Structural and Dynamic Characterization of the Molecular Hub Early Region 1A (E1A) from Human Adenovirus

The small‐DNA human adenovirus encodes one of the most versatile molecular hubs, the E1A protein. This protein is essential for productive viral infection in human cells and a vast amount of biologically relevant data are available on its interactions with host proteins. Up to now, however, no high‐resolution structural and dynamic information on E1A is available despite its important biological role. Among the different spliced variants of E1A, two are expressed at high level in the early stage of infection. These are 243 and 289 residues isoforms. Herein, we present their NMR characterization, showing that they are both highly disordered, but also demonstrate a certain heterogeneous behavior in terms of structural and dynamic properties. Furthermore, we present the characterization of the isolated domain of the longer variant, known as CR3. This study opens the way to understanding at the molecular level how E1A functions.     

Molecular‐level structures at poly(4‐vinyl pyridine)/acid interfaces probed by nonlinear vibrational spectroscopy

The molecular structures of the interfaces between a solid poly(4‐vinyl pyridine) (P4VP) surface and poly(acrylic acid) (PAA) as well as hydrochloric acid (HCl) solutions were probed using sum frequency generation (SFG) vibrational spectroscopy in situ in real time. Spectroscopic results clearly reveal that the PAA molecules are adsorbed onto the P4VP surface via hydrogen bonding at the P4VP/PAA solution interface while the P4VP surface is protonated at the P4VP/HCl solution interface. Consequently, the water molecules near the interfaces are strongly perturbed by these two interactions, exhibiting different orderings at the two interfaces. This work clearly demonstrates the power of studying the interfacial molecular‐level structures via nonlinear vibrational spectroscopy when molecular adsorption happens at the solid–liquid interface and paves a way for our future study on tracing the adsorption dynamics of polymer chains onto solid surfaces. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 848–852     

Quantitative modeling and mapping of blistering zone of the Magoksa Temple stone pagoda (13th century,Republic of Korea) by graduated heating thermography

Blistering occurring at the stone’s subsurface layer is easily overlooked compared to different deterioration types, so conservation treatments are not applied often. Therefore, non-destructive detection and mapping of blistering zones with the infrared thermography are very important for preservation of the original forms of stone monuments. In this study, the critical temperature and transitional zone of the blistering zone were established by drawing the temperature distribution curve and the mapping for blistering zone was completed by monochrome process and extraction of vector lines. Analysis of the blistering deterioration degree of the Magoksa Temple stone pagoda with the quantitative modeling yielded a total area and average rate of blistering zones of approximately 2.6 m² and 7.4%, respectively. Thus, there is a high probability of scaling on the stone pagoda (area of approximately 2.6 m²) if conservation treatment is not applied to the blistering zones as early as possible. Therefore, the blistering zones require joining and filling, and state changes of the blistering zones should be continuously monitored after completion of the intensive conservation treatments. Modeling will improve the reliability of deterioration maps by mapping for blistering zone; most deterioration maps to date have overlooked blistering zones.     

Sulphur dioxide insertion into tin―carbon bonds: solvent effects and the nature of the transition state

Data describing the insertion of sulphur dioxide into the carbon―tin bond of a range of substituted phenyltrimethyltin compounds in methanol and benzene solvents have been reconsidered. The reaction in methanol is cleanly second order, but the reaction in benzene has both a second‐order and third‐order component, the latter ascribable to an initial equilibrium formation of a SO₂ complex with the phenyl ring followed by the insertion of a second SO₂ molecule into the carbon–tin bond. Molecular orbital calculations have identified the transition states (TS) and the favoured reaction pathways for the second‐order and third‐order reaction pathways in benzene. The effects of solvents on TS and enthalpies of reaction have also been examined. New insights into the types of TS involved in electrophilic substitution reactions are revealed. Copyright © 2013 John Wiley & Sons, Ltd.     

