Sulfur analysis of Bolu-Mengen lignite before and after microbiological treatment using reductive pyrolysis and gas chromatography/mass spectrometry

Atmospheric pressure-temperature programmed reduction coupled with on-line mass spectrometry (AP-TPR/MS) is used for the first time on microbiologically treated coal samples as a technique to monitor the degree of desulfurization of the various sulfur functionalities. The experimental procedure enables the identification of both organic and inorganic sulfur species present in the coal matrix. A better insight in the degradation of the coal matrix and the accompanying processes during the AP-TPR experiment is obtained by a quantitative differentiation of the sulfur. The determination of the sulfur balance for the reductive pyrolysis gives an overview of the side reactions and their relative contribution in the total process. The volatile sulfur species are unambiguously identified using AP-TPR off-line coupled with gas chromatography/mass spectrometry (GC/MS). In this way, fundamental mechanisms and reactions that occur during the reductive pyrolysis could be quantified, explaining the differences in AP-TPR recoveries. Therefore, this study gives a clearer view on the possibilities and limitations of AP-TPR as a technique to monitor sulfur functionalities in coal

Divergent roles of CprK paralogues from Desulfitobacterium hafniense in activating gene expression

Gene duplication and horizontal gene transfer play an important role in the evolution of prokaryotic genomes. We have investigated the role of three CprK paralogues from the cAMP receptor protein-fumarate and nitrate reduction regulator (CRP-FNR) family of transcriptional regulators that are encoded in the genome of Desulfitobacterium hafniense DCB-2 and possibly regulate expression of genes involved in the energy-conserving terminal reduction of organohalides (halorespiration). The results from in vivo and in vitro promoter probe assays show that two regulators (CprK1 and CprK2) have an at least partially overlapping effector specificity, with preference for ortho-chlorophenols, while meta-chlorophenols proved to be effectors for CprK4. The presence of a potential transposase-encoding gene in the vicinity of the cprK genes indicates that their redundancy is probably caused by mobile genetic elements. The CprK paralogues activated transcription from promoters containing a 14 bp inverted repeat (dehalobox) that closely resembles the FNR-box. We found a strong negative correlation between the rate of transcriptional activation and the number of nuclecitide changes from the optimal dehalobox sequence (TTAAT-N-4-ATTAA). Transcription was initiated by CprK4 from a promoter that is situated upstream of a gene encoding a methyl-accepting chemotaxis protein. This might be the first indication of taxis of an anaerobic bacterium to halogenated aromatic compounds

The compositional and evolutionary logic of metabolism

Metabolism displays striking and robust regularities in the forms of modularity and hierarchy, whose composition may be compactly described. This renders metabolic architecture comprehensible as a system, and suggests the order in which layers of that system emerged. Metabolism also serves as the foundation in other hierarchies, at least up to cellular integration including bioenergetics and molecular replication, and trophic ecology. The recapitulation of patterns first seen in metabolism, in these higher levels, suggests metabolism as a source of causation or constraint on many forms of organization in the biosphere. We identify as modules widely reused subsets of chemicals, reactions, or functions, each with a conserved internal structure. At the small molecule substrate level, module boundaries are generally associated with the most complex reaction mechanisms and the most conserved enzymes. Cofactors form a structurally and functionally distinctive control layer over the small-molecule substrate. Complex cofactors are often used at module boundaries of the substrate level, while simpler ones participate in widely used reactions. Cofactor functions thus act as "keys" that incorporate classes of organic reactions within biochemistry. The same modules that organize the compositional diversity of metabolism are argued to have governed long-term evolution. Early evolution of core metabolism, especially carbon-fixation, appears to have required few innovations among a small number of conserved modules, to produce adaptations to simple biogeochemical changes of environment. We demonstrate these features of metabolism at several levels of hierarchy, beginning with the small-molecule substrate and network architecture, continuing with cofactors and key conserved reactions, and culminating in the aggregation of multiple diverse physical and biochemical processes in cells.Comment: 56 pages, 28 figure

Holomorphic harmonic analysis on complex reductive groups

We define the holomorphic Fourier transform of holomorphic functions on complex reductive groups, prove some properties like the Fourier inversion formula, and give some applications. The definition of the holomorphic Fourier transform makes use of the notion of $K$-admissible measures. We prove that $K$-admissible measures are abundant, and the definition of holomorphic Fourier transform is independent of the choice of $K$-admissible measures.Comment: 15 pages, revision of a preprint by the first author in 200

The electrochemical stability of thiols on gold surfaces

In this paper we present a comparative analysis of the electrochemical stability of alkanethiols, aromatic and heterocyclic thiols on the Au(111) and Au(100) faces in relation to the theoretical energetic data. The peak potential and surface coverage are used as the key parameters to estimate the electrochemical stability while work function changes, adsorption energies and surface free energies calculated from periodic DFT, including van der Waals interactions, are used for the theoretical estimation. We find that the peak potentials do not correlate with work function changes and adsorption energies in particular for aromatic and heterocyclic thiols. In contrast, the reductive desorption potentials for the different thiols show a good correlation with the surface free energy of the SAMs estimated by density functional theory calculations. Surface coverage is a key factor that controls reductive desorption through van der Waals interactions.Fil: Salvarezza, Roberto Carlos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Carro, Pilar. Universidad de La Laguna; Españ

Dynamics of shallow dark solitons in a trapped gas of impenetrable bosons

The dynamics of linear and nonlinear excitations in a Bose gas in the Tonks-Girardeau (TG) regime with longitudinal confinement are studied within a mean field theory of quintic nonlinearity. A reductive perturbation method is used to demonstrate that the dynamics of shallow dark solitons, in the presence of an external potential, can effectively be described by a variable-coefficient Korteweg-de Vries equation. The soliton oscillation frequency is analytically obtained to be equal to the axial trap frequency, in agreement with numerical predictions obtained by Busch {\it et al.} [J. Phys. B {\bf 36}, 2553 (2003)] via the Bose-Fermi mapping. We obtain analytical expressions for the evolution of both soliton and emitted radiation (sound) profiles.Comment: 4 pages, Phys. Rev. A (in press

Discrete Reductive Perturbation Technique

We expand a partial difference equation (P$\Delta$E) on multiple lattices and obtain the P$\Delta$E which governs its far field behaviour. The perturbative--reductive approach is here performed on well known nonlinear P$\Delta$Es, both integrable and non integrable. We study the cases of the lattice modified Korteweg--de Vries (mKdV) equation, the Hietarinta equation, the lattice Volterra--Kac--Van Moerbeke (VKVM) equation and a non integrable lattice KdV equation. Such reductions allow us to obtain many new P$\Delta$Es of the nonlinear Schr\"odinger (NLS) type.Comment: 18 pages, 1 figure. submitted to Journal of Mathematical Physic