基于生物酶法的酰基化桑椹花青素的制备与特性

为尽可能减少花青素的降解,提高其稳定性,采用生物酶法,对桑椹花青素进行酰基化修饰,并与非酰基化花青素进行对比研究。运用单因素试验筛选脂肪酶、反应溶剂和酰基供体,分析对花青素酰基转化率的影响。确定酰基化反应的优化条件为南极假丝酵母脂肪酶为酰基化催化酶、吡啶为催化反应溶剂、苯甲酸甲酯为酰基供体,酰基化效果最好,转化率最大为13.5%。采用傅里叶红外、高效液相色谱对产物进行分析,经鉴定,酰基化产物为单酰基或多酰基花青素。此外,研究了酰基化对花青素稳定性和抗氧化性的影响。酰基化可提高花青素的热稳定性、光稳定性和耐酸碱稳定性。相同温度下,酰基化花青素保留率提高约5.0%,光照6d后,酰基化花青素的保留率仍高达96.1%。酰基化可以显著增加花青素体外抗氧化性,增强DPPH自由基清除能力,总还原能力比非酰基化花青素提高30%,金属离子螯合能力高达90%。酰基化花青素肿瘤细胞活性抑制率可达81%,而非酰基化花青素仅为50%。该研究为花青素稳定性提高和性能改善提供参考的理论依据。     

Mixed acylation of Scots pine sawdust and impact on hydrophobicity

Abstract

Acetic–fatty esters of Scots pine sawdust (SPS) were obtained by reaction of SPS with mixtures containing acetic–fatty anhydrides and no solvent or catalyst. Such mixtures were synthesized by reaction between a carboxylic acid and acetic anhydride. The global reaction of acetic anhydride and a fatty acid yields at equilibrium a mixture of five compounds: acetic–fatty anhydride, acetic anhydride, fatty acid, acetic acid and fatty anhydride. The influence of temperature, molar ratio, reaction time and length of the fatty chain on the esterification and on the ratio of grafted acetyl/fatty acyl was investigated. Static contact angles (CAs) with water were measured over 5 min. CA values were dependent on the fatty acyl content and independent of the acetyl content. The minimum ester content of the oleoyl group required to obtain permanent water repellency was 25 mmol kg^?1. Water vapour adsorption measurements indicated that in contrast to water repellency, hydrophobicity to water vapour was correlated with the total mass acyl content.     

植物花青素研究进展

综述了花青素的分离与分析方法、生理活性、酰基化以及生物合成的基因工程等方面的研究进展,并展望了花青素研究发展方向。     

大豆磷脂羟酰化的研究

对大豆磷脂羟酰化的研究，所得产品具有良好的乳化性、润湿性和乳化稳定性．结果表明，过氧化氢加入量对产品的质量和主要性质有显著影响，温度对碘值和过氧化值分别有一定的和显著影响，低压蒸汽的量对过氧化值有一定的影响，氢氧化钠加入量对乳化稳定性有一定的影响，并得出磷脂羟酰化的最佳工艺条件．     

广谱驱虫药帕苯达唑的合成

以对正丁基苯胺为原料,经乙酰化、硝化、水解、还原、闭环反应合成了5-正丁基-1H-苯并咪唑-2-氨基甲酸甲酯（帕苯达唑）。首先将乙酰化和硝化采用“一锅法”得到4-正丁基-2-硝基乙酰苯胺,再以甲醇作溶剂,碱性水解后直接以钯碳为催化剂,在40℃、0.5MPa条件下反应得到4-正丁基邻苯二胺。最后选用氰氨基甲酸甲酯为闭环剂,制得目标产物。整个工艺流程简化了工艺条件,降低了生产成本,总收率可达41.8%,适合工业化生产。     

Synthesis and Characterization of 2-Decenoic Acid Modified Chitosan for Infection Prevention and Tissue Engineering

Chitosan nanofiber membranes are recognized as functional antimicrobial materials, as they can effectively provide a barrier that guides tissue growth and supports healing. Methods to stabilize nanofibers in aqueous solutions include acylation with fatty acids. Modification with fatty acids that also have antimicrobial and biofilm-resistant properties may be particularly beneficial in tissue regeneration applications. This study investigated the ability to customize the fatty acid attachment by acyl chlorides to include antimicrobial 2-decenoic acid. Synthesis of 2-decenoyl chloride was followed by acylation of electrospun chitosan membranes in pyridine. Physicochemical properties were characterized through scanning electron microscopy, FTIR, contact angle, and thermogravimetric analysis. The ability of membranes to resist biofilm formation by S. aureus and P. aeruginosa was evaluated by direct inoculation. Cytocompatibility was evaluated by adding membranes to cultures of NIH3T3 fibroblast cells. Acylation with chlorides stabilized nanofibers in aqueous media without significant swelling of fibers and increased hydrophobicity of the membranes. Acyl-modified membranes reduced both S. aureus and P. aeruginosa bacterial biofilm formation on membrane while also supporting fibroblast growth. Acylated chitosan membranes may be useful as wound dressings, guided regeneration scaffolds, local drug delivery, or filtration.     

