1H NMR spectral analysis and conformational behavior of n‐alkanes in different chemical environments

Alkyl chains are common structural units, for example in lipids, and their ¹H NMR spectral parameters offer valuable information about their conformational behavior in solvent environment. Even the spectra of short n‐alkanes are complex, which is obviously a reason why their accurate spectral analyses have not been reported before. The present study reports the quantum mechanical analysis of ¹H NMR spectra of n‐butane, n‐pentane, n‐hexane, and n‐heptane. The spectral parameters were used to characterize the conformational behavior of n‐alkanes. The temperature dependence analysis of coupling constants suggests that the enthalpy difference between the gauche (g) and trans (t) conformations (ΔH_g) of n‐butane in chloroform is 2.55–2.85 kJ mol^?1. The difference between the trans–gauche (tg) and all‐trans (tt) conformers of n‐pentane (ΔH_tg) seems to be 0.1–0.2 kJ mol^?1 higher. The coupling constant information shows that the t_n conformations become more favored with longer chains, although not only for energetic reasons but also partly because the g⁺g^‐ arrangements become sterically unfavorable, which decreases the number of favorable g_n‐type conformations. The analysis of the ¹H NMR spectra of n‐pentane and n‐hexane in solvents representing different chemical environments indicates that polar and spherical dimethyl sulfoxide favors clearly the g conformations, whereas n‐hexane‐d₁₄ favors slightly the extended t_n conformation. In addition to the intrinsic scientific importance for NMR spectral parameter prediction and molecular modeling in solution, the results provide some insights to behavior of hydrocarbon chains and their spectra in different chemical environments. Copyright © 2012 John Wiley & Sons, Ltd.     

Enhancement of equity portfolio performance using data envelopment analysis

This paper examines the applicability of data envelopment analysis (DEA) as a basis of selection criteria for equity portfolios. It is the first DEA application for constructing a combined equity investment strategy that aims to integrate the benefits of both value investing and momentum investing. The 3-quantile portfolios are composed of a comprehensive sample of Finnish non-financial stocks based on their DEA efficiency scores that are calculated using three variants of DEA models (the constant returns-to-scale, the super-efficiency, and the cross-efficiency models). The performance of portfolios is evaluated on the basis of the average return and several risk-adjusted performance metrics throughout the 1994–2010 sample period.     

A rotating holographic imager for stationary cloud droplet and ice crystal measurements

Optical Review - An optical cloud droplet and ice crystal measurement system ICEMET (icing condition evaluation method), designed for present icing condition monitoring in field conditions, is...     

Eine Methode zur quantitativen Bestimmung der Alkaloidsalze durch Kationenaustausch und nachfolgende komplexometrische Titration

Zusammenfassung Es wird eine Methode mitgeteilt, nach der Alkaloidsalze durch Kationenaustausch mit Magnesium in wäßriger Lösung bestimmt werden können. Das Magnesium wird nach Waschung der Austauschersäule im Durchlauf komplexometrisch titriert. Die Methode ist schnell, zur Messung kleiner Mengen von Alkaloidsalzen verwendbar und ergibt genaue Resultate.     

Electronic spectroscopy of I(2)-Xe complexes in solid Krypton

In the present work, we have studied ion-pair states of matrix-isolated I(2) with vacuum-UV absorption and UV-vis-NIR emission, where the matrix environment is systematically changed by mixing Kr with Xe, from pure Kr to a more polarizable Xe host. Particular emphasis is put on low doping levels of Xe that yield a binary complex I(2)-Xe, as verified by coherent anti-Stokes Raman scattering (CARS) measurements. Associated with interaction of I(2) with Xe we can observe strong new absorption in vacuum-UV, redshifted 2400 cm(-1) from the X → D transition of I(2). Observed redshift can be explained by symmetry breaking of ion-pair states within the I(2)-Xe complex. Systematic Xe doping of Kr matrices shows that at low doping levels, positions of I(2) ion-pair emissions are not significantly affected by complexation with Xe, but simultaneous increase of emissions from doubly spin-excited states indicates non-radiative relaxation to valence states. At intermediate doping levels ion-pair emissions shift systematically to red due to change in the average polarizability of the environment. We have conducted spectrally resolved ultrafast pump-probe ion-pair emission studies with pure and Xe doped Kr matrices, in order to reveal the influence of Xe to I(2) dynamics in solid Kr. Strikingly, relaxed emission from the ion-pair states shows no indication of complex presence. It further indicates that the complex escapes detection due to a non-radiative relaxation.     

Feasibility of density functional methods to predict dielectric properties of polymers

Feasibility of density functional theory (DFT) to predict dielectric properties such as polarizability of saturated polymers is investigated. Small saturated molecules, methane and propane, which is a monomer of polypropylene chain, are used in testing the methods. Results for polarizabilities based on several density functionals together with different basis sets are compared and contrasted with each other, with results by Hartree-Fock and second-order Moller-Plesset perturbation theory, as well as experimental data. The generalized gradient approximation PW91 method together with the 6-311++G(**) basis set is found to be the most suitable method, in terms of sufficient accuracy and computational efficiency, to calculate polarizabilities for large oligomers of polypropylene. The dielectric constant is then determined using the calculated polarizabilities and the Clausius-Mossotti equation. The molecular DFT methods at the PW916-311++G(**) level together with the Clausius-Mossotti equation give dielectric constants for saturated polymers such as polypropylene in good accordance with the experimental values.     

Rapid Cationization of Gold Nanoparticles by Two‐Step Phase Transfer

Cationic gold nanoparticles offer intriguing opportunities as drug carriers and building blocks for self‐assembled systems. Despite major progress on gold nanoparticle research in general, the synthesis of cationic gold particles larger than 5 nm remains a major challenge, although these species would give a significantly larger plasmonic response compared to smaller cationic gold nanoparticles. Herein we present the first reported synthesis of cationic gold nanoparticles with tunable sizes between 8–20 nm, prepared by a rapid two‐step phase‐transfer protocol starting from simple citrate‐capped particles. These cationic particles form ordered self‐assembled structures with negatively charged biological components through electrostatic interactions.