esterification

酯化
  • 文章类型: Journal Article
    人参C.A.Meyer(人参)是一种广泛用于促进长寿的药用植物。最近,据报道,从某些植物中纯化的富含高半乳糖醛酸(HG)结构域的果胶具有抗衰老相关活性,引导我们探索人参中HG果胶的长寿促进作用。在这项研究中,我们发现两种低甲酯化人参HG果胶(分别命名为WGPA-2-HG和WGPA-3-HG),甲酯化程度(DM)分别为16%和8%,促进秀丽隐杆线虫的长寿。结果表明,WGPA-2-HG/WGPA-3-HG受损胰岛素/胰岛素样生长因子1(IGF-1)信号通路(IIS),从而增加转录因子SKN-1/Nrf2和DAF-16/FOXO的核积累并增强相关抗衰老基因的表达。BLI和ITC分析表明,胰岛素受体结合,激活IIS通路的第一步,由于WGPA-2-HG/WGPA-3-HG与胰岛素的接触而受阻。通过化学修饰,我们发现WGPA-2-HG/WGPA-3-HG的高甲酯化对它们的长寿促进作用是有害的。这些发现为人参果胶的长寿促进作用的精确分子机制提供了新的见解,并提出了利用具有适当DM值的人参HG果胶作为天然营养素来增加人类寿命的潜力。
    Panax ginseng C. A. Meyer (ginseng) is a medicinal plant widely used for promoting longevity. Recently, homogalacturonan (HG) domain-rich pectins purified from some plants have been reported to have anti-aging-related activities, leading us to explore the longevity-promoting activity of the HG pectins from ginseng. In this study, we discovered that two of low methyl-esterified ginseng HG pectins (named as WGPA-2-HG and WGPA-3-HG), whose degree of methyl-esterification (DM) was 16 % and 8 % respectively, promoted longevity in Caenorhabditis elegans. Results showed that WGPA-2-HG/WGPA-3-HG impaired insulin/insulin-like growth factor 1 (IGF-1) signalling (IIS) pathway, thereby increasing the nuclear accumulation of transcription factors SKN-1/Nrf2 and DAF-16/FOXO and enhancing the expression of relevant anti-aging genes. BLI and ITC analysis showed that the insulin-receptor binding, the first step to activate IIS pathway, was impeded by the engagement of WGPA-2-HG/WGPA-3-HG with insulin. By chemical modifications, we found that high methyl-esterification of WGPA-2-HG/WGPA-3-HG was detrimental for their longevity-promoting activity. These findings provided novel insight into the precise molecular mechanism for the longevity-promoting effect of ginseng pectins, and suggested a potential to utilize the ginseng HG pectins with appropriate DM values as natural nutrients for increasing human longevity.
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  • 文章类型: Journal Article
    为了提高酶法合成L-抗坏血酸棕榈酸酯的酯化效率,研究了黑曲霉脂肪酶催化酯化过程的底物模拟印迹。选择油酸作为印迹分子,油酸印迹固定化脂肪酶在pH8.0,0.1g油酸,1.5mL的95%乙醇,和0.1克吐温-20。通过维生素C的溶解和过饱和,维生素C在二恶烷中的反应浓度达到5.00%(m/v),酯化率为93.99%,产物浓度为110.72g/L。此外,采用分阶段底物饲喂,维生素C反应浓度可达8.00%,28h后酯化率和产物浓度分别为156.34g/L和82.96%。此外,通过荧光和红外光谱表征了印迹诱导的酶蛋白构象变化。该方法提供了酶促生产1-抗坏血酸棕榈酸酯的途径。
    In order to improve the esterification efficiency of the enzymatic synthesis of l-ascorbic acid palmitate, the substrate analogue imprinting of the Aspergillus niger lipase-catalyzed esterification process was studied. Oleic acid was selected as the imprinting molecule, oleic acid imprinting immobilized lipase was prepared at pH 8.0, 0.1 g oleic acid, 1.5 mL of 95 % ethanol, and 0.1 g Tween-20. Through solubilization and supersaturation of Vitamin C, the reaction concentration of Vitamin C reached 5.00 % (m/v) in dioxane with 93.99 % esterification rate and 110.72 g/L of product concentration. Moreover, the Vitamin C reaction concentration can reach 8.00 % by using staged substrate feeding, and the esterification rate and product concentration of esterification after 28 h was 156.34 g/L and 82.96 %. Besides, the imprinting-induced conformational changes in enzyme proteins was characterized by fluorescence and infrared spectroscopy. This method provides a pathway for enzymatic production of l-ascorbic acid palmitate.
