Chemical Shift and Its Uses as an Electronic Parameter in Structure-Activity Correlations

Apparent correlations are found between the N-H chemical shifts of congeneric series of compounds and the dipole moments of the molecules, such as lactams and thiolactams, cyclic ureas and thioureas. When there is a high degree of correlation, either the N-H chemical shift or the dipole moment of the molecule can be used as an electronic parameter in correlating the biological activity with the chemical structure. In a series of substituted salicylaldehydes the Hammett σ constant gives better correlation with the biological activity than the O-H chemical shift. This is probably due to the anisotropic effect of the substituent besides the electronic effect. Other factors affecting the N-H chemical shift, e.g. intramolecular hydrogen-bonding of nitrosoureas and the deshielding effect of a benzene ring, in o-phenyleneureas are also presented. In spite of the limitations, the chemical shifts of many compounds can be obtained very easily, therefore, their uses in structure-activity correlations deserve further investigation.     

PIXE analysis of Tillandsia usneoides for air pollution studies at an industrial zone in Central Mexico

In order to find out if there is a relation between atmospheric particulate matter composition and human health effects, metals and other elements measurement are performed. Analysis of atmospheric aerosols collected in filters is the usual method to achieve this task. Biological monitors provide an advantageous alternative way of sampling, since there is no need of special sampling devices, and accumulation time can be as long as desired. In this study, Tillandsia usneoides a reliable air pollution biological monitor that occurs naturally throughout Mexico was used to monitor air quality of Tula–Tepeji corridor at central Mexico. This area is considered critical zone because of atmosphere contaminants high concentration. Some biomonitors were transplanted from a clean environment to four sites at the Tula corridor. Plants samples were collected every two weeks from February to April 2008. PM₁₀ sampling in filters was also performed simultaneously at three locations where T. usneoides was transplanted, for a comparison. Chemical composition was determined by PIXE. Results showed that T. usneoides incorporates anthropogenic elements reaching maximal levels after 6 to 10 weeks approximately. Since results obtained with biomonitors agree with those obtained with aerosol filters, T. usneoides could be employed as a first approximation to provide insights of the atmospheric pollution level previous to a detailed study using filters.     

Examination of Contemporary Lake Sediments by Means of Thermal Analysis: The Dabie lake near Szczecin

An attempt was made to use thermal analysis (DTA, TG, DTG) for identification of the mineralogical composition of contemporary lake sediments. Sediments were investigated both in the natural state and after ignition at 300°C. Selected fractions of the sediments in the natural state were also studied. The thermoanalytical curves of mollusca shells, reed and plankton were also recorded for use in the interpretation of the thermoanalytical curves of sediments.This revised version was published online in November 2005 with corrections to the Cover Date.     

Polyisoprenylated benzophenone derivatives from the fruits of Garcinia cambogia and their absolute configuration by quantum chemical circular dichroism calculations

Three new tetracyclic polyisoprenylated xanthones, named oxy-guttiferones M, K2, and I, along with oxy-guttiferone K and guttiferone M, have been isolated from the fruits of Garcinia cambogia. Their structures were elucidated by MS and NMR spectroscopic experiments. The absolute configurations of oxy-guttiferone K, taken as a model of tetracyclic xanthones, and guttiferone M, as a model of polyisoprenylated benzophenones, have been determined by comparison of their experimentally measured circular dichroism (CD) curves with the TDDFT-predicted curves.     

Phase transitions for Belousov–Zhabotinsky reactions

The main objective of this article is to study the dynamic phase transitions associated with the spatial–temporal oscillations of the BZ reactions, given by Field, Körös and Noyes, also referred as the Oregonator. Two criteria are derived to determine (1) the existence of either multiple equilibria or spatiotemporal oscillations and (2) the types of transitions. These criteria gives a complete characterization of the dynamic transitions of the BZ systems from the homogeneous states. The analysis is carried out using a dynamic transition theory developed recently by the authors, which has been successfully applied to a number of problems in science. Copyright © 2011 John Wiley & Sons, Ltd.     

Formation of Pyrogenic Silica: Spectroscopic and Quantum Chemical Insight

This article describes the genesis of amorphous silica under high-heat conditions from SiO₂ molecules through protoparticles, primary particles, and aggregates to agglomerates using vibrational spectra and quantum chemical simulations data. The impact of small molecules (water, HCl, CO₂) is also discussed. The article also explains the nature of the pyrogenic silica amorphism.