrofuran antibacterial agents has been widely used as an antibacterial and antiprotozoal feed additive for poultry, cattle, and farmed fish in China. During application a large proportion of the administered drug may reach the environment directly or via feces. Although the use of furazolidone is prohibited in numerous countries, there are indications of its illegal use. It is known that furazolidone can be rapidly metabolized to 3-amino-2-oxazolidinone (AOZ) in the body of the target organism. In this study, a total of 21 fish feed samples, including 17 commercial fish feeds from local markets in China (representing 15 different formulations) and 4 fish feeds obtained from Germany and Turkey, respectively, are analyzed to determine whether the drug is still illegally used or commercially available feeds are contaminated by this drug. High-performance liquid chromatography (HPLC) and liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) methods have been implemented to determine furazolidone and its metabolite AOZ in fish feeds containing animal protein, respectively. An efficient and convenient cleanup method for the determination of furazolidone in fish feeds is developed, and a simple cleanup method for the determination of AOZ is used. Method recoveries for samples used were determined as 87.7-98.3% for furazolidone at two spike levels of 2.0 and 5.0 ng g(-1) and as 95.6-102.8% for AOZ at spike levels of 0.4 and 0.8 ng g(-1). Limits of detections were 0.4 ng g(-1) for furazolidone and 0.05 ng g(-1) for AOZ. The established methods are therefore suitable for the determination of furazolidone and its metabolite AOZ in fish feeds at trace contamination levels. Using the established methods, all fish feed samples have been proved to be furazolidone negative; however, AOZ is tested in 16 of 17 fish feeds obtained from local markets in the Hubei province of China, with a positive rate as high as 94.1%.

Optimization of RP-HPLC analysis of low molecular weight organic acids in soil

RP-HPLC analysis for low molecular weight organic acids in soil solution has been optimized. An Atlantis (TM) C-18 column was used for the analyses. An optimal determination for eleven organic acids in soil solution was found at room temperature (25 degrees C) and 220 nm detection wavelength, with a mobile phase of 10 mM KH2PO4 -CH3OH (955, pH 2.7), a flow rate of 0.8 mL/min and 10 mu L sample size. The detection limits ranged 3.2-619 ng/mL, the coefficients of variation ranged 1.3-4.6%, and the recoveries ranged 95.6-106.3% for soil solution with standard addition on the optimal conditions proposed.

旋光性聚合物HPLC-CSP的制备及手性拆分能力的研究

手性是自然界的一种普遍现象，生命现象离不开手性。手性物质在有机化学、药物化学、生物化学以及功能材料等领域显示出诱人的应用前景。外消旋体的拆分是手性研究的重要基础工作。高效液相色谱手性固定相法（HPLC-CSP）在对映体化合物的分离分析和制备方面表现出独特的优势。本论文以旋光性联萘类聚合物和纤维素类衍生物涂敷的手性固定相进行分析级和半制备级色谱拆分，研究和探讨了它们对外消旋化合物的手性识别能力。1. 纤维素类聚合物的合成 将微晶纤维素与相应的酰氯或异氰酸酯反应获得四种纤维系类衍生物，纤维素三苯甲酸酯（CTB）、纤维素三苯基氨基甲酸酯（CTPC）、纤维素三（3,5-二甲基苯基氨基甲酸酯）（CDMPC）、纤维素三联萘甲酸酯（CTBPT）。红外、核磁、元素分析证明原料纤维素已酯化完全。2. 旋光性聚合物手性固定相及HPLC手性柱的制备采用聚合物涂敷硅胶方法制备了四种纤维素类、三种联萘聚酰胺手性固定相和二种半制备级纤维素手性固定相，匀浆法装柱。研究了不同的涂敷液对色谱柱效的影响。3. 旋光性联萘聚酰胺手性柱拆分能力的探讨 在三种由（S）-联萘聚酰胺涂敷的色谱柱上，以多种流动相体系对多种外消旋化合物进行手性折分试验。4. 纤维素类手性分析柱拆分能力的研究 对手性柱进行塔板数和稳定性测试及拆分能力研究。对一些外消旋化合物实现了手性拆分。由实验结果可以看出，以CDMPC涂敷的手性柱对多种外消旋化合（包括药物）具有手性拆分能力，具分离度较高。5. 半制备级拆分 对三种外消旋药物在纤维素半制备色谱柱上进行了半制备级拆分。我们在分析型色谱柱进行了流动相条件的选择，将优化后的分析条件直接放大到半制备色谱中，不仅节省了模索条件的时间，而且可以节省大量的流动相，预计一天内所能达到的对外消旋体最大拆分量可达克级以上。6. 进行了HPLC-UV-旋光仪的联用检测研究，实现了在线流动过程中旋光曲线的绘制。