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  • 文章类型: Journal Article
    高甲酯化柑橘果胶(HMCP)通常用作食品中的厚度,被认为是一种较差的乳化剂,尤其是在中性pH溶液中。我们先前的发现表明,钙阳离子可以显着提高HMCP的乳化能力。此外,在存在钙阳离子的情况下,溶液的pH降低。然而,在钙阳离子存在下,溶液pH值对HMCP乳化能力的影响尚不清楚。在这项研究中,在添加钙阳离子之前,将HMCP溶液的pH从3.00调节至8.00。根据钙阳离子的存在,分析了溶液性质和乳化性质。结果表明,将钙阳离子带入HMCP溶液后,HMCP溶液的pH值降低。钙阳离子可以改变溶液的流变性,粒度分布和形态,和HMCP溶液中的颗粒微环境疏水区域,同时增加HMCP溶液的pH值,有助于提高HMCP的乳化能力。当HMCP溶液的pH保持在中性水平时,HMCP具有最佳的乳化能力。该研究为调节HMCP的乳化性能提供了新思路。
    High methyl-esterified citrus pectin (HMCP) is often used as a thickness in food products and is considered a poor emulsifier, especially in neutral pH solutions. Our previous findings show that the emulsifying capacity of HMCP could be significantly enhanced by calcium cations. Besides, the pH of the solution decreased in the presence of calcium cations. However, the impact of solution pH on HMCP emulsifying capacity in the presence of calcium cations is unclear. In this study, the pH of the HMCP solution was adjusted from 3.00 to 8.00 before adding calcium cations. The solution properties and emulsifying properties were analyzed in light of the existence of calcium cations. The results showed that the pH of the HMCP solutions decreased after bringing calcium cations into them. Calcium cations could change the solution rheological properties, particle size distributions and morphologies, and the particle microenvironmental hydrophobic areas in HMCP solutions while increasing the pH of HMCP solutions, contributing to improving the emulsifying capacity of HMCP. HMCP had the best emulsifying ability when the pH of the HMCP solutions was kept at a neutral level. This research gives us new ideas to adjust the emulsifying property of HMCP.
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  • 文章类型: Journal Article
    部分酰基甘油因其乳化和稳定性能而受到重视,然而,由于收率和选择性低,精确的绿色合成仍然具有挑战性。本研究旨在阐明“脂肪酶选择性-底物结构-产物组成”的关系,以提高靶向部分酰基甘油的产量。结果表明,脂肪酶对具有较短链长和较高不饱和度的脂肪酸表现出更高的选择性。羟基供体也影响酯化过程,其中酶-酰基复合物表现出对羟基供体的选择性如下:甘油>单酰基甘油>二酰基甘油。底物比例显着影响酶促反应;10:1的比例有利于三酰甘油的形成(>80%),而1:1的比例产生>90%的部分酰基甘油。分子对接模拟表明,底物主要通过氢键和疏水相互作用与脂肪酶相互作用。对脂肪酶选择性模式的全面了解可以促进更有效的反应系统的设计,能够将基础脂质资源转化为所需的高附加值产品。
    Partial acylglycerols are valued for their emulsifying and stabilizing properties, yet precise green synthesis remains challenging due to low yield and selectivity. This study aimed to elucidate the \"lipase selectivity-substrate structure-product composition\" relationship to enhance the yield of targeted partial acylglycerol. The results showed that lipase exhibited a greater selectivity towards fatty acids with shorter chain lengths and higher unsaturation. Hydroxyl donors also affected the esterification process, with the enzyme-acyl complex exhibiting selectivity towards hydroxyl donors as follows: glycerol > monoacylglycerol > diacylglycerol. Substrate ratio significantly influenced enzymatic reactions; a 10:1 ratio favored triacylglycerol formation (>80 %), while a 1:1 ratio produced > 90 % partial acylglycerols. Molecular docking simulations revealed that substrates primarily interacted with lipase through hydrogen bonding and hydrophobic interactions. A comprehensive understanding of lipase selectivity patterns could facilitate the design of more efficient reaction systems, enabling the conversion of basic lipid resources into desired high value-added products.
