A novel bio‐based phthalonitrile resin derived from catechin: synthesis and comparison of curing behavior with petroleum‐based counterpart

The development of bio‐based thermosetting resins with good thermal stability can potentially afford sustainable polymers as replacements for petroleum‐based polymers. We report a practical route to a novel catechin‐based phthalonitrile resin precursor (CA‐Ph), which contains free phenolic hydroxyl groups that result in ‘self‐curing’ at elevated temperatures to afford a thermostable polymer. Comparison of the performance of this CA‐Ph resin with that of a conventional petroleum‐based bisphenol A phthalonitrile resin (BPA‐Ph; containing 5 wt% of the curing agent 4,4′‐diaminodiphenylsulfone) revealed that CA‐Ph exhibits a lower melting point and curing temperature. Cured CA‐Ph resin retains 95% of its weight at 520 °C under a nitrogen atmosphere, which compares favorably with results obtained for BPA‐Ph resin that retains 95% of its weight at a lower temperature of 484 °C. Kinetic results indicated that the curing reactions of both CA‐Ph and BPA‐Ph systems follow an autocatalytic mechanism. These results suggest that catechin is a useful bio‐based feedstock for the preparation of self‐curing and thermally stable phthalonitrile resins for advanced technological applications. © 2017 Society of Chemical Industry     

低聚体葡萄籽原花青素对顺铂损伤HEK293细胞及抗癌活性的影响

目的:探讨低聚体葡萄籽原花青素(grape seed proanthocyanidins extract,GSPE)及其结构单元儿茶素(catechin,C)对顺铂(cis-dichlorodiamineplatinum(II),DDP)损伤HEK293人胚肾细胞的保护作用以及对DDP抗A549人肺腺癌细胞活性的影响。方法:体外培养HEK293细胞和A549细胞,以DDP建立损伤模型,分别用不同质量浓度的低聚体GSPE和儿茶素对细胞进行预处理,四甲基偶氮唑蓝(methyl thiazolyl tetrazolium,MTT)法测定细胞抑制率和存活率。结果:当低聚体GSPE质量浓度为16 mg/L时,对DDP诱导的HEK293细胞损伤的保护作用最佳,与DDP损伤组相比有显著差异(P0.05),并且在达到此质量浓度时可显著增强DDP对A549细胞的损伤效果(P0.05)。相同条件下儿茶素对DDP诱导的HEK293细胞损伤无显著影响(P0.05)。结论:体外培养条件下,一定质量浓度的低聚体GSPE对DDP诱导的HEK293细胞损伤具有一定的保护作用,同时能增强DDP对A549细胞的杀伤作用。儿茶素对DDP诱导HEK293细胞损伤的保护作用不明显。     

不同茶类陈年茶的生化成分分析及其抗氧化活性

本文研究了三个不同茶类陈年茶的生化成分及其抗氧化活性。采用比色法测定了这些茶样中水浸出物、茶多酚、总黄酮、可溶性总糖、游离氨基酸、茶黄素、茶红素及茶褐素的含量,同时采用高效液相色谱仪测定了这些陈年茶样中没食子酸、儿茶素单体及咖啡碱含量,采用FRAP法测定了其总抗氧化能力。结果显示不同茶类陈年茶样中主要品质生化成分含量相差较大,同一茶类不同品种或产地的陈年老茶样中主要品质生化成分含量也有差别。三个不同茶类供试茶样中EGC均未检出;陈年红茶样中GC和CG未检出;陈年乌龙茶样中GC和EGCG含量显著高于其他茶叶;陈年黑茶样中GA含量普遍较低,滇药香熟普砖茶中各儿茶素组分均未检出。不同茶类陈年茶样总抗氧化能力相差较大,其中以陈年千家寨生普散茶的抗氧化能力最强,且它的抗氧化活性与其茶多酚和儿茶素总含量呈浓度依赖关系。     

Chemistry of Secondary Polyphenols Produced during Processing of Tea and Selected Foods

This review will discuss recent progress in the chemistry of secondary polyphenols produced during food processing. The production mechanism of the secondary polyphenols in black tea, whisky, cinnamon, and persimmon fruits will be introduced. In the process of black tea production, tea leaf catechins are enzymatically oxidized to yield a complex mixture of oxidation products, including theaflavins and thearubigins. Despite the importance of the beverage, most of the chemical constituents have not yet been confirmed due to the complexity of the mixture. However, the reaction mechanisms at the initial stages of catechin oxidation are explained by simple quinone–phenol coupling reactions. In vitro model experiments indicated the presence of interesting regio- and stereoselective reactions. Recent results on the reaction mechanisms will be introduced. During the aging of whisky in oak wood barrels, ellagitannins originating from oak wood are oxidized and react with ethanol to give characteristic secondary ellagitannins. The major part of the cinnamon procyanidins is polymerized by copolymerization with cinnamaldehyde. In addition, anthocyanidin structural units are generated in the polymer molecules by oxidation which accounts for the reddish coloration of the cinnamon extract. This reaction is related to the insolubilization of proanthocyanidins in persimmon fruits by condensation with acetaldehyde. In addition to oxidation, the reaction of polyphenols with aldehydes may be important in food processing.     

黑茶水提取物的碳谱分析

通过文献查找和标准样测定,将茶叶的九种化学成分的碳谱特征峰进行整理归属,以此为标准,将十六种黑茶水提取物的碳谱进行对照分析,可将黑茶中的各类成分做出定性确认,但其中仍有许多未知成分,需要使用其他方法分离分析。     

Procyanidin Content of Grape Seed and Pomace, and Total Anthocyanin Content of Grape Pomace as Affected by Extrusion Processing

ABSTRACT: Grape juice processing by‐products, grape seed and pomace are a rich source of procyanidins, compounds that may afford protection against chronic disease. This study was undertaken to identify optimal extrusion conditions to enhance the contents of monomers and dimers at the expense of large molecular weight procyanidin oligomers and polymers in grape seed and pomace. Extrusion variables, temperature (160, 170, and 180 °C in grape seed, and 160, 170, 180, and 190 °C in pomace) and screw speed (100, 150, and 200 rpm in both) were tested using mixtures of grape seed as well as pomace with decorticated white sorghum flour at a ratio of 30 : 70 and moisture content of 45%. Samples of grape seed and pomace were analyzed for procyanidin composition before and after extrusion, and total anthocyanins were determined in pomace. Additionally, chromatograms from diol and normal phase high‐performance liquid chromatography were compared for the separation of procyanidins. Extrusion of both grape by‐products increased the biologically important monomer and dimers considerably across all temperature and screw speeds. Highest monomer content resulted when extruded at a temperature of 170 °C and screw speed of 200 rpm, which were 120% and 80% higher than the unextruded grape seed and pomace, respectively. Increases in monomer and dimer contents were apparently the result of reduced polymer contents, which declined by 27% to 54%, or enhanced extraction facilitated by disruption of the food matrix during extrusion. Extrusion processing reduced total anthocyanins in pomace by 18% to 53%. Practical Applications: Extrusion processing can be used to increase procyanidin monomer and dimer contents in grape seed and pomace. Procyanidins in grape by‐products have many health benefits, but most are present as large molecular weight compounds, which are poorly absorbed. Extrusion processing appears to be a promising technology to increase levels of the bioactive low molecular weight procyanidins.