Aromaticity as a Quantitative Concept. 6. Aromaticity Variation with Molecular Environment

The classical aromaticity of most heterocycles, and of some carbocycles such as azulene, increases with the polarity of the medium as shown by experimental and calculated bond lengths, aromaticity indices, and dipole moments.     

2016 Liquid Surface X-ray Scattering School: Data Analysis

X-ray surface scattering is the most powerful probe of near-atomic-level structure at liquid-vapor and liquid-liquid interfaces. Synchrotron X-ray sources throughout the world have specialized instruments available for the study of these interfaces. Since 2002, the ChemMatCARS facility at Sector 15 of the Advanced Photon Source near Chicago, IL, USA, has assisted general users in the study of liquid surfaces and interfaces to model processes of interest to physical, chemical, and biological scientists. ChemMatCARS recently sponsored its third School for Liquid Surface X-ray Scattering (LSXS 2016), held at the Advanced Photon Source (APS) at Argonne National Laboratory on May 12–13, 2016. Methods of data analysis were featured, providing students with the opportunity to fit data, analyze errors, and participate in virtual experiments. Techniques covered this year included X-ray reflectivity (XR), grazing incidence diffraction (GID), X-ray fluorescence near total reflection (XFNTR), and X-ray photon correlation spectroscopy (XPCS). This is the third year that the LSXS School has been held at APS, the first year being in 2007 and the second in 2012.     

ESI‐MS studies of the non‐covalent interactions between biologically important metal ions and N‐sulfonylcytosine derivatives

The aim of this report is to present the electrospray ionization mass spectrometry results of the non‐covalent interaction of two biologically active ligands, N‐1 ‐ (p‐toluenesulfonyl)cytosine, 1‐TsC, 1 and N‐1 ‐ methanesulfonylcytosine, 1‐MsC, 2 and their Cu(II) complexes Cu(1‐TsC‐N3)₂Cl₂, 3 and Cu(1‐MsC‐N3)₂Cl₂ and 4 with biologically important cations: Na⁺, K⁺, Ca²⁺, Mg²⁺ and Zn²⁺. The formation of various complex metal ions was observed. The alkali metals Na⁺ and K⁺ formed clusters because of electrostatic interactions. Ca²⁺ and Mg²⁺ salts produced the tris ligand and mixed ligand complexes. The interaction of Zn²⁺ with 1–4 produced monometal and dimetal Zn²⁺ complexes as a result of the affinity of Zn²⁺ ions toward both O and N atoms. Copyright © 2016 John Wiley & Sons, Ltd.     

On an Inequality for the Entropy of a Probability Distribution

We strengthen a theorem of Allouche, Mendès France and Tenenbaum and also a recent generalization of Daróczy.     

Chirality of amyloid suprastructures

Amyloids are pathological fibrillar aggregates of proteins related to more than 20 different diseases. Amyloid fibers have a characteristic cross-beta structure consisting of a series of beta-strands extended perpendicular to the fiber axis and joined by hydrogen bonds parallel to the fiber direction. Fibril aggregation results in helical suprastructures. Here we used high-resolution SEM and cryo-SEM for the study of chirality in the amyloid suprastructure. We found that amyloids of Abeta1-40 and hen lysozyme form at all hierarchical levels always and only left-handed helices. In contrast, amyloid fibers formed by the N-terminal sequence of serum amyloid A (SAA1-12) consist of right-handed helices exclusively. Consistently, the peptide enantiomer, formed of (R)-aminoacids, aggregates exclusively in left-handed helices. We conclude that the opposite handedness of the SAA1-12 amyloids is an intrinsic feature of the peptide structure. The left-handed chirality observed for the Abeta1-40 and hen lysozyme amyloid suprastructures is consistent with the conventional beta-sheet structural model. In contrast, the right-handedness observed in (all-S) SAA1-12 fibers indicates that the cross-beta structure of SAA1-12 fibers is probably not formed of beta-sheets. Whatever the answer to the dilemma of the right-handed helicity of SAA1-12 amyloid fibers is, its existence shows that the supramolecular chirality of amyloid fibers is not only dictated by the molecular chirality of the component molecules but also by their structural organization.     

Path Integral for an Effective Two Level Atom in a Kerr-Like Medium and Stark Shift with a Pseudo Hermitian Hamiltonian

We use the coherent state path integral and a angular model for the spin to solve the generalized Jaynes-Cummings model with a pseudo-hermitian Hamiltonian and nonlinear Kerr cavity. The propagators are given explicitly as perturbation series. These are summed up exactly. The energy spectrum and the bi-orthonormal basis of states are deduced.     

Quantum chemical modelling of the effect of proline residues on peptide conformation

Semiempirical AM1 calculations were performed for quantum chemically optimized minimum-energy conformations of L -alanine oligomers (A)_n at n = 7 and their derivatives containing one, two, or three proline residues at various positions along the peptide chain. The effect of proline residues on the peptide conformation was quantified in terms of the conformational “strain energy” and also analyzed in terms of the spatial compatibility of peptides. The defined “strain energy” corresponds to the transformation of the polyalanine peptide from its minimum conformation to the conformation corresponding to that of the proline-containing peptide. The results of calculations indicate that the “strain effect” of proline residues is additive at all locations along the peptide chain, except at the first and the second positions of its N-terminal part. Also, the regular α-helical polyalanine structure was most significantly altered by the presence of some specific motifs around the proline location in the peptide. This, in turn, has its implications in the prediction of the protein secondary structure, as well as in the design of peptide inhibitors and substrates for enzymes and receptors. © 1998 John Wiley & Sons, Inc. Int J Quant Chem 66 : 391–396, 1998     

Comparison of Algorithms for the Degree Constrained Minimum Spanning Tree

The Degree Constrained Minimum Spanning Tree (DCMST) on a graph is the problem of generating a minimum spanning tree with constraints on the number of arcs that can be incident to vertices of the graph. In this paper we develop three heuristics for the DCMST, including simulated annealing, a genetic algorithm and a method based on problem space search. We propose alternative tree representations to facilitate the neighbourhood searches for the genetic algorithm. The tree representation that we use for the genetic algorithm can be generalised to other tree optimisation problems as well. We compare the computational performance of all of these approaches against the performance of an exact solution approach in the literature. In addition, we also develop a new exact solution approach based on the combinatorial structure of the problem. We test all of these approaches using standard problems taken from the literature and some new test problems that we generate.     

Effect of partial oxidation and repolarization of TiC-derived nanoporous carbon electrodes on supercapacitor performance using a pH-neutral aqueous electrolyte

Journal of Solid State Electrochemistry - The present study considers TiC-derived carbon (CDC) and its partially oxidized derivative (ox-red-CDC) as potential electrode materials for pH-neutral...     

Continuity of Almost Harmonic Maps with the Perturbation Term in a Critical Space

The authors study the continuity estimate of the solutions of almost harmonic maps with the perturbation term f in a critical integrability class (Zygmund class) L^n/2 log^q L, n is the dimension with n ≥ 3. They prove that when q > n/2 the solution must be continuous and they can get continuity modulus estimates. As a byproduct of their method, they also study boundary continuity for the almost harmonic maps in high dimension.