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  • 文章类型: Journal Article
    旨在为当前有关反应条件对柠檬酸淀粉的化学结构和目标性质的影响的知识做出贡献,在目前的贡献中,通过操纵反应时间制备了不同的玉米淀粉柠檬酸盐,温度和柠檬酸浓度。改性淀粉的特征在于化学结构,形态学,结晶度溶胀力和抗性淀粉含量。第一次,总替代,定量测定了交联度和单取代度;最终化学结构之间的关系,反应条件和目标淀粉柠檬酸盐的性质进行了综合分析。总取代值在0.075-0.24范围内,交联度在0.005-0.11区间内的产品,单取代程度在0.05-0.12范围内,是生产出来的。通过适当选择反应条件,获得了几乎100%抗性淀粉的产物。结果表明,柠檬酸淀粉的性质(主要是溶胀力和RS含量)取决于化学结构和所采用的反应条件。事实上,反应温度设定(120°C或150°C)被证明在最终产品的性质中起决定性作用,如从具有相似化学结构和基本上不同的溶胀和消化率性质的柠檬酸淀粉证明的。
    Aiming to contribute to the current knowledge on the impact of reaction conditions on the chemical structure and target properties of starch citrates, in the current contribution different corn starch citrates were prepared by manipulation of reaction time, temperature and citric acid concentration. Modified starches were characterized in terms of chemical structure, morphology, crystallinity, swelling power and resistant starch content. For the first time, total substitution, crosslinking and monosubstitution degrees were quantitatively determined; and the relationship among final chemical structure, reaction conditions and target starch citrates properties was comprehensively analyzed. Products with total substitution values in the range of 0.075-0.24, crosslinking degrees in the 0.005-0.11 interval, and monosubstitution extents within the 0.05-0.12 range, were produced. By proper selection of reaction conditions products with almost 100 % of resistant starch were obtained. Results evidenced that starch citrates properties (mainly swelling power and RS content) depend on both chemical structure and the reaction conditions employed. Actually, the reaction temperature set (120 °C or 150 °C) proved to play a determinant role in the final products properties as evidenced from starch citrates with similar chemical structure and substantially different swelling and digestibility properties.
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  • 文章类型: Journal Article
    葡萄籽原花青素(GSP),作为一种天然抗氧化剂,有很大的潜力发展成为一种降脂药,但其低的亲脂性和稳定性极大地限制了其应用。在这项研究中,开发了一种酶促酯化策略,将脂肪酸链引入GSP,成功合成了一系列新的GSP衍生物。结果表明,GSP的转化率高达85%,GSP衍生物的TAG抑制率高达35%。GSP衍生物的结构通过UPLC-MS/MS鉴定,和七种衍生物被证实为儿茶素-3'-O-月桂酸酯,表儿茶素-3\'-O-月桂酸酯,表儿茶素没食子酸酯-3″,5″-二-O-月桂酸盐,表儿茶素没食子酸盐-3',3″,5″-三-O-月桂酸盐,原花青素B1-3',3″-二-O-月桂酸盐,原花青素B2-3',3″-二-O-月桂酸和原花青素C1-3',3″,3-三-O-月桂酸酯的NMR。GSP衍生物对脂质积累表现出更高的抑制作用,胞内TAG和TC比亲本GSP。这些结果表明GSP衍生物具有作为在食品工业中使用的降脂剂的潜力。
    Grape seed proanthocyanidin (GSP), as a natural antioxidant, has great potential to be developed into a lipid-lowering agent, but its low lipophilicity and stability greatly limit its application. In this study, an enzymatic esterification strategy was developed to introduce fatty acid chains into GSP, resulting in the successful synthesis of a series of new GSP derivatives. The results showed that up to 85% conversion of GSP and 35% TAG inhibition rate of GSP derivatives were achieved. The structures of GSP derivatives were identified by UPLC-MS/MS, and seven derivatives were confirmed as catechin-3\'-O-laurate, epicatechin-3\'-O-laurate, epicatechin gallate-3″,5″-di-O-laurate, epicatechin gallate-3\',3″,5″-tri-O-laurate, procyanidin B1-3\',3″-di-O-laurate, procyanidin B2-3\',3″-di-O-laurate and procyanidin C1-3\',3″,3‴-tri-O-laurate by NMR. GSP derivatives exhibited higher inhibitory effects on lipid accumulation, intracellular TAG and TC than parent GSP. These results indicate that GSP derivatives have potential as lipid-lowering agents for utilization in the food industry.
