Sulphate preconcentration by anion exchange resin in flow injection and its turbidimetric determination in water

A preconcentration procedure was established for sulphate determination in rain waters at the mg/l level, employing a small column packed with the AG1-X8 (200-400 mesh) anionic resin inserted into a flow injection system. Sulphate determination was performed by using the turbidimetric method based on reaction with barium. For concentrations within 0.10 and 2.0 MgSO(2-)(4)/l, a throughput of 50 determinations/hr was achieved, and the relative standard deviation of results was better than 2%.     

Facts and artifacts about aromatic stability estimation

The stability of a set of 105 five-membered π-electron systems (involving aromatic, non-aromatic and anti-aromatic species) was evaluated using six isodesmic reactions of which two belong to the subclass of homodesmotic reactions, which are based on cyclic and acyclic reference systems. We demonstrate that the ‘Resonance Energies’ derived from isodesmotic schemes have obvious flaws and do not correct or cancel other contributions to the energy, such as the changes of hybridization, homoconjugation of heterosubstituted cyclopentadienes, conjugative interactions of CC or CX (X=N or P) with a π or pseudo π orbital at Y (Y=O, S, NH, PH), strain, etc. as effectively as possible. Likewise, ‘aromatic stabilization energies (ASE)’ derived from homodesmotic schemes based on the acyclic reference compounds do not give satisfactory results. We strongly recommend that only cyclic reference compounds should be used for ASE and other aromaticity evaluations. The analysis is based on ab initio optimized geometries at B3LYP/6-311+G^∗∗.     

Microwave-assisted extraction of zearalenone from wheat and corn

A microwave-assisted extraction (MAE) method has been developed for determination of zearalenone in wheat and corn by LC-MS with an atmospheric pressure chemical ionization interface (APCI). Matrix effects were minimized by use of matrix-matched standard curves for quantification of the analyte. The limit of quantification (LOQ) of the method was 30 ng g(-1) in wheat and 20 ng g(-1) in corn. The rapid LC-MS method enabled analysis of the extracts without clean-up, thereby reducing analyte losses, the time required for the analytical procedure, and costs. A factorial design approach was used to examine the effect on extraction efficiency of the main extraction conditions - time, temperature, and solvent. On the basis of results from statistical assessment extraction was performed with 1:1 (v/v) methanol-acetonitrile at 80 degrees C for 5 min. When these extraction conditions were applied to a wheat sample from a recently conducted international proficiency test, 92% (103 ng g(-1)) of the assigned zearalenone concentration (112 ng g(-1)) in the test material was obtained. This result was within the uncertainty (u) range of the assigned value of the test material (u=+/-15.8 ng g(-1), alpha=0.05) thereby demonstrating the accuracy of the method was sufficient. The precision of the whole method was also confirmed to be adequate, because the observed relative standard deviation (RSD) of 12% (n=10) also fulfils the quality criteria recommended by European guidelines for in-house method validation.     

Delocalization resonance energy of the allylic radical from the geometrical isomerization of hexa-1,3,5-trienes

Thermal cis, trans geometrical isomerization theoretically involves a 90° twisted, singlet diradical-like transition state which may serve as a base for the examination of structural perturbations. Although thermal rearrangement of hexa-1, trans-3,5-triene (and all-trans octa-2,4,6-triene) to the cis isomer cannot be followed directly owing to subsequent cyclization and 1,5 hydrogen shifts, activation parameters for disappearance have been determined. Experimental complications and mechanistic uncertainties which make interpretation difficult are removed in the bicyclic hexatriene, cyclopentenylidenecyclopentene. These geometrical isomers undergo uncomplicated thermal cis, trans isomerization in vessels of lead-potash glass: log k₁ = 12·03±0·32?41·7±0·8/(0·004575T_abs). Extraction of a value for allylic delocalization energy from the behavior of hexa-1, trans-3,5-triene [log k₁ = 12·91 ± 0·47?44·3±1·2/(0·004575 T_abs)] requires corrections of the Dewar-Schmeising type for changes in hybridization of the σ bonds. Depending on whether ethylene or trans-butene is taken as standard, values of 12·2 and 13·1 kcal/mol are obtained (estimated uncertainty ± 2 kcal/mol).     

