碳酸酐酶在硅藻土上的固定化及其性质研究

以硅藻土为载体,通过共价结合法固定化碳酸酐酶.对制备固定化晦过程中的pH值、加酶量、反应温度、反应时间几个重要的影响因素进行了研究和优化,并对固定化酶和游离酶的酶学性质进行了比较.结果表明,固定化酶的最适反应温度为30℃,比游离酶高了5℃;最适反应pH值为6.0,比游离酶低了2个pH值单位.该固定化酶的热稳定性、酸碱稳定性和操作稳定性均高于游离酶.     

水热合成单斜晶系BiVO4可见光催化剂及其性能

采用水热法合成了纯单斜晶系的可见光催化剂BiVO4,考察了水热温度、水热时间和体系的pH值对BiVO4结构和光催化性能的影响。利用XRD、SEM、BET和UV-VIS对样品进行了表征,结果表明:获得的BiVO4具有中空棒状结构,升高水热温度、提高反应溶液的pH值、延长水热时间有利于单斜晶系BiVO4的生成。确定了BiVO4的最优合成条件为:水热温度140℃,水热时间6h,反应体系pH=9。选择亚甲基蓝溶液作为光催化降解物质,研究BiVO4的可见光催化性能和催化机理。结果表明,最优条件下制备的BiVO4具有较好的可见光催化性能;同时,增加降解体系的pH值提高了催化剂对亚甲基蓝的吸附能力和活化电子的利用效率,有利于提高BiVO4的光催化性能。     

SiO2/海藻酸钠复合水凝胶作为固定化纤维素酶载体

以海藻酸钠和γ-氨丙基三乙氧基硅烷为原料,在一定条件下使二者发生交联反应生成复合水凝胶,并以此复合凝胶作为固定化纤维素酶的载体。纤维素酶的包埋率超过了85%, 酶固定前后的SEM图表明纤维素酶非常均匀地分布在载体中。探讨了pH、 温度对固定化酶和游离酶活力的影响, 结果表明固定化酶具有对pH和温度更高的稳定性, 固定化酶的最适宜pH为3.6,最佳催化温度为50℃。通过Michaelis Menten（米氏）方程计算得到的固定化酶的米式常数（K_m）值较游离酶大,表明固定化酶的可重复使用性和储藏稳定性良好,连续使用10次后依然保留>50%酶活力,储藏1个月后固定化酶依然有81%的相对酶活力。      

一体式陶瓷膜反应器在对硝基苯酚催化加氢中的应用

设计了液固一体式陶瓷膜反应器,开展对硝基苯酚加氢过程的研究,着重考察了不同膜组件对加氢反应和膜过滤的影响,并对一体式反应器的反应分离性能进行了研究.结果表明,膜组件的引入都会增加纳米镍催化剂的吸附,使加氢速率降低,其中水平膜组件使加氢速率下降了36.4%,影响最大.L型膜组件的渗透性能最高,且对加氢速率的影响较小.一体式陶瓷膜反应器中催化加氢速率的衰减程度小于分置式膜反应器,随着催化剂套用次数的增加,膜处理能力先明显下降后趋于平缓.     

基于聚乙烯醇微球为载体固定化脂肪酶的研究

以具有广泛工业应用性和生物相容性的聚乙烯醇(PVA)为原料,利用PVA分子结构特点对其进行改性,进一步采用高速搅拌制备聚乙烯醇微球,采用扫描电镜表征其形貌。采用1,1′-羰基二(1,2,3-三氮唑)将聚乙烯醇微球活化,以活化后的聚乙烯醇微球为载体固定化脂肪酶,并采用聚乙烯醇物理吸附脂肪酶为实验对照组。结果表明:聚乙烯醇微球粒径分布在2～3μm之间,微球表面形态较为光滑。聚乙烯醇微球固定化脂肪酶可重复使用,重复10次酶催化水解反应,相对酶活仍维持在70%以上。固定化脂肪酶的最优催化水解反应温度为30℃,与游离酶相比降低了10℃,最佳催化水解反应pH为8,与游离酶最佳催化pH相比,催化反应条件更温和。     

