离子强度和溶质浓度对蛋白质在Q Sepharose FF中吸附动力学的影响

采用孔扩散模型, 模拟不同盐浓度和不同蛋白质初始浓度条件下,吸附牛血清白蛋白(BSA)的动态吸附曲线并获得孔扩散系数;考察了离子强度和溶质浓度对蛋白质在阴离子交换剂Q Sepharose FF中吸附动力学的影响.结果表明,蛋白质的孔扩散系数随初始浓度的增大而下降;在氯化钠浓度小于0.10 mol•L^-1的范围内,蛋白质的孔扩散系数随着盐浓度的增加而增大,但当盐浓度增大到0.15 mol•L^-1时又有所降低,表明存在着一个最佳的离子强度,使蛋白质的孔扩散系数最大.     

MODELLING AND CORRELATING THE PERMEABILITY OF PULP AND PAPER

ABSTRACT

A sheet of paper is modelled as a network of cellulose fibres, either cylindrical or band-shaped. The equations for creeping flow through such structures are solved, and The calculated permeabilities are compared with measured values. Flow through some paper structures such as pulp sheets and handsheets of unbeaten sulphate pulp is adequately described by the structural model involving band-shaped fibres when a fibre aspect ratio of 3.5 is used. For newsprint sheets the measured permeability is lower than that predicted by the models when physically realistic values of the aspect ratio are taken. A total of 19 different paper grades have been characterised by measurement of the total specific surface area and The fibre orientation ratio in addition to the measurements of effective diffusivity, permeability and porosity. Permeability and effective diffusivity correlate with each other and permeability correlates with fibre orientation, so that at constant porosity, permeability decreases with increasing fibre orientation.     

A triangle lattice model that predicts transmembrane helix configuration using a polar jigsaw puzzle

We developed a method of predicting the tertiary structuresof seven transmembrane helical proteins in triangle latticemodels, assuming that the configuration of helices is stabilizedby polar interactions. Triangle lattice models having 12 or11 nearest neighbor pairs were used as general templates ofa seven-helix system, then the orientation angles of all heliceswere varied at intervals of 15°. The polar interaction energyfor all possible positions of each helix was estimated usingthe calculated polar indices of transmembrane helices. An automatedsystem was constructed and applied to bacteriorhodopsin, a typicalmembrane protein with seven transmembrane helices. The predictedoptimal and actual structures were similar. The top 100 predictedhelical configurations indicated that the helix-triangle, CFG,occurred at the highest frequency. In fact, this helix-triangleof bacteriorhodopsin forms an active proton-pumping site, suggestingthat the present method can identify functionally importanthelices in membrane proteins. The possibility of studying thestructure change of bacteriorhodopsin during the functionalprocess by this method is discussed, and may serve to explainthe experimental structures of photointermediate states.     

MODELLING AND CORRELATING THE PERMEABILITY OF PULP AND PAPER

A sheet of paper is modelled as a network of cellulose fibres, either cylindrical or band-shaped. The equations for creeping flow through such structures are solved, and The calculated permeabilities are compared with measured values. Flow through some paper structures such as pulp sheets and handsheets of unbeaten sulphate pulp is adequately described by the structural model involving band-shaped fibres when a fibre aspect ratio of 3.5 is used. For newsprint sheets the measured permeability is lower than that predicted by the models when physically realistic values of the aspect ratio are taken. A total of 19 different paper grades have been characterised by measurement of the total specific surface area and The fibre orientation ratio in addition to the measurements of effective diffusivity, permeability and porosity. Permeability and effective diffusivity correlate with each other and permeability correlates with fibre orientation, so that at constant porosity, permeability decreases with increasing fibre orientation.     

Theoretical investigation of ethylene adsorbed on Ni(100) surface by the multiple-scattering cluster method

In this paper the carbon K-edge near edge X-ray absorption fine structure spectra (NEXAFS) of adsorption system C₂H₄/Ni(100) are calculated using the multiple-scattering cluster method. By a comparison between the theoretical results and experimental spectra, the chemisorption geometry of this system has been determined. The result shows that the molecule is adsorbed on the perpendicular bridge site, and the distance between the C atom and the nearest Ni atom is 1.70 Å, while the molecular plane tilting to the surface is 50°. It is found that the interaction between hydrogen atom and Ni substrate plays an important role in the formation of the adsorption structure. The above results are supported by other evidences.     

