LiCl／DMAc溶剂体系中长链脂肪酸纤维素酯的制备及其药物释放性能

在ＬｉＣｌ／ＤＭＡｃ溶剂体系中由纤维素与长链脂肪酸氯反应制备长链脂肪酸纤维素酯，并研究了反应条件对酯化反应取代度的影响。结果表明在适当的反应条件下，酯化聚代度可达到２．８５（９５％）。还研究了纤维酯作为药物控制释放载体对ＬＮＧ、Ａｓｐｉｒｉｎ、ＢＡＳ的释放性能。     

L—赖氨酸酯聚酰胺Gd（Ⅲ）配合物的合成

Ｌ－赖氨酸长链烷基酯与二乙三胺五乙酸双酸酐共缩聚，制得大分子配体，它与ＧｄＣｌ３反应得到相应的配合物．这些配合物具有比现在用于临床诊断的造影剂Ｇｄ（ＤＴＰＡ）更高的弛豫速率．     

检测饲料、蛋黄及鸡肝中长链饱和及不饱和脂肪酸的毛细管气相色谱法

探索检测饲料、蛋黄和鸡肝中长链饱和、单烯及多烯键脂肪酸的前处理步骤,样品匀浆后,用氯仿－丙酮混合溶剂提取,以氢氧化钾－甲醇酯化反使生成相应的脂肪酸甲 酯,再转溶于异辛烷中,采用不分流进样技术注入气相色谱仪中,经毛细管柱分离,用火焰离子化检测器检测。应用该法能检测出含量较低、具有生理活性意义但易于氧化的ｗ－３长链多烯键脂肪酸,如二十碳五烯酸（ＥＰＡ）、二十二碳五烯酸（ＤＰＡ）、二十二碳六烯酸（ＤＨＡ）。     

心理治疗在急性脑卒中患者ADL训练中的应用

对５３例急性脑卒中患者进行分组训练，分别采取ＰＴ、ＡＤＬ以及ＡＤＬ与心理治疗相结合三种形式，为期三个月，采用Ｂａｒｔｈｅｌ指数评佑结果表明：ＡＤＬ训练组比ＰＴ训练组的ＡＤＬ能力提高显著，ＡＤＬ与心理治疗相结合训练组比单纯ＡＤＬ训练组的ＡＤＬ能力提高显著。因此，心理治疗在急性脑卒中患者ＡＤＬ训练中的应用是非常重要的。     

脑卒中临床治疗康复ADL的应用

介绍了日常生活活动在脑卒中临床治疗和康复中中的应秀，提出了评价ＡＤＬ的注意事项的对ＡＤＬ恢复的影响因素的认识。     

脂肪醇和电解质对丙酸十二铵盐在四氯化碳中增溶水的影响

研究了己醇，辛醇、Ｋｕｉ醇和月桂醇对丙酸十二铵（ＤＡＰ）－四氯化碳反胶束溶液增溶水和氯化钠水溶液的影响，在ＤＡＰ浓度固定时，水增溶量对醇浓度的关系出现极大值，在醇浓度相同时，长碳链醇较短碳链醇有更大的增溶水能力，在固定ＤＡＰ浓度和增溶水量最大时，氯化钠的存在将导致水溶液增溶量的显著下降，乙酸十二铵（ＤＡＡ）、ＤＡＰ和丁酸十二铵（ＤＡＢ ）的四氯化碳溶液对氯化钠水溶液的增溶量随氯化钠浓度的升高而有不     

可生物降解的聚乳酸弹性体的合成与表征

本文将丙交酯（ＤＬ－ＬＡ）与聚乙二醇（ＰＥＧ）的预聚体用甲苯－二异氰酸酯８０（ＴＤＩ）扩链，得到了一系列的聚乳酸（聚醚）型聚氨酯（ＰＥＧ－ＰＬＡ／ＰＵ）弹性体。对预聚体和弹性体分别进行了ＩＲ、ＨＮＭＲ和ＤＭＡ表征，并测定了弹性体的力学性能。结果表明，ＬＡ与ＰＥＧ生成的预聚体是一种三嵌段结构：ＨＯ－ＰＬＡ－ＰＥＧ－ＰＬＡ－ＯＨ。随着ＰＥＧ含量的增加，弹性体的玻璃化温度下降；ＰＥＧ分子量增大时，弹性体     

