温度对蛋白和β-环糊精手性固定相拆分对映体的影响

 采用三聚氯氰为活化剂分别合成了牛血清白蛋白 (BSA)、人血清白蛋白 (HSA)和 β 环糊精手性固定相 ,研究了温度在色氨酸 ,华法令 ,酮基布洛芬和丹酰化苏氨酸手性拆分中的影响。结果表明 ,在蛋白手性固定相上对映体间的熵变对色氨酸 ,华法令和酮基布洛芬的拆分有很大的影响 ,而丹酰化苏氨酸对映体在 β 环糊精手性固定相上的拆分为典型的焓控过程 ,与蛋白柱有着不同的热力学特性。由于键合方式不同 ,色氨酸在我们合成的BSA手性固定相上的最佳分离温度为 35℃左右 ,而不是文献报道的以戊二醛为活化剂的 2 4℃。     

Solvent-dependent assembly of terphenyl- and quaterphenyldithiol on gold and gallium arsenide

The assembly of terphenyldithiol (TPDT) and quaterphenyldithiol (QPDT) on gold and gallium arsenide from ethanol (EtOH), tetrahydrofuran (THF), and solutions consisting of both solvents has been characterized by near-edge X-ray absorption fine structure spectroscopy. The surface coverage and the average orientation of both TPDT and QPDT on gold are solvent-independent. These molecules readily form monolayers on gold with an ensemble-average backbone tilt of 30 degrees +/- 3 degrees from the substrate normal. In sharp contrast, the assembly of TPDT and QPDT on gallium arsenide is extremely solvent-sensitive. At high ethanol fractions, both molecules form monolayers with an ensemble-average orientation that is indistinguishable from those on gold substrates. At low ethanol fractions and in pure THF, however, these molecules are disordered on gallium arsenide and the surface coverage is poor.     

Effect of mixed solvent media on the sorption and separation of uranium and plutonium on macroporous resins

Ion-exchange studies on uranium and plutonium using macroporous (MP) anion-exchange resins from an aqueous-organic solvent mixed media were carried out to develop a separation method. Out of the several water miscible organic solvents tried methanol and acetone were found to be best suited. Distribution data were obtained for U(VI) and Pu(IV) using three macroporous resins under various parameters. Based on these data, separation factors for Pu/U were calculated. Column experiments using Tulsion A-27(MP) were also carried out. The method has the advantage of loading plutonium from as low as 1M nitric acid in the presence of methanol or acetone and could be used satisfactorily for its recovery from solutions containing plutonium and uranium.     

Effect of anions and pH on the adsorption and oxidation of methanol on a platinum electrode

The influence of various anions and pH on methanol oxidation as well as its products of chemisorption on platinum has been studied by voltammetric and radiometric methods. It was found that the rate of methanol oxidation from the bulk solution was lowest for Na₂CO₃ and highest for NaOH solutions. The influence of anions on the chemisorbed species of methanol on a platinum electrode has also been investigated.     

Adsorption of cellulose derivatives on flat gold surfaces and on spherical gold particles

The adsorption of hydroxyethylcellulose (HEC), ethyl(hydroxyethyl)cellulose (EHEC), and their hydrophobically modified counterparts HM-HEC and HM-EHEC has been studied on planar gold and citrate-covered gold surfaces by means of quartz crystal microbalance with dissipation monitoring (QCM-D), and on citrate-covered gold particles with the aid of dynamic light scattering (DLS). The QCM-D results indicate that larger amounts of polymer are adsorbed from aqueous solutions of HM-HEC and HM-EHEC on both substrates than from solutions of their unmodified analogues. The adsorption affinity for all the polymers, except EHEC, is higher on the citrate-covered surfaces than on the bare gold substrate. This indicates that more adsorption sites are activated in the presence of the citrate layer. The experimental adsorption data for all the polymers can be described fairly well by the Langmuir adsorption isotherm. However, at very low polymer concentrations significant deviations from the model are observed. The value of the hydrodynamic thickness of the adsorbed polymer layer (delta h), determined from DLS, rises with increasing polymer concentration for all the cellulose derivatives; a Langmuir type of isotherm can be used to roughly describe the adsorption behavior. Because of good solvent conditions for HEC the chains extend far out in the bulk at higher concentrations and the value of delta h is much higher than that of HM-HEC. The adsorption of EHEC and HM-EHEC onto gold particles discloses that the values of delta h are considerably higher for the hydrophobically modified cellulose derivative, and this finding is compatible with the trend in layer thickness estimated from the QCM-D measurements.     