Solid state structure and oxygen transport properties of copolyesters based on smectic poly(hexamethylene 4,4′-bibenzoate)

This study examined the solid state structure and oxygen barrier properties of copolyesters based on smectic poly(hexamethylene 4,4′-bibenzoate) (PHBB) and non-liquid crystalline poly(hexamethylene isophthalate) (PHI). The isophthalate content was varied from 10 to 75 mol%. Differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), dynamic mechanical thermal analysis (DMTA), and atomic force microscopy (AFM) were employed to characterize the polymers. The strong ordering tendency of 4,4′-bibenzoate was demonstrated by the persistence of ordered PHBB structures in copolymers with large amounts of the kinked isophthalate comonomer. Copolymers with up to 50 mol% isophthalate gave evidence of liquid crystalline (LC) character in the precursor melt. Copolymers with up to 75 mol% isophthalate crystallized in the PHBB α-crystal form with only small perturbations of the unit cell. The copolymers provided insight into the low gas permeability of LC polymers. Changes in both solubility and diffusivity contributed to the lower oxygen permeability of the smectic glass compared to the amorphous glass. Smaller free volume hole size of the smectic glass gave rise to lower oxygen solubility and contributed to lower diffusivity. The extended chain conformation in the smectic glass, which reduced the fraction of glycol units in gauche conformations, was a second factor that contributed to lower diffusivity.     

Effect of multistratification and film depth on the visualized dynamic sorption behavior of perylene in cellulose acetate films by a confocal laser scanning microscope technique

The sorption behavior of a fluorescent reagent into a polymer film was visualized by confocal laser scanning microscopy (CLSM), and the effects of the additives, film types, and film depth on the diffusion coefficient (D) of the fluorescence reagent were examined. Perylene and cellulose acetate (CA) were used as a fluorescent reagent and a polymer material, respectively. Perylene dissolved in the additives triethylene glycol diacetate (TEGDA) and glycerol triacetate (GTA) was added to the CA film. Then, the evaluation of two types of CA films, a closed‐system cellulose acetate (CCA) sample and an open‐system cellulose acetate (OCA) sample, was conducted. At optimized CLSM conditions (with a scanning range at a 20‐μm depth from the CA film surface with 1‐μm intervals and a scanning speed of 1 fps), the sorption of perylene at the inner CA film was determined. The D values of perylene in the CA film were calculated pursuant to Fick's second law. Higher D values of perylene mixed with TEGDA versus those of perylene mixed with GTA were commonly obtained for the CCA sample (TEGDA: 8.9 × 10⁻¹⁵ m²/s > GTA: 1.7 × 10⁻¹⁵ m²/s) and the OCA sample (TEGDA: 11 × 10⁻¹⁵ m²/s > GTA: 3.3 × 10⁻¹⁵ m²/s) because of the higher chemical affinity of TEGDA with perylene than that of GTA. Perylene indicated a higher D value and was homogeneously distributed in the case of the OCA sample; we found that diffusivity and distribution of perylene in CA film were largely affected by the multistratification treatment. We also proved that the deeper the film depth was, the lower the diffusivity of perylene was, regardless of the types of additives and films. The factors considered for the film‐depth dependence of D were a gradual increase in the diffusion pathway for perylene caused by additive diffusion and the concentration dependence of the perylene D. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

一种用于神经网络样本划分的自聚类算法

建立神经网络模型时 ,能否合理地划分训练样本和检验样本直接关系到建模的效率 .在很多实际应用中 ,检验样本是随机抽取的 .本文提出了一种基于欧氏距离的自聚类算法 ,根据样本的空间分布情况对其自动分类 ,然后确定检验样本 .算例研究表明 ,应用此算法能够改善检验效果 ,从而提高建模效率 .     

Temperature effect on diffusion of carbon dioxide through upper layers of Yucca Mountain

The effective diffusivities of carbon dioxide through the Tiva Canyon tuff and the lower lithophysal zone of the Topopah Spring tuff (outcrop samples of the layer above the proposed nuclear repository site layer) were determined using a steady-state method (counter diffusion). The diffusivity of carbon dioxide through the Tiva Canyon and lithopysal zone tuffs increased with temperature. The following correlation was obtained to estimate the effective diffusivity of carbon dioxide through the Tiva Canyon tuff in cm² s⁻¹ as a function of temperature (K). D_e = 1.22 × 10⁻² − 3.77 × 10⁻⁵T + 9.95 × 10⁻⁸T²The effective diffusivity of carbon dioxide through the lower lithophysal zone of the Topopah Spring tuff (layer right above the proposed repository site) also increased with temperature. For this layer, the following correlation was obtained to estimate the effective diffusivity of carbon dioxide in cm² s⁻¹ as a function of temperature (K). D_e = − 1.11 × 10⁻³ + 1.25 × 10⁻⁵T + 1.83 × 10⁻⁹T²     

Novel method to detect a motif of local structures in different protein conformations