低密度脂蛋白吸附剂的研究 Ⅱ

本文研究了葡聚糖凝胶经磺化反应后接上磺酸团并制成珠状的吸附剂，对血浆中低密度脂蛋白（ＬＤＬ）和极低密度脂蛋白（ＶＬＤＬ）的选择性吸附。实验结果表明：该吸附剂可使血浆中的ＬＤＬ＋ＶＬＤＬ降低９０％以上，而使高密度脂蛋白（ＨＤＬ），总蛋白（ＴＰ）有较小的降低，并讨论了葡聚糖凝胶的交联度和磺化程度对其吸附性能的影响。     

用酶法测定血浆中1,6-二磷酸果糖含量

建立了用酶法测定血浆中１，６－二磷酸果糖（ＦＤＰ）的方法，为含１，６－二磷酸果糖制剂的药代动力学研究提供基础。血浆用３０％（ψ）的高氯酸沉淀蛋白后，分别在样品中加入０．５６ｍｇ还原型烟酰胺腺嘌啉二核苷酸（ＮＡＤＨ），０８５ｕ（酶活单位）３－磷酸甘没脱氢酶（ＧＤＨ）和６０ｕ磷酸甘油醛异构酶（ＴＩＭ）后１５ｍｉｎ在３４０ｎｍ处测定吸光值Ａ１，然后加入０．２５ｕ醛缩酶（ＡＬＤ），１５ｍｉｎ后在３４０ｎｍ     

血浆中长链不饱和脂肪酸的毛细管气相色谱分析

脂类物质是细胞膜的主要组成,具有多种重要的生物功能。通过检测血浆中脂肪酸水平,可以研究某些重要疾病与脂质及脂肪酸的关系。特别是长链不饱和脂肪酸,由于它们是前列腺素的前体,更具有重要意义,血浆中长链不饱和脂肪酸,其中8,11,14—廾碳三烯酸(C_(20:)     

Separation and determination of saturated very-long-chain free fatty acids in plasma of patients with adrenoleukodystrophy using solid-phase extraction and high-performance liquid chromatographic analysis

An improved method was developed for the isolation of very-long-chain free fatty acids (VLCFFAs) in plasma and their separation and determination by high-performance liquid chromatography (HPLC). The method includes sample clean-up using solid-phase extraction, fluorophoric labelling of the FFAs and reversed-phase HPLC separation. The solid-phase extraction was carried out with aminopropyl-bonded phase columns. The FFAs were then derivatized with 9-anthryldiazomethane (fluorescent) reagent and separated by HPLC on an RP-18 column with methanol as the mobile phase. Using this method, the concentrations of C20:0, C22:0, C24:0 and C26:0 were determined in the plasma of five adrenoleukodystrophy (ALD) patients, one obligatory heterozygote, four healthy male volunteers and one child with cerebral leukodystrophy but without any other ALD symptoms. Statistically significant differences were found in the levels of C24 and C26 and in the ratios C24/C22 and C26/C22 in ALD patients and in normal controls. The values were higher in patients with X-ALD. This method therefore provides a rapid and accurate procedure for the laboratory confirmation of X-ALD.     

大鼠肝过氧化物酶体中脂肪酸的分析

 用双 (2 乙基己基 )酚酞酸酯 (DEHP)诱导大鼠肝过氧化物酶体增殖 ,再用蔗糖密度梯度离心法分离大鼠肝细胞过氧化物酶体 ,并用十七烷酸作内标 ,以毛细管气相色谱法在非极性SPB 1石英毛细管柱上对其中的 11种脂肪酸进行分离测定。正常组和诱导组的大鼠肝过氧化物酶体中的不饱和脂肪酸和长链脂肪酸所占总脂肪酸的比例及总脂肪酸的统计结果是 :诱导组的不饱和脂肪酸的含量高于正常组的 (P <0 0 5 ) ,而两个组的脂肪酸总量及长链脂肪酸的含量无明显差别。结果提示 :诱导组的大鼠肝过氧化物酶体的脂肪酸成分发生了变化 ,其膜结构与正常组的不相同。     

