手性农药与手性技术（二）

(接上期)2.1.3 不对称催化技术(1)不对称环丙烷化反应 通过烯烃与重氮乙酸酯的不对称环丙烷化反应合成手性菊酸是受人们关注的合成路线之一。在不同手性构型的铜络合物催化下,2,5-二甲基-2,4-己二烯、1,1-二氯-4-甲基-1,5-戊烯、5,5,5.三氯-2-甲基-2-戊烯与重氮羧酸酯反应,选择性生成手性菊酸酯。目前尚存在配     

过渡金属Mn配合物催化芳香胺和重氮酯交叉偶联反应的理论研究

采用密度泛函理论对醋酸锰催化N,N-二乙基苯胺和重氮二乙酸乙酯交叉偶联反应进行理论计算研究,具体研究包括反应历程及速控步,H2 O与催化剂金属中心的配位作用及对催化活性的促进作用,光引发剂产生的碳自由基攫氢的能力比较.通过理论计算研究,期望为过渡金属Mn配合物催化N,N-二乙基苯胺和重氮二乙酸乙酯交叉偶联反应提供理论基...     

二苯胺型光敏重氮树脂光化学反应动力学研究方法初探

用动态红外、紫外光谱法研究了二苯胺型光敏重氮树脂在水溶液中光分解反应动力学，得到了二苯胺型光敏重氮树脂在水溶液中光分解反应速率方程、动力学方程及量子效率。     

聚乙二醇相转移催化合成二乙酸酯

聚乙二醇相转移催化合成二乙酸酯谢筏娟，陈传峰．张忠书（安徽师范大学化学系，芜湖２４１０００）应用季铵盐、冠醚等相转移催化制备二乙酸酯已有报道［１，２］。我们首次应用聚乙二醇（ＰＥＧ－４００和ＰＥＧ－６００）相转移催化制备４个二乙酸酯，结果表明，在固－...     

乙二醇二乙酸酯的合成

讨论了金属氯化物为催化剂,用甲苯为脱水共沸剂,将乙二醇与乙酸进行酯化反应生成二醇二乙酸酯,经试验得出氧化锌具有较好的催化性能,另外,研究了催化剂用量,脱水共沸剂,酸醇比例等对酯收率的影响。     

4’-甲氧基-4-重氮二苯胺金属复盐稳定性的研究

本文研究了4′-甲氧基-4-重氮二苯胺(VB)金属复盐的稳定性,提出红外密度比值(D),热分解温度和光、热分解指数作为稳定性的量度。本文认为,4′-甲氧基-4-重氮二苯胺盐的分解为异裂反应。感光性能试验指出,感光胶片保存性参数与重氮盐稳定性参数之间有良好的相关性。     

二维金属有机框架及其衍生物用于电催化分解水的研究进展

氢能是一种具有发展前景的可再生清洁能源，电催化分解水是产生氢气的有效途径，设计高效、经济的分解水电催化剂对促进可再生能源的发展至关重要。二维金属有机框架材料（MOFs）具有独特的二维层状结构和灵活可调的化学组成，近年来被广泛应用于电催化分解水领域。二维金属有机框架材料可进一步衍生形成氧化物、磷化物、硫化物、金属-碳复合物等材料，也表现出良好的电催化分解水性能。通过组分调节和结构调控能有效地优化二维金属有机框架及其衍生的材料的本征活性和反应动力学特性，进而提高其电催化性能。此综述介绍了二维MOFs材料及其衍生物在电催化水分解领域的最新研究进展，并展望了其未来研究方向和发展空间。     

国内资料文摘(81024～81039)

一、三氯酚制备过程中三氯化铁的催化作用。试验和生产证明由于三氯化铁的催化作用,使多氯酚迅速生成,降低三氯酚的质量,反应终点很难控制。所以不要采用碳钢制作的设备和管道。二、2,4,6-三氯酚的精制。粗品2,4,6-三氯酚必须用亚硫酸钠进行还原精制,并且需在激烈搅拌下进行。     

常温常压低成本聚合硫酸铁、三氯化铁生产技术

常温常压低成本聚合硫酸铁、三氯化铁生产技术这两种化工产品主要用作净水剂，广泛用于自来水、工业清水净化、多种工业污水、污泥处理。三氯化铁还用于印刷线路板、印花辊筒、标牌刻蚀、不合格塑料镀件退镀及某些化工生产中作氧化剂、氯化剂。本技术以氧为氧化剂，催化氧...     