唐古特瑞香和大果大戟的化学成分研究

本学位论文由两部分共3章组成。第一部分分别报道2种藏药唐古特瑞香和大果大戟化学成分的研究成果，从2种药用植物共分离鉴定了60个不同的化合物，其中12个为新结构，特别有意义的是发现了2个具有同一新骨架的二萜化合物。第二部分概述了大戟科植物多环二萜的研究进展。 第一部分包括第1和2章。在这2章中分别报道了唐古特瑞香（Daphne tangutica Maxim）和大果大戟（Euphorbia wallichii Hook. f. Fl）化学成分的分离纯化与结构鉴定。实验采用正、反相硅胶柱层析、薄层制备及HPLC等分离方法，从唐古特瑞香的根皮中共分离出32个化合物，通过红外、质谱及核磁共振等波谱方法鉴定了其中的31个，结构类型分别属于瑞香二萜类、木脂素类、香豆素类、苯丙素类及甾体类，其中有三个新的瑞香二萜型化合物，经波谱分析将它们的结构分别鉴定为1,2a-二氢-20-棕榈酰瑞香毒素、1,2a-二氢-5b-羟基-6a,7a-环氧-树脂大戟醇-14-苯甲酸酯及1,2b-二氢-5b-羟基-6a,7a-环氧-树脂大戟醇-14-苯甲酸酯，另外还有13个已知化合物为首次从该植物中分离得到。从大果大戟的根部共分离出33个化合物，鉴定了其中的30个，其主要成分为种类丰富的二萜，包括巨大戟烷型、续随子烷型、对映－阿替生烷型、对映－贝壳杉烷型、对映－松香烷型、ent-trachylobane型、对映－异海松烷型及一新骨架五环二萜ent-wallichane型，另外还有香豆素、甾体、三萜和一些简单的小分子化合物。其中新化合物有9个，经波谱分析将它们的结构分别鉴定为5-O-(2E,4E,6E)-癸三烯酰基-3,20-O-二乙酰基巨大戟醇、5-O-(2E,4Z)-癸二烯酰基-3-O-乙酰基-20-去氧巨大戟醇、3-O-(2E,4Z)-癸二烯酰基-5b,6b-氧-交京大戟醇、7-苯甲酰氧基-3,5,15-三乙酰基-续随子醇、ent-trachylobane-3-one-17-oic-acid、3α-羟基-对映-阿替斯-16-烯-14-酮、3α,6-二羟基-对映-异海松-7-烯-2,15-二酮、wallichanol A 和 wallichanol B，其中，wallichanol A 和 wallichanol B属于一新骨架类型的五环二萜。除此以外，另有13个已知化合物为首次从该植物中分离得到。 第2部分即第3章，首次概述了大戟属植物中多环二萜的化学和药理研究进展。 This dissertation is composed by two parts. The first part reports the phytochemical investigation of two Tibetan medicine plants, Daphne tangutica Maxim and Euphorbia wallichii Hook. f. Fl. Sixty different compounds including ten new compounds and two novel diterpenoids possessing a new carbon skeleton were isolated and identified. The second part is a review about the progress of studies on the polycyclic diterpeniods of the plant family of Euphorbia. The first part consists two chapters, which expatiate on the isolation and identification of chemical constituents from D. tangutica and E. wallichii. Thirty-one compounds were isolated from the root barks of D. tangutica by methods of column chromatography (silica gel, including reversed phase), preparative TLC and HPLC, and their structure were identified as nine daphnane diterpenes, six lignans, nine cumarin derivatives, five phenylpropanoid derivatives, a steroids and a benzoate on the basis of spectroscopic methods including IR, MS and NMR. Among them, three are new diterpenes with skeleton of daphnane and the structure were determined as 1,a-dihydro-20-palimoyl-daphnetoxin, 1,2a-dihydro-5b- hydroxy-6a,7a-epoxy-resiniferonol-14-benzoate and 1,2b-dihydro-5b-hydroxy- 6a,7a-epoxy-resiniferonol-14-benzoate. In addition, thirteen known ones were isolated from this plant for the first time. Isolation of the roots of E. wallichii yielded thirty compounds, twenty-four of them were elucidated as diterpenoids, which belong to different skeleton types of ingenol, lathyrane, ent-atisane, ent-kaurane, ent-abietane, ent-trachylobane, ent-isopimarane and a new pentacyclic skeleton ent-wallichane respectively. The remains including a cumarine, a triterpenoid, a steroid and three compounds with small molecule. Nine new compounds were characterized as 5-O-deca-2E,4E,6E- trienoyl-3,20-O-diacetylingenol, 5-O-deca-2E,4Z-dienoyl-3-O-acetyl-20- deoxyingenol, 3-O-deca-2E,4Z-dienoyl-jolkinol-5b,6b-oxide, 7-benzoyl-3,5,15- triacetyl-7-hydroxylathyrol, ent-trachylobane-3-one-17-oic-acid, 3α-hydroxy-ent- atis-16-en-14-one, 3α,6-dihydroxy-ent-isopimarane-7-en-2,15-dione, wallichanol A and wallichanol B, respectively, by means of comprehensive spectroscopic analysis. Among them, wallichanol A and wallichanol B were two notable novel pentacyclic diterpenoids processing a new rearranged carbon skeleton. And more, thirteen ones were firstly reported from this plant. The third chapter summarizes the research development on chemistry and pharmacology of polycyclic diterpenes from the plant family of Euphorbia for the first time.

HPLC与MALDI-TOFMS联用技术分析蛋黄中的磷脂

蛋黄中含有大量磷脂,其中磷脂酰胆碱(PC)和磷脂酰乙醇胺(PE)最为丰富。本研究采用高效液相色谱法(HPLC)与基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)联用技术分析了蛋黄中磷脂粗提物。将从蛋黄中提取的多种磷脂通过HPLC预先分离,收集各组分后分别进行MALDI-TOF MS分析得到比较清晰的质谱图。通过质谱图解析确定了蛋黄中磷脂酰胆碱、神经鞘磷脂(SM)的脂肪酸组成。