PREPARATION AND CATALYTIC ACTIVITY OF BIOACTIVE FIBERS

Two kinds of water-soluble metallophthalocyanines, binuclear cobalt phthalocyanine （Co2Pc2） and binuclear ferric phthalocyanine （Fe2Pc2）, were synthesized through phenylanhydride-urea route and characterized by elemental analysis and FT-IR spectra. Binuclear metallophthalocyanine derivatives （Mt2Pc2） were immobilized on silk fibers and modified viscose fibers to construct bioactive fibers of mimic enzyme. Mt2Pc2 was used as the active center of bioactive fibers, viscose and silk fibers as the microenvironments. The catalytic oxidation ability of bioactive fibers on the malodors of methanthiol and hydrogen sulfide was investigated at room temperature. The experimental results indicated that the catalytic activity of such bioactive fibers was closely correlative to the types ofbioactive fibers and substrates.     

Target-induced mimic enzyme deactivation based on mixed-node metal-organic frameworks for colorimetric assay of hydrogen sulfide

Accurate detection of hydrogen sulfide (H₂S) is of great significance for environmental monitoring and protection. We propose a colorimetric method for the detection of H₂S by the use of mixed-node Cu-Fe metal organic frameworks (Cu-Fe MOFs) as highly efficient mimic enzymes for target-induced deactivation. The Cu-Fe MOFs were synthesized by a simple solvothermal method and could catalyze the H₂O₂ mediated oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) to oxTMB with a blue color. The presence of dissolved H₂S would deactivate the mimic enzymes, and then the blue color disappeared. The mechanism of the sensor was discussed by steady-state kinetic analysis. The designed assay was highly sensitive for H₂S detection with a linear range of 0−80 μmol/L and a detection limit of 1.6 μmol/L. Moreover, some potential substances in the water samples had no interference. This method with the advantages of low cost, high sensitivity, selectivity, and visual readout with the naked eye was successfully applied to the determination of H₂S in industrial wastewater samples.     

牛血清白蛋白模板法制备的金属复合纳米材料在生物检测中的应用

随着纳米科技的快速发展,纳米材料得到广泛应用,其功能也得到全面的研究。由于蛋白质外壳和金属内核,以牛血清白蛋白为模板制备的金属复合纳米材料拥有很好的稳定性、高荧光特性、优良的催化活性、环保的制备过程和潜在的多功能特性。本文综述了近年来牛血清白蛋白-金属复合纳米材料的相关研究,包括已开发的种类、制备方法、性能、生物检测及临床相关应用。     

新型钒卤代过氧化物酶模型化合物的合成结构及仿生催化活性

模拟卤代过氧化物酶活性中心钒的配位环境设计合成了新的蝎型聚吡唑硼酸盐钒氧化合物VO(HB(3,5-Me<,2> pz)<,3>)(3,5-Me<,2>pz)(HOOCCH<,2>CH<,2>COO)(1)和VO(HB(3,5-Me<,2>pz)<,3>)(3,5-Me<,2> pz)(C<,5>H<,4>NCOO)(2...     

Thermally Robust yet Deconstructable and Chemically Recyclable High-Density Polyethylene (HDPE)-Like Materials Based on Si−O Bonds

Polyethylene (PE) is the most widely produced synthetic polymer. By installing chemically cleavable bonds into the backbone of PE, it is possible to produce chemically deconstructable PE derivatives; to date, however, such designs have primarily relied on carbonyl- and olefin-related functional groups. Bifunctional silyl ethers (BSEs; SiR₂(OR′₂)) could expand the functional scope of PE mimics as they possess strong Si−O bonds and facile chemical tunability. Here, we report BSE-containing high-density polyethylene (HDPE)-like materials synthesized through a one-pot catalytic ring-opening metathesis polymerization (ROMP) and hydrogenation sequence. The crystallinity of these materials can be adjusted by varying the BSE concentration or the steric bulk of the Si-substituents, providing handles to control thermomechanical properties. Two methods for chemical recycling of HDPE mimics are introduced, including a circular approach that leverages acid-catalyzed Si−O bond exchange with 1-propanol. Additionally, despite the fact that the starting HDPE mimics were synthesized by chain-growth polymerization (ROMP), we show that it is possible to recover the molar mass and dispersity of recycled HDPE products using step-growth Si−O bond formation or exchange, generating high molecular weight recycled HDPE products with mechanical properties similar to commercial HDPE.     