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  • 文章类型: Journal Article
    这项工作通过化学和酶促酯交换(CSL和ESL)评估了结构化脂质(SL)。使用大豆油和花生油1:1重量%的混合物,逐渐加入完全氢化的crambe,以获得最终的二十二烷酸浓度为6、12、18和24%。化学催化在100°C下使用甲醇钠(0.4wt%)30分钟,而酶催化使用LipozymeTLIM(5wt%)在60°C持续6小时。鉴定出的主要脂肪酸为C16:0,C18:0和C22:0。观察到随着硬脂肪的逐渐增加,CSL显示出高浓度的反应中间体,进一步表明空间位阻,不像ESL。增加的硬脂肪也改变了结晶曲线和三酰基甘油组成和ESL显示较低的固体脂肪,与CSL不同。两种方法都有效地产生了SL作为反式和棕榈脂肪的替代品,着眼于未来在食品中的潜在应用。
    This work evaluated structured lipids (SLs) through chemical and enzymatic interesterification (CSLs and ESLs). Blends of soybean oil and peanut oil 1:1 wt% were used, with gradual addition of fully hydrogenated crambe to obtain a final behenic acid concentration of 6, 12, 18, and 24 %. Chemical catalysis used sodium methoxide (0.4 wt%) at 100 °C for 30 min, while enzymatic catalysis used Lipozyme TL IM (5 wt%) at 60 °C for 6 h. Major fatty acids identified were C16:0, C18:0, and C22:0. It was observed that with gradual increase of hard fat, the CSLs showed high concentrations of reaction intermediates, indicating further a steric hindrance, unlike ESLs. Increased hard fat also altered crystallization profile and triacylglycerols composition and ESLs showed lower solid fat, unlike CSLs. Both methods effectively produced SLs as an alternative to trans and palm fats, view to potential future applications in food products.
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  • 文章类型: Journal Article
    在乙酰辅酶A的生物合成中使用了硫代化(也称为转硫酯化)反应,脂肪酸和聚酮化合物,并用于泛素(Ub)和泛素样(Ubl)蛋白1-3的翻译后修饰。对于Ub途径,E1酶催化从E1〜Ub硫酯到E2〜Ub硫酯的硫醇转移。为了将Ub从E2〜Ub硫酯转移到HECT(与E6APC末端同源)和RBR(环间环)E3连接酶以形成E3〜Ub硫酯4-6,也需要进行巯基转移。硫酯键的等能量转移如何由Ub途径中的酶驱动。在这里,我们使用天然酶和近天然Ub的化学策略分离了E1-Ub(T)-E2和E2-Ub(T)-E3HECT复合物(其中T表示硫酯或Ub中的Ub)的瞬时硫醇化中间体的模拟物。捕获和可视化通过单粒子低温电子显微镜确定的连续结构。这些结构和伴随的生化实验阐明了Ub的构象变化,E1,E2和E3与化学反应协调,以促进Ub从每种酶到下一种酶的定向转移。
    Transthiolation (also known as transthioesterification) reactions are used in the biosynthesis of acetyl coenzyme A, fatty acids and polyketides, and for post-translational modification by ubiquitin (Ub) and ubiquitin-like (Ubl) proteins1-3. For the Ub pathway, E1 enzymes catalyse transthiolation from an E1~Ub thioester to an E2~Ub thioester. Transthiolation is also required for transfer of Ub from an E2~Ub thioester to HECT (homologous to E6AP C terminus) and RBR (ring-between-ring) E3 ligases to form E3~Ub thioesters4-6. How isoenergetic transfer of thioester bonds is driven forward by enzymes in the Ub pathway remains unclear. Here we isolate mimics of transient transthiolation intermediates for E1-Ub(T)-E2 and E2-Ub(T)-E3HECT complexes (where T denotes Ub in a thioester or Ub undergoing transthiolation) using a chemical strategy with native enzymes and near-native Ub to capture and visualize a continuum of structures determined by single-particle cryo-electron microscopy. These structures and accompanying biochemical experiments illuminate conformational changes in Ub, E1, E2 and E3 that are coordinated with the chemical reactions to facilitate directional transfer of Ub from each enzyme to the next.
