A new sulfate acid polymorph of 1,3‐dihydrobenzotriazole

A new sulfate acid polymorph of 1,3‐dihydrobenzotriazole, viz. 1,3‐dihydrobenzotriazolium hydrogensulfate, C₆H₆N₃⁺·HSO₄⁻, differs from an existing polymorph in that the polymeric interaction between the HSO₄⁻ anions, together with different classical (D—H...A) and nonclassical (C—H...A) interactions, changes the space group.     

Secondary molecular mobility in amorphous ethyl cellulose: Aging effects and degree of co‐operativity

The secondary relaxations in amorphous ethyl cellulose are studied using thermally stimulated depolarization currents (TSDCs) in the temperature region from 165 °C (108 K) up to 145 °C (418 K). The influence of aging on the current peaks of the secondary relaxation is discussed, and it is concluded that some modes of motion of this mobility are aging independent, while others are affected by aging. A particular attention is focused on the discussion of the degree of co‐operativity of the motional modes of the secondary relaxation. The conclusion to be driven from the obtained TSDC results is that the aging‐independent motional modes, as well as those that are aging dependent, do not show any appreciable co‐operative character. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 820–829, 2009     

New Lower Bounds for the Number of (≤ k)-Edges and the Rectilinear Crossing Number of K<Subscript>n</Subscript>

We provide a new lower bound on the number of (≤ k)-edges of a set of n points in the plane in general position. We show that for the number of (≤ k)-edges is at least

A fourth-order Runge–Kutta method based on BDF-type Chebyshev approximations

In this paper we consider a new fourth-order method of BDF-type for solving stiff initial-value problems, based on the interval approximation of the true solution by truncated Chebyshev series. It is shown that the method may be formulated in an equivalent way as a Runge–Kutta method having stage order four. The method thus obtained have good properties relatives to stability including an unbounded stability domain and large α$\alpha$-value concerning A(α)$A(\alpha )$-stability. A strategy for changing the step size, based on a pair of methods in a similar way to the embedding pair in the Runge–Kutta schemes, is presented. The numerical examples reveals that this method is very promising when it is used for solving stiff initial-value problems.     

Determination of nitrofurans in animal feeds by liquid chromatography-UV photodiode array detection and liquid chromatography-ionspray tandem mass spectrometry

Within the EU, the use of nitrofurans is prohibited in food production animals. For this reason detection of these compounds in feedingstuffs, at whatever limit, constitutes an offence under EU legislation. This detection generally involves the use of analytical methods with limits of quantification lowers than 1 mg kg(-1). These procedures are unsuitable for the detection and confirmation of trace amounts of nitrofurans in feedingstuffs due to contamination. It is well known that very low concentrations of these compounds can be the source of residues of nitrofuran metabolites in meat and other edible products obtained from animals consuming the contaminated feed. The present multi-compound method was capable of measuring very low concentrations of nitrofurantoin (NFT), nitrofurazone (NFZ), furazolidone (FZD) and furaltadone (FTD) in animal feed using nifuroxazide (NXZ) as internal standard. Following ethyl acetate extraction at mild alkaline conditions and purification on NH2 column, the nitrofurans are determined using liquid chromatography with photodiode-array detection (LC-DAD). It was observed a CCalpha ranged from 50 to 100 microg kg(-1). The liquid chromatography-tandem mass spectrometric (LC-MS/MS) procedure was used to confirm the identity of the suspected presence of any of the nitrofuran compounds.     

Recent developments in the analysis of brominated flame retardants and brominated natural compounds

This article reviews recent literature on the analysis of brominated flame retardants (BFRs) and brominated natural compounds (BNCs). The main literature sources are reviews from the last five years and research articles reporting new analytical developments published between 2003 and 2006. Sample pretreatment, extraction, clean-up and fractionation, injection techniques, chromatographic separation, detection methods, quality control and method validation are discussed. Only few new techniques, such as solid-phase microextraction (SPME) or pressurized liquid extraction (PLE), have been investigated for their ability of combining the extraction and clean-up steps. With respect to the separation of BFRs, the most important developments were the use of comprehensive two-dimensional gas chromatography for polybrominated diphenyl ethers (PBDEs) and the growing tendency for liquid-chromatographic techniques for hexabromocyclododecane (HBCD) stereoisomers and of tetrabromobisphenol-A (TBBP-A). At the detection stage, mass spectrometry (MS) has been developed as well-established and reliable technology in the identification and quantification of BFRs. A growing attention has been paid to quality assurance. Interlaboratory exercises directed towards BFRs have grown in popularity and have enabled laboratories to validate analytical methods and to guarantee the quality of their results. The analytical procedures used for the identification and characterization of several classes of BNCs, such as methoxylated polybrominated diphenyl ethers (MeO-PBDEs) (also metabolites of PBDEs), halogenated methyl or dimethyl bipyrroles (DBPs), are reviewed here for the first time. These compounds were generally identified during the routine analysis of BFRs and have received little attention until recently. For each topic, an overview is presented of its current status.     

Nondegenerate pi-donor/pi-acceptor [2]catenanes containing proton-ionizable 1H-1,2,4-triazole subunits: synthesis and spontaneous resolution

Chirality can hold the key to inducing directionality of motion in components of molecular devices. With this idea in mind, we describe here 1) the template-directed synthesis of two [2]catenanes wherein cyclobis(paraquat-p-phenylene) is interlocked with polyether macrocycles containing, in addition to one 3,5-bis(oxymethylene)-1H-1,2,4-triazole unit, either one 1,4-dioxybenzene or one 1,5-dioxynaphthalene ring system. We also report 2) the full characterization of both [2]catenanes by fast atom bombardment mass spectrometry (FABMS), X-ray crystallography, and dynamic (1)H NMR spectroscopy. We reveal 3) the fact that the [2]catenanes not only exist, both in the solution-state and in the solid-state, as strictly one of the two possible translational isomers, but that they also exhibit spontaneous resolution on crystallization leading to formation of homochiral crystals, as indicated by X-ray crystallography and circular dichroism (CD) experiments. Finally, we comment 4) on the chances of switching these catenanes chemically.     

Intermediates in the destruction of chlorinated C1 hydrocarbons on La-based materials: mechanistic implications

Activity experiments using GC analysis of reactor effluent have been combined with in situ IR spectroscopy to elucidate the reaction steps in the destructive adsorption of CHCl3, CH2Cl2, and CH3Cl over LaOCl. The IR results show that during reaction, LaOCl is covered with carbonate, formate, and methoxy groups. The relative amount of each of these surface intermediates depends on the Cl/H ratio of the reactant. The decomposition of the surface species leads to formation of the reaction products, and is influenced by the temperature and the relative amount of Cl present on the surface. The GC results show that the activity for the destructive adsorption of H-containing chlorinated C1 compounds decreases with increasing hydrogen content of the reactant. The acquired insight into the mechanism of destructive adsorption is crucial to the design of new catalyst materials for the efficient conversion of chlorinated hydrocarbons into nonhazardous products or reusable chemicals.