固定化脂肪酶生产生物柴油的研究进展

脂肪酶作为一种清洁的催化剂,可用在生物柴油的生产中,解决燃油危机,环境污染等诸多问题。固定化脂肪酶与游离脂肪酶相比具有很好的稳定性和催化性能,脂肪酶固定化的方法主要有吸附、共价结合,交联、包埋等。影响固定化脂肪酶催化酯交换反应生产生物柴油的主要因素有温度、甲醇、甘油和含水量。本文就固定化脂肪酶催化生产生物柴油方面的研究进展作一综述,希望引起对固定化脂肪酶催化生产生物柴油技术的更多关注。     

酸度计温度补偿的解读及温度示值的影响

一、酸度计温度补偿的意义 1.温度对缓冲液标称值的影响 虽然温度对溶液的pH标称值有一定影响,但是影响不大.例如邻苯二甲酸氢钾、混合磷酸盐和硼砂3种缓冲液在25c℃时,pH值分别为4.00、6.86和9.18,当温度升高到45℃时,pH值分别为4.04、6.83和9.04,即它们的温度系数分别为0.0012pH/℃、-0.0028pH/℃和-0.0082pH/℃.可见除了硼砂等少数溶液,温度对溶液的pH值影响很小.而且不同溶液pH值的温度系数差别很大,要将不同温度下的pH值折算到25℃时的值是很困难的,也没有必要.     

储氢材料65Mg35C用于噻吩加氢的研究

以氢气反应球磨法制备出储氢材料65Mg35C,并利用储氢材料加热放出的高活性氢与噻吩发生加氢反应,采用TEM、XRD、DSC及自行设计的排水法放氢装置等对噻吩加氢反应前后的储氢材料进行性能测试及结构表征。分别研究了反应温度和反应时间对噻吩加氢反应的影响,并分析了加氢产物。结果表明,储氢材料与噻吩的加氢反应是在一定温度范围内进行的,同时也要考虑储氢材料的放氢温度,温度低于300℃或高于400℃时均不利于反应的进行;在一定温度下,储氢材料对噻吩加氢反应的时间短有利于产物H2S气体的逸出,时间过长有利于H2S和放氢后储氢材料中的高活性单质Mg发生反应;常压下,在适宜的反应温度范围内,储氢材料对噻吩具有加氢脱硫作用。     

单宁微球固载α-淀粉酶及其催化性能

以单宁微球为载体,采用戊二醛交联法固定α-淀粉酶。探讨了最佳固定化条件,并考察了温度、pH值和淀粉初始浓度等对固定α-淀粉酶催化淀粉水解的影响。结果表明,单宁微球对α-淀粉酶的吸附率达到了96.99%。最佳固定条件为:戊二醛质量分数0.10%,pH5.5,温度25℃,时间2h。固定α-淀粉酶的重复5次后仍具有较好的催化效果。     

交联海藻酸钠磁性微球的制备及固定化胰蛋白酶研究

制备了交联海藻酸钠磁性微球,并以磁性微球为载体,戊二醛为交联剂,将胰蛋白酶固定化;利用透射电镜、粒度分析、红外分析对交联海藻酸钠磁性微球进行了表征;探讨给酶量、戊二醛浓度和pH值对固定化酶活性的影响;与自由酶比较,考察了固定酶的酶学性质.结果表明:交联海藻酸钠磁性微球是固定化胰蛋白酶的良好载体,固定化酶最适宜的条件是吸附时间12h,给酶量为100mg/0.1g磁性载体、交联剂戊二醛浓度为5%、溶液pH值为6,同时将酶固定化后,酶的稳定性和催化性能均有所提高.     

Selective oxidation of benzyl alcohol using RuHAp-containing sheet composites

Ru-containing hydroxyapatite (RuHAp) powder was successfully impregnated into sheet composites using a papermaking technique, and its catalytic efficiency was investigated. The RuHAp powder was homogeneously scattered over the fiber-mix networks that had been tailored within the catalyst sheet. RuHAp-containing sheets demonstrated superior performance to RuHAp beads for the selective oxidation of benzyl alcohol to benzaldehyde in a batch reaction process and the efficiency was equivalent to that of RuHAp powder. Catalytic performance was also evaluated in a continuous fixed-bed column reactor and RuHAp sheets showed higher oxidation efficiency than both RuHAp powder and beads. The porous structure of composites seemed to improve the effective transport of benzyl alcohol to RuHAp surfaces which were immobilized within the sheets, resulting in enhanced catalytic performance.     

