竞争包结法研究β-环糊精对氨基酸的分子配位作用

以酚酞作为光谱探针,在25℃采用紫外-可见光谱滴定法测定了β-环糊精（β-CD）与三种氨基酸分子形成超分子配合物的稳定常数。结果表明,三种生物分子客体与β-环糊精主体之间的键合能力和选择性主要受疏水相互作用和空腔大小匹配程度的影响,几种非共价键弱相互作用力协同贡献于主-客体的包结配位过程。     

高效液相色谱手性流动相添加法分离氟比洛芬对映体及其分离机制

以羟丙基-β-环糊精(HP-β-CD)为手性流动相添加剂,研究了氟比洛芬对映体在反相高效液相色谱中的拆分。考察了羟丙基-β-环糊精的浓度、流动相pH值、有机调节剂、柱温对手性分离的影响,同时探讨了HP-β-CD对氟比洛芬对映体在反相高效液相中的分离机制且计算出相应的包结常数。确定了色谱条件:YMC-Pack ODS-A C18(150 mm×4.6 mm,5μm)色谱柱,流动相为0.5%乙酸(pH3.5,三乙胺调节)含25 mmol/L羟丙基-β-环糊精:甲醇(80:20,v/v),流速为1.0 mL/min,柱温为30℃,紫外检测波长为247 nm。通过容量因子(k’)的倒数1/k’对[HP-β-CD]的良好的线性关系证明氟比洛芬与HP-β-CD形成包结比为1:1包结物,(+)-氟比洛芬的包结常数为1.83 L/mol,(-)-氟比洛芬的包结常数为1.67 L/mol。     

4-溴联苯甲酸的合成

以4-溴联苯为原料,经过乙酰化、卤仿反应制备出标题化合物,并通过核磁共振、红外光谱分析、元素分析及质谱分析对其结构进行了确认和表征。该方法成本低、工艺简单、后处理方便,反应总收率达95%以上。     

医药中间体3-联苯甲酸的合成

本论文以3-溴苯甲酸钠为原料,在钯试剂催化下与溴苯的格利雅试剂反应得到重要的医药中间体3-联苯甲酸,产率88%.所得化合物的结构通过红外和核磁波谱的表征,让明该化合物为目标产物.     

β-环糊精包结维生素A醋酸酯的条件研究

研究了β-环糊精与维生素A醋酸酯的包结,探讨了客体添加速度、溶剂、温度等对包结物产率的影响。25℃下,往1 g的β-环糊精水溶液(60 mL)中滴加0.289 0 g的维生素A醋酸酯乙醇溶液(6 mL),滴加时间70 min,搅拌10 h,包结率可达78.0%。利用分子模拟软件模拟了β-环糊精与维生素A醋酸酯的包结。     

4′-羟基-4-联苯甲酸的合成

以4-羟基联苯为原料,经酯化、傅-克酰基化、相转移催化下的苄基化、氯仿反应、催化氢解等反应,合成了标题化合物,总收率57.8%。化合物4′-苄氧基-4-乙酰基联苯、4′-苄氧基-4-联苯甲酸的结构经1HNMR、IR、MS及元素分析确证。与文献比较,该路线选择性好、产率较高。     

液质联用法测定2,3,4,5-四氟苯甲酸示踪剂研究与应用

氟苯甲酸类示踪剂因其环境友好、稳定性好、无放射性等优点,具有极好应用前景。针对目前检测方法存在问题,研究了2,3,4,5-四氟苯甲酸示踪剂痕量检测方法。采用三重串联四极杆液质联用仪(Agilent G6410),ZORBAX SB-C18色谱柱(2.1 mm×50 mm,1.8μm),乙腈-甲酸水溶液为流动相,质谱应用电喷雾(ESI)离子源和负离子多反应监测(MRM)方式,在碰撞电源80 V、碰撞能6 V的条件下,1.0～200μg/L浓度范围内线性关系良好,R²=0.999 9。该方法已在渤海油田成功应用17井次。     

4‘—庚氧基—4—联苯甲酸的合成

改进了４‘－庚氧基－４－联苯甲酸的合成路线。经元素分析,ＩＲ,＾１ＨＮＭＲ和ＭＳ确证了中间产物４’－庚氧基－４－乙酰基联苯的结构。ＤＳＣ及织构图证实其具有液晶性。     

