Influence of RANEY nickel on the formation of intermediates in the degradation of lignin

Lignin forms an important part of lignocellulosic biomass and is an abundantly available residue. It is a potential renewable source of phenol. Liquefaction of enzymatic hydrolysis lignin as well as catalytical hydrodeoxygenation of the main intermediates in the degradation of lignin, that is, catechol and guaiacol, was studied. The cleavage of the ether bonds, which are abundant in the molecular structure of lignin, can be realised in near-critical water (573 to 673 K, 20 to 30MPa). Hydrothermal treatment in this context provides high selectivity in respect to hydroxybenzenes, especially catechol. RANEY Nickel was found to be an adequate catalyst for hydrodeoxygenation. Although it does not influence the cleavage of ether bonds, RANEY Nickel favours the production of phenol from both lignin and catechol. The main product from hydrodeoxygenation of guaiacol with RANEY Nickel was cyclohexanol. Reaction mechanism and kinetics of the degradation of guaiacol were explored

Stewart-Treves syndrome: MR imaging of a postmastectomy upper-limb chronic lymphedema with angiosarcoma

The rare occurrence of angiosarcoma in postmastectomy upper-limb lymphedema with magnetic resonance (MR) imaging is discussed. Unfamiliarity with this aggressive vascular tumor and its harmless appearance often leads to delayed diagnosis. Angiosarcoma complicating chronic lymphedema may be low in signal intensity on T2-weighting and short tau inversion recovery (STIR) imaging reflecting the densely cellular, fibrous stroma, and sparsely vascularized tumor histology. Additional administration of intravenous contrast medium revealed significant enhancement of the tumorous lesions. Awareness of angiosarcoma and its MR imaging appearance in patients with chronic lymphedema may be a key to early diagnosis or allow at least inclusion in the differential diagnosi

Wire scanners in low energy accelerators

Fast wire scanners are today considered as part of standard instrumentation in high energy synchrotrons. The extension of their use to synchrotrons working at lower energies, where Coulomb scattering can be important and the transverse beam size is large, introduces new complications considering beam heating of the wire, composition of the secondary particle shower and geometrical consideration in the detection set-up. A major problem in treating these effects is that the creation of secondaries in a thin carbon wire by a energetic primary beam is difficult to describe in an analytical way. We are here presenting new results from a full Monte Carlo simulation of this process yielding information on heat deposited in the wire, particle type and energy spectrum of secondaries and angular dependence as a function of primary beam energy. The results are used to derive limits for the use of wire scanners in low energy accelerators.Comment: 20 pages, 8 Postscript figures, uses elsart.cl

Crystal structure of a ring-cleaving cyclohexane-1,2-dione hydrolase, a novel member of the thiamine diphosphate enzyme family

The thiamine diphosphate (ThDP) dependent flavoenzyme cyclohexane-1,2-dione hydrolase (CDH) (EC 3.7.1.11) catalyses a key step of a novel anaerobic degradation pathway for alicyclic alcohols by converting cyclohexane-1,2-dione (CDO) to 6-oxohexanoate and further to adipate using NAD(+) as electron acceptor. To gain insights into the molecular basis of these reactions CDH from denitrifying anaerobe Azoarcus sp. strain 22Lin was structurally characterized at 1.26 Å resolution. Notably, the active site funnel is rearranged in an unprecedented manner providing the structural basis for the specific binding and cleavage of an alicyclic compound. Crucial features include a decreased and displaced funnel entrance, a semi-circularly shaped loop segment preceding the C-terminal arm and the attachment of the C-terminal arm to other subunits of the CDH tetramer. Its structural scaffold and the ThDP activation is related to that observed for other members of the ThDP enzyme family. The selective binding of the competitive inhibitor 2-methyl-2,4-pentane-diol (MPD) to the open funnel of CDH reveals an asymmetry of the two active sites found also in the dimer of several other ThDP dependent enzymes. The substrate binding site is characterized by polar and non-polar moieties reflected in the structures of MPD and CDO and by three prominent histidine residues (His28, His31 and His76) that most probably play a crucial role in substrate activation. The NAD(+) dependent oxidation of 6-oxohexanoate remains enigmatic as the redox-active cofactor FAD seems not to participate in catalysis, and no obvious NAD(+) binding site is found. Based on the structural data both reactions are discussed

Cyclohexane-1,2-Dione Hydrolase from Denitrifying Azoarcus sp Strain 22Lin, a Novel Member of the Thiamine Diphosphate Enzyme Family