Synthesis of yttria-based crystalline and lamellar nanostructures and their formation mechanism

A nonaqueous synthetic route for the preparation of a regular crystalline yttria mesostructure is presented. The reaction between yttrium alkoxides and benzyl alcohol results in the formation of a highly ordered lamellar nanocomposite consisting of yttria layers with a confined thickness of about 0.6 nm, separated from each other by organic layers of intercalated benzoate molecules. Doping with europium leads to strong red luminescence. The nanostructure formation proceeds via two reactions. A C--C bond formation occurs between benzyl alcohol and the isopropanolate ligand. At the same time, yttrium oxide catalyzes two low-temperature hydride-transfer reactions to form benzoic acid and toluene from benzyl alcohol via benzaldehyde, thus limiting the growth of the thickness of the lamellae.     

Catalytic hydrogenation of various organic substrates using a reusable polymer-anchored palladium(II) complex

A stable, reusable, and highly active catalyst for liquid phase hydrogenation reaction has been developed by reacting poly(3,6-diamino N-vinylcarbazole) with benzaldehyde to get polymer-anchored Schiff base which was then reacted with bis(benzonitrile)palladium(II)chloride [Pd(PhCN)₂Cl₂] to get the polymer-anchored complex. The complex was characterized by using scanning electron microscope (SEM), thermogravimetric analysis (TGA), elemental analysis, atomic absorption spectroscopy (AAS), and spectrometric methods like diffuse reflectance spectra of solid (DRS) and Fourier transform infrared spectroscopy (FTIR). The catalytic performance of this catalyst was investigated in hydrogenation of various organic substrates under high-pressure condition. The results showed that the catalyst were highly efficient for hydrogenation reaction and gave excellent yields of products. At the same time, the catalyst was very stable and could be reused for more than five times without noticeable loss of its catalytic activity.     

Spongiform immobilization architecture of ionotropy polymer hydrogel coentrapping alcohol oxidase and horseradish peroxidase with octadecylsilica for optical biosensing alcohol in organic solvent

An organic-phase optical alcohol biosensor consisting of alcohol oxidase and horseradish peroxidase coimmobilized in a spongiform hydrogel matrix of hydroxethyl carboxymethyl cellulose, an adduct of 3-methoxy-4-ethoxy benzaldehyde, 4-tert-butylpyridinium acetohydrazone, silica gel particles, and octadecylsilica particles in conjunction with an optical oxygen transducer has been successfully fabricated. The novel enzyme entrapment structure was mainly characterized with desirable solvent permeability, high efficiency of mass transfer for reactants, and good accessibility and stability of the immobilized enzymes. The biosensor could work in water-miscible solvent such as a solvent mixture of acetonitrile and phosphate aqueous buffer, as well as hydrophobic organic solvent such as n-hexane. The biosensor had the highest sensitivity to methanol in both solvent systems. Under the stop-flow mode, the biosensor had the analytical working ranges from 80 microM to 90 mM methanol in n-hexane and 0.10 to 90 mM methanol in acetonitrile/buffer. When the biosensor functioned in n-hexane, it could take benzaldehyde as an alcohol substrate and was free from any pH disturbance. In the presence of coimmobilized horseradish peroxidase, the operational life of the biosensor was 60 assays and the shelf life was longer than two weeks. The biosensor has been satisfactorily applied to the determination of methanol in commercial gasoline-methanol blend samples.     

耐盐性海藻酸钙纤维的制备及性能研究

针对海藻酸钙在盐溶液中易溶问题,利用戊二醛交联反应制备了耐盐海藻酸钙纤维,红外光谱及溶胀度的测试证明发生了缩合交联反应;讨论了不同工艺条件下,改性纤维的溶胀度和力学性能。结果表明,最佳合成条件为温度30℃、交联剂含量8%、反应时间3.0h、pH=5;改性海藻酸钙纤维的溶胀度只有98%,为纯海藻酸钙纤维的27%,改性纤维断裂强度为2.23cN/dtex。     

Synthesis of surface controlled nickel/palladium hydride nanodendrites with high performance in benzyl alcohol oxidation

Benzaldehyde byproduct is an imperative intermediate in the production of fine chemicals and additives. Tuning selectivity to benzaldehyde is therefore critical in alcohol oxidation reactions at the industrial level. Herein, we report a simple but innovative method for the synthesis of palladium hydride and nickel palladium hydride nanodendrites with controllable morphology, high stability, and excellent catalytic activity. The synthesized dendrites can maintain the palladium hydride phase even after their use in the chosen catalytic reaction. Remarkably, the high surface area morphology and unique interaction between nickel-rich surface and palladium hydride (β-phase) of these nanodendrites are translated in an enhanced catalytic activity for benzyl alcohol oxidation reaction. Our Ni/PdH_0.43 nanodendrites demonstrated a high selectivity towards benzaldehyde of about 92.0% with a conversion rate of 95.4%, showing higher catalytic selectivity than their PdH_0.43 counterparts and commercial Pd/C. The present study opens the door for further exploration of metal/metal-hydride nanostructures as next-generation catalytic materials.

