根霉胞外羧甲基纤维素酶和β－葡糖苷酶的纯化研究

采用柱层析等步骤纯化了根霉Ｇ７的羧甲基纤维素酶及β－葡糖苷酶,回收率分别为４．５％和１９．６％．二种酶的最适酶反应温度都为５５°Ｃ,并都能在较大ｐＨ范围内保持稳定,其中羧甲基纤维素酶具有很高的耐热性,在１００°Ｃ水浴中保持１ｈ也仍可检测出约２０％的酶活性,最适反应ｐＨ为７．０～７．５;而β－葡糖苷酶的热稳性较差,其最适反应ｐＨ为５．０．该两种酶的分子量分别为２．５×１０４和９．５×１０４,而Ｋｍ值则分别为７．４０ｍｇｍＬ－１和０．２１３ｍｇｍＬ－１．     

A new mechanism for the addition of alcohols to disilenes revealed by DFT and ONIOM calculations

Density functional and ONIOM calculations of alcohol and phenol additions to two (tetramethyl and tetramesityl) disilenes were carried out. The dimer of MeOH adds to Me₂SiSiMe₂ more readily than the monomer. The trimer does not afford the adduct, but a zwitter-ionic intermediate. In the (CF₃OH)₂ addition to Me₂SiSiMe₂, H?Si bond formation is more advanced than O?Si bond formation in the transition state (TS). Addition of seven phenol derivatives to Me₂SiSiMe₂ was examined, and the dimer reactions were found to be superior to the monomer reaction regardless of the substituents on the benzene rings. (MeOH)₂ reacts also with Mes₂SiSiMes₂ favorably, and an isomer of the reactant-like complex (precursor) may afford an adduct of different stereochemistry via internal rotations. Generally, the dimer of the alcohol or phenol is the reactant toward the disilenes. Exceptionally, a monomer of p-(dimethylamino)phenol reacts with Mes₂SiSiMes₂ owing to steric congestion by the four mesityl groups.     

The salt-induced sphere-rod transition of micelles of dodecylpyridinium iodide in aqueous NaI solutions

Static light scattering has been measured on aqueous NaI solutions of dodecylpyridinium iodide (DPI) over NaI concentrations from 0 to 0.05 M. Reduced intensity of scattered light increases with increasing DPI concentration above the critical micelle concentration. The Debye plot is generally a curve with an initially positive slope and with a weakly convex, upward curvature, when the NaI concentration ranges from 0 to 0.005 M. The molecular weight of the spherical micelle of DPI is 28400 in water, and it increases slightly with increasing NaI concentration. The initial slope decreases with increasing NaI concentration and changes from positive to negative across 0.007 M NaI, which is the threshold for the sphere-rod transition and where the micelle has a molecular weight of 34400. At NaI concentrations from 0.01 to 0.05 M, the Debye plot is a curve with an initially negative slope and with a convex, downward curvature. The magnitudes of slope and curvature are larger, and the rodlike micelles of DPI have larger molecular weight and stronger mutual interaction, as the NaI concentration increases. The linear double logarithmic relationship between molecular weight and ionic strength holds for spherical and rodlike micelles, respectively.     

Cascade reaction including a formal [5 + 2] cycloaddition by use of alkyne-Co2(CO)6 complex

A new cascade reaction including formal [5?+?2] cycloaddition was developed. Treatment of homocinnamyl alcohol and Co₂(CO)₆-complexed arylpropynal with BF₃·OEt₂ resulted in the generation of hydrobenzocycloheptafuran having an alkyne-Co₂(CO)₆ complex. The reaction consists of 5-membered ring selective Prins cyclization and subsequent Friedel-Crafts cyclization. The cascade reaction was applied to a further multi-step cascade cyclization, which resulted in the formation of more complex polycyclic hydrofurans.     

Effect of Solvent Diols and Ligands on the Properties of Sol-Gel Alumina-Silicas

Amorphous alumina-silicas were prepared from a tetra-alkoxysilane and anhydrous aluminum trichloride or an aluminum alkoxide by a sol-gel process using 2-methyl-2,4-pentanediol, pinacol, 1,2-propanediol, 2,3-butanediol or ethylene glycol as the solvent or complexing agent, and the effect of diols and alkoxy groups on the physical and chemical properties of the alumina-silicas was examined. When the diol or the alkoxy group was bulky, the alumina-silicas had relatively larger micropores, a larger pore volume and higher surface areas. In the conversion of methanol catalyzed by the alumina-silicas, the bulkier diols and alkoxides gave catalysts that produced dimethyl ether in higher yield and hydrocarbons in lower yield. Thus, when ethylene glycol was used as the diol, the best catalyst for the production of hydrocarbons, especially the production of olefins such as ethylene, propylene and butene, was obtained. Furthermore, in comparison with alumina-silica prepared by a traditional kneading process, it was found that the sol-gel alumina-silica could efficiently convert methanol to dimethyl ether and hydrocarbons, but the material prepared by kneading had a very low conversion of methanol to other compounds.     

