Supercritical <Emphasis Type="Italic">n</Emphasis>-butane isomerization

Supercritical n-butane isomerization over the solid acid catalysts sulfated zirconia, TiO₂-supported H₄[Si(W₃O₁₀)₄] · xH₂O (Keggin-type heteropoly acid), and H-mordenite is studied in a flow reactor. The critical parameters of n-butane are calculated for a wide range of reaction conditions. Changing from gaseous n-butane to supercritical n-butane markedly extends the lifetime of the catalysts. Under supercritical conditions, the activity and selectivity of the catalysts are invariable, provided that the density of the reaction mixture is in the vicinity of the critical density of n-butane. After the catalysts are deactivated in the gas medium, they can be partially or completely reactivated in the supercritical fluid.Translated from Kinetika i Kataliz, Vol. 45, No. 6, 2004, pp. 942–946.Original Russian Text Copyright © 2004 by Bogdan, Klimenko, Kustov, Kazanskii.     

Coherent structures and their influence on the dynamics of aeroelastic panels

A panel forced by a supersonic unsteady flow is numerically investigated using a finite difference method, a Galerkin approach, and proper orthogonal decomposition (POD). The aeroelastic model investigated is based on piston theory for modeling the flow-induced forces, and von Karman plate theory for modeling the panel. Structural non-linearity is considered, and it is due to the non-linear coupling between bending and stretching. Several novel facets of behavior are explored, and key aspects of using a Galerkin method for modeling the dynamics of the panel exhibiting limit cycle oscillations and chaos are investigated. It is shown that multiple limit cycles may co-exist, and they are both symmetric and asymmetric. Furthermore, the level of spatial coherence in the dynamics is estimated by means of POD. Reduced order models for the dynamics are constructed. The sensitivity to initial conditions of the non-linear aeroelastic system in the chaotic regime limits the capability of the reduced order models to identically model the time histories of the system. However, various global characteristics of the dynamics, such as the main attractor governing the dynamics, are accurately predicted by the reduced order models. For the case of limit cycle oscillations and stable buckling, the reduced order models are shown to be accurate and robust to parameter variations.     

Effective Field Theory Description of the Higher Dimensional Quantum Hall Liquid

We derive an effective topological field theory model of the four dimensional quantum Hall liquid state recently constructed by Zhang and Hu. Using a generalization of the flux attachment transformation, the effective field theory can be formulated as a U(1) Chern–Simons theory over the total configuration space CP₃, or as a SU(2) Chern–Simons theory over S⁴. The new quantum Hall liquid supports various types of topological excitations, including the 0-brane (particles), the 2-brane (membranes), and the 4-brane. There is a topological phase interaction among the membranes which generalizes the concept of fractional statistics.     

Hyper-Hermitian Quaternionic Kähler Manifolds

We call a quaternionic Kähler manifold with nonzero scalar curvature, whosequaternionic structure is trivialized by a hypercomplex structure, ahyper-Hermitian quaternionic Kähler manifold. We prove that every locallysymmetric hyper-Hermitian quaternionic Kähler manifold is locally isometricto the quaternionic projective space or to the quaternionic hyperbolic space.We describe locally the hyper-Hermitian quaternionic Kähler manifolds withclosed Lee form and show that the only complete simply connected suchmanifold is the quaternionic hyperbolic space.     

Fluorescence Study of Sinapic Acid Interaction with Bovine Serum Albumin and Egg Albumin

The mechanism of interaction of protein with compounds used for preparation of matrices for matrix-assisted laser desorption ionization–mass spectrometry (MALDI-MS) methods is unknown. This paper reports the investigation of this mechanism for sinapic acid and bovine serum albumin and egg albumin. To examine these interactions in water a fluorescence method was applied. Sinapic acid can exist in three different forms, depending on pH: undissociated and with one or two deprotonated groups. pK_as of these states are: 4.47 for the COOH group and 9.21 for the OH group [1]. Therefore the interactions were examined at pH: 2.0, 6.4, and 10.5. The results show that sinapic acid at pH 10.5, being a bivalent anion, does not form any complex with these two proteins. At pH 2.0, sinapic acid, being undissociated, interacts weakly with egg albumin. Sinapic acid does not interact with bovine serum albumin at this pH. At pH 6.4, sinapic acid interacts only with bovine serum albumin. Parameters of the sinapic acid and bovine serum albumin complex were calculated based on the theory of multiple equlibria: the total number of binding sites, N = 15; the binding constant, K = 600 M ^–1; and the Hill's coefficient, j = 0.97. These parameters indicate (but not definitively because a large saturation was not obtained) that this is a simple binding of sinapic acid to bovine serum albumin with the binding sites of the same type.     

