有机相中脂肪酶催化合成乳酸乙酯

 考察了在双底物抑制下脂肪酶催化合成乳酸乙酯,最佳溶剂为叔丁醇,在所选的几种脂肪酶中,固定化于大孔丙烯酸树脂的南极假丝酵母脂肪酶B (Novozym 435)的催化活性最好. 对反应条件进行了优化,当酸醇摩尔比为1∶8, 反应温度60 ℃, 酸浓度0.3 mol/L, 酶浓度45 g/mol, 摇床转速200 r/min时产率达到77%, 脂肪酶Novozym 435重复使用6次后产率仍然可达到60%.     

无溶剂体系酶促阿魏酸双甘酯合成的研究

对酶催化合成阿魏酸双甘酯的脂肪酶进了筛选和比较,并对影响合成阿魏酸双甘酯的因素(助溶剂、转速、底物比、时间、温度、水含量和硅藻土添加量)进行了探讨,结果表明无溶剂反应体系中阿魏酸双甘酯的产率远远高于含有助溶剂体系中反应.同时优化了反应条:无溶剂体系中在70mg CRL催化下,转速为150 r/m in,底物比为1:1,反应时间为120 h,水含量为10 ug/g,硅藻土添加量为40 mg时产率可达33.25%.     

Lipozyme TL IM催化油酸酯化反应制备1,3-甘油二酯

探究了固定化脂肪酶Lipozyme TL IM催化单甘酯与油酸进行酯化反应制备1,3-甘油二酯的可能性,考察了溶剂、水活度、反应温度、底物摩尔比以及溶剂用量对甘油二酯产率及脂肪酶1,3-位置选择性的影响.在优化的实验条件(45℃,1.5 g Lipozyme TL IM,油酸与单甘酯摩尔比1.5∶1,6.0 g三氯甲烷,水活度为0.33)下,反应6 h时,甘油二酯产率可达80%,其中1,3-甘油二酯产率高达92%以上.Lipozyme TL IM循环使用5次后,甘油二酯产率及脂肪酶选择性无明显下降.     

棕榈酸维生素C酯的酶催化合成

以棕榈酸甲酯和维生素C为原料,以脂肪酶(LIPOZYM IM)为催化剂,催化合成了棕榈酸维生素C酯.详细研究了几种因素(维生素C与棕榈酸甲酯的摩尔比,反应温度,反应时间及脂肪酶用量)对合成反应的影响,确立了棕榈酸维生素C酯的较佳合成条件底物摩尔比为31,反应温度55℃,反应时间8h,脂肪酶用量为反应体系的3%(重量),产品一次收率为68.2%.     

离子液体中聚乙二醇维生素E琥珀酸酯的合成

以离子液体为催化剂,由维生素E经两步酯化反应合成了聚乙二醇1000(PEG1000)维生素E琥珀酸酯。以离子液体1-(N',N'-二甲胺乙基)-3-甲基咪唑四氟硼酸盐为催化剂、1,2-二氯乙烷为助溶剂、维生素E与琥珀酸酐摩尔比为1:1.2,在80 ℃条件下反应4 h,维生素E琥珀酸酯(TAS)的产率为90%。以1-丙磺酸基-3-甲基咪唑硫酸氢盐/甲苯为反应体系,TAS与PEG1000摩尔比为1:2,在100 ℃下反应5 h,PEG1000维生素E琥珀酸酯(TPGS)收率为91%。     

脂肪酶催化吉法酯的合成研究

吉法酯(Gefarnate)是一种异戊间二烯化合物,化学名为5,9,13-三甲基-4,8,12-十四三烯酸-3',7'-二甲基-2',6'-辛二烯醇酯。本文主要目的是通过对脂肪酶催化法尼基乙酸和香叶醇的酯化反应合成吉法酯的化学反应条件进行优化,初步建立一套条件温和且污染小的酶催化法制备吉法酯的合成工艺。本文在脂肪酶(Lipozyme 435)催化法尼基乙酸和香叶醇发生酯化反应的条件下,系统研究了酶催化剂、溶剂、投料比、温度等合成条件对酯化反应的影响;结果表明,以Lipozyme 435(0.2 eq)作为催化剂,环已烷作为溶剂,在30℃条件下得到了78.4%的GC收率。该方法具有反应条件温和,副反应少,产率高,催化剂可重复利用等优点,这为进一步吉法酯的工业化合成奠定了良好的基础。     

