脂肪酶催化合成内酯化合物的研究

羟基脂肪酸形成的内酯是一类十分有经合物。与传统的化学合成法相比,脂肪酶催化合物内酯具有方法简单,反应条件温和和产率高等特点,在脂肪酶催化合成内酯时,对羟基脂肪酸链长度,溶剂效应,脂肪酶选择和立体因素等对于内酯的产率以及内酯产物分布的影响进行了研究。     

应用生物法合成内酯化合物

内酯是广泛存在于自然界中具有生活活性的一类化合物,由于大多数内酯化合物具有手性,用化学方法合成不仅过程复杂,而且产率也不高。本文报道这些领域的进展。     

脂肪酸代谢途径影响聚酮化合物生物合成的机制及应用研究进展

聚酮化合物（PKs）作为一大类次级代谢产物，有着重要的生物活性和潜在的应用价值。链霉菌具有合成多种聚酮化合物的潜力，但野生型菌株合成聚酮化合物的产量难以满足工业化生产的需求。贮藏脂质的降解能为聚酮化合物生物合成提供大量的酰基CoA前体，因此，控制好脂肪酸与聚酮化合物生物合成通量，有利于促进目标聚酮化合物的合成。本文综述了强化脂肪酸β-氧化途径提高聚酮化合物产量的研究进展，为利用β-氧化途径促进聚酮化合物生物合成提供了新的研究策略。     

凯林内酯类香豆素的研究进展

本文综述了近年来凯林内酯衍生物的化学和药理研究概况,内容主要包括化合物的提取分离,光谱特征,立体结构,化学转化及合成等。着重指出了该类化合物具有显著的扩张冠状动脉的作用,在治疗心血管疾病方面有广阔的应用前景。     

有机介质中脂肪酶催化反应在有机合成中的应用

综述了近年来有机介质中脂肪酶催化反应在酯合成,酯交换,内酯合成,多肽合成,高聚物合成及立体异构体拆分等有机合成领域的应用。对脂肪酶催化不对称反应合成光学纯化合物进行了较详细的介绍。     

有机介质中脂肪酶催化反应在有机合成中的应用

综述了近年来有机介质中脂肪酶催化反应在酯合成、酯交换、内酯合成、多肽合成、高聚物合成及立体异构体拆分等有机合成领域的应用。对脂肪酶催化不对称反应合成光学纯化合物进行了较详细的介绍。     

真菌苯二酚内酯聚酮类化合物生物合成研究进展

真菌苯二酚内酯类聚酮化合物具有抗癌和调节免疫系统等重要的生物活性,其生物合成是近年来的研究热点。介绍了苯二酚内酯的双聚酮合酶协作合成机制和组合生物合成,并以几种真菌苯二酚内酯生物合成途径为例,综述了相关的研究进展,以期为研究者提供参考。     

工程大肠杆菌合成游离脂肪酸的研究进展

游离脂肪酸作为一种重要的平台化合物,其衍生产品被广泛应用到能源、化学工业中。作为更加可持续、绿色的生产策略,利用工程微生物合成游离脂肪酸是以石油基和动植物为原料生产脂肪酸类产品的重要补充。大肠杆菌作为经典的模式微生物,通过对其进行代谢工程改造,脂肪酸的积累已经从痕量提高到了约9g/L,展示了其作为脂肪酸合成菌株的巨大应用潜力。随着合成生物学技术的涌现,“感应-调控器”、体外重构、β氧化逆循环、异源合成途径的整合等思路的引入极大地加快了工程大肠杆菌脂肪酸合成的进化速率,并赋予大肠杆菌合成多种脂肪酸产品的能力。对近年来通过代谢工程和合成生物学手段改造大肠杆菌合成游离脂肪酸的研究进展进行综述,对其发展前景进行展望。     

中链化学品微生物制造

中链脂肪酸（C₆-C₁₂）衍生的化学品包括脂肪醇、脂肪烃、中链酯、ω-修饰脂肪酸等,这些化合物是生物燃料、聚合物、日用化学品、特种化学品的重要组分。天然微生物底盘不能合成中链脂肪酸,而通过操纵脂肪酸合成、逆β-氧化等碳链延伸途径,尤其是表达生成游离中链脂肪酸的硫酯酶,可使大肠埃希菌、酿酒酵母等微生物细胞合成超过1 g/L的中链脂肪酸。引入脂肪酸衍生反应,如羧基还原、脱羧、ω-氧化等,可合成许多中链化学品。本文综述了中链化学品合成的酶学基础以及代谢工程策略,为中链化学品高效生物制造提供参考和思路。     

新型可再生工业用油脂的代谢工程

植物种子油是一种可再生资源,亦用作生物燃油和化学工业原料. 一些野生植物能高水平合成积累羟化、环氧化和共轭脂肪酸等具有重要工业应用价值的特异脂肪酸.催化这些特异脂肪酸合成的酶主要是类脂肪酸去胞和酶2(类FAD2). 由特异脂肪酸合成到三酰基甘油脂 (TAG) 形成还需要酰基转移酶 (如DGAT) 的参与. 在油料作物种子中表达类FAD2酶及其相关基因(如DGAT),已培育出了能合成积累一定含量特异脂肪酸的工程油料品系,为基于农作物生产高附加值工业用油脂开辟了新途径. 本文论述了参与特异脂肪酸生物合成途径的关键酶基因、油料作物代谢工程策略,以及应用工程油料作物大规模生产重要工业用脂肪酸的研究进展、存在问题和应用前景等.     