In order to detect a motif of local structures in different protein conformations, the Delaunay tessellation is applied to protein structures represented by C(alpha) atoms only. By the Delaunay tessellation the interior space of the protein is uniquely divided up into Delaunay tetrahedra whose vertices are the C(alpha) atom positions. Some edges of the tetrahedra are virtual bonds connecting adjacent residues' C(alpha) atoms along the polypeptide chain and others indicate interactions between residues nearest neighbouring in space. The rules are proposed to assign a code, i.e., a string of digits, to each tetrahedron to characterize the local structure constructed by the vertex residues of one relevant tetrahedron and four surrounding it. Many sets comprised of the local structures with the same code are obtained from 293 proteins, each of which has relatively low sequence similarity with the others. The local structures in each set are similar enough to each other to represent a motif. Some of them are parts of secondary or supersecondary structures, and others are irregular, but definite structures. The method proposed here can find motifs of local structures in the Protein Data Bank much more easily and rapidly than other conventional methods, because they are represented by codes. The motifs detected in this method can provide more detailed information about specific interactions between residues in the local structures, because the edges of the Delaunay tetrahedra are regarded to express interactions between residues nearest neighbouring in space.      

Oxide–Oxide Interfaces: Atomistic and Density Functional Study of Cubic-ZrO2 (100) ‖ NiO (111)

The cubic-ZrO₂ (100) ‖ NiO (111) interface provides an opportunity for comparison between atomic-scale measurements, atomistic simulations, and theoretical electronic structures. High-resolution electron microscopy indicates that the oxides share a common oxygen layer and that the small lattice strain is largely taken up by NiO near the interface. Using simple Coulomb plus Buckingham-type interatomic potentials, we are able to provide a more focused picture, revealing two types of boundary. The lowest energy interface is highly planar, almost ideal in structure; there is a second interface, of higher energy, that shows a rumpled structure with strain taken up by deformation of nickel chains. Depth profiling of atomic site energies permits calculation of interface versus bulk and surface energies, and it shows that the interface effects penetrate only two to three atomic layers. Embedded cluster density functional studies of bulk and interface-region sites permit the characterization of perturbations of electronic density around the boundaries.     

Methanol diffusion in polyimides: A molecular description

In this contribution the diffusion of methanol in two commercial polyimides (6FDA-ODA and Ultem^® 1000) is investigated in detail by gravimetric analysis and in-situ, time-resolved FTIR spectroscopy. Two methods of spectral data analysis are employed, namely difference spectroscopy (DS) and least-squares curve fitting (LSCF). These approaches provided complementary information about the overall diffusivity, the interactions and the dynamics of the molecular species present in the investigated systems. Spectroscopic measurements on thin film samples (2–4 μm) allowed us to identify the interaction site(s) on the polymer backbone and to propose likely structures for the H-bonding molecular aggregates.     

Determination of the structures of small gold clusters on stepped magnesia by density functional calculations

The structural modifications of small supported gold clusters caused by realistic surface defects (steps) in the MgO(001) support are investigated by computational methods. The most stable gold cluster structures on a stepped MgO(001) surface are searched for in the size range up to 24 Au atoms, and locally optimized by density-functional calculations. Several structural motifs are found within energy differences of 1 eV: inclined leaflets, arched leaflets, pyramidal hollow cages and compact structures. We show that the interaction with the step clearly modifies the structures with respect to adsorption on the flat defect-free surface. We find that leaflet structures clearly dominate for smaller sizes. These leaflets are either inclined and quasi-horizontal, or arched, at variance with the case of the flat surface in which vertical leaflets prevail. With increasing cluster size pyramidal hollow cages begin to compete against leaflet structures. Cage structures become more and more favourable as size increases. The only exception is size 20, at which the tetrahedron is found as the most stable isomer. This tetrahedron is however quite distorted. The comparison of two different exchange-correlation functionals (Perdew-Burke-Ernzerhof and local density approximation) show the same qualitative trends.     

Brownian dynamics simulation of the aggregation of submicron particles in static gas

A Brownian dynamics simulation was conducted to investigate the formation of aggregates that are composed of submicron particles such as soot. Three models were considered for aggregation: a diffusion-limited aggregation model, in which an aggregate grows around a fixed particle; a particle–cluster aggregation model, in which a single aggregate grows by collisions between particles and the aggregate; and a cluster–cluster aggregation (CCA) model, in which many particles and aggregates form multiple aggregates. A comparison of the three aggregation models showed that the CCA model resulted in a soot-like branching shape. The aggregation was investigated by employing the CCA model; it was determined that increase in gas temperature affected the shielding effect of the aggregate branch by changing the displacement and velocity of Brownian particles. Furthermore, these simulations demonstrated that the size and aspect ratio of the field and the particle density also affected aggregation shape.     