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  • 文章类型: Journal Article
    通过辛烯基琥珀酸酐(OSA)改性同步制备的酯化淀粉(ES)和颗粒酯化预糊化淀粉(EPS)的形成条件和功能特性差异尚不清楚。在这项研究中,探讨了OSA改性后ES和EPS的形成条件和理化性质。改性温度控制了OSA改性过程中两种淀粉的形成量和时间。与ES相比,每股收益表现出更高的替代度,冷水膨胀力,在冷水中的吸水能力和表观粘度。结构表征证实ES和EPS的分子量和短/长程分子有序性降低。此外,扫描电镜显示EPS保持其颗粒状形态。X射线衍射图证实了EPS中形成的淀粉-脂质复合物比ES中存在更多。这项研究提供了一种制备酯化和颗粒酯化预糊化淀粉的新方法,这些淀粉可用作低能量配方食品中的有前途的添加剂。
    The formation conditions and functional property differences of esterified starch (ES) and granular esterified-pregelatinized starch (EPS) synchronously prepared by octenyl succinic anhydride (OSA) modification remain unclear. In this study, we explored the formation conditions and physicochemical properties of ES and EPS after OSA modification. The modification temperature controlled the formation amount and time for both starch types during OSA modification. Compared to ES, EPS exhibited a higher degree of substitution, cold-water swelling power, water-absorption capacity and apparent viscosity in cold water. The structural characterization confirmed the molecular weight and short/long-range molecular order of ES and EPS decreased. Moreover, scanning electron microscopy indicated EPS retained its granular morphology. The X-ray diffraction patterns confirmed the presence of more starch-lipid complexes formed in EPS than in ES. This study provides a novel method for preparing esterified and granularly esterified-pregelatinized starches that could be used as promising additives in low-energy formula foods.
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  • 文章类型: Journal Article
    微结构反应器提供快速的化学工程转移和精确的微流体控制,能够确定反应的动力学参数。这篇综述探讨了测量微反应动力学的最新进展。它探索了动力学建模,反应机制,和与两种类型的微反应有关的固有动力学方程:涉及酸的酯化和酯交换反应,基地,或生物催化剂。利用微填充床反应器成功地实现了微分散状态和反应动力学特性的和谐结合。此外,这篇综述介绍了微过程模拟软件,并探讨了微反应器与光谱分析的先进集成,用于反应监测和数据采集。此外,阐述了微平台的控制原理。在线测量的优越性,自动化,并强调了用于动力学测量的微反应过程的数字化,展示了人工智能应用的广阔前景。
    Microstructured reactors offer fast chemical engineering transfer and precise microfluidic control, enabling the determination of reactions\' kinetic parameters. This review examines recent advancements in measuring microreaction kinetics. It explores kinetic modeling, reaction mechanisms, and intrinsic kinetic equations pertaining to two types of microreaction: esterification and transesterification reactions involving acids, bases, or biocatalysts. The utilization of a micro packed-bed reactor successfully achieves a harmonious combination of the micro-dispersion state and the reaction kinetic characteristics. Additionally, this review presents micro-process simulation software and explores the advanced integration of microreactors with spectroscopic analyses for reaction monitoring and data acquisition. Furthermore, it elaborates on the control principles of the micro platform. The superiority of online measurement, automation, and the digitalization of the microreaction process for kinetic measurements is highlighted, showcasing the vast prospects of artificial intelligence applications.
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