Derivatisation in gas chromatographic determination of acidic herbicides in aqueous environmental samples

This paper reviews derivatisation processes applied in chromatographic determination of acidic herbicides (with carboxyl and phenol groups), mainly in aqueous environmental samples. The discussion focuses on the basic derivatisation reactions used to convert herbicides to derivatives to make them analysable by gas chromatography, and possibly to reduce detection limits and/or increase extraction recovery from aqueous samples. The reactions are transesterification, esterification, silylation, alkylation, and extractive and pyrolytic alkylation. The reagents used to conduct the reactions are numerous. Diazomethane is a very efficient methylation reagent but explosive and toxic. Methyl iodide also ensures rapid and efficient methylation. Benzyl bromide can be used directly in water but derivatisation yield is low and reproducibility is poor. Butyl chloroformate and dimethyl sulfite can also be used for derivatisation in water, and acetic anhydride can be used for in-situ derivatisation of phenolic herbicides. For increasing selectivity of GC detection pentafluorobenzyl bromide (for ECD) and (2-cyanethyl)dimethyl(diethylamino)silane (for NPD) have been applied. Very characteristic ions are produced in mass spectra if silyl groups are introduced, e.g. by using bis(trimethylsilyl)trifluoroacetamide. Tetramethylammonium, trimethylphenylammonium, tetraalkylammonium, and trimethylsulfonium hydroxides and salts can by used for derivatisation at elevated temperature in the GC injection port. Extractive alkylation is relatively efficient if tetraalkylammonium salts with long chain alkyl groups are used.     

Stabilizing effect of cholesterol on the state of β2-adrenergic receptor with a broken ionic lock: a molecular dynamics study

A molecular dynamics simulation of the β₂-adrenergic receptor (β₂AR) embedded in a hydrated lipid bilayer showed that the state with a broken ionic lock (salt bridge) between the arginine residue Arg131 and the glutamic acid residue Glu268 is stabilized in the presence of cholesterol molecules. This should be considered as a transient state to the active state of the receptor.     

Polonium 210Po activities in human blood of patients with ischaemic heart disease from Gdańsk in Poland

The determination of polonium ²¹⁰Po in human blood samples is presented and discussed in this paper. The human blood samples were collected from patients of Medical University of Gdańsk with ischaemic heart disease (morbus ischaemicus cordis, MIC). The polonium concentrations in analyzed human blood samples are very differentiated. ²¹⁰Po is of particular interest in public health and although is present in the environment in extremely low amounts, it is easily bioaccumulated to the human body. The study shows that the amount of ²¹⁰Po that is incorporated into the human body depends on the food habits and some difference in its levels could be observed between smokers and non-smokers.     

Temperature Dependence of Integrated Intensity Bands in IR-Absoption Spectra of (NH4)2AF6 Complexes

The contribution refers to the temperature dependence of IR-absorption spectra (NH₄)₂AF₆ (A - Si and Ge). It is found that with temperature decreasing, the integrated intensities of the bands corresponding to anion fundamentals, increase, while those of cation, decrease. An explanation is given to the phenomena detected, which is based on variations in the strength of the outer-sphere interaction with the temperature, and subsequent redistribution of electron density.     

Risk averse decision making under catastrophic risk

A nonstandard probabilistic setting for modeling of the risk of catastrophic events is presented. It allows random variables to take on infinitely large negative values with non-zero probability, which correspond to catastrophic consequences unmeasurable in monetary terms, e.g. loss of human lives. Thanks to this extension, the safety-first principle is proved to be consistent with traditional axioms on a preference relation, such as monotonicity, continuity, and risk aversion. Also, a robust preference relation is introduced, and an example of a monotone robust preference relation, sensitive to catastrophic events in the sense of Chichilnisky (2002), is provided. The suggested setting is demonstrated in evaluating nuclear power plant projects when the probability of a catastrophe is itself a random variable.     

The complexation of flurbiprofen with β-cyclodextrin: a NMR study in aqueous solution

The complexation process between racemic flurbiprofen and β-cyclodextrin in solution was investigated by 1D and 2D proton NMR spectroscopy. In the presence of β-cyclodextrin, the aromatic protons of flurbiprofen were the most affected, suggesting a strong involvement of the phenyl groups in the inclusion mechanism. The stoichiometry of the complex was determined by the method of continuous variation, using the chemical induced shifts of both host and guest protons. The association constant, K_a of the obtained complex was calculated and found to be 2483.8 M^?1. On the other hand, signals belonging to the protons associated with the carboxyl group are split in the presence of β-cyclodextrin indicating enantiomeric differentiation. Rotating frame NOE spectroscopy, (ROESY), was used to ascertain the solution geometry of the host–guest complex. The result suggested that the flurbiprofen molecule fully penetrates the β-cyclodextrin cavity with the carboxyl group protruding from the primary hydroxyl side and the phenyl group close to the secondary rim.     

Ambident Reactivity of Imidazolium Cations as Evidence of the Dynamic Nature of N-Heterocyclic Carbene-Mediated Organocatalysis

This work reveals ambident nucleophilic reactivity of imidazolium cations towards carbonyl compounds at the C2 or C4 carbene centers depending on the steric properties of the substrates and reaction conditions. Such an adaptive behavior indicates the dynamic nature of organocatalysis proceeding via a covalent interaction of imidazolium carbenes with carbonyl substrates and can be explained by generation of the H-bonded ditopic carbanionic carbenes.     

Influence of heat treatment on the size of sodium lignosulfonate particles in water—ethanol media

Russian Chemical Bulletin - Dynamic light scattering and size exclusion chromatography were used to investigate the size of sodium lignosulfonate particles in water—ethanol media and the...