Transition-state structures for the reaction between styrene and tbutyl cyanoketene: Theoretical evidence for antarafacial characteristics in a π2 + π2 thermal cycloaddition

Semiempirical AM 1 SCF ? MO models for the cycloaddition between monosubstituted alkenes (RCH = CH₂, R = Me, Ph, CF₃) and ^tbutyl cyanoketene predict the lowest-energy transition state to be relatively polar and asynchronous in character and to have a cis relationship between the R and the ^tbutyl groups, in agreement with the experimentally determined product for R = Ph. We interpret this stereochemistry as resulting from the presence of a significant antarafacial component in the transition state, which enables these two bulky groups to adopt pseudoequatorial positions in which steric interactions are minimized. The alternative higher energy trans geometry forces the R and the cyano groups to adopt more sterically hindered pseudoaxial positions. Alternative biradical-like transition states inferred by others from ab initio MCSCF calculations on the reaction between ketene and ethene do not retain any significant antarafacial component on the ketene and, therefore, form less satisfactory models for this specific reaction. © 1992 John Wiley & Sons, Inc.     

\bar K^{0*} (892) andK 0*(892) production at lowp t and the quark parton model

Data on the production of the neutralK ^*(892) resonances at lowp _t by 200 GeVK ^? and π^? is compared with the predictions of various models based on the quark parton model of hadrons.     

Mass spectrometric mapping of disulfide bonds in recombinant human interleukin-13

Interleukin 13 (IL-13), a member of the a-helical family of cytokines, has approximately 30% primary sequence homology with IL-4 and shares a common receptor component. The biologically active rhIL-13 is monomeric and non-glycosylated, and contains two disulfide bonds as determined by comparative electrospray mass spectrometric (MS) analysis of the protein before and after reduction with dithiothreitol-dithioerythritol. A trypsin-resistant core peptide of rhIL-13 was isolated and analyzed by plasma desorption (PD) MS, identifying a disulfide-linked core peptide. Subsequent digestion of this core peptide by pepsin, followed by PDMS analysis of the resulting cystine-containing peptic fragments, provided rapid determination of the existing disulfide bonds between cysteine residues 28-56 and 44-70. This disulfide arrangement is similar to that observed for the analogous four internal cysteine residues in hIL-4. The conservation of disulfide bond arrangements between hIL-13 and hIL-4, coupled with their alpha-helical structure and sequence homologies, confirms that IL-13 and IL-4 are structural homologues. It is also consistent with their reported similarities in biological function and receptor binding kinetics.     

An investigation of gas chromatography with atomic emission detection for the determination of empirical formulas

The atomic emission detector (AED) is a valuable tool for the identification of unknowns in complex mixtures. To the extent that elemental response factors are independent of compound structure, gas chromatographic results allow calculation of atomic ratios for unknown compounds. In favorable cases, empirical formulas can be found. An algorithm for automated calculation of empirical formulas for all the peaks in a chromatogram has been developed. When finite accuracy prevents an exact determination of empirical formulas, the algorithm gives a list of all formulas for each compound which are compatible with the user-defined limits. Examples are given of calculations for fatty acid methyl esters, substituted phenols, and pesticides. Analyses of volatile pollutants and polychlorinated biphenyls reveal a nonlinearity for hydrogen response, and an interference of chlorine on hydrogen. A lubricating oil analysis is used to illustrate the identification of unknowns.     

Headspace analysis with cryogenic focusing: A procedure for increasing the sensitivity of automated capillary headspace analysis

Summary A convenient procedure has been described for enhancing the sensitivity of equilibrium headspace gas chromatography. The technique involves the cryogenic focusing of headspace vapors at the head of a 0.32 mm fusedsilica capillary column which has been coupled to a packed column injection port. Cryofocusing is accomplished automatically by cooling the GC oven and results in enhanced sensitivity with improved resolution. With this simple focusing technique no sample splitting is required which gives at least a 10-fold increase in sensitivity. A Multiple Headspace Injection (MHI) technique has been described which allows several rapid headspace injections to be made at the start of a single chromatographic run. Cryofocusing causes the injections to be superimposed, thus increasing the sensitivity even further. These procedures have been demonstrated for flavor and aroma analyses of toothpaste and soft drink samples. Presented at the Symposium on Headspace GC, National American Chemical Society Meeting, Chicago, Ill., September 8–13, 1985     

