Moderate antioxidative efficiencies of flavonoids during peroxidation of methyl linoleate in homogeneous and micellar solutions

The relative reactivities as well as the stoichiometric coefficients for a number of flavonoids, catechols, and—for comparison—standard phenolic antioxidants were determined by analyzing the kinetics of oxygen consumption in organic and micellar systems, with peroxidation initiated by lipid- and water-soluble azo initiators. The results demonstrated that the flavonoids did not behave as classic phenolic antioxidants such as α-tocopherol, but showed only moderate chain-breaking activities. The results were in line with other structure-activity relationship studies on the importance of the B-ring catechol structure, the 2,3-double bond, and the 3,5-hydroxy groups. The data are discussed in view of possible explanations of the deviations flavonoids reveal in their behavior compared with regular phenolic antioxidants.     

Al-P-Ti-Si-O催化剂上合成邻羟基苯乙醚

采用不均匀沉淀法制备了Al-P -Ti-Si-O催化剂 ,并研究了邻苯二酚与乙醇在该催化剂上的气相O -乙基化反应 ,考察了催化剂组成、反应温度、邻苯二酚 /乙醇摩尔比、进料速率对反应性能的影响 ,同时考察了催化剂的稳定性。结果表明 ,催化剂组成对反应性能有较大影响 ,在研究的范围内 ,四组分催化剂Al1 P1 3 0 Ti0 3 0 Si0 1 7显示出了较好的催化性能 ,当催化剂用量 1 4g、n(邻苯二酚 ) /n(乙醇 ) =1/5、进料速率 0 5ml/h ,反应温度 2 6 0℃时 ,邻苯二酚转化率和邻羟基苯乙醚收率分别可达到 91 5 %和 85 3% ,并在 10 0h内催化剂具有很好的稳定性     

苯酚羟基化制邻苯二酚催化剂的活性评价

对苯酚羟基化反应铁复合氧化物类催化剂进行了活性评价的实验研究 ,实验表明 ,Cat980 5的选择性好 ,但邻对位比倒置 ,Cat980 8的选择性差 ,但邻对位比正常 ,其性能与国外催化剂的性能相近     

Degradation of cellulosic and hemicellulosic substrates using a chelator‐mediated Fenton reaction

The involvement of catechol and hydroxamate chelators, along with hydrogen peroxide and Fe³⁺, in the degradation of cellulosic and hemicellulosic substrates was examined with the purpose of improving our current knowledge of the non‐enzymatic mechanisms involved in wood biodegradation by fungi. It could be demonstrated that a catechol chelator‐mediated Fenton reaction not only clearly degraded hemicellulosic substrates but also significantly accelerated and increased the effectiveness of degradation reactions. On the other hand, when a hydroxamate chelator‐mediated Fenton reaction was used, an inhibitory effect was observed. When cellulosic substrates underwent a chelator‐mediated Fenton reaction, no significant difference in degradation was observed between catechol and hydroxamate chelator‐mediated reactions. However, a catechol‐mediated reaction did accelerate the degradation of cellulosic substrates at the beginning of reactions. In addition, it was observed that with a chelator‐mediated Fenton reaction, oxidation of cellulose proceeds depolymerization. Copyright © 2005 Society of Chemical Industry     

多壁碳纳米管与聚(2-乙酰基-5-溴噻吩)复合纳米材料修饰玻碳电极同时检测对苯二酚、邻苯二酚和对甲苯酚

该文利用多壁碳纳米管(MWCNTs)和聚(2-乙酰基-5-溴噻吩)复合纳米材料修饰电极,用于同时检测对苯二酚(HQ)、邻苯二酚(CC)和对甲苯酚(PC)。通过循环伏安法(CV),示差脉冲伏安法(DPV)和透射电镜(TEM)表征了该复合纳米材料的电化学性能和表面形貌。结果表明该电极对HQ、CC和PC具有较高的灵敏度和选择性。DPV峰电流与HQ、CC和PC的浓度在1.0×10-5～8.0×10-4mol/L,5.0×10-6～5.5×10-4mol/L和5.0×10-6～7.5×10-4mol/L范围内分别呈良好的线性关系,且检测限分别为3.0×10-6 mol/L,1.7×10-6 mol/L和2.0×10-6mol/L。     

Liquid-Phase Catalytic Hydroxylation of Phenol Using Cu(II), Ni(II) and Zn(II) Complexes of Amidate Ligand Encapsulated in Zeolite-Y as Catalysts

