Molecular dynamics model structures for the molten globule state of {alpha}-lactalbumin: aromatic residue clusters I and II

To model the molten globule structure of -lactalbumin, moleculardynamics (MD) simulations were carried out for the protein inexplicit water at high temperature. In these simulations, long-rangeCoulomb interactions were evaluated explicitly with an originalmethod (particle–particle and particle–cell: PPPC)to avoid artifacts caused by the cut-off. The MD simulationswere started from two initial conditions to verify that similarresults would be obtained. From the last 150 ps trajectoriesof the two MD simulations, two partially unfolded average structureswere obtained. These structures had the following common structuralfeatures which are characteristic of the molten globule state.The radii of gyration for these conformations were 7.4 and 9.6%larger than that of the native state. These values were almostthe same as the experimental value (9.6%) observed recentlyby small-angle X-ray scattering (Kataoka,M., Kuwajima,K., Tokunaga,F.and Goto,Y., 1997, Protein Sci., 6, 422–430). Furthermore,aromatic residues of clusters I and II in these structures werefar apart from each other except for Try103–Trp104. Thisresult is in good agreement with NMR experimental results forthe acid-denatured molten globule state (Alexandrescu et al.,1992, 1993); that is, NOE signals between the aromatic residueswere not observed, except for that of Try103–Trp104 inthe molten globule state. Other structural features of thesemodels for the molten globule state are discussed with referenceto native state structures.     

Domain Adaptation for Structured Regression

Discriminative regression models have proved effective for many vision applications (here we focus on 3D full-body and head pose estimation from image and depth data). However, dataset bias is common and is able to significantly degrade the performance of a trained model on target test sets. As we show, covariate shift, a form of unsupervised domain adaptation (USDA), can be used to address certain biases in this setting, but is unable to deal with more severe structural biases in the data. We propose an effective and efficient semi-supervised domain adaptation (SSDA) approach for addressing such more severe biases in the data. Proposed SSDA is a generalization of USDA, that is able to effectively leverage labeled data in the target domain when available. Our method amounts to projecting input features into a higher dimensional space (by construction well suited for domain adaptation) and estimating weights for the training samples based on the ratio of test and train marginals in that space. The resulting augmented weighted samples can then be used to learn a model of choice, alleviating the problems of bias in the data; as an example, we introduce SSDA twin Gaussian process regression (SSDA-TGP) model. With this model we also address the issue of data sharing, where we are able to leverage samples from certain activities (e.g., walking, jogging) to improve predictive performance on very different activities (e.g., boxing). In addition, we analyze the relationship between domain similarity and effectiveness of proposed USDA versus SSDA methods. Moreover, we propose a computationally efficient alternative to TGP (Bo and Sminchisescu 2010), and it’s variants, called the direct TGP. We show that our model outperforms a number of baselines, on two public datasets: HumanEva and ETH Face Pose Range Image Dataset. We can also achieve 8–15 times speedup in computation time, over the traditional formulation of TGP, using the proposed direct formulation, with little to no loss in performance.     

Application of enzymatically gelled chitosan solutions to water‐resistant adhesives

An investigation was undertaken on the application of dilute chitosan solutions gelled by tyrosinase‐catalyzed reaction with 3,4‐dihydroxyphenethylamine (dopamine). The tyrosinase‐catalyzed reaction with dopamine conferred water‐resistant adhesive properties to the semidilute chitosan solutions. The viscosity of the chitosan solutions increased highly by the tyrosinase‐catalyzed reaction and the subsequent reactions between o‐quinone compounds and chitosan. These highly viscous, gel‐like modified chitosan materials were allowed to spread onto the surfaces of the glass slides, which were tightly lapped together and held them in water. Tensile shear adhesive strength of over 400 kPa was observed for the modified chitosan samples. The increase in the amino group concentration of the chitosan solutions and the molecular mass of the chitosan used effectively led to the increase in adhesive strength of the glass slides. In addition, in the case where the chitosan solution was gelled by the enzymatic reaction with dopamine in the presence of poly(ethylene glycol), adhesive strength sharply increased at shorter reaction times concomitantly with the increase in the viscosity of the chitosan solutions because the tyrosinase activity effectively was retained by poly(ethylene glycol). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1818–1827, 2007     

Properties of networks obtained by internal plasticization of epoxy resin with aromatic and aliphatic glycidyl compounds

In order to improve the fracture properties of p, p′-diaminodiphenylmethane-cured epoxy resin, various kinds of aromatic and aliphatic glycidyl compounds were investigated as a modifier at an amount of 30 wt %. Several compounds promoted the fracture toughness. In any glycidyl compounds, however, heat resistance was decreased by the modification. The dynamic mechanical properties of the modified epoxy resins were measured. The crosslinking density ρ was calculated from the theory of rubber elasticity, and the mechanical properties of the resins were discussed in regard to the crosslinking density. Tensile strength was scarcely affected by the crosslinking density. Elongation at break and Izod impact strength increased remarkably with decrease in crosslinking density. The fracture toughness K_Ic- increased with decrease in crosslinking density except at small ρ.     