高温裂解蓖麻油合成10-羟基癸酸研究

以碱和蓖麻油为原料,在高温下碱催化裂解合成10-羟基癸酸,通过对裂解反应的溶剂体系、反应时间、碱类型和碱用量研究,确立了合成10-羟基癸酸的最佳反应条件:邻甲酚与仲辛醇(2.8/1,v/v)为反应溶剂,氢氧化钠为裂解催化剂(60g),反应温度180-200℃,反应时间5小时。在最佳条件下,10-羟基癸酸产率可高达71%,目标产物经HRMS和NMR证实,与文献一致。     

香草醇酯类物质的酶促合成

通过脂肪酶催化酯交换反应,设计并合成了一系列脂肪链长为C2-C18的辣椒素酯同系物(3a-3h),其结构经UV,1H NMR,13C NMR,IR及MS表征.最佳反应条件为:香草醇5 mmol,n,(香草醇):n(脂肪酸酯)=50∶75,脂肪酶Novozyme 435(1 g)为催化剂,丙酮(100 mL)为溶剂,摇床转速为200 r·min-1,于30℃反应10 h,收率18%～93%.对3c高通量筛选结果表明,具有激活PPARγ(过氧化物酶受体)的生物活性.     

5-氟尿苷5’-棕榈酸酯的酶法合成

考察了10 ml丙酮-四氢呋喃(85/15,体积比)混合溶剂体系中,各关键因素对脂肪酶Lipozyme TL IM催化5-氟尿苷5’-棕榈酸酯合成反应的影响.结果表明,添加分子筛能有效除去溶剂中的水分,从而极人地提高了目标产物收率.在最优反应条件下,该体系被成功放大至200 ml (5-氟尿苷克级用量),产物收率高达9...     

有机相中固定化脂肪酶催化合成植物甾醇酯

酶法合成植物甾醇酯具有反应条件温和、产物纯度和产量高等优点,但非水相酶催化的活性和稳定性普遍较低.本文以大孔树脂固定化脂肪酶为催化剂,并在催化过程中添加乳糖的类似物,构建了有机相高效合成植物甾醇酯的工艺过程.以酯化率为考察指标,对脂肪酶和反应溶剂进行筛选,对酯化条件进行优化,同时考察了糖的种类及添加量对酶催化性能的影响.结果表明,大孔树脂NKA吸附固定化的褶皱假丝酵母(Candida rugosa)脂肪酶(NKA-CRL)为最适宜的催化剂,以正己烷为反应介质,在酸醇摩尔比为2和添加酶蛋白质量7.5%的海藻糖的条件下,40°C反应10 h,酯化率达到96.6%.连续6次催化后,植物甾醇的酯化率仍维持在85.0%以上.     

Separation and Assay of Cholecalciferol in Vitamin A + D Ointment

Summary. In this paper two methods are presented. One involves the separation of cholecalciferol from a topical ointment. The other involves the assay of cholecalciferol in this ointment. The study was performed with normal-phase high performance liquid chromatography using a NP-L3 column and UV detection. Applying a mobile phase mixture containing n-hexane:2-propanol (99:1) a total separation was achieved within 15 min. For isolation and assay of cholecalciferol from an ointment (vitamin A + D), dissolution in n-hexane gave the highest recovery (>95%). The isolation and assay process can be performed within 3.5 h.     

紫外分光光度法直接测定AD钙盐中维生素A的含量

AD钙盐中的维生素A是以其乙酸酯的形态加入，而后者不溶于水。根据此性质，将AD钙盐试样用水浸取即可使维生素A与基体组分离，将不溶物分出，溶于乙醇中并定客为10mL，随即可在此试样乙醇溶液中用UV-分光光度法测定维生素A。在维生素A的吸收峰325nm波长处，用1cm石英吸收皿以乙醇作参比液测得其吸光度。用高纯度的维生素A乙醇酯（纯度99．9％）作标准制作标准曲线，得其线性回归方程为CVC=16．899A＋0．059，r=0．9996，方法的回收率在97．7％至100．1％之间。此方法远较国家标准方法和药典方法简单、可行。     

Stereocontrolled synthesis and configurational assignment of (R)-all-trans-11,12-dihydro-3-hydroxyretinol

The synthesis of (R)-all-trans-11,12-dihydro-3-hydroxyretinol and putative metabolites of the side-chain functional group has been achieved in a stereocontrolled manner via the Suzuki-Hiyama cross-coupling reaction of an enantiopure (hydroxycyclohexenyl)alkenyliodide and non-conjugated pinacolboranedienoate, which allowed the absolute configuration of this natural product to be confirmed.     