α-三联噻吩的β-环糊精包结物荧光检测

α-三联噻吩是广泛存在于菊科植物中的一种光活化物质，但含量较低，一般很难检测。本试验报道了一种利用荧光分光光度法分析痕量α-三联噻吩的方法。结果显示：在激发波、发射波狭缝宽度均为5．0nm，激发波长为352nm，发射波长428nm时，经肛环糊精包结后的α-三联噻吩荧光强度比同浓度未包结的α-三联噻吩荧光强度显著增强，在浓度为0．02～0．10μg／g的范围内呈良好的线性关系(R值为0．9998)。     

4′-庚氧基-4-联苯甲酸的合成

改进了４′－庚氧基－４－联苯甲酸的合成路线。经元素分析、ＩＲ、１ＨＮＭＲ和ＭＳ确证了中间产物４′－庚氧基－４－乙酰基联苯的结构。ＤＳＣ及织构图证实其具有液晶性。     

枞酸单离与应用研究进展

枞酸是从天然可再生资源松香中分离得到的产品,由于松香是包含13种树脂酸的混合物,而且这些树脂酸多为同分异构体,导致其物理性质相近,使得枞酸单离非常困难,很多情况下是以混合物的形式应用于各种工业领域中,用途受到了一定的限制。本文介绍了枞酸的几种主要单离方法,分析了各种单离方法的优缺点,认为有机胺盐结晶法是枞酸工业生产最可行的方法。此外,本文还介绍了枞酸在合成生物活性物质方面的应用以及在医药、农药、精细化学品等领域的应用研究进展,最后,指出将松香所含的多种树脂酸逐一分离提纯,并以之作为原料,合成一系列具有生物活性的物质和药物,是未来枞酸综合开发利用的重点。     

Optimizing two-phase system by experiment and simulation for high-speed counter-current chromatographic separation of 2-phenylbutyric acid enantiomer

High-speed counter-current chromatographic preparative separation of 2-phenylbutyric acid (2-PBA) was successfully proposed. The two-phase solvent system was composed of n-hexane/butyl acetate/aqueous phase (7:3:10, v/v/v). Factors influencing the chiral separation efficiency (e.g. types and concentrations of chiral selector (CS), pH of aqueous phase and temperature) were investigated. A mathematical model was established and verified by conducting experiments. Results showed that the model predictions were in good agreement with the experimental results. Under optimal conditions, 2-PBA was successfully separated. The monomer purity reached 99.5%, and the recovery of enantiomers was 91–93%.     

Enrichment of high-purity nervonic acid ethyl ester from Acer truncatum Bunge seed oil by combination method of urea inclusion and molecular distillation

Acer truncatum Bunge is a type of maple that is unique to China. Its fruit setting rate and seed oil content are both high. The oil is mainly composed of C16–C24 fatty acids and contains 5%–7% nervonic acid (NA). NA and its derivatives can delay ageing and prevent and treat disorders such as senile dementia and Alzheimer's disease. The content of NA ethyl ester prepared by the seed oil of A. truncatum Bunge is 5.84%. We report a new process for the enrichment of NA ethyl ester by urea inclusion (UI) and molecular distillation (MD), with the aim of obtaining highly pure NA ethyl ester. First, based on the difference in fatty acid ethyl ester saturation and carbon chain length, unwanted compounds such as oleic acid ethyl ester, linoleic acid ethyl ester, and sterol were removed by one-stage UI, the content of NA ethyl ester was increased to 18.69%. The oil in the UI compound was used as a feed, and differences in the mean molecular free paths between the components were exploited to separate the C16–C20 fatty acid ethyl esters (FAEEs) by two-stage MD. The total content of C16–C20 FAEEs decreased to 3.69% and the purity of NA ethyl ester increased to 47.47%. A new purification process of UI-MD-UI was established and NA ethyl ester could be purified to 91.8%. The combination of MD and UI has an important reference value for the industrialization of producing high-purity NA ethyl ester.     

环糊精对黄酮的包合作用及其在银杏黄酮提取中的应用

对β-环糊精(-βCD)进行甲基化修饰和表征,并通过相溶解度法研究了β-CD以及甲基化β-环糊精(M-β-CD)对银杏黄酮的替代品———芦丁的包合作用。实验表明,两种环糊精都能有效增加芦丁在水中的溶解度,尤其是M--βCD可使溶解度增加30倍。以此为依据,该研究用含有β-CD和M-β-CD的水溶液来提取银杏叶中的黄酮,探讨了环糊精与黄酮的摩尔比、提取温度和提取时间对提取效果的影响,结果发现:当n(M--βCD)∶n(黄酮)=3∶1,60℃下提取3 h后,黄酮的提取率达72%,w(黄酮)=12.4%,较传统的水浸法〔提取率42%,w(黄酮)=4.5%〕和醇提法〔提取率63%,w(黄酮)=6.1%〕有明显的提高。这表明通过-βCD及M--βCD对银杏黄酮的溶解和包合作用,可有效地提高黄酮的提取率以及提取物纯度。     