Synthesis of Monofunctionalized Silsesquioxanes (RSiMe2O)(iBu)7Si8O12 via Alkene Hydrosilylation

The research presented in this work comprehensively describes hydrosilylation of a wide spectrum of alkenes which contain one or more reactive groups with (HSiMe₂O)(iBu)₇Si₈O₁₂, in the presence of different types of catalysts. Special attention is paid to the influence of alkene, catalyst, and reaction conditions on process effectiveness and selectivity by the precise monitoring of the experiments with in situ FTIR and NMR spectroscopies. More than twenty silsesquioxanes bearing reactive groups (OH, Br, NR₂, CO, COOR, NCO, epoxy, SiR₃) commonly used in organic and polymer chemistry, were obtained, isolated and characterized by ¹H, ¹³C, ²⁹Si NMR and MALDI TOF. Importantly, in the presented syntheses, commercially available reagents and catalysts were used, meaning that the presented methods could be easily repeated, rapidly scaled up, and widely applied.     

Molecular docking performance evaluated on the D3R Grand Challenge 2015 drug-like ligand datasets

The D3R Grand Challenge 2015 was focused on two protein targets: Heat Shock Protein 90 (HSP90) and Mitogen-Activated Protein Kinase Kinase Kinase Kinase 4 (MAP4K4). We used a protocol involving a preliminary analysis of the available data in PDB and PubChem BioAssay, and then a docking/scoring step using more computationally demanding parameters that were required to provide more reliable predictions. We could evidence that different docking software and scoring functions can behave differently on individual ligand datasets, and that the flexibility of specific binding site residues is a crucial element to provide good predictions.     

Prediction of cyclohexane-water distribution coefficients for the SAMPL5 data set using molecular dynamics simulations with the OPLS-AA force field

All-atom molecular dynamics simulations were used to predict water-cyclohexane distribution coefficients \(D_{cw}\) of a range of small molecules as part of the SAMPL5 blind prediction challenge. Molecules were parameterized with the transferable all-atom OPLS-AA force field, which required the derivation of new parameters for sulfamides and heterocycles and validation of cyclohexane parameters as a solvent. The distribution coefficient was calculated from the solvation free energies of the compound in water and cyclohexane. Absolute solvation free energies were computed by an established protocol using windowed alchemical free energy perturbation with thermodynamic integration. This protocol resulted in an overall root mean square error in \(\log D_{cw}\) of almost 4 log units and an overall signed error of ?3 compared to experimental data. There was no substantial overall difference in accuracy between simulating in NVT and NPT ensembles. The signed error suggests a systematic error but the experimental \(D_{cw}\) data on their own are insufficient to uncover the source of this error. Preliminary work suggests that the major source of error lies in the hydration free energy calculations.     

Halogen aggregation in chlorobenzene-<Emphasis Type="Italic">o</Emphasis>-dichlorobenzene solutions

The chlorobenzene (CB)–o-dichlorobenzene (o-DCB) liquid system has been studied by classical molecular dynamics simulation over the entire range of concentrations. The structure of the solutions is characterized by using radial angular distribution functions for the distances between the planes of benzene rings and the angle between them, using radial distribution functions for the distances between chlorine atoms, and by calculating the self-diffusion coefficients and local dipole moments. Halogen aggregation in the pure components and solutions is analyzed. It is found that in pure CB, chlorine aggregates consisting of four to ten molecules are most likely to form. The sizes of chlorine aggregates increase with increasing o-DCB concentration, and at a o-DCB concentration of 0.50-1.00 ppm, an extended system of chlorine–chlorine contacts is formed. In pure o-DCB, the chlorine aggregation system includes 99% of the molecules of the simulated system. The agglomeration of solute molecules in the range of dilute solutions (x < 0.1 ppm) is investigated.     

Symmetry‐Breaking Charge Transfer and Hydrogen Bonding: Toward Asymmetrical Photochemistry

Symmetry‐breaking charge transfer upon photoexcitation of a linear A‐π‐D‐π‐A molecule (D and A being electron donating and accepting groups) could be visualized using ultrafast time‐resolved infrared spectroscopy by monitoring the CN stretching modes on the A units. Whereas in apolar solvents, the S₁ state remains symmetric and quadrupolar, symmetry breaking occurs within ca. 100 fs in polar solvents as shown by the presence of two CN bands, instead of one in apolar solvents, with a splitting that increases with polarity. In protic solvents, symmetry breaking is significantly amplified by H‐bonding interactions, which are the strongest at the CN group with the highest basicity. In strongly protic solvents, the two CN bands transform in about 20 ps into new bands with a larger splitting, and the lifetime of the S₁ state is substantially reduced. This is attributed to the formation of an excited asymmetric tight H‐bond complex.