高效液相色谱法测定微量全血中维生素A

建立了反相高效液相色谱法测定微量全血样品中维生素A的方法。取全血50μL,用100μL无水乙醇沉淀蛋白后,加入400μL×2正己烷漩涡混匀提取维生素A,高速离心分层后取正己烷层在弱氮气流下挥干,加100μL甲醇溶解后用反相色谱柱C8(150 mm×4.6 mmi.d.,5μm)分离,紫外检测波长325nm,外标法定量。色谱条件:柱温,60℃;流动相为V(甲醇)∶V(水)=92∶8;流速:0.8 mL/min。用本法同时测定了27例成人微量全血及其血清中的维生素A。标准曲线的相关系数大于0.999;相对标准偏差(RSD)小于5%。对于50μL全血,方法检出限为0.02μg/mL。加标回收率为88%~115%。成人血清与其全血中维生素A含量之比为2.907±0.160(x-±s)。方法适合于微量全血中维生素A的测定,并可以通过测定全血中维生素A含量推算血清中维生素A的含量。     

Enzymatic determination of vitamin A in pharmaceutical formulations with spectrophotometric detection

An enzymatic method for the determination vitamin A (retinol) is reported using soluble and immobilized alcohol dehydrogenase, isolated from rabbit liver. The reaction is based on the oxidation of retinol and simultaneous reduction of NAD⁺ to NADH followed by spectrophotometric detection at 340 nm. The calibration graph was linear over the range of 2.0–10 μM with correlation coefficients of 0.9967 and 0.9992 (n = 5) for soluble and immobilized alcohol dehydrogenase respectively, with relative standard deviations (n = 3) in the range of 0.5–1.2%. The limit of detection was lower than 1.0 μM. The proposed method was applied to determine vitamin A in pharmaceuticals, and the results obtained were in reasonable agreement with the amount labeled. The results were compared using spectrophotometric reference method, and no significant difference was found between the results of the both methods.     

维生素A衍生物合成工艺的改进

维生素A衍生物合成工艺的改进;多双键烷基膦衍生物;Wittig-Horner反应     

A Comparison of the Retention Behaviour of Vitamin A and Some Metabolites Eluted from Four Different Reversed Phase High Performance Liquid Chromatographic Stationary Phases

Five retinoids, 13-cis-retinoic acid, 9-cis-retinoic acid, all-trans-retinoic acid, all-trans-retinol and 13-cis-retinal were isocratically separated from four different reversed phase high performance liquid chromatographic stationary phases. By taking advantage of the different retention mechanisms, present between the stationary phases and the analytes, the retinoids were separated with different elution orders using the same mobile phase composition. Two of the stationary phases appeared to have more possibilities to interact with the analytes than the usual hydrophobic interactions. The stationary phase with embedded polar groups showed hydrogen bonding properties and the calix[4]arene based stationary phase showed possibilities to form inclusion complexes with the analytes. These additional interactions appeared to benefit the separations of the analytes. This publication shows the benefits by isocratically separate retinoids employing other stationary phases than the conventional C₁₈ stationary phase.     

Development of coupled ultrasound‐assisted and reversed‐phase dispersive liquid–liquid microextraction before high‐performance liquid chromatography for the sensitive determination of vitamin A and vitamin E in oil samples

A new approach based on the ultrasound‐assisted reversed‐phase dispersive liquid–liquid microextraction technique is developed for the extraction and determination of vitamin A and vitamin E from oil matrices before high‐performance liquid chromatography analysis. A methodology based on the full factorial design is carried out to choose the significant parameters. Then the significant factors affecting the extraction efficiency including pH, volume of extraction solvent, and volume of disperser solvent are optimized using a Box–Behnken design. After analyzing the results obtained, the optimum conditions were: pH 4.5, 80–20 μL of the ethanol/water solvent mixture as extraction solvent, 110 μL of 1,4‐dioxane as the disperser solvent, and a sonication time of 10 min. For validation of the developed method, the linear dynamic range, repeatability, limit of detection, and recoveries were obtained under the optimum conditions. The detection limits of the method were 1.6 and 2.3 ng/mL for vitamin A and vitamin E, respectively. The extraction recovery percentages for the studied drugs were above 91%, with acceptable relative standard deviation. The proposed methodology was successfully applied for the determination of the vitamins in different oil samples.