The effect of disulfide bonds on protein folding,unfolding, and misfolding investigated by FT–Raman spectroscopy

Disulfide bond is relevant to many protein folding/unfolding functions and conformational diseases. To elucidate the effects of disulfide bonds on protein folding, unfolding, and misfolding, we performed Fourier transform–Raman measurements on serial chemical‐induced denaturations of bovine serum albumin (BSA). By directly monitoring Raman stretching at S–S (~507 cm⁻¹), S–H (~2566 cm⁻¹), amide I (1655 cm⁻¹ for α‐helix; 1667 cm⁻¹ for β‐sheet structure), and amide III (>1300 cm⁻¹ for α‐helix; 1246 cm⁻¹ for β‐sheet structure), the status of disulfide bonds and secondary structure of BSA at different states were elucidated. Both disulfide bonds and secondary structure (mostly in α‐helix) of BSA appeared relatively stable even when the protein was unfolded by urea solution. However, disulfide bonds were completely reduced and protein secondary structure changed from α‐helix to a relatively β‐sheet dominant when the protein was modified by the mixed solution of urea and dithiothreitol (urea/DTT). Adhering to these structural changes, the protein proceeded to different degrees of polymerization. BSA would aggregate into a high molecular mass (over 700 kDa) of protein ensemble when it was exposed to the mixed urea/DTT solution. An irreversible change in S–S/S–H conversion and secondary structure was responsible for protein misfolding. We demonstrate here that Fourier transform–Raman directly probe S–S/S–H conversion and secondary structural change of BSA at different states, and these results clearly indicate that disulfide bonds and secondary structure of BSA serve as concrete frameworks to stabilize protein structure. As the frameworks collapse, the protein undergoes an irreversible structural change and results in protein misfolding. Copyright © 2016 John Wiley & Sons, Ltd.     

Two‐dimensional reactive scattering with transmitted quantum trajectories

A simple and easy‐to‐implement method is presented for the study of time‐dependent reaction dynamics by propagating an ensemble of transmitted quantum trajectories. During the trajectory evolution, reflected trajectories are gradually removed and all the remaining trajectories represent the transmitted subensemble. The removal process of reflected trajectories avoids numerical instabilities arising from node formation in the reactant region, and allows stable long‐time propagation of transmitted trajectories. This method is applied to a two‐dimensional model chemical reaction. Excellent computational results are obtained for the time‐dependent reaction probabilities evaluated by the time integration of the probability flux. © 2014 Wiley Periodicals, Inc.     

Nonlinear bending of rectangular orthotropic plate with two free edges and the other edges having nonuniform rotational flexibility

this paper presents a series solution to von Kármán nonlinear equations of a rectilinearly orthotropic rectangular plate under the combined action of lateral load and in-plane tension with the titled edge restraints. In the formulation the edge moments are replaced by an equivalent pressure near the edges. Using generalized double Fourier series for the deflection and stress function, governing equations are reduced to an infinite set of algebraic equations for coefficients in these series. Numerical results for deflections, bending moments and in-plane forces are graphically presented for various values of aspect ratio and material properties and for different edge conditions.     

Postbuckling of angle-ply and anisotropic plates

Summary An analysis based on the von Kármán-type large-deflection equations of plates is presented for the postbuckling behavior of homogeneous and symmetrically laminated anisotropic rectangular plates. Boundary conditions for both simply supported and clamped edges are considered. A solution is obtained by expressing the force function and transverse deflection as double series involving the appropriate beam eigen-functions. Numerical results are presented for graphite-epoxy angle-ply laminates and homogeneous anisotropic plates. In the cases of buckling of anisotropic plates and postbuckling of isotropic and orthotropic plates, the present solution is in good agreement with existing solutions.

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Übersicht Es wird das Nachbeulverhalten von homogenen, symmetrisch geschichteten, anisotropen Rechteckplatten auf der Grundlage der von Kármán angegebenen Platten-Gleichungen für große Auslenkungen untersucht. Dabei werden sowohl einfach aufliegende, wie auch eingespannte Ränder als Randbedingungen berücksichtigt. Lösungen werden dadurch gewonnen, daß die Belastungsfunktion und die Querauslenkung als doppelte Reihen von geeigneten Balken-Eigenfunktionen angesetzt werden. Für Graphit-Epoxid-Schichtplatten und anisotrope homogene Platten werden numerische Ergebnisse mitgeteilt. Die erhaltenen Lösungen stimmen in den Fällen des Beulens von anisotropen Platten sowie des Nachbeulens von isotropen und orthotropen Platten gut mit bekannten Lösungen überein.