     

海藻酸钠固定化简单节杆菌的研究

研究了用海藻酸钠作载体，用包埋法固定化简单节杆菌（ＡｒｔｈｒｏｂａｃｔｅｒＳｉｍｐｌｅｘ）Ｂｙ－２－１３的制备条件及固定化菌的一般性质。用１０ｍｌ４％海藻酸钠包埋０．５ｇ湿菌体活力收率可达８７％。固定化菌的最适ｐＨ与最适温度与游离菌相同；固定化菌的储存稳定性高于游离菌。     

Highly basic CaO nanoparticles in mesoporous carbon materials and their excellent catalytic activity

Highly basic CaO nanoparticles immobilized mesoporous carbon materials (CaO-CMK-3) with different pore diameters have been successfully prepared by using wet-impregnation method. The prepared materials were subjected to extensive characterization studies using sophisticated techniques such as XRD, nitrogen adsorption, HRSEM-EDX, HRTEM and temperature programmed desorption of CO2 (TPD of CO2). The physico-chemical characterization results revealed that these materials possess highly dispersed CaO nanoparticles, excellent nanopores with well-ordered structure, high specific surface area, large specific pore volume, pore diameter and very high basicity. We have also demonstrated that the basicity of the CaO-CMK-3 samples can be controlled by simply varying the amount of CaO loading and pore diameter of the carbon support. The basic catalytic performance of the samples was investigated in the base-catalyzed transesterification of ethylacetoacetate by aryl, aliphatic and cyclic primary alcohols. CMK-3 catalyst with higher CaO loading and larger pore diameter was found to be highly active with higher conversion within a very short reaction time. The activity of 30% CaO-CMK3-150 catalyst for transesterification of ethylacetoacetate using different alcohols increases in the following order: octanol > butanol > cyclohexanol > benzyl alcohol > furfuryl alcohol.     

Suzuki–Miyaura reaction and solventfree oxidation of benzyl alcohol by Pd/nitrogen-doped CNTs catalyst

Suzuki–Miyaura C–C coupling reactions were investigated with Pd/nitrogen-doped carbon nanotubes (Pd/N-CNTs) as a catalyst. Also, the same catalyst was examined for the solventfree oxidation of benzyl alcohol to benzaldehyde. Nitrogen-doped carbon nanotubes (N-CNTs) were synthesized from 1-ferrocenylmethyl(2-methylimidazole) and benzophenone via a chemical vapour deposition technique. Acetonitrile was used as a solvent and source of both carbon and nitrogen constituents of N-CNTs. Pd nanoparticles (Pd NPs) were successfully dispersed on N-CNTs via a metal organic chemical vapour deposition method. SEM, TEM, XRD, elemental analysis and ICP-OES measurements were used to characterize the nanomaterials. From the TEM analysis, it was observed that Pd NPs were spherical and with particle sizes ranging from 3 to 8 nm. For Suzuki C–C coupling reactions, phenylboronic acid, aryl halide, Pd/N-CNTs catalyst and a base (NaOAc, K₂PO₄, K₂CO₃, NaOH, Et₃N and Na₂CO₃) were used. The optimized experiments indicate that K₂CO₃, as the base, and ethanol/water (1:1 v/v, 10 mL) mixture, as a solvent, are the best reaction conditions. The solventfree oxidation reactions of benzyl alcohol were also done with Pd/N-CNTs catalyst and benzyl alcohol as a substrate. In both sets of reactions, C–C coupling and oxidation, the increase in pyrrolic nitrogen species was found to be responsible for higher catalytic activities of Pd/N-CNT catalysts, and this was attributed to the ease of Pd NP dispersion on N-CNTs, relative to pristine CNTs. Also, the higher catalytic activity of Pd/N-CNTs could be ascribed not only to the smaller Pd NP size or surface area, but to also the surface properties and the nature of the support when compared with the undoped counterpart, Pd/CNTs.