Binding of Ricinus communis agglutinin to a galactose-carrying polymer brush on a colloidal gold monolayer

A polymer with many pendent galactose residues was prepared by atom-transfer radical polymerization (ATRP) of galactose-carrying vinyl monomer, 2-lactobionamidoethyl methacrylate (LAMA), with a disulfide-carrying ATRP initiator, 2-(2'-bromoisobutyroyl)ethyl disulfide (DT-Br). The galactose-carrying polymer obtained (DT-PLAMA) was accumulated as a polymer brush via Au-S bond on a colloidal gold monolayer deposited on a cover glass. For comparison, a disulfide which carried one galactose residue at both ends (2-lactobionamidoethyl disulfide, Cys-Lac) was accumulated as a self-assembled monolayer (SAM) on the colloidal gold monolayer, too. The association and dissociation processes of galactose residues on the colloidal gold with a lectin, Ricinus communis agglutinin (RCA(120)), were observed by the increase and decrease in absorbance at 550nm corresponding to localized surface plasmon resonance (LSPR) phenomena. The Cys-Lac SAM-carrying glass chip showed a strong non-specific adsorption of the lectin, whereas the DT-PLAMA brush-carrying one reversibly associated with the lectin, indicating reusability of the latter device. The apparent association constant of the lectin with the galactose residues in the DT-PLAMA brush was much larger than the association constant for free galactose, and the detection limit of RCA(120) by the glycopolymer brush-modified device was satisfactorily low. Furthermore, a microscopic observation clearly indicated that the DT-PLAMA brush could reversibly associate with a HepG2 cell having galactose receptors, though these processes could not be observed spectrophotometrically due to a gigantic size of the cell.     

Amperometric determination of choline with enzyme immobilized in a hybrid mesoporous membrane

Choline sensor is successfully prepared by using immobilized enzyme, i.e., choline oxidase (ChOx) within a hybrid mesoporous membrane with 12 nm pore diameter (F127M). The measurement was based on the detection of hydrogen peroxide, which is the co-product of the enzymatic choline oxidation. The determination range and the response time are 5.0-800 μM and approximately 2 min, respectively. The sensor is very stable compared to the native enzyme sensor and 85% of the initial response was maintained even after storage for 80 days. These results indicate that ChOx is successfully immobilized and well stabilized, and at the same time, enzyme reaction proceeds efficiently. Such ability of hybrid mesoporous membrane F127M suggests great promise for effective immobilization of enzyme useful for electrochemical biosensors.     

Photodegradation of some ethylene-norbornene random copolymers

We investigated the photodegradation of specific ethylene-norbornene random copolymers (ENRC) - a group of substances which has been attracting much attention in recent years. ENRCs having various contents of norbornene were studied. After irradiation, each sample was separated into chloroform-insoluble and soluble portions. The chloroform-insoluble portion was weighed and analyzed by FTIR. The chloroform-soluble portion was analyzed by size elimination chromatography (SEC), FTIR and ¹H NMR. The yield of the chloroform-insoluble portion increased with increased irradiation time. Formyl, formate, acyl, hydroxy groups and a carbon-carbon double bond were formed by photo-irradiation. Apparently, hydrogen atoms bound to the tertiary and secondary carbon atom in the parent ENRCs are abstracted. From these results, it is suggested that auto-oxidation results from photo-irradiation of the ENRCs. In ENRCs with similar stereoregularity, the degree of photodegradation increases with increasing norbornene content.     

A general mathematical modelling for heat and mass transfer in unsaturated porous media: an application to free evaporative cooling

The present paper develops a general mathematical model with some improvements in mass, momentum and energy equations, which introduce more transport mechanisms to simulate simultaneous transfer of heat and mass in the porous media unsaturated with liquid. Numerical calculation results in two-dimension are obtained for the vertical packed bed with its right opening surface exposing to atmospherical environment. The calculating data can demonstrate the cooling effect of the water evaporation for the bed if it is used as a cooling wall of building for room air-conditioning in the hot and dry climate.     

采用PTV技术研究循环流化床内气固两相流动

采用PTV技术对循环流化床顶部颗粒稀疏流动区域进行了测量，其中采用先进的高速摄像技术获取流动的连续图像，并采用目前有望在气固两相流动测量中发挥较大作用的四种PTV算法：BICC法、VGT法、SPRING法和4-FRAME法，对所获取的图像进行颗粒配对处理，从而得到流场中运动颗粒的速度信息。所得到的结论为：本文所采用的PTV算法在图像处理中都产生少量的伪矢量，通过采取简单的伪矢量识别算法就可以剔除大部分伪矢量；本文实验条件下，测得循环流化床顶部区域内颗粒运动速度差别较小。本文工作为进一步详细实验测量研究奠定了理论与技术基础。