The influence of micro- and nanoparticles on model atomically flat surfaces on crystallization of polyethylene

Crystallization of high density polyethylene (PE) from the melt on model atomically flat solid surfaces decorated with micro- and nanoparticles of gold or NaCl of different size and densities is investigated. The morphology of the contact layer of PE after its detachment from the support is studied using atomic force microscopy (AFM). It is shown that the nucleating and ordering effect of the solid on PE crystallization depends to a large extend on the nanostructure of its surface, in particular on the size of the atomically flat domains and on the presence of nanoscopic obstacles. The minimum size of the flat domain which can significantly influence the PE crystallization is estimated to be of the order of 150 nm.     

Effect of Polycaprolactam Fiber on Coagulation of Rubbers and on Properties of Rubbers,Rubber Stocks,and Vulcanizates

The effect of polycaprolactam fiber on the coagulation of butaidene-styrene rubber from the latex was studied.     

Solvent effects on the adsorption and self-organization of Mn12 on Au(111)

A sulfur-containing single molecule magnet, [Mn12O12(O2CC6H4SCH3)16(H2O)4], was assembled from solution on a Au(111) surface affording both submonolayer and monolayer coverages. The adsorbate morphology and the degree of coverage were inspected by scanning tunneling microscopy (STM), while X-ray photoelectron spectroscopy (XPS) allowed the determination of the chemical nature of the adsorbate on a qualitative and quantitative basis. The properties of the adsorbates were found to be strongly dependent on the solvent used to dissolve the magnetic complex. In particular, systems prepared from tetrahydrofuran solutions gave arrays of isolated and partially ordered clusters on the gold substrate, while samples prepared from dichloromethane exhibited a homogeneous monolayer coverage of the whole Au(111) surface. These findings are relevant to the optimization of magnetic addressing of single molecule magnets on surfaces.     

The Effects of Salts on the Room-Temperature Fluorescence and Room-Temperature Phosphorescence of Tetrols on Filter Paper and Filter Paper with Silicone

Abstract

Several salts were investigated to enhance the room-temperature solid-matrix phosphorescence of the four stereoisomeric tetrols on filter paper. Thallium acetate was found to enhance the phosphorescence to the greatest extent, but it was necessary to prepare the thallium acetate in an acetic acid solution to achieve the maximum phosphorescence from the solid matrix. Also, thallium acetate essentially quenched the solid-matrix fluorescence of the tetrols. Without thallium acetate adsorbed on filter paper, strong room-temperature fluorescence signals were observed from the tetrols adsorbed on filter paper. With a new solid matrix, filter paper which contained silicone, no heavy-atom was needed to obtain strong phosphorescence from the adsorbed tetrols. In fact, the room-temperature fluorescence from the tetrols adsorbed on this type of filter paper was very strong. The room-temperature fluorescence gave a limit of detection in the sub-picogram range for one of the tetrols with the silicone treated filter paper.     

Viscodensitometer Studies on Gelatine and the Sorption of Gelatine on Glass

The sorption of polymers on glass surfaces, and the effects produced thereby on measurements of intrinsic viscosity, hitherto studied in capillary viscometers, is here analyzed by the sensitive viscodensitometric technique, based on the principle of the moving-sphere viscometer. By working with several spheres of equal size, the errors in viscometry due to sorption can be practically eliminated. The use of two spheres differing in radius by a factor of 10 allows the direct weighing of the polymer sorbed per unit geometric surface. In this way the sorption isotherm of an alkali-bone gelatin on Pyrex glass from 0.17 M KCl solution was found to rise to a plateau of 3 mg/m² at a gelatin concentration of 0.1 g/dl. The plateau extends from this lower limit to 0.5 g/dl. The partial specific volume of gelatin, directly obtained in the viscodensitometer along with the viscosity, was found to be 0.702 cc/g in water and 0.725 cc/g in 0.95 M KCl.     