Multidimensional solid state NMR of anisotropic interactions in peptides and proteins

Accurate determinations of chemical shift anisotropy (CSA) tensors are valuable for NMR of biological systems. In this review we describe recent developments in CSA measurement techniques and applications, particularly in the context of peptides and proteins. These techniques include goniometeric measurements of single crystals, slow magic-angle spinning studies of powder samples, and CSA recoupling under moderate to fast MAS. Experimental CSA data can be analyzed by comparison with ab initio calculations for structure determination and refinement. This approach has particularly high potential for aliphatic (13)C analysis, especially Calpha tensors which are directly related to structure. Carbonyl and (15)N CSA tensors demonstrate a more complex dependence upon hydrogen bonding and electrostatics, in addition to conformational dependence. The improved understanding of these tensors and the ability to measure them quantitatively provide additional opportunities for structure determination, as well as insights into dynamics.     

Axial Elongation of Mononuclear Lanthanide Metallocenophanes: Magnetic Properties of Dysprosium- and Terbium-[1]Ruthenocenophane Complexes

We report the first f-block-ruthenocenophane complexes 1 (Dy) and 2 (Tb) and provide a comparative discussion of their magnetic structure with respect to earlier reported ferrocenophane analogues. While axial elongation of the rare trigonal-prismatic geometry stabilizes the magnetic ground state in the case of Dy³⁺ and results in a larger barrier to magnetization reversal (U), a decrease in U is observed for the case of Tb³⁺.     

Investigation of mechanisms for the reductive dechlorination of chlorinated ethylenes using electroanalytical techniques.

Chlorinated ethenes in the environment can dechlorinate by accepting electrons from electron donors fortuitously found in nature under a wide range of conditions in the sub-surface by both abiotic and biotic pathways. A source of electron donors is a range of dehalorespiratory bacteria, in which Co(I) in vitamin B12, in the presence of strong reductants such as Ti(III) citrate, aids dehalogenation. In this work we investigated a range of reducing conditions using electron donors of varying strengths and proposed mechanisms for dechlorination. Initially, the reducing abilities of one of the strongest electron donors known, tetrakis(dimethylamino)ethylene (TDAE), was studied. Subsequently, the reducing ability of a cobalt salt under reducing conditions was examined. Molasses was used as a source of hydrogen. The reactions were followed using electrochemistry, UV-Vis spectroscopy and ion chromatography. TDAE was found to form adducts with tetrachloroethylene and trans-dichloroethylene and to reduce trichloroethylene and cis-dichloroethylene very rapidly. On application of a negative potential, cobalt, in the presence of molasses, was also found to dechlorinate trichloroethylene rapidly. Dechlorination of PCE was considerably slower.     

Axial Elongation of Mononuclear Lanthanide Metallocenophanes: Magnetic Properties of Dysprosium‐ and Terbium‐[1]Ruthenocenophane Complexes

We report the first f‐block‐ruthenocenophane complexes 1 (Dy) and 2 (Tb) and provide a comparative discussion of their magnetic structure with respect to earlier reported ferrocenophane analogues. While axial elongation of the rare trigonal‐prismatic geometry stabilizes the magnetic ground state in the case of Dy³⁺ and results in a larger barrier to magnetization reversal (U), a decrease in U is observed for the case of Tb³⁺.     

Sorption of Cadmium from Aqueous Solutions at Different Temperatures by Mexican HEU-type Zeolite Rich Tuff

Many factors may affect the heavy metals sorption on natural zeolites among them the temperature, for this reason in this paper the cadmium retention behavior on Mexican zeolitic rich tuff as a function of temperature is considered. The kinetic and the isotherms were determined at 303, 318, and 333 K, the remaining cadmium in the solution samples was analyzed by atomic absorption spectrometry. The pseudo-second order rate constant, k, as well as the apparent diffusion coefficients were calculated from the cadmium uptake by the zeolitic rock as a function of the contact time and temperature, the highest amounts were found for the experiments done at 333 K. The maximum cadmium adsorption capacity by the zeolitic material was 12.2 mg Cd²⁺/g at 318 K corresponding to 20% of the effective ion exchange capacity of the Chihuahua zeolitic rock. In order to explain the cadmium sorption behavior different kinetics and isotherm models were considered.