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The results presented in this paper were obtained in the course of research sponsored by the National Research Council of Canada.     

IR,Raman, and Surface‐enhanced Raman Spectroscopic Study on Triruthenium Dipyridylamide Diruthenium Nickel Dipyridylamide Family: Metal‐metal Bonding and Structures

We report the infrared, Raman, and surface‐enhanced Raman scattering (SERS) spectra of triruthenium dipyridylamido complexes and of diruthenium mixed nickel metal‐string complexes. From the results of analysis on the vibrational modes, we assigned their vibrational frequencies and structures. The infrared band at 323–326 cm^?1 is assigned to the Ru₃ asymmetric stretching mode for [Ru₃(dpa)₄Cl₂]^0–2+. In these complexes we observed no Raman band corresponding to the Ru₃ symmetric stretching mode although this mode is expected to have substantial Raman intensity. There is no frequency shift in the Ru₃ asymmetric stretching modes for the complexes with varied oxidational states. No splitting in Raman spectra for the pyridyl breathing line indicates similar bonding environment for both pyridyls in dpa^– , thus a delocalized structure in the [Ru₃]^6–8+ unit is proposed. For Ru₃(dpa)₄(CN)₂ complex series, we assign the infrared band at 302 cm^?1 to the Ru₃ asymmetric stretching mode and the weak Raman line at 285 cm^?1 to the Ru₃ symmetric stretching. Coordination to the strong axial ligand CN^– weakens the Ru‐Ru bonding. For the diruthenium nickel complex [Ru₂Ni(dpa)₄Cl₂]^0–1+, the diruthenium stretching mode ν_Ru‐Ru is assigned to the intense band at 327 and 333 cm^?1 in the Raman spectra for the neutral and oxidized forms, respectively. This implies a strong Ru‐Ru metal‐metal bonding.     

Influence of bromoalkyloxy side chain on mesomorphic behavior in heterocyclic 7-(4-bromoalkyloxy)-3-(4′-decyloxyphenyl)-4H- 1-benzopyran-4-ones

A new homologous series of isoflavone-based ethers,7-(4-bromoalkyloxy)-3-(4’-decyloxyprienyl)-4H-1-benzopyran-4-ones were synthesized and characterized.The mesomorphic properties of all homologues were investigated by differential scanning calorimetry(DSC) and polarizing optical microscopy(POM).Enantiotropic smectic A(SmA) phase was observed for all homologues.The structure-property study was carried out by comparing the mesomorphic behavior of the homologues with those previously reported analogues.The bromine atom from the alkyloxy side chain of the benzene ring fused to the heterocyclic moiety was found to be capable of changing the mesomorphic properties.     

Determination of melamine in milk powder using gas chromatography-high-resolution isotope dilution mass spectrometry

A GC-high-resolution isotope dilution MS (IDMS) method for the quantification of melamine in milk powder is described. The developed technique is compared to the LC-IDMS/MS technique, typically used for the determination of melamine in various matrices. The accuracy of the GC-high-resolution IDMS method was demonstrated when a small degree of equivalence was obtained in a regional comparative study involving the determination of melamine in milk powder.     

Enantioselective de novo synthesis of 4-deoxy-D-hexopyranoses via hetero-Diels-Alder cycloadditions: total synthesis of ezoaminuroic acid and neosidomycin

The de novo synthesis of carbohydrates constitutes an important aspect of organic chemistry, and its application toward deoxy sugars is particularly noteworthy in targeting biologically active compounds. The enantioselective preparation of 4-deoxy-D-ribo-, 4-deoxy-D-lyxo-, and 4-deoxy-D-xylo-hexopyranosides, along with their uronate counterparts has been successfully accomplished using hetero-Diels-Alder reactions as the key step. Jacobsen chromium(III) catalyst and a titanium-binaphthol complex have been used to successfully catalyze diene and aldehyde cycloadditions, leading to optically active dihydropyran templates. 6-Hydroxydesosamine, orthogonally protected ezoaminuroic acid, and neosidomycin were synthesized using a comparative study. Also, a novel chiron approach to 4-deoxy-lyxo-hexopyranosiduronic acid methyl ester derivatives was efficiently accomplished starting from readily accessible starting materials. This work represents a systematic and comprehensive study toward a de novo synthesis of 4-deoxy-hexopyranoses via enantioselective hetero-Diels-Alder reactions.     

Liquid-phase catalytic transfer hydrogenation and cyclization of levulinic acid and its esters to γ-valerolactone over metal oxide catalysts

Levulinic acid and its esters are converted to γ-valerolactone over metal oxide catalysts by catalytic transfer hydrogenation via the Meerwein-Ponndorf-Verley reaction.