Preparation and properties of high‐performance recyclable ethylene propylene diene rubber

To obtain high‐performance recyclable ethylene propylene diene rubber (EPDM), EPDM was chemically functionalized as follows: EPDM was grafted with citraconic acid (CCA) by radical melt polymerization to produce a grafted EPDM (EPDM‐g‐CCA), and EPDM‐g‐CCA was reacted with various amino acids by melt condensation reaction to give amidated copolymers (EPDM‐g‐CCA‐2‐Am, EPDM‐g‐CCA‐7‐Am, and EPDM‐g‐CCA‐12‐Am, where the n indicates the carbon number of amino acid), and then ionomers (EPDM‐g‐CCA/n‐Am/Io) were prepared by melt reaction of EPDM‐g‐CCA/n‐Ams with Zinc oxide (ZnO)/zinc stearate (ZnSt). The mechanical properties/compression set (CS) resistance (elasticity)/recyclability of pristine EPDM, EPDM‐g‐CCA, EPDM‐g‐CCA/n‐Am, and ionomers sheet samples were compared. The tensile strength/modulus, tear strength, and elasticity of samples were mostly increased in the order of ionomers>EPDM‐g‐CCA/n‐Ams>EPDM‐g‐CCA>pristine EPDM. The properties of ionomers increased significantly with increasing the carbon number in amino acid up to seven, and then levelled off or decreased a little. The tensile strength/elasticity (compression set resistance) of recyclable ionomer (EPDM‐g‐CCA/7‐Am/Io) was found to be ～9.42/～2.31 times of pristine EPDM, respectively. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42718.     

NO adsorption on Pd clusters. A density functional study

The interaction of NO with Pd clusters has been studied by means of the LCGTO-DF method. Metal cluster models (up to 13 atoms) with different size and geometry have been used to describe the atop, bridge and three-fold sites. The use of different model core potentials to increase the size of the cluster model treated and to save computational time has been discussed. The binding energies of N(1s), 4σ, 5σ and 1π electrons are calculated and compared directly to the experimental XPS and UPS data available. The NO is tilted with respect to the surface normal axis when adsorbed on top and bridge sites by about 52.6 and 46.7 degrees, respectively. On the two types of three-fold sites (hcp and fcc) the NO remains upright. The bending angle is very sensitive to the cluster size and affects the binding energies of N(1s), 4σ, 5σ and 1π orbitals. The NO adsorption energies on the different adsorption sites have been estimated using different cluster models. The vibrational frequencies have been calculated in the harmonic approximation and they are in reasonable agreement with the available experimental values. The cluster model approach is discussed in terms of its reliability to determine the adsorption energies and the favored site of adsorption. This revised version was published online in June 2006 with corrections to the Cover Date.     

Determination of appropriate effective diffusivity for different food materials

Effective diffusivity is the most important key parameter needed in the analysis, design, and optimization of heat and mass transfer during food drying process. In general, two types of effective diffusivities are used to develop the mathematical modeling of food drying, namely, moisture-dependent effective diffusivity (MDED) and temperature-dependent effective diffusivity (TDED). However, no study has extensively investigated which effective diffusivity is more accurate in predicting drying kinetics. The main goal of this study is to determine the appropriate effective diffusivity for predicting the drying kinetics. Drying models were developed for different fruits and vegetables based on moisture-dependent and temperature-dependent effective diffusivities. COMSOL Multiphysics, a finite element-based engineering simulation software is used to solve the coupled heat and mass transfer equations. 3D moisture profiles were developed to investigate the spatial moisture distribution during drying. Extensive experimental investigation on five types of fruits and vegetables was conducted and results were compared with the simulated results. The experiments were repeated thrice, and the average of the moisture content at each value was used for constructing the drying curves. Close agreement between experimental and simulated results validates the models developed. It was observed that the moisture profile and temperature profile in case of MDED were more closely fitted with the experimental results. For all fruits and vegetables, the moisture ratio with MDED was significantly lower than moisture ratio with TDED. This finding confirms that the MDED is more accurate for predicting kinetics in food drying. Moreover, the moisture ratio of apple was lowest whereas pear showed the highest moisture ratio. On the other hand, carrot showed a considerably lower moisture ratio compared to potato.     

Crystallinity,thermal diffusivity,and electrical conductivity of carbon black filled polyamide 46

Polyamide 46 (PA 46) with carbon black (CB) has been subjected to a heat treatment. Crystallinity, specific heat capacity, crystalline melting peak temperature, thermal diffusivity, and electrical conductivity were measured. The crystallinity increases with duration of thermal treatment. The maximum value is dependent on the filler fraction. A lower CB content leads to a higher crystallinity at maximum tempering time. The crystalline melting peak temperature increases with decreasing filler fraction and duration of thermal treatment due to different crystal types and/or diverging geometric forms of the crystals. Thermal diffusivity and electrical conductivity act positively proportional to each other and increase with CB content and tempering time. The thermal diffusivity decreases with increasing temperature. The volume resistance of PA 46 is lowered by heat treatment. By CB addition in combination with a tempering process, the PA 46 can be transferred into a conductor. CB is moved by PA 46 crystals into amorphous regions forming conductive pathways. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48882.