Mechanism of multi‐metal(loid) methylation and hydride generation by methylcobalamin and cob(I)alamin: a side reaction of methanogenesis

Metal(loid)s are subject to many transformation processes in the environment, such as oxidation, reduction, methylation and hydride generation, predominantly accomplished by prokaryotes. Since these widespread processes affect the bioavailability and toxicity of metal(loid)s to a large extent, the investigation of their formation is of high relevance. Methanogenic Archaea are capable of methylating and hydrogenating Group 15 and 16 metal(loid)s arsenic, selenium, antimony, tellurium, and bismuth due to side reactions between central methanogenic cofactors, methylcobalamin (CH₃Cob(III)) and cob(I)alamin (Cob(I)). Here, we present systematic mechanistic studies on methylation and hydride generation of Group 15 and 16 metal(loid)s by CH₃Cob(III) and Cob(I). Pentavalent arsenical species showed neither methylation nor reduction as determined by using a newly developed oxidation state specific hydride generation technique, which allows direct determination of tri‐ and pentavalent arsenic species in a single batch. In contrast, efficient methylation of trivalent species without a change in oxidation state indicated that the methyl transfer does not proceed via a Challenger‐like oxidative methylation, but via a non‐oxidative methylation. Our findings also point towards a similar mechanism for antimony, bismuth, selenium, and tellurium. Overall, we suggest that the transfer of a methyl group does not involve a free reactive species, such as a radical, but instead is transferred either in a concerted nucleophilic substitution or in a caged radical mechanism. For hydride generation, we propose the intermediate formation of hydridocobalamin, transferring a hydride ion to the metal(loid)s. Copyright © 2012 John Wiley & Sons, Ltd.     

Liquid analysis dielectric capillary barrier discharge

In this study a simple micro-tube-based system for analysis of metal-containing liquids is introduced and its analytical performance is evaluated. It is based on a miniaturised dielectric barrier discharge driven at atmospheric pressure. The emission lines of various elements are observed. The system is developed for quantitative measurements and the limits of detection are determined. Because of very low flow rates of just μL min⁻¹ the approach requires extremely low sample volumes.     

Pressure–volume–temperature data and surface tension of blends of poly(ethylene oxide) and poly(methyl acrylate) in the melt

The pressure–volume–temperature behavior of miscible blends of poly(ethylene oxide) (PEO) and poly(methyl acrylate) (PMA) was studied over extended ranges of temperature and pressure. From pressure–volume–temperature data, the reduction parameters for the Flory‐Orwoll‐Vrij equation‐of‐state were determined. It was found that reduction parameters as well as density, thermal expansion coefficient, and isothermal compressibility vary with composition in a nonlinear manner. The surface tension of the blends in the molten state was measured over the whole composition range using the sessile drop method. The surface tension was found to display negative deviation from additivity pointing toward a remarkable surface excess of PMA. Moreover, surface tension displays a minimum in the range of low PEO content at weight fraction of ～0.19. In addition, the temperature coefficient of surface tension shows negative deviation from linearity. It stays constant when PMA is in excess. Results are discussed in terms of equation‐of‐state thermodynamics. The minimum of surface tension can be well explained by weak self‐association of PEO in the bulk. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1893–1900, 2010     

Post‐Grignard Reagents: Influence of the Coligands L on the Molecular Structures of Phenylcalcium Iodides [(L)nCa(R)I] and Calcium Diiodides [(L)nCaI2]