Long-chain acyl-homoserine lactone quorum-sensing regulation of Rhodobacter capsulatus gene transfer agent production

Many proteobacteria use acyl-homoserine lactones as quorum-sensing signals. Traditionally, biological detection systems have been used to identify bacteria that produce acyl-homoserine lactones, although the specificities of these detection systems can limit discovery. We used a sensitive approach that did not require a bioassay to detect production of long-acyl-chain homoserine lactone production by Rhodobacter capsulatus and Paracoccus denitrificans. These long-chain acyl-homoserine lactones are not readily detected by standard bioassays. The most abundant acyl-homoserine lactone was N-hexadecanoyl-homoserine lactone. The long-chain acyl-homoserine lactones were concentrated in cells but were also found in the culture fluid. An R. capsulatus gene responsible for long-chain acyl-homoserine lactone synthesis was identified. A mutation in this gene, which we named gtaI, resulted in decreased production of the R. capsulatus gene transfer agent, and gene transfer agent production was restored by exogenous addition of N-hexadecanoyl-homoserine lactone. Thus, long-chain acyl-homoserine lactones serve as quorum-sensing signals to enhance genetic exchange in R. capsulatus.     

Antimalarial compounds from Parinari capensis

The antimalarial activity of the raw petroleum ether and dichloromethane extracts of the stems of Parinari capensis (Chrysobalanceae) was determined. Phytochemical investigation of these extracts led to the isolation of three diterpene lactones that possess antimalarial activity with IC(50) values of 0.54, 0.67, and 1.57 microg/mL. Although their antimalarial activity is promising, the toxicity profiles of these diterpene lactones prevent further biological evaluation. They could however be used effectively as lead compounds in the synthesis of novel antimalarial agents.     

Structure-activity relationships among mycotoxins

Relationships between structural features and biological effects of mycotoxins are reviewed. Structure-activity relationships are characterized at the molecular, subcellular, cellular, or supracellular level. Major chemical and physicochemical factors responsible for bioactivity of mycotoxins are stressed. A variety of chemical families of mycotoxins are then discussed from the point of view of structure-activity relationships. The structurally related families comprise small lactones, macrocyclic lactones, isocoumarin derivatives, aflatoxins and related compounds trichothecenes, anthraquinones, indole-derived tremorgens and selected amino acid-derived mycotoxins such as sporidesmins and cyclosporines. Biological effects of mycotoxins include acute and chronic toxicity, antimicrobial activity, mutagenicity and genotoxicity, carcinogenicity and biochemical modes of action.     

Guaianolides from Saussurea lappa

Two new sesquiterpene lactones with an ,β-unsaturated aldehyde group have been isolated from the roots of Saussurea lappa. Their stereostructures have been established by the combined use of spectroscopic as well as chemical methods via their synthesis from dehydrocostus lactone.     

α-Humulene derivatives including a sesquiterpene acid with a rearranged carbon skeleton from Lychophorora columnaris

An investigation of Lychnophora columnaris afforded in addition to known compounds six new α-humulene derivatives and a rearranged sesquiterpene with a new carbon skeleton. These compounds and several sesquiterpene lactones isolated from this species seem to be of chemotaxonomic importance. The structures were elucidated by spectroscopic methods and a few chemical transformations including partial synthesis.     

Stereostructures of inunal and isoalloalantolactone,two biologically active sesquiterpene lactones from Inula racemosa

Two new sesquiterpene lactones, inunal and isoalloalantolactone, have been isolated from Inula racemosa. Inunal, an aldehydolactone, displays considerable biological activity as a plant growth regulator. Structures have been assigned to these compounds on the basis of spectral data and chemical correlation with alantolactone and isotelekin.     

A single-host fermentation process for the production of flavor lactones from non-hydroxylated fatty acids

Lactone flavors with fruity, milky, coconut, and other aromas are widely used in the food and fragrance industries. Lactones are produced by chemical synthesis or by biotransformation of plant-sourced hydroxy fatty acids. We established a novel method to produce flavor lactones from abundant non-hydroxylated fatty acids using yeast cell factories. Oleaginous yeast Yarrowia lipolytica was engineered to perform hydroxylation of fatty acids and chain-shortening via β-oxidation to preferentially twelve or ten carbons. The strains could produce γ-dodecalactone from oleic acid and δ-decalactone from linoleic acid. Through metabolic engineering, the titer was improved 4-fold, and the final strain produced 282 mg/L γ-dodecalactone in a fed-batch bioreactor. The study paves the way for the production of lactones by fermentation of abundant fatty feedstocks.     

Synthesis of lactones using substituted benzoic anhydride as a coupling reagent

This protocol describes a procedure for the synthesis of a 29-membered macrolactone. The facile mixed-anhydride method is very effective for the preparation of carboxylic esters and lactones using substituted benzoic anhydrides by the promotion of Lewis acid or basic catalysts under mild reaction conditions. Owing to the reaction rapidly proceeding to produce the monomeric compounds with high chemoselectivity, the protocol is quite powerful for the synthesis of not only the giant-sized lactones but also the highly strained cyclic compounds such as medium-sized lactones. The remarkable efficiency of the lactonizations promoted by the substituted benzoic anhydrides has been already shown in the synthesis of many natural complex molecules. It takes approximately 19 h to complete the protocol: 0.5 h to set up the reaction, 13.5 h for the reaction and 5 h for isolation and purification.