氟碳化合物与环糊精包合物的制备及其对牛血清白蛋白的影响

以氟碳化合物FC-77作为模型药物,制备FC-77与β-环糊精（卢一cD）包合物。考察包合物与牛血清白蛋白（BSA）的相互作用。通过紫外-可见光谱、红外光谱、热重分析等方法研究包合物的物理化学性能。通过荧光光谱法研究包合物对BSA的荧光猝灭作用。结果为Fc-77与β-cD之间存在强烈的相互作用,从而增加了FC-77的稳定性和水中的溶解性。荧光猝灭结果显示FC-77分子能进入BSA的疏水区域。结论是以β-CD为介质,能显著改善FC-77的理化性能,使FC-77粉末化,便于制成多种剂型,扩大给药方式。     

基于Critic赋权法的隔离矿柱安全厚度优选研究

崩落法转充填法过渡层隔离矿柱的厚度对矿山安全生产和经济效益有着重要影响.以某镍矿为研究背景,在4种理论计算结果的基础上,应用MIDAS/FLAC3D研究不同隔离矿柱厚度对矿房顶底板应力及位移的影响,最后基于Critic客观赋权法对4种隔离矿柱厚度方案进行综合评价,结果表明:以回采率为经济指标,最大主应力、最小主应力、顶...     

通过带有裸露羧酸根的Suzuki反应合成联苯羧酸衍生物的研究

Suzuki偶联反应是合成联苯结构的重要方法之一,本文以溴带芳烃和有机硼酸酯为原料,尝试了带有裸露羧酸根的Suzuki反应,并以62%的产率得到了联苯羧酸衍生物。这为联苯衍生物以及含有联苯结构的生物活性分子的快速生产提供了更为多样化的合成路线,为有效地推动联苯结构化合物的工业化生产做出了贡献。     

密封条件下超声法制备薄荷油β-环糊精包合物研究

研究超声法制备薄荷油β-环糊精包合物的最佳工艺,采用L9(34)正交实验设计,以综合评分为总评价指标,优选其制备工艺。最佳工艺条件:温度为60℃,挥发油/β-CD(mL:g)配比为1:5,超声时间为45min。本法优选工艺条件下挥发油包合物收率和包合率均较高,稳定性强,生产效率高,实用性强,具有可行性,为薄荷油的进一步利用奠定基础。     

透明质酸分离纯化研究进展

微生物发酵法是生产透明质酸的主要方法,分离纯化是发酵法制备高分子量、高纯度透明质酸的关键环节。本文探讨了透明质酸发酵液的特性和分离纯化过程中工艺条件对透明质酸分子量和结构的影响,对预处理、分离、纯化各阶段的工艺方法进行了系统比较和分析,指出了透明质酸分离纯化工艺中存在的问题,并提出了今后分离纯化研究的重点。     

Processing of crambe for oil and isolation of erucic acid

Crambe seed (Crambe abyssinica) is an excellent, recently established source of high-erucic acid oil. Erucic acid has a number of important and potential applications. To develop this potential, a rapid bench-scale method was desired whereby purified erucic acid in up to several 100-g quantities could be produced from crambe seed. Using the method developed, oil was expressed from dried, intact seed; clarified, degummed, and bleached; and saponified and acidified to obtain the free fatty acids. Analysis by inductively coupled plasma of the free fatty acids showed negligible levels of phosphorus and most minerals. Erucic acid was twice crystallized from 95% ethanol at −14°C, resulting in a purity of 87.1%. This process yielded 365 g erucic acid crystals per kg bleached oil. Nuclear magnetic resonance analysis showed that the prepared erucic acid had an excellent pattern of correlation with a commercial standard. The time needed to convert 1 kg of crambe seed to erucic acid is about 48 h. Crystal filtration and drying stages under the current process conditions require 30% of the overall time. The method is suitable for producing adequate quantities of erucic acid for use in studies of its bench-scale conversion. There is obviously, still, a fruitful field of work to be explored in the formalization of refining procedures for crambe oil. It seems that crambe is destined to continue expansion into the high-erucic acid oil markets.