Iodide is a very soft and large anion and as such its extreme ability to be polarized leads to a flat energy surface with respect to the variation of the Ca–I distances in [(L)_nCaI₂] and [(L)_nCa(R)I]. The influence of the donor strength and the bulkiness of the neutral coligands L on the Ca–I distances is studied. The base adducts of calcium diiodide can be isolated after the addition of L to CaI₂ or from the Schlenk equilibrium after the direct synthesis of calcium powder with aryl iodides. As L the ethers diethyl ether (Et₂O), tetrahydrofuran (thf), tetrahydropyran (thp), 1,2‐dimethoxyethane (dme), 18‐crown‐6 (18C6), bis(methoxyethyl)ether (diglyme), and amines tetramethylethylenediamine (tmeda), and hexamethyltriethylenetetramine (hmteta) are studied yielding the adducts [(thp)₄Ca(Ph)I] ( 1a ), [(thf)₄Ca(Ph)I] ( 1b ), [(dme)₂(thf)Ca(Ph)I] ( 1c ), [(18C6)Ca(Ph)I] ( 1d ), and [(tmeda)₂Ca(Ph)I] ( 1e ), as well as [(thp)₄CaI₂] ( 2a ), [(thf)₄CaI₂] ( 2b ), [(Et₂O)₄CaI₂] ( 2c ), [(diglyme)(thf)₂CaI₂] ( 2d ), [(diglyme)(dme)CaI₂] ( 2e ), [(dme)₂(thf)CaI₂] ( 2f ), [(18C6)CaI₂] ( 2g ), [(tmeda)₂CaI₂] ( 2h ), and [(hmteta)CaI₂] ( 2i ). For comparison reasons, [(thf)₄Ca(Ph)Br] ( 3a ), [(thp)₄CaBr₂] ( 4a ), [(thf)₄CaBr₂] ( 4b ), and [(dme)₂(AcOH)CaBr₂] ( 4c ) with AcOH being acetic acid are included as well. The comparison shows that the coordination number of calcium itself only plays an insignificant role whereas bulkiness and donor strength of L represent the key influences.     

New efficient reaction media for SET‐LRP produced from binary mixtures of organic solvents and H2O

SET‐LRP is mediated by a combination of solvent and ligand that promotes disproportionation of Cu(I)X into Cu(0) and Cu(II)X₂. Therefore, the diversity of solvents suitable for SET‐LRP is limited. SET‐LRP of MA in a library of solvents with different equilibrium constants for disproportionation of Cu(I)X such as DMSO, DMF, DMAC, EC, PC, EtOH, MeOH, methoxyethanol, NMP, acetone and in their binary mixtures with H₂O was examined. H₂O exhibits the highest equilibrium constant for disproportionation of Cu(I)X. The apparent rate constant of the polymerization exhibits a linear increase with the addition of H₂O. This is consistent with higher equilibrium constants for disproportionation generated by addition of H₂O to organic solvents. Furthermore, with the exception of alcohols and carbonates, the rate constant of polymerization in binary mixtures could be correlated with the Dimroth‐Reichardt solvent polarity parameter. This is consistent with the single‐electron transfer mechanism proposed for SET‐LRP that involves a polar transition state. These experiments demonstrate that the use of binary mixtures of solvents with H₂O provides a new, simple and efficient method for the elaboration of a large diversity of reaction media that are suitable for SET‐LRP even when one of the two solvents does not mediate disproportionation of Cu(I)X. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5577–5590, 2009     

Sonic spray ionization interface for liquid chromatography-mass spectrometry

A sonic spray ionization (SSI) interface for liquid chromatography-mass spectrometry (LC-MS) analysis was optimized for analysis of 2-[(1R)-3-[bis(1-methylethyl)amino]-1-phenylpropyl]-4-methyl-phenol (tolterodine), used as a model drug substance, and the influence of different parameter settings was evaluated using factorial design. A comparison between SSI and electrospray ionization (ESI) was made for tolterodine, tolterodine metabolites, and a set of steroids.SSI was found to give slightly poorer repeatability and broader peaks for tolterodine compared to ESI. However, there was no significant difference in chromatographic peak shape, and the repeatability using SSI was similar to that obtained using ESI if a ratio (area of tolterodine/area of metabolite) was used. In this study, the sensitivity was higher using SSI. For the analysis of pregnanolone, less water loss was obtained using SSI, probably due to less energy being transferred to the analyte upon ionization.     

Correlation effects in the electronic coupling between π electrons through a cyclohexane spacer

The electronic coupling between symmetrically placed π electrons through a cyclohexane spacer is calculated using ab initio methods. In particular we have performed a multiconfigurational configuration interaction study involving the broken symmetry Hartree—Fock solutions. The value of Δ, in a simplified model the splitting between the symmetric and antisymmetric π orbitals, is moderately changed compared to the Koopmans theorem value. The influence of the basis set on the calculated splittings is also analyzed.