酰基化对花色苷呈色及抗氧化性影响

以紫甘蓝、茄皮为原料,分别提取矢车菊素及飞燕草素衍生物,进行脱酰基反应。对脱酰基前后花色苷的结构、颜色、紫外-可见光谱及抗氧化性进行分析。结果表明,矢车菊素衍生物以cyanidin-3-diglucoside-5-glucoside为母核,带有1个或2个酰基化的基团,形成酰基化的酸有咖啡酸、香豆酸、阿魏酸和芥子酸;飞燕草素衍生物以delphinidin-3-rutinose-5-glucoside为母核,带有1个香豆酰基。酰基的存在会降低花色苷的明暗度。酰基化飞燕草素衍生物色度角为(15.99±0.24)°,脱酰基后色度角为(42.43±0.49)°,酰基化矢车菊素衍生物色度角为(334.32±0.04)°,脱酰基后色度角为(13.94±0.13)°。带酰基的花色苷在330nm左右有吸收峰,为B环上酰基基团引发。飞燕草素衍生物比矢车菊素衍生物的氧自由基清除能力、Fe~(3+)还原能力以及1,1-二苯基-2-三硝基苯肼(2,2-diphenyl-1-picrylhydrazyl,DPPH)自由基清除能力强。酰基的存在提高了飞燕草素衍生物的氧自由基清除能力、Fe~(3+)还原能力、DPPH自由基清除能力和矢车菊素衍生物的Fe~(3+)还原能力及DPPH自由基清除能力,但是降低了矢车菊素衍生物的氧自由基清除能力。     

曲酸及氯曲酸衍生物的合成及抑菌活性

以曲酸为原料,设计合成了16个曲酸衍生物(QI-01~QI-16)和10个氯曲酸衍生物(QII-01~QII-10),通过核磁共振氢谱及元素分析对其结构进行了表征。初步抑菌活性测定结果表明:所有供试化合物对苹果炭疽病菌Glomerella cingulata和番茄灰霉病菌Botrytis cinerea的菌丝生长均有不同程度的抑制作用,其中化合物QI-07和QI-11对苹果炭疽病菌活性最高,50μg/mL时的抑制率分别为79.3%和86.2%;化合物QII-04、QII-08和QII-09对番茄灰霉病菌活性最高,50μg/mL时的抑制率分别为70.0%、70.0%和76.7%。     

Preparation and Characterization of O-Acylated Fucosylated Chondroitin Sulfate from Sea Cucumber

Fucosylated chondroitin sulfate (FuCS), a kind of complex glycosaminoglycan from sea cucumber, has potent anticoagulant activity. In order to understand the relationship between structures and activity, the depolymerized FuCS (dFuCS) was chosen to prepare its derivates by selective substitution at OH groups. Its O-acylation was carried out in a homogeneous way using carboxylic acid anhydrides. The structures of O-acylated derivatives were characterized by NMR. The results indicated that the 4-O-sulfated fucose residues may be easier to be acylated than the other ones in the sulfated fucose branches. But the O-acylation was always accompanied by the β-elimination, and the degree of elimination was higher as that of acylation was higher. The results of clotting assay indicated that the effect of partial O-acylation of the dFuCS on their anticoagulant potency was not significant and the O-acylation of 2-OH groups of 4-O-sulfated fucose units did not affect the anticoagulant activity.     

Facile synthesis of rubiadin by microwave heating

Rubiadin (4) (1,3-dihydroxy-2-methylanthraquinone), which is one of the natural dyes from the roots of Rubiaceae, was synthesized from phthalic anhydride (1) and 2,6-dihydroxytoluene (3) by two reaction steps, that is, a Friedel-Crafts reaction with AlCl₃ and a cyclization with H₂SO₄/HBO₂. Microwave heating resulted in remarkable acceleration of the reaction rate in the first reaction, and had an effect in reducing the reaction time and increasing the yield of rubiadin (4) in the second reaction.