Alicyclic compounds with hydroxyl groups represent common structures in numerous natural compounds, such as terpenes and steroids. Their degradation by microorganisms in the absence of dioxygen may involve a C—C bond ring cleavage to form an aliphatic intermediate that can be further oxidized. The cyclohexane-1,2-dione hydrolase (CDH) (EC 3.7.1.11) from denitrifying Azoarcus sp. strain 22Lin, grown on cyclohexane-1,2-diol as a sole electron donor and carbon source, is the first thiamine diphosphate (ThDP)-dependent enzyme characterized to date that cleaves a cyclic aliphatic compound. The degradation of cyclohexane-1,2-dione (CDO) to 6-oxohexanoate comprises the cleavage of a C—C bond adjacent to a carbonyl group, a typical feature of reactions catalyzed by ThDP-dependent enzymes. In the subsequent NAD+-dependent reaction, 6-oxohexanoate is oxidized to adipate. CDH has been purified to homogeneity by the criteria of gel electrophoresis (a single band at ∼59 kDa; calculated molecular mass, 64.5 kDa); in solution, the enzyme is a homodimer (∼105 kDa; gel filtration). As isolated, CDH contains 0.8 ± 0.05 ThDP, 1.0 ± 0.02 Mg2+, and 1.0 ± 0.015 flavin adenine dinucleotide (FAD) per monomer as a second organic cofactor, the role of which remains unclear. Strong reductants, Ti(III)-citrate, Na+-dithionite, and the photochemical 5-deazaflavin/oxalate system, led to a partial reduction of the FAD chromophore. The cleavage product of CDO, 6-oxohexanoate, was also a substrate; the corresponding cyclic 1,3- and 1,4-diones did not react with CDH, nor did the cis- and trans-cyclohexane diols. The enzymes acetohydroxyacid synthase (AHAS) from Saccharomyces cerevisiae, pyruvate oxidase (POX) from Lactobacillus plantarum, benzoylformate decarboxylase from Pseudomonas putida, and pyruvate decarboxylase from Zymomonas mobilis were identified as the closest relatives of CDH by comparative amino acid sequence analysis, and a ThDP binding motif and a 2-fold Rossmann fold for FAD binding could be localized at the C-terminal end and central region of CDH, respectively. A first mechanism for the ring cleavage of CDO is presented, and it is suggested that the FAD cofactor in CDH is an evolutionary relict

Quantum Effects in Small-Capacitance Single Josephson Junctions

We have measured the current-voltage (I-V) characteristics of small-capacitance single Josephson junctions at low temperatures (T=0.02-0.6 K), where the strength of the coupling between the single junction and the electromagnetic environment was controlled with one-dimensional arrays of dc SQUIDs. The single-junction I-V curve is sensitive to the impedance of the environment, which can be tuned IN SITU. We have observed Coulomb blockade of Cooper-pair tunneling and even a region of negative differential resistance, when the zero-bias resistance R_0' of the SQUID arrays is much higher than the quantum resistance R_K = h/e^2 = 26 kohm. The negative differential resistance is evidence of coherent single-Cooper-pair tunneling within the theory of current-biased single Josephson junctions. Based on the theory, we have calculated the I-V curves numerically in order to compare with the experimental ones at R_0' >> R_K. The numerical calculation agrees with the experiments qualitatively. We also discuss the R_0' dependence of the single-Josephson-junction I-V curve in terms of the superconductor-insulator transition driven by changing the coupling to the environment.Comment: 11 pages with 14 embedded figures, RevTeX4, final versio

eBay users form stable groups of common interest

Market segmentation of an online auction site is studied by analyzing the users' bidding behavior. The distribution of user activity is investigated and a network of bidders connected by common interest in individual articles is constructed. The network's cluster structure corresponds to the main user groups according to common interest, exhibiting hierarchy and overlap. Key feature of the analysis is its independence of any similarity measure between the articles offered on eBay, as such a measure would only introduce bias in the analysis. Results are compared to null models based on random networks and clusters are validated and interpreted using the taxonomic classifications of eBay categories. We find clear-cut and coherent interest profiles for the bidders in each cluster. The interest profiles of bidder groups are compared to the classification of articles actually bought by these users during the time span 6-9 months after the initial grouping. The interest profiles discovered remain stable, indicating typical interest profiles in society. Our results show how network theory can be applied successfully to problems of market segmentation and sociological milieu studies with sparse, high dimensional data.Comment: Major revision of the manuscript. Methodological improvements and inclusion of analysis of temporal development of user interests. 19 pages, 12 figures, 5 table

Thomas-Fermi-Dirac-von Weizsacker hydrodynamics in laterally modulated electronic systems

We have studied the collective plasma excitations of a two-dimensional electron gas with an arbitrary lateral charge-density modulation. The dynamics is formulated using a previously developed hydrodynamic theory based on the Thomas-Fermi-Dirac-von Weizsacker approximation. In this approach, both the equilibrium and dynamical properties of the periodically modulated electron gas are treated in a consistent fashion. We pay particular attention to the evolution of the collective excitations as the system undergoes the transition from the ideal two-dimensional limit to the highly-localized one-dimensional limit. We also calculate the power absorption in the long-wavelength limit to illustrate the effect of the modulation on the modes probed by far-infrared (FIR) transmission spectroscopy.Comment: 27 page Revtex file, 15 Postscript figure

Biological weed control to relieve millions from ambrosia allergies in Europe

Invasive alien species (IAS) can substantially affect ecosystem services and human well-being. However, quantitative assessments of their impact on human health are rare, and the benefits of implementing sustainable IAS management likely to be underestimated. Here we report the effects of the allergenic plant Ambrosia artemisiifolia on public health in Europe and the potential impact of the accidentally introduced leaf beetle Ophraella communa on the number of patients and healthcare costs. We find that, prior to the establishment of O. communa, some 13.5 million persons suffered from Ambrosia-induced allergies in Europe, causing costs of Euro 7.4 billion annually. Our projections reveal that biological control of A. artemisiifolia will reduce the number of patients by approximately 2.3 million and the health costs by Euro 1.1 billion per year. Our conservative calculations indicate that the currently discussed economic costs of IAS underestimate the real costs and thus also the benefits from biological control