Proton-impact excitation of HeI triplet levels

We investigated the excitation of the λ(1s3d ³ D?1s2p ³ P)=588 nm line of atomic helium by proton and deuteron impact for projectile energies 10 keV≦E _p≦25 keV. In apparent contradiction to Wigner's spin conservation rule, the emission cross section does not vanish. By measuring the intensity of the impact radiation as a function of homogeneous magnetic and electric fields applied to the collision volume, it has been shown thatp- andd-impact excitation of the 1s3d ³ D level of HeI proceeds via 1snl states withl≧3, which populate the 3³ D states by cascade decays. The well-known strong singlet-triplet mixing of these 1snl states enables a population of triplet states in accord with Wigner's rule. Accordingly, we determine the excitation cross section of the 1s4f multiplet from the measured emission cross section of the 588 nm line. The field-dependent signals give evidence that predominantly substates with |m _L|≦1 are excited.     

One-Bond 13C, 13C-Spin Coupling in η4-, η3- and η2-Olefin Transition Metal Complexes

One-bond ¹³C, ¹³C-spin-coupling constants have been measured, with natural isotope abundance, in η⁴-diene, η³-allyl and η²-ene transition-metal carbonyl complexes. Typical values of ¹J(C,C) are given for Fe-, Ru- and Os-complexes with the three types of olefinic ligands. The effects of substituents and the structural significance of the C,C-coupling constants are discussed.     

Carbohydrate chain of ganglioside GM1 as a ligand: identification of the binding strategies of three 15 mer peptides and their divergence from the binding modes of growth-regulatory galectin-1 and cholera toxin

The branched pentasaccharide chain of ganglioside GM1 is a prominent cell surface ligand, for example, for cholera toxin or tumor growth-regulatory homodimeric galectins. This activity profile via protein recognition prompted us to examine the binding properties of peptides with this specificity. Our study provides insights into the mechanism of molecular interaction of this thus far unexplored size limit of the protein part. We used three pentadecapeptides in a combined approach of mass spectrometry, NMR spectroscopy and molecular modelling to analyze the ligand binding in solution. Availability of charged and hydrophobic functionalities affected the intramolecular flexibility of the peptides differently. Backfolding led to restrictions in two cases; the flexibility was not reduced significantly by association of the ligand in its energetically privileged conformations. Major contributions to the interaction energy arise from the sialic acid moiety contacting Arg/Lys residues and the N-terminal charge. Considerable involvement of stacking between the monovalent ligand and aromatic rings could not be detected. This carbohydrate binding strategy is similar to how an adenoviral fiber knob targets sialylated glycans. Rational manipulation for an affinity enhancement can now be directed to reduce the flexibility, exploit the potential for stacking and acquire the cross-linking capacity of the natural lectins by peptide attachment to a suitable scaffold.     

Detection of fragment genesis in the mass spectrometer. III. Analysis of amino-acid sequence in oligopeptides and in mixtures of oligopeptides by DADI-mass spectrometry (author's transl)]

Detection of Fragment Genesis in the Mass Spectrometer. III. Analysis of Amino-Acid Sequence in Oligopeptides and in Mixtures of Oligopeptides by DADI-Mass Spectrometry. The amino acid sequence was analysed by DADI mass spectrometry in simple oligopeptides and in mixtures containing two or three peptides.     

Multicomponent coupling reactions for organic synthesis: chemoselective reactions with amide-aldehyde mixtures

The acid-catalyzed condensation chemistry of simple amides and aldehydes provides a highly prolific source of diverse reactants for irreversible follow-up reactions. Amide-aldehyde mixtures have been successfully employed in multicomponent syntheses of N-acyl alpha-amino acids (via palladium-catalyzed amidocarbonylation) and various cyclohexene, cyclohexadiene, and benzene derivatives (via the amide-aldehyde-dienophile (AAD) reaction).     

Alkaloids from marine organisms. Part 8: Isolation of bisdemethylaaptamine and bisdemethylaaptamine-9-O-sulfate from an Indonesian Aaptos sp. marine sponge

Bisdemethylaaptamine (6), a proposed biosynthetic precursor of the aaptamines has been isolated from an Aaptos sp. marine sponge harvested off the Indonesian coast, and its identity confirmed by comparison of its spectral data with that of synthetic material. Bisdemethylaaptamine-9-O-sulfate (7) was also isolated from the same source. This is the first report of a sulfated aaptamine.