Ab Initio Study of the Dehydrogenation of 3-Pyrroline, 2,5-Dihydrofuran and 2,5-Dihydrothiophene

Abstract

The nature of the transition state structures of the decomposition of 3-pyrroline (1), 2,5-dihydrofuran (2) and 2,5-dihydrothiophene (3) were investigated usingab initio Molecular Orbital (MO) and Density Factional Theory (DFT) methods. The energy barrierof the decomposition of compound 1 is smaller than compound 2 and compound 2 is smaller than compound 3. The energy barriers for the decomposition of compounds 1–3 are 46.20, 50.17, and 61.34 kcal mol^?1, respectively, which is calculated by B3LYP/6-31G^*//HF/6-31G^* level of theory. Which is ingood agreement with reported experimental data. Contrary to the previously reported data, the distance between the cis-2-and-5-hydrogen atoms in compound 1 is greater than compound 2. The transition-state structures of the decomposition of compounds 1–3 are formed by interaction of the cis-2-and-5-hydrogen atoms. Also, the rings of compounds 1–3 in the transition state structures are puckered.     

Molecular simulations of solute transport in xylose isomerase crystals

Cross-linked enzyme crystals (CLECs) enclose an extensive regular matrix of chiral solvent-filled nanopores, via which ions and solutes travel in and out. Several cross-linked enzyme crystals have recently been used for chiral separation and as biocatalysts. We studied the dynamics of solute transport in orthorhombic d-xylose isomerase (XI) crystals by means of Brownian dynamics (BD) and molecular dynamics (MD) simulations, which show how the protein residues influence the dynamics of solute molecules in confined regions inside the lattice. In the BD simulations, coarse-grained beads represent solutes of different sizes. The diffusion of S-phenylglycine molecules inside XI crystals is investigated by long-time MD simulations. The computed diffusion coefficients within a crystal are found to be orders of magnitude lower than in bulk water. The simulation results are compared to the recent experimental studies of diffusion and reaction inside XI crystals. The insights obtained from simulations allow us to understand the nature of solute-protein interactions and transport phenomena in CLECs, which is useful for the design of novel nanoporous biocatalysts and bioseparations based on CLECs.     

Failure of standard thermodynamics in planck scale black hole system

The final stage of the black hole evaporation is a matter of debates in the existing literature. In this paper, we consider this problem within two alternative approaches: noncommutative geometry (NCG) and the generalized uncertainty principle (GUP). We compare the results of two scenarios to find a relation between parameters of these approaches. Our results show some extraordinary thermodynamical behavior for Planck size black hole evaporation. These extraordinary behavior may reflect the need for a fractal non-extensive thermodynamics for Planck size black hole evaporation process.     

Layered Surface Acoustic Wave Hydrogen Sensor Based on Polyethylaniline Nanofibers

Here we report on a layered Surface Acoustic Wave (SAW) gas sensor featuring polyethylaniline nanofibers as the active layer. A rapidly-mixed reaction was employed to synthesize polyethylaniline nanofibers. The product was deposited on a microfabricated ZnO/36° YX LiTaO₃ SAW transducer. Scanning Electron Microscopy (SEM) and Ultraviolet-visible spectroscopy (UV-vis) were utilized to characterize the nanomaterials. The novel sensor was tested towards different concentrations of hydrogen at room temperature. It was observed that the sensor maintained a stable baseline with good repeatability. Hence, the sensor is expected to be potentially attractive for industrial applications.