席夫碱配合物在表面活性剂胶束中难过氧化氢分解的催化作用

合成了水杨醛缩牛磺酸席夫碱合铜配合物，研究了该配合物分别在阴离子表面活性剂十二烷基苯磺酸钠（SDBS）、阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）和非离子表面活性剂辛基酚聚氧乙烯醚（OP-10）的胶束中对H2O2分解的催化性能，探讨了pH、过氧化氢浓度对催化性能的影响。结果表明：该配合物在阳离子胶束中对H2O2的分解具有快速催化作用，其催化速率远远高于铜离子本身的催化速率，而且在碱性介质中催化速率明显提高；非离子和阴离子表面活性刺胶束对配合物的催化有禁阻作用。     

我国脂肪酸的生产和应用

简要介绍脂肪酸的分类、原料来源、生产工艺、品种以及用途。并对我国脂肪酸的生产现状进行了分析。重点介绍了脂肪酸在我国橡胶工业中、塑料助剂等领域的应用,脂肪酸甲酯作为表面活性剂在不同领域的广泛应用,最后还简述了癸二酸和改性醇酸树脂应用。     

酸液体系的研究现状分析和现场应用

酸化解堵与压裂改造相比,它具有施工相对简单和成本相对较低等特点,所以酸化解堵是一项各油田广泛使用的油气田增产技术。酸化解堵技术已有将近100历史,现已研制出具有不同特点的酸液体系,如乳化酸、泡沫酸、固体酸、多氢酸等,基本能满足复杂地质条件对酸液的要求。     

油酸的精制研究

油酸酰胺是一种很好的塑料添加剂 ,可用作塑料加工成型时的脱膜剂、润滑剂。油酸的原料来源很广 ,牛油、羊油、猪油等动物油油脂以及大豆油、花生油、棕榈油等植物油脂中都含有大量的油酸。由于油酸的来源和生产方法多种多样 ,因此其所含的脂肪酸种类及含量都不尽相同。除油酸外 ,还有亚油酸、亚麻酸等高不饱和脂肪酸。针对油酸中因含有大量的多不饱和组分如亚油酸、亚麻酸而容易产生氧化泛黄的问题 ,采取了尿素络合法对原料油酸进行精制 ,以减少原料中亚油酸、亚麻酸组分的含量。经气相色谱验证 ,产品达到了应用指标 ,提高了产品的抗氧性。     

磷钼杂多酸的合成研究

介绍了磷钼杂多酸的合成。通过正交试验探讨了反应物料量比、三氧化钼浓度、反应温度和反应时间对产物产率的影响。结果表明,最适宜的反应条件为:反应物量比n(三氧化钼)∶n(磷酸)=12∶1.0、反应温度t=70℃、反应时间7 h、三氧化钼与水的质量比1∶8。经红外光谱分析及熔点测定确定所得产品为磷钼杂多酸化合物。并以磷钼杂多酸取代硫酸作催化剂制备乙酸乙醋来研究其催化活性,并与硫酸做催化剂进行对比实验收率为70.75%,超过硫酸催化剂水平。     

The Growth‐Inhibiting Effects of Beef Fatty Acids on MCF‐7 Cells Are Influenced Mostly by the Depot Location and Inconsistently by the Biohydrogenation Intermediate Content

Biohydrogenation intermediates (BHI) including conjugated linoleic acid (CLA) isomers are formed during ruminal biohydrogenation of polyunsaturated fatty acids (PUFA) in ruminants. Although many studies have examined the anticarcinogenic effects of CLA, few studies have reported the anticarcinogenic properties of BHI in their natural form found in dairy and beef fats. The present study compared the growth‐inhibitory effects of fatty acids from beef perirenal fat (PRF) or subcutaneous fat (SCF) with low or high levels of BHI in MCF‐7 human breast cancer cells. Cells were exposed for 72 h to media containing increasing doses (50 to 400 μM) of different beef fat treatments. Fatty‐acid analysis showed that BHI were readily incorporated into cell phospholipids (PL) in a treatment‐dependent manner, but higher BHI in PL did not consistently inhibit growth. Culturing with low‐BHI PRF or high‐BHI PRF did not lead to growth inhibition, but low‐BHI SCF inhibited growth, and inhibition was further increased by high‐BHI SCF. Other classes of fatty acids may, therefore, be interacting with BHI resulting in differential effects on growth inhibition in human breast cancer cells.     