Copper(II), nickel(II) and zinc(II) complexes of amidate ligand 1,2-bis(2-hydroxybenzamido)ethane(H₂hybe) encapsulated in the super cages of zeolite-Y have been prepared and characterized by spectroscopic studies and thermal as well as X-ray diffraction (XRD) patterns. These complexes catalyze the liquid-phase hydroxylation of phenol with H₂O₂ to catechol as a major product and hydroquinone as a minor product. Considering the concentration of substrate and oxidant, amount of catalyst, temperature of the reaction and volume of solvent, a best-suited reaction condition has been optimized to get maximum hydroxylation. Under the optimized reaction conditions, [Cu(hybe)]-Y has shown the highest conversion of 40% after 6h, which is followed by [Ni(hybe)]-Y with 37% conversion and [Zn(hybe)]-Y has shown the poorest performance with 33% conversion. All these catalysts are more selective towards catechol formation (90%), irrespective of their catalytic performance.     

Biodegradation of catechol by Pseudomonas fluorescens isolated from petroleum‐impacted soil

Bioremediation strategies have been applied to clean up petroleum hydrocarbon (PHC) impacted sites. Introducing PHC degrading microorganisms (bioaugmentation) and enhancing the in‐situ nutrients availability (biostimulation) are widely used strategies. These strategies can be combined to lead to a better bioremediation performance. In this work, Pseudomonas fluorescens was isolated from a PHC impacted site. Through a 2³ factorial design plan, the effect of various combinations of nitrate, sulphate, and phosphate ions on the PHC bioremediation performance by P. fluorescens was investigated using catechol, an essential metabolic intermediate of BTEX degradation, as the sole carbon source. The maximum specific catechol degradation rate was chosen as the response to evaluate the catechol bioremediation performance. The ANOVA results indicated that the presence of nitrate ions alone lowered the maximum specific catechol degradation rate, which can be explained by the accumulation of nitrites and ammonia during the denitrification process by P. fluorescens. It was noted that dosing sulphate ions alone did not affect the bioremediation performance, which indicates P. fluorescens can grow in a sulphur‐limited environment. In contrast, the presence of sulphate and nitrate ions together can lead to a higher specific catechol degradation rate. This may be caused by the presence of sulphate that can suppress the production of nitrites. The importance of phosphate ions on catechol biodegradation was investigated. The absence of phosphate led to incomplete biodegradation. Introducing phosphate ions can accelerate catechol degradation, which can be explained by the secretion of organic acids.     

Catechol-containing waterborne polyurethane adhesive inspired by mussel proteins

A series of waterborne polyurethane (PDMAPU) containing catechol group were prepared by double-bond random copolymerization of terminated double bond polyurethane prepolymer with modified acrylamido dopamine under thermal initiation. This kind of mussel-like waterborne polyurethane adhesive is inspired by marine mussel, as well as it is environment-friendly and used in bonding of leather. FTIR and ¹H NMR proved the successful introduction of catechol group into polyurethane matrix. Oxidative cross-linking between catechol unit and molecular chain in PDMAPU structure, the thermal stability and crystallization ability of PDMAPU was significantly improved. The increase of the particle size of PDMAPU emulsion showed that the introduction of catechol group changed the microstructure of polyurethane and enhanced the cross-linking degree. The water resistance of polyurethane emulsion was further improved. Compared with PU without catechol group, the peel strength of leather substrate adhered by PDMAPU emulsion increased from 0.42 to 1.93 MPa, which indicated that PDMAPU has better bonding properties with leather. The bidentate hydrogen bond formed with catechol group as the reaction sites is considered to be the key reason for the adhesion of mussel-like polyurethane adhesive to hydrophilic substrates. This work provides an alternative to prepare environment-friendly high performance adhesive for hydrophilic substrates.     

基于有序介孔碳/PDDA固定化漆酶的邻苯二酚传感器性能研究

采用有机交联水性环氧树脂为碳源,以SBA-15为模板,制备了有序介孔碳(OMC),并对其电化学性能进行研究。透射电镜结果表明其具有典型的二维有序六角介孔结构,孔径大约为3nm。电化学测试结果表明OMC/Lac/Au电极对邻苯二酚具有很好的电催化氧化活性。将OMC应用于构建漆酶生物传感器,结果表明,传感器对邻苯二酚的线性检测范围为0.67~8.59μmol/L,灵敏度为0.349A/(mol/L),检测限为0.117μmol/L。     

黄樟油素的合成研究

本文研究以邻苯二酚为起始原料，经亚甲基化、选择性溴化、武兹—菲提格反应三步合成黄樟油家，其三步收率分别为85．1％，74．1％，72．8％，以邻苯二酚计，总收率达45．9％。