Sorption of zinc and cadmium on zeolite rocks

The sorption of zinc and cadmium on zeolite rocks from different locations in Bulgaria is studied. The basic equilibrium and kinetic parameters are determined. It has been found that the clinoptilolite rock from the location Bali plast may be used as a sorbent for zinc and cadmium.     

Effects of trichloroethylene and tetrachloroethylene on fine structure of wool

Studies have been made on the structure of wool fibres treated with trichloroethylene (TRI) and tetrachloroethylene (PER) by means of differential thermal analysis (DTA), differential scanning calorimetry (DSC) and X-ray diffractometry. The samples were treated with TRI at temperatures ranging from 40? to 87?, and with PER at temperatures from 40? to 121?. TRI and PER treatment caused changes in the wool samples which were detected on the DTA curves. Changes in the degree of order brought about by TRI and PER, calculated from the DSC scans, were in accord with those determined from the X-ray data. The wool samples treated with TRI showed an increase, and those treated with PER a decrease, in the content of the ordered phase as the treatment time was increased.     

Dimensions and specificities of recognition sites on lectins and antibodies.

A comparison is made of the specific combining sites of a number of lectins and of antibodies with emphasis on those reacting with blood group A, B, and H determinants. The ranges of site sizes and specificities of both groups are similar both from immunochemical studies and from the limited x-ray diffraction data available.     

Computational study of the adsorption and dissociation of phenol on Pt and Rh surfaces

The adsorption of phenol on flat and stepped Pt and Rh surfaces and the dissociation of hydrogen from the hydroxyl group of phenol on Pt(111) and Rh(111) were studied by density functional calculations. On both Pt(111) and Rh(111), phenol adsorbs with the aromatic ring parallel to the surface and the hydroxyl group tilted away from the surface. Furthermore, adsorption on stepped surfaces was concluded to be unfavourable compared to the (111) surfaces due to the repulsion of the hydroxyl group from the step edges. Transition state calculations revealed that the reaction barriers, associated with the dissociation of phenol into phenoxy, are almost identical on Pt and Rh. Furthermore, the oxygen in the dissociated phenol is strongly attracted by Rh(111), while it is repelled by Pt(111).     

甜茶苷的酶法制备及其对肝肠胃细胞的抑制作用

甜茶苷是一种自然界中含量稀少的甜味剂。 本实验从多种糖苷酶中筛选出一种来自Aspergillus niger的β-葡萄糖苷酶,用以特异性水解斯替夫苷而高通量制备甜茶苷。 最适条件下反应12 h后,甜茶苷的产率为90.4%,斯替夫苷的转化率达98.8%。 为了进一步考察甜茶苷的安全性并拓展其潜在的用途,实验考察了甜茶苷对人胃肠道和肝脏细胞的细胞毒性,即甜茶苷对3种正常细胞以及11种癌细胞生长的抑制效果。 实验结果表明,在250 μg/mL的质量浓度下,甜茶苷对正常人胃肠肝细胞无毒性;相同质量浓度下,甜茶苷对人体肝癌细胞BEL-7404的抑制率是5-氟尿嘧啶的30％。     

Influence of solution chemistry on the deposition and detachment kinetics of RNA on silica surfaces

The deposition kinetics of RNA extracted from both virus and bacteria on silica surfaces were examined in both monovalent (NaCl) and divalent (CaCl(2)) solutions under a wide range of environmentally relevant ionic strength and pH conditions by utilizing a quartz crystal microbalance with dissipation (QCM-D). To better understand the RNA deposition mechanisms, QCM-D data were complemented by diffusion coefficients and zeta potentials of RNA as a function of examined solution chemistry conditions. Favorable deposition of RNA on poly-l-lysine-coated (positively charged) silica surfaces was governed by the convective-diffusive transport of RNA to the surfaces. The deposition kinetics of RNA on bare silica surfaces were controlled by classic Derjaguin-Landau-Verwey-Overbeek (DLVO) interactions. The presence of divalent cations (Ca(2+)) in solutions greatly enhanced the deposition kinetics of RNA on silica surfaces. Solution pH also affected the deposition behavior of RNA on silica surfaces. Release experiments showed that detachment of RNA from silica surfaces was significant in NaCl solutions, whereas, the deposited RNA on silica surfaces in CaCl(2) solutions was more likely to be irreversible.     