A fluorimetric liquid chromatography for highly sensitive analysis of very long chain fatty acids as naphthoxyethyl derivatives

Summary A simple and sensitive liquid chromatographic method is described for the simultaneous determination of biologically important very long chain fatty acids (docosanoic, tetracosanoic and hexacosanoic acids) as fluorogenic derivatives. The method is based on the derivatization of the fatty acids with 2-(2-naphtoxy)ethyl 2-(piperidino)ethanesulfonate (NOEPES) in toluene in the presence of potassium carbonate and 18-crown-6. Several parameters affecting the derivatization were studied, including reaction temperature, reaction time, reaction solvent, base catalyst and the amount of the reagent. The resulting derivatives were analyzed by HPLC with fluorimetric detection (λex=235 nm; λem=366 nm). The linear range for the determination of docosanoic, tetracosanoic and hexacosanoic acids was 0.028–1.4 μM with a detection limit of about 5.6 nM (S/N=3) (56 fmol per 10 μL injection). Application of the method to the analysis the non-esterified (free) very long chain fatty acids spiked in plasma proved feasible.     

Separation and quantitation of plasma free fatty acids as phenacyl esters by HPLC

We have developed a rapid method for the separation of plasma free fatty acids as their phenacyl esters by high-performance liquid chromatography (HPLC) using a reversed-phase (C18) column. The derivatives of series of both saturated and unsaturated fatty acids (C12:0-C22:6) are simultaneously separated within 45 min and detected with ultraviolet at 241 nm. The limit of detection of fatty acids was approximately 0.5 nmol in 20 microL injected volume of extracts, and the coefficient of variation of the present method did not exceed 3.0%. Comparison of the results of the present HPLC method with those of gas chromatography, gave very good correlations for all fatty acids in human plasma.     

Quantitative analysis of aberrant fatty acid composition of zebrafish hepatic lipids induced by organochlorine pesticide using stable isotope-coded transmethylation and gas chromatography-mass spectrometry

Organochlorine pesticides have been extensively used worldwide for agricultural purposes. Due to their resistance to metabolism, a major public health concern has been raised. Aberrant hepatic lipid composition has been a hallmark of many liver diseases associated with exposure to various toxins and chemicals. And thus lots of efforts have been focused on the development of analytical techniques that can rapidly and quantitatively determine the changes in fatty acid composition of hepatic lipids. In this work, changes in fatty acid composition of hepatic lipids in response to DDT (dichlorodiphenyltrichloroethane) exposure were quantitatively analyzed by a gas chromatography-mass spectrometric approach based on stable isotope-coded transmethylation. It has been quantitatively demonstrated that polyunsaturated fatty acids including C20:3n3, C20:4n6, and C22:6n3 decrease in response to DDT exposure. However, saturated long chain fatty acids including C16:0, C18:0, as well as monounsaturated long chain fatty acid C18:1n9 consistently increase in a DDT-concentration-dependent manner. In particular, much higher changes in the level of hepatic C16:0 and C18:0 for male fish were observed than that for female fish. These experimental results are in accordance with qualitative histopathological analysis that revealed liver morphological alterations. The stable isotope-coded mass spectrometric approach provides a reliable means for investigating hepatotoxicity associated with fatty acid synthesis, desaturation, mitochondrial beta-oxidation, and lipid mobilization. It should be useful in elucidation of hepatotoxic mechanisms and safety assessment of environmental toxins.     

Alkyldimethylaminoethyl ester iodides for improved analysis of fatty acids by electrospray ionization tandem mass spectrometry

The development of a new class of derivatives, the alkyldimethylaminoethyl ester iodides, for the analysis of fatty acids by electrospray ionization tandem mass spectrometry is described. They are prepared by quaternization of dimethylaminoethyl esters with alkyl iodides. The trimethylaminoethyl (choline) ester iodide affords between 8 and 12 times greater signal intensity than the corresponding dimethylaminoethyl ester used in the analysis of long to very long chain fatty acids in plasma samples. It is a superior derivative for unsaturated and monohydroxylated long chain fatty acids but unsuitable for bile acids and dicarboxylic acids.     

