1-Oxo-1,3-dithiolanes--synthesis and stereochemistry

1-Oxo-1,3-dithiolane (4) and its cis- and trans-2-methyl (5,6), -4-methyl (7,8) and -5-methyl (9,10) derivatives were prepared by oxidizing the corresponding 1,3-dithiolanes (1-3) with NaIO(4) in water. The oxides were purified and their isomers separated using thin layer chromatography. The structural characterization was carried out with (1)H and (13)C NMR spectroscopy and molecular modelling. The sulfoxides 4-6 and 8-10 attain two S(1) type envelopes (sometimes slightly distorted) the S=O(ax) envelope greatly dominating. Cis-4-methyl-1-oxo-1,3-dithiolane is a special case exhibiting both two closely related S=O(ax) (30 and 27%) as well as S=O(eq) (21 and 22%) forms [S(1) and C(4) envelopes, respectively]. The relative energies of these conformations, the values of (1)H-(1)H coupling constants and (1)H and (13)C chemical shifts were estimated by computational methods and they support well the conclusions based on the experimental data.     

High Temperature Gas Chromatography with a Glass Capillary Column for the Analysis of High Molecular Weight Tracers in Smoke Samples from Biomass Burning

A custom-made glass capillary column coated with OV-1701-OH (88% methyl, 7% cyanopropyl, 5% phenylpolysiloxane) was used to analyze smoke samples from biomass combustion of different species of plants collected in the Amazon forest. CS₂ was used as solvent in order to enhance the dissolution and analysis of the heavier molecular weight components. The performance of the column was monitored during the experiments and a moderate increase in activity was observed after taking the column to high analytical temperatures (390°C). Trennzahl values typically dropped 20–30% from 1.7/m to the average of 1.35/m. In general, the performance of the custom-made column was satisfactory and comparable to the commercial high temperature columns. The high temperature high resolution GC and GC-MS analyses revealed the presence of a number of high molecular weight components reported to occur in smoke aerosols for the first time. These components consisted of series of wax esters (long chain alcohols esterified with long chain fatty acids) with up to 58 carbon numbers, aliphatic hydrocarbons, triglycerides, triterpenyl esters (e.g. α- and β-amyryl stearate). Although other types of compounds were also detected, their complete structure elucidation solely by electron impact MS was not adequate and other techniques will be required.     

13C, 15N and 113Cd NMR and Molecular Orbital Studies of Novel Bile Acid N-(2-aminoethyl)amides and Their Cd2+-complexes

Lithocholic acid N-(2-aminoethyl)amide (1) and deoxycholic acid N-(2-aminoethyl)amide(2) have been prepared and characterized by¹H, ¹³C and ¹⁵N NMR. The accurate molecular masses of 1 and 2 have been determined by ESI MS. The formation of the Cd²⁺-complexes (1+Cd and 2+Cd) in CD₃OD solution have been detected by ¹H,¹³C, ¹⁵N and ¹¹³Cd NMR. The ¹³C NMR chemical shift assignments of 1 and 2 and their Cd²⁺-complexes are based on DEPT-135 and z-GS ¹H,¹³C HMQC experiments as well as comparison with the assignments of the related structures. The ¹⁵N NMR chemical shiftassignments of the ligands and theirCd²⁺-complexes are based on z-GS¹H,¹⁵N HMBC experiments. ¹³C NMR chemical shift differences between 1and its 1:1 Cd²⁺-complex based on ab initiocalculations at Hartree-Fock SCI-PCM level using3-21G(d) basis set are in agreement with theexperimental shift changes observed onCd²⁺-complexation.     

Enhanced chromatographic NMR with polyethyleneglycol. A novel resolving agent for diffusion ordered spectroscopy

NMR analysis of complex mixtures can be significantly simplified using polyethyleneglycol (PEG) as resolving additive in DOSY NMR technique, which allows the extraction of individual spectra of mixture components with differing polarity. Resolving power of PEG‐assisted DOSY was demonstrated with natural product mixtures. Copyright © 2010 John Wiley & Sons, Ltd.     