Comparative chromatography of lectins and bioactivity recovery of the immunologic hormone leukoregulin on derivatized silica and on cross-linked agarose molecular sizing high-performance liquid chromatographic matrices

This investigation compares the performance of the new zirconia stabilized silica and cross-linked agarose size-exclusion matrices to Spherogel-TSK 3000 SWG silica in high-performance liquid chromatographic separation of proteins possessing a range of molecular weights present in many lymphokine preparations and in recovery of bioactivity as measured by leukoregulin proliferation inhibitory activity. Retention time versus log molecular weight of protein standards was linear from 12,500 to 290,000 on the agarose and from 32,000 to 290,000 on the other columns. Recovery of leukoregulin proliferation inhibitory activity directed against RPMI 2650 epidermoid carcinoma cells was 90% from the silica, 88% from the agarose and 35% from the zirconia stabilized silica columns.     

Polyelectrolyte Hydrogels Based on Radiation-Modified Polyacrylamide and Products of Its Alkali Hydrolysis

The effect of molecular mass on the formation of polyelectrolyte hydrogels made from polyacrylamide (PAAm) and products of its alkali hydrolysis and on their water sorption capacity was studied. It was found that the efficiency of crosslinking of both the initial polymer and its hydrolyzates noticeably decreased on passing from high-molecular-mass to low-molecular-mass PAAm. Hydrogels prepared from high-molecular-mass PAAm and its hydrolyzates exhibited a greater limiting water uptake as compared with hydrogels made from low-molecular-mass PAAm and its hydrolyzates. A change in the degree of conversion of amide to acrylate groups from 35–41 to 47–54% had a slight effect on the maximum water uptake.     

Adsorption and desorption of atrazine on carbon nanotubes

The potential impact of carbon nanotubes (CNTs) on human health and the environment is receiving more and more attention. The high surface area of CNTs tends to adsorb a large variety of toxic chemicals, which may enhance the toxicity of CNTs and/or toxic chemicals. In this study, adsorption and desorption of atrazine on carbon nanotubes from aqueous solution were studied through batch reactors. The adsorption equilibrium isotherms were nonlinear and were fitted by Freundlich, Langmuir, and Polanyi-Manes models. It was found that the Polanyi-Manes model described the adsorption process better than other two isotherm models. Together with the "characteristic curve," the Polanyi adsorption potential theory is applicable to describe the adsorption process of atrazine on CNTs. Thermodynamic calculations indicated that the adsorption reaction of atrazine on CNTs is spontaneous and exothermic. The desorption data showed that no significant desorption hysteresis occurred. High adsorption capacity and adsorption reversibility of atrazine on CNTs suggest that CNTs have high health and environmental risks, whereas they have potential applications for atrazine removal from water.     

改性Y分子筛的酸碱性能及吸附性能的研究

吡啶、吡咯、苯、甲苯、乙苯作为探针分子，在Li＋, Na＋, K＋, Cs＋改性的Y型分子筛上进行吸附，用TPD及IR方法系统地研究了不同碱金属离子改性的Y型分子筛的酸碱性能和吸附性能的变化. 结果表明，按Li、Na、K、Cs的顺序, 随着碱金属离子半径的增大, 其L酸酸强度依次减弱，L碱的强度逐渐增强.由于改性Y型分子筛所含碱金属离子的不同，其对芳烃的吸附的强弱及吸附量的大小亦不同.随着骨架外的阳离子的半径逐渐增大，碱的强度逐渐增强，与芳烃的作用愈强烈，导致TPD脱附峰温增高及芳烃和侧链上的C－H伸缩振动谱带向低波数位移愈多.由于位阻的原因，对含同一种碱金属离子的分子筛来说，随着芳烃侧链C数的增加，芳烃的吸附量逐渐减小.