Chemoenzymatic and yeast-catalysed synthesis of diastereomeric ethyl γ-phenyl and γ-(n-pyridyl)paraconates

The synthesis of γ-phenyl and γ-(n-pyridyl)paraconates was accomplished by chemical reduction of their respective ketodiester precursors followed by cyclisation of the resulting hydroxy diester intermediates. The cis- and trans-lactones thus obtained were separated and separately subjected to enzymatic hydrolysis with HLAP. The cis-lactonic esters had enantiomeric excesses ranging from 94% to 99%, while for the trans-isomers the ee’s ranged from 80% to 93%. The same ketodiester precursors were subjected to reduction with a series of yeasts. The absolute configuration of trans-(−)-2-pyridyl paraconic acid was assigned by means of X-ray analysis of its hydrobromide salt, while the absolute configurations of the other lactones were determined via analysis of their respective CD curves.     

Thin‐Film Properties of DNA and RNA Bases: A Combined Experimental and Theoretical Study

The structures of the DNA and RNA bases cytosine, uracil, and thymine in thin films with a nominal film thickness of about 20 nm are studied by using X‐ray photoemission spectroscopy (XPS) and Fourier‐transform infrared spectroscopy. The molecules are evaporated in situ from powder on a gold foil. The experimental results indicate that cytosine is composed of two energetically close tautomeric forms, whereas uracil and thymine exist in only one tautomeric form. Additionally, quantum chemical calculations are performed to complement the experimental results. The relative energies of the tautomeric forms of cytosine, uracil, and thymine are calculated using Hartree–Fock (HF), density functional theory (DFT), and post‐HF methods. Furthermore, the assignment of the XPS spectra is supported by using simple model considerations employing Koopmans ionization energies and Mulliken net atomic charges.     

Modulation of the optical response of polyethylene films containing luminescent perylene chromophores

In this work, two perylene derivatives containing different peripheral alkyl chains (i.e., N,N'-bis-(hexyl)perylene-3,4,9,10-tetracarboxyldiimide (ES-PTCDI) and N,N'-bis-(2'-ethylhexyl)perylene-3,4,9,10-tetracarboxyldiimide (EE-PTCDI)) were synthesized and efficiently dispersed at low loadings (from 0.01 to 0.1 wt %) into linear low-density polyethylene (LLDPE) by processing in the melt. Spectroscopic investigations (UV-vis and fluorescence) combined with quantum-mechanical studies demonstrated the ability of both chromophores to generate aggregates among the planar structure of dyes when dissolved in solution or dispersed into LLDPE above a certain concentration. The data acquired for dyes' dispersions into the polymer matrix reveal that the optical properties and responsiveness to mechanical stimuli are strongly dependent on the compactness of perylene aggregates provided by the different molecular structure of dyes. In particular, the strong intermolecular aggregates of ES-PTCDI resulted in being more resistant toward mechanical stress and less orientable by uniaxial drawing along the drawing direction of the film, whereas the less compact and distorted supramolecular architecture of EE-PTCDI chromophores provided composite films with a remarkable optical response to mechanical solicitations.     

Modeling the solvation of peptides. The case of (s)-N-acetylproline amide in liquid water

The structure and properties of (s)-N-acetylproline amide (NAP) in aqueous solution are studied by exploiting a continuum solvation model. The conformational preference of NAP as a function of the environment is discussed as well as data for a number of chiral and non-chiral spectroscopic and response properties (IR/VCD, Raman/VROA, UV/CD, ORD, NMR), whose calculation with the accounting of solvent effects is now possible due to recent developments introduced in the PCM approach. When available, calculated results are compared with experimental data, so as to evaluate the quality of the continuum approach to the solvation of this system.     

Electron transfer in a radical ion pair: quantum calculations of the solvent reorganization energy

Results are presented for an investigation of intermolecular electron transfer (ET) in solution by means of quantum calculations. The two molecules that are involved in the ET reaction form a solvent-separated radical ion pair. The solvent plays an important role in the ET between the two molecules. In particular, it can give rise to specific solute-solvent interactions with the solutes. An example of specific interactions is the formation of a hydrogen bond between a protic solvent and one of the molecules involved in the ET. We address the study of this system by means of quantum calculations on the solutes immersed in a continuum solvent. However, when the solvent can give rise to hydrogen bond formation with the negatively charged ion after ET, we explicitly consider solvent molecules in the solute cavity, determining the hydrogen bond energetic contribution to the overall interaction energy. Solute-solvent pair distribution functions, showing the different arrangement of solvent molecules before and after ET in the first solvation shell, are reported. We provide results of the solvent reorganization energy from quantum calculations for both the two isolated fragments and the ion pair in solution. Results are in agreement with available experimental data.     

Self-consistent quantum mechanical model for the description of excitation energy transfers in molecules at interfaces

In this paper we present a quantum mechanical model to study excitation energy transfers in molecular systems located in the vicinity of an interface. The model is based on an approximate solution of the time-dependent density functional theory equations and solvent effects are introduced in terms of the integral equation formalism version of the polarizable continuum model. A unique characteristic of this model is that environment induced polarizing effects on the interacting molecules and screening effects on their interaction are included in a coherent and self-consistent way. The model is applied to different situations of the ethylene dimer in the vicinity of an air/water interface and compared with an alternative quantum electrodynamics approach.     

Regularization and preconditioning of KKT systems arising in nonnegative least‐squares problems

A regularized Newton‐like method for solving nonnegative least‐squares problems is proposed and analysed in this paper. A preconditioner for KKT systems arising in the method is introduced and spectral properties of the preconditioned matrix are analysed. A bound on the condition number of the preconditioned matrix is provided. The bound does not depend on the interior‐point scaling matrix. Preliminary computational results confirm the effectiveness of the preconditioner and fast convergence of the iterative method established by the analysis performed in this paper. Copyright © 2008 John Wiley & Sons, Ltd.     

Periodic solutions of competition systems with delays by an average approach

A delayed competition system of Lotka-Volterra equations, with periodic coefficients, is considered. Such a differential system admits at least a periodic positive solution if and only if the corresponding autonomous, averaged system has a positive stationary solution.