GSH对两种谷胱甘肽过氧化物酶模拟物活性影响的研究

设计并合成了谷胱甘肽过氧化物酶(GPX)模拟物6A,6A’-二苯胺-6B,6B’-二硒桥联-β-环糊精(6-AnSeCD). 采用双酶偶联法测定GPX的活力结果显示, 6A,6A’-二环己胺-6B,6B’-二硒桥联-β-环糊精(6-CySeCD)催化谷胱甘肽还原H2O2和枯烯H2O2的活力均比6-AnSeCD的高. 为了进一步考察6-CySeCD和6-AnSeCD与GSH之间的相互作用, 进行了分子动力学(MD)模拟和分子对接研究. 结果表明, 与GSH的结合使GPX模拟物的构象发生变化, 这种改变可能是影响桥连GPX模拟物催化活性的关键因素.     

CTAB在硅胶表面吸附引起的润湿性变化和模拟驱油

用椭圆偏振法测定溴代十六烷基三甲胺（CTAB）水溶液在光滑的二氧化硅膜片上的吸附，其结果符合两阶段模型，即在不同浓度下发生单分子层和近似双分子层的吸附，并与其表面润湿性变化的数据吻合.用改进的Washburn方程测量改性硅胶粉末的润湿性, 研究了CTAB水溶液在硅胶粉末表面上吸附引起的润湿性变化.并由此探讨了CTAB水溶液在硅胶粉末表面的润湿性,表面活性剂的临界胶束浓度（CMC）与表面含油粉末脱油率的关系，对在非超低界面张力条件下通过改变固/液界面润湿性提高原油采收率作了实验探讨.     

四氢叶酸辅酶模型化合物的研究Ⅱ .碘化 1 ,2 -二甲基 - 3-芳磺酰基 -△~2 -咪唑啉的一碳单元转移反应

四氢叶酸辅酶模型化合物与邻苯二胺、乙二胺、邻氨基酚作用则得到相应的一碳单元转移,而与芳胺、丙二腈碳负离子以及苯基溴化镁反应分别生成辅酶模型化合物的衍生物。讨论了其可能的一碳单元转移机制。     

Mn(II)-sodium dodecyl sulphate complex mimic enzyme-catalyzed fluorescence quenching of Pyronine B by hydrogen peroxide

Mn(II)-sodium dodecyl sulphate complex (Mn(II)-SDS) is used to mimic the active group of peroxidase. The catalytic characteristic of this mimic enzyme catalyst in the oxidation reaction of fluorescence substrate, tetraethyldiaminoxanthyl chloride (Pyronine B (PB)), with hydrogen peroxide has been studied. The experimental results show that Mn(II)-SDS complex has similar catalytic activity that of peroxidase. The steady-state catalytic rate depends upon mimic enzyme and substrate concentrations, and the Michaelis-Menten parameters K_m, V_max and K_cat are 7.6×10⁻⁶ M, 7.9×10⁻⁷ M s⁻¹ and 7.9 s⁻¹, respectively. The catalytic activity of Mn(II)-SDS complex is compared with those of HRP and Hemin. Though the catalytic activity of Mn(II)-SDS complex is 15.9% of that of HRP, it can catalyze the oxidation reaction of PB with hydrogen peroxide lead to fluorescence quenching of PB. Under optimum conditions, linear relationship between fluorescence quenching F₀/F and concentration of H₂O₂ is in the range of (0.0-3.6) × 10⁻⁷ M. The detection limit is determined to be 3.0×10⁻⁹ M. By coupling this mimic catalytic reaction with the catalytic reaction of glucose oxidase (GOD), glucose can be detected. Linear relationship between F₀/F and concentration of glucose is in the range of (0.0-1.4) × 10⁻⁷ M. The detection limit is determined to be 4.2×10⁻⁹ M. This method is applied to the determination of glucose in human serum and the results are in good agreement with the phenol-4-aminoantipyrine (4-AAP).     

Citrinin selective molecularly imprinted polymers for SPE

Molecularly imprinted polymers (MIPs) for citrinin (Cit) with 1‐hydroxy‐2‐naphthoic acid (HNA) as mimic template were prepared and the molecularly imprinted SPE method was developed for the detection of Cit in rice with HPLC. The adsorption properties of HNA and Cit on the MIPs and nonimprinted polymers were investigated. It proved that MIPs showed higher selectivity adsorption to HNA and Cit than nonimprinted polymers were. The recoveries of Cit in rice were in the range of 86.7–97.7%. The spiked rice samples and five rice samples in Beijing market were detected using molecularly imprinted SPE method and satisfied results were obtained as discussed in this article.