Phenolic compounds from Eucalyptus gomphocephala with potential cytotoxic and antioxidant activities

Two new phenolic compounds, 2,4,6-trihydroxy-5-methyl-acetophenone 2-O-beta-D-glucopyranoside (3), and benzyl alcohol 7-O-(3',4',6'-tri-O-galloyl)-beta-D-glucopyranoside (8), together with eight known phenolic compounds, were isolated from the 70% aqueous acetone extract of Eucalyptus gomphocephala DC. (Myrtaceae). The isolated compounds were elucidated based on their 1H, 13C, DQF-COSY, selective 1D-TOCSY, HSQC, and HMBC NMR spectroscopic and ESI-MS data. The antioxidant effect of the phenolic compounds was tested using 1,1-diphenyl-2-picrylhydrazyl (DPPH), hydroxyl radical and super oxide anion radical scavenging assays. The cytotoxicity of the isolated compounds was evaluated using HeLa cell line.     

Statistical inverse problems: Discretization,model reduction and inverse crimes

The article discusses the discretization of linear inverse problems. When an inverse problem is formulated in terms of infinite-dimensional function spaces and then discretized for computational purposes, a discretization error appears. Since inverse problems are typically ill-posed, neglecting this error may have serious consequences to the quality of the reconstruction. The Bayesian paradigm provides tools to estimate the statistics of the discretization error that is made part of the measurement and modelling errors of the estimation problem. This approach also provides tools to reduce the dimensionality of inverse problems in a controlled manner. The ideas are demonstrated with a computed example.     

Stable quasiperiodic icosahedral states

The discovery of icosahedral quasicrystals five years ago, has challenged the validity of the well-known conjecture that the ground state of a system of particles interacting via short-range forces is always crystalline at absolute zero. We have calculated the classical cohesive energies and pair distribution functions of a large class of monatomic icosahedral structures, interacting via the Lennard-Jones (LJ) and the Square-Well (SW) potentials. For the SW potential, we have found an icosahedral phase, with lower enthalpy than the BCC, FCC and HCP phases. The phase is robust with respect to small changes in the potential, pressure and even structure, and transforms to the BCC phase above a critical pressure. Our results suggest that icosahedral ground states may indeed be possible for a class of potentials with Friedel-like oscillations, whose extremal positions satisfy geometric constraints favoring icosahedral order.     

Total syntheses of oxygenated brazanquinones via regioselective homologous anionic Fries rearrangement of benzylic O-carbamates

Using new variations of anionic aromatic chemistry, the total synthesis of oxygenated brazanquinones (1a-1c), derived from beta-brasan, a natural product isolated from Caesalpina echinata, via carbamates 2a-2c is described.     

Spectral and network methods in the analysis of correlation matrices of stock returns

Correlation matrices inferred from stock return time series contain information on the behaviour of the market, especially on clusters of highly correlating stocks. Here we study a subset of New York Stock Exchange (NYSE) traded stocks and compare three different methods of analysis: (i) spectral analysis, i.e. investigation of the eigenvalue-eigenvector pairs of the correlation matrix, (ii) asset trees, obtained by constructing the maximal spanning tree of the correlation matrix, and (iii) asset graphs, which are networks in which the strongest correlations are depicted as edges. We illustrate and discuss the localisation of the most significant modes of fluctuation, i.e. eigenvectors corresponding to the largest eigenvalues, on the asset trees and graphs.     

Numerical Comparison of Some Penalty-Based Constraint Handling Techniques in Genetic Algorithms

We study five penalty function-based constraint handling techniques to be used with genetic algorithms in global optimization. Three of them, the method of superiority of feasible points, the method of parameter free penalties and the method of adaptive penalties have already been considered in the literature. In addition, we introduce two new modifications of these methods. We compare all the five methods numerically in 33 test problems and report and analyze the results obtained in terms of accuracy, efficiency and reliability. The method of adaptive penalties turned out to be most efficient while the method of parameter free penalties was the most reliable.