Development of three-electrode type micro-electrochemical reactor on anodized aluminum with photon rupture and electrochemistry

Photon rupture with a focused single pulse of pulsed YAG-laser irradiation was used to fabricate an aluminum electrochemical micro-reactor. Porous type anodic oxide film formed on aluminum specimens was irradiated in solutions with a pulsed Nd-YAG laser beam through a convex lens to fabricate micro-channels, micro-electrode, and through holes (for reference electrode, solution inlet, and outlet). During irradiation, specimens were moved by a computer controlled XYZ stage. After irradiation, the surface of the micro-channel and through hole were again treated to form anodic oxide film and the surface of the micro-electrode was treated electrochemically to provide an Au layer. The calculated volume of the micro-reactor including micro-channel and through holes is about 1.5 μl. The cyclic voltammogram of the micro-electrochemical cell was measured in K₃Fe(CN)₆/K₄Fe(CN)₆ with both static and flowing solution at different scanning rates. The anodic and cathodic peak currents were measured and the values depended on scanning rate and ion concentration when the solution was static. With the flowing solution, limiting currents were observed and the anodic limiting current was increased with the cubic root of the solution flow rate.     

Hydrogen adsorption and hydrogen evolution reaction on a polycrystalline Pt electrode studied by surface-enhanced infrared absorption spectroscopy

Hydrogen evolution reaction (HER) on a polycrystalline Pt electrode has been investigated in Ar-purged acids by surface-enhanced infrared absorption spectroscopy and electrochemical kinetic analysis (Tafel plot). A vibrational mode characteristic to H atom adsorbed at atop sites (terminal H) was observed at 2080-2095 cm⁻¹. This band appears at 0.1 V (RHE) and grows at more negative potentials in parallel to the increase in hydrogen evolution current. Good signal-to-noise ratio of the spectra enabled us to establish the quantitative relation between the band intensity (equivalently, coverage) of terminal H and the kinetics of HER, from which we conclude that terminal H atom is the reaction intermediate in HER and the recombination of two terminal H atoms is the rate-determining step. The quantitative analysis of the infrared data also revealed that the adsorption of terminal H follows the Frumkin isotherm with repulsive interaction.     

Sesamin is a potent and specific inhibitor of Δ5 desaturase in polyunsaturated fatty acid biosynthesis

Incubation with sesame oil increases the mycelial dihomo-γ-linolenic acid content of an arachidonic acid-producing fungus,Mortierella alpina, but decreases its arachidonic acid content [Shimizu, S., K. Akimoto, H. Kawashima, Y. Shinmen and H. Yamada (1989)J. Am. Oil Chem. Soc. 66, 237–241]. The factor causing these effects was isolated and identified to be (+)-sesamin. The results obtained in experiments with both a cell-free extract of the fungus and with rat liver microsomes demonstrated that (+)-sesamin specifically inhibits Δ5 desaturase at low concentrations, but does not inhibit Δ6, Δ9 and Δ12 desaturases. Kinetic analysis showed that (+)-sesamin is a noncompetitive inhibitor (K_i for rat liver Δ5 desaturase, 155 μM). (+)-Sesamolin, (+)-sesaminol and (+)-episesamin, also inhibited only Δ5 desaturases of the fungus and liver. These results demonstrate that (+)-sesamin and related lignan compounds present in sesame seeds or its oil are specific inhibitors of Δ5 desaturase in polyunsaturated fatty acid biosynthesis in both microorganisms and animals. On leave from Suntory Ltd.     

Characterization of styrene–methyl methacrylate–n-butyl acrylate terpolymers. II. Effects of sequence distribution on glass transition temperature

The effects of sequence distribution on the glass transition temperature (T_g) of the title terpolymers prepared by radical polymerization were studied. T_g was examined by thermomechanical analysis. The average diad concentrations, as estimation of sequence distributions were calculated from monomer reactivity ratios. A modified Gibbs–Dimarzio equation for binary copolymers was extended to terpolymers to explain the relation between observed T_g and average diad concentrations. The observed T_g showed good agreement with the calculated values determined by the extended equation.     

Measurement of the melting points of oligomers obtained in the manufacture of poly(ethylene terephthalate)

The melting points (T_m) were measured for oligomers obtained by a direct continuous esterification process between terephthalic acid and ethylene glycol. Multiple regression analyses of data were carried out, and an equation was obtained for predicting melting points with correlation coefficient of ～0.99.     

Preparation of poly(p-phenylene terephthalamide)/poly(vinyl chloride) molecular composite and its thermal and mechanical properties

Poly(p-phenylene terephthalamide) (PPTA) was blended with poly(vinyl chloride) (PVC) by solution-blending method. PPTA was metalated for dissolving in dimethyl sulfoxide. Dimethyl sulfoxide was used as a common solvent. In PPTA/PVC composite, PPTA accelerated the thermal degradation of PVC. PPTA molecules are aggregated as microfibrillar form in PVC matrix. Such microfibrils are dispersed homogeneously in PVC matrix, according to polarizing microscopic observation. The average diameter of the microfibrils becomes smaller in the composite with lower content of PPTA. In the surface region of PPTA microfibrils the intermolecular hydrogen bonds between C? Cl of PVC and N? H of PPTA are formed. Young's modulus and the yield stress at room temperature were higher in the composites than those in PVC. The modulus of the composites was higher, especially at the high temperatures above their glass transition temperatures, than that in PVC. The temperature dependence of modulus can be calculated by using the mechanical model equivalent to the quasi-3-dimensional microfibrillar model which will be approximately applied to the composite structure. It becomes apparent that the modulus of the PPTA microfibrils evaluated by using the mechanical model is higher in the higher molecular weight PPTA.