Study of electron-vibrational interaction and concentration quenching effect of Cu+ ions in lithium based sulphate phosphors

The objective of this work is to study electron-vibrational interaction (EVI) and concentration quenching and their manifestation in experimental photoluminescence spectra of Cu⁺ ion in various lithium based phosphors namely, Li₂SO₄, LiNaSO₄ and LiKSO₄. The main parameters of EVI, such as the Stokes shift, Huang-Rhys factor and zero-phonon line positions, were estimated. The studied systems shows strong electron lattice coupling. The validity of results was established by modeling the shape of the emission spectra, which was found to be in good agreement with experimental photoluminescence spectra. The concentration quenching study is also carried out for these compounds. The studied systems correspond to the nearest neighbor energy transfer mechanism.     

Concise Synthesis of Photocleavable Molecular Tag for Laser Desorption Ionization Mass Spectrometry via Fries Reaction

Abstract

A new synthetic route for the photocleavable molecular tag for laser desorption ionization mass spectrometry (LDI-MS) was achieved using the Fries reaction of 2,6-dimethylphenyl ester as its key reaction. Zirconium chloride was used as uniquely efficient adjuvant to promote the reaction. The molecular tag was obtained in five steps without chromatographic purification.

Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file.     

Organic field effect transistor composed by fullerene C60 and heterojunctions

We present a study of the complex electronic behavior of a fullerene (C₆₀) molecule attached to six leads (heterojunctions), which works as a three-dimension rectifier. In addition, we confirmed that the fullerene works not only as an electron donor, but also as barrier and transport channel to electrons through the molecule. Moreover, when the phenylpropanodinilla (PPP) lead is orthogonally subjected to bias voltage, the charge distribution and the current displays regions of saturation and resonance similar to semiconductor devices. In order to understand the electronic transport in the molecule, we applied non-equilibrium green function (NEGF) method and performed Fowler-Nordheim (FN) and Millikan-Lauritsen (ML) analyses. The ML curves proved to be sufficient to describe the FN characteristics. In this work, we report the theoretical design for electronic transport of a 3D device (6-terminal).     

Effect of nematic ordering on the elasticity and yielding in disordered polymeric solids

The relation between elasticity and yielding is investigated in a model polymer solid by Molecular‐Dynamics simulations. By changing the bending stiffness of the chain and the bond length, semicrystalline and disordered glassy polymers — both with bond disorder — as well as nematic glassy polymers with bond ordering are obtained. It is found that in systems with bond disorder the ratio τ_Y/G between the shear yield strength τ_Y and the shear modulus G is close to the universal value of the atomic metallic glasses. The increase of the local nematic order in glasses leads to the increase of the shear modulus and the decrease of the shear yield strength, as observed in experiments on nematic thermosets. A tentative explanation of the subsequent reduction of the ratio τ_Y/G in terms of the distributions of the per‐monomer stress is offered. © 2017 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2017 , 55, 1760–1769     

Organometallic Molecular Wires with Thioacetylene Backbones,trans-{RS-(C≡C)n}2Ru(phosphine)4: High Conductance through Non-Aromatic Bridging Linkers

In this work, the design, synthesis, and single-molecule conductance of ethynyl- and butadiynyl-ruthenium molecular wires with thioether anchor groups [RS=n-C₆H₁₃S, p-tert-Bu−C₆H₄S), trans-{RS−(C≡C)_n}₂Ru(dppe)₂ (n=1 ( 1^R ), 2 ( 2^R ); dppe: 1,2-bis(diphenylphosphino)ethane) and trans-(n-C₆H₁₃S−C≡C)₂Ru{P(OMe)₃}₄ 3^hex ] are reported. Scanning tunneling microscope break-junction study has revealed conductance of the organometallic molecular wires with the thioacetylene backbones higher than that of the related organometallic wires having arylethynylruthenium linkages with the sulfur anchor groups, trans-{p-MeS−C₆H₄-(C≡C)_n}₂Ru(phosphine)₄ 4 ⁿ (n=1, 2) and trans-(Th−C≡C)₂Ru(phosphine)₄ 5 (Th=3-thienyl). It should be noted that the molecular junctions constructed from the butadiynyl wire 2^R , trans-{ Au −RS−(C≡C)₂}₂Ru(dppe)₂ ( Au : gold metal electrode), show conductance comparable to that of the covalently linked polyynyl wire with the similar molecular length, trans-{ Au −(C≡C)₃}₂Ru(dppe)₂ 6³ . The DFT non-equilibrium Green's function (NEGF) study supports the highly conducting nature of the thioacetylene molecular wires through HOMO orbitals.