Fatty-acid composition of rat brain lipids. Determined by support-coated open-tubular gas chromatography.

The nonhydroxy fatty acid composition of rat brain lipids (except gangliosides) was determined by support-coated open-tubular (SCOT) gas chromatography. Fatty acids of both odd and even chain lengths ranging from C14 to C26 were detected. Brain lipids contained 49% saturated, 29% monounsaturated, and 22% polyunsaturated fatty acids. Monoenoic fatty acids were mainly of the omega-9 and omega-7 series with minor amounts of omega-10 and amega-11 isomers. Dienes and trienes consisted of omega-6, amega-7, and omega-9 series. Tetraenes were of the omega-6 series. Small amounts of omega-6 and omega-3 pentaenes were detected. The most abundant polyunsaturated fatty acid was 22:6omega-3. The advantages of support-coated open-tubular columns over wall-coated open-tubular columns for the analysis of brain lipid fatty acids are discussed.     

Chemical synthesis of deuterium-labeled and unlabeled very long chain polyunsaturated fatty acids

First syntheses of a deuterium-labeled very long C34-containing polyunsaturated fatty acid, 34:5n5, and three other unlabeled very long chain C30-32 containing polyunsaturated fatty acids are reported. These syntheses were achieved by coupling chemically modified C22- and C20-containing polyunsaturated fatty acids with carbanions derived from arylalkyl sulfones, followed by sodium amalgam-mediated desulfonylation.     

Dimethylaminoethyl esters for trace, rapid analysis of fatty acids by electrospray tandem mass spectrometry

The development of a new derivative, the dimethylaminoethyl ester, for the analysis of fatty acids by electrospray tandem mass spectrometry is described. Qualitative and quantitative analyses of long to very long chain fatty acids in plasma, blood, urine and wax were performed. Branched chain, unsaturated, dicarboxylic, hydroxy, amino and keto acids were studied. The quantitative analysis method using the new derivative is simple, rapid and precise with small sample size. It has good potential as a screening method for biologically important fatty acids. Copyright 1999 John Wiley & Sons, Ltd.     

Development and validation of LC-MS/MS method for determination of very long acyl chain (C22:0 and C24:0) ceramides in human plasma

Ceramide is a key metabolite in both anabolic and catabolic pathways of sphingolipids. The very long fatty acyl chain ceramides N-(docosanoyl)-sphing-4-enine (Cer(22:0)) and N-(tetracosanoyl)-sphing-4-enine (Cer(24:0)) are associated with multiple biological functions. Elevated levels of these sphingolipids in tissues and in the circulation have been associated with insulin resistance and diabetes. To facilitate quantification of these very long chain ceramides in clinical samples from human subjects, we have developed a sensitive, accurate, and high-throughput assay for determination of Cer(22:0) and Cer(24:0) in human plasma. Cer(22:0) and Cer(24:0) and their deuterated internal standards were extracted by protein precipitation and chromatographically separated by HPLC. The analytes and their internal standards were ionized using positive-ion electrospray mass spectrometry, then detected by multiple-reaction monitoring with a tandem mass spectrometer. Total liquid chromatography–tandem mass spectrometry (LC-MS/MS) runtime was 5 min. The assay exhibited a linear dynamic range of 0.02–4 and 0.08–16 μg/ml for Cer(22:0) and Cer(24:0), respectively, in human plasma with corresponding absolute recoveries from plasma at 109 and 114 %, respectively. The lower limit of quantifications were 0.02 and 0.08 μg/ml for Cer(22:0) and Cer(24:0), respectively. Acceptable precision and accuracy were obtained for concentrations over the calibration curve ranges. With the semi-automated format and short LC runtime for the assay, a throughput of ～200 samples/day can easily be achieved.