Fatty Acid Profiles in Sunflower Grains During Storage in Different Environments

This study aimed to evaluate the fatty acid profiles of sunflower oil extracted from hybrid grains produced and stored in different environments. The trials were conducted in Teresina (Piauí), Vilhena (Rondônia), and Jaguariúna (São Paulo) in randomized complete block design with 4 replicates. After harvesting, grains from 1 high oleic and 3 traditional hybrids were packed in kraft paper bags and stored in a covered shed and in a cold chamber up to 12 months. The fatty acid profiles were determined by gas chromatography after 0, 4, 8, and 12 months of storage. Analyses of variance were conducted in a split‐plot design, with hybrids being considered as whole plots and storage times as subplots. Tukey's test was performed to compare hybrids and regression analyses for storage times. The initial fatty acid profile of the grains of the same hybrid varied depending on the production location. The grain storage of high oleic and traditional sunflower hybrids during 12 months in covered shed and in cold chamber resulted in little changes in oil fatty acid profiles, regardless of the initial contents. These changes occurred only for linoleic and palmitic acids.     

质子酸催化合成α-氯代十二酸工艺研究

采用廉价的浓硫酸为催化剂,氧气为自由基捕集剂,以十二酸为原料,经氯化合成α-氯代十二酸。系统考察了反应温度、催化剂用量、氯气流量、氧氯比、反应时间等因素的影响,得到最佳工艺条件:十二酸20 g,在反应温度135℃、催化剂10%、氯气流量50 mL·min-1、vO2/vCl2=1∶2、反应时间3 h,可实现十二酸基本完全转化,目标产物α-氯代十二酸选择性达到94.5%。     

Fatty Acid Profiles of Oil Obtained from Mid-Oleic Sunflowers Grown in Tropical Region

This study aimed to verify whether the fatty acid profiles of mid-oleic genotypes grown in the tropical region of Brazil fit the Codex Alimentarius and to examine the possibility of using traditional inbred lines to produce high-oleic hybrids. For this purpose, we assessed the fatty acid profile of six mid-oleic hybrids grown in environments with different minimum temperatures during oil formation in the achenes. The tests were conducted between 2015 and 2017 in an experimentally randomized complete block design with four replications. The oleic, linoleic, palmitic, and stearic acid contents were determined using gas chromatography. The mid-oleic hybrids presented varying levels of fatty acids, with oleic acid ranging between 43.6% and 84.6%, linoleic acid between 8.5% and 45.6%, palmitic acid between 3.9% and 5.7%, and stearic acid between 2.2% and 6.2%. Some of the fatty acid values were outside the ranges established by the CODEX STAN 210-1999 and were characteristic of high-oleic type sunflowers. This finding shows that we can take advantage of the potential of combining traditional inbred lines to produce high-oleic hybrids for faster and more economical breeding programs in these environments.     

Quality of Sunflower Oil Obtained in the Main Producing Region of Brazil: Adherence to the Codex Alimentarius

The objective of this work was to evaluate the quality of the oil extracted from sunflower achenes grown in Campo Novo de Parecis, the main producing region of Brazil, to optimize its use by the processing and food industries. In addition, the fatty acid profiles of the oil were checked for their adherence to the CODEX STAN 210–1999. Traditional and high-oleic genotypes were grown between 2014 and 2017 during trials with a randomized complete block experimental design with four replications. The contents of oleic, linoleic, palmitic, and stearic acids were determined using gas chromatography. The fatty acid profiles of traditional genotypes were observed to be outside the ranges established by the CODEX, with an oleic acid content above 39.4% and linoleic, palmitic, and stearic acid values lower than 48.3%, 2.7%, and 5.0%, respectively, as well as high-oleic sunflower oil with a stearic acid content of less than 2.6%. The availability of this information can, on the one hand, positively impact industries and encourage the use of better quality raw materials that are more technologically and nutritionally adequate. On the other hand, the commercialization of sunflower oil with a fatty acid profile outside the ranges established by CODEX can be difficult, because the contents are out of specification due to the climatic conditions in the cropping region.     

热盐酸缓蚀抑雾剂

在实验室合成的一种咪唑啉类化合物与其它物质复配得到了一种适合于碳钢在高温盐酸中酸洗浸蚀的复合缓蚀抑雾剂。采用失重法和中和滴定法对其性能进行评定 ,实验结果表明 :该缓蚀抑雾剂在 2 0 %盐酸中 ,酸洗温度在常温至 85℃范围内缓蚀率达 90 %左右 ,抑雾率达 85%左右 ,并具有较好的综合性能