204 research outputs found

    Holographic recording of laser-induced plasma

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    We report on a holographic probing technique that allows for measurement of free-electron distribution with fine spatial detail. Plasma is generated by focusing a femtosecond pulse in air. We also demonstrate the capability of the holographic technique of capturing the time evolution of the plasma-generation process

    Sequential Catalytic Modification of the Lignin alpha-Ethoxylated beta-O-4 Motif To Facilitate C-O Bond Cleavage by Ruthenium-Xantphos Catalyzed Hydrogen Transfer

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    Lignin is an abundant natural biopolymer that has the potential to act as a renewable feedstock for valuable aromatic compounds via selective catalytic depolymerization. In recent years, elegant, mild, catalytic hydrogen neutral C-O bond cleavage methodologies have been developed on model compounds yielding acetophenone derivatives. However, none of these have been reported to be effective once applied to lignin. One of the reasons for this is the highly functionalized nature of the native lignin beta-O-4 motif; which is often not taken into account in the beta-O-4 model compounds used for methodology development. In this work, we demonstrate the development of a stepwise modification protocol on lignin beta-O-4 model compounds to overall yield a partially defunctionalized beta-O-4 motif. This was achieved by making use of an a-ethoxylated beta-O-4 motif that is readily available from ethanosolv extraction of lignocellulosic biomass. This specific motif allowed us to apply selective copper catalyzed aerobic oxidation and subsequent rhodium catalyzed decarbonylation of the primary hydroxyl group in the y position. The obtained partially defunctionalized beta-O-4 lignin motif allowed effective homogeneous ruthenium catalyzed hydrogen neutral C-O bond cleavage (>99% of 3,4-dimethoxyacetophenone and >99% of guaiacol). The stepwise modification strategy was extended to walnut ethanosolv lignin, demonstrating that the specific structural motifs are accessible from such a readily available lignin. Overall, this work illustrates that the structure of lignin can be strategically modified to allow access to otherwise inaccessible specific aromatic compounds via selective depolymerization methodologies

    Experimental studies on a combined pyrolysis/staged condensation/hydrotreatment approach to obtain biofuels and biobased chemicals

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    Fast pyrolysis is an efficient technology to convert lignocellulosic biomass to a liquid product. However, the high contents of oxygenated compounds and water hinder the direct utilization of pyrolysis oils. Here, we report an upgrading concept to obtain liquid products with improved product properties and enriched in valuable low molecular weight chemicals and particularly alkylphenols. It entails two steps, viz. i) pyrolysis with in-situ staged condensation at multiple kg scale followed by ii) a catalytic hydrotreatment of selected fractions using a Ru/C catalyst. Of all pyrolysis oil fractions after staged condensation, the product collected in a condenser equipped with an electrostatic precipitator (ESP) at 120 °C was identified as the most attractive for hydrotreatment when considering product yields and composition. The best hydrotreatment results (Ru/C, 350 °C, 100 bar H2, 4 h) were achieved using beechwood and walnut shells as feedstock, resulting in a high oil yield (about 64 wt% based on pyrolysis oil fraction intake) with a higher heating value of about 37 MJ/kg and enriched in alkylphenols (about 16 wt%). Overall, it was shown that the type of biomass (beech sawdust, walnut granulates, and pine/spruce sawdust) has a limited impact on liquid and alkylphenols yields which implies feedstock flexibility of this integrated concept

    Multi-threshold second-order phase transition

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    We present a theory of the multi-threshold second-order phase transition, and experimentally demonstrate the multi-threshold second-order phase transition phenomenon. With carefully selected parameters, in an external cavity diode laser system, we observe second-order phase transition with multiple (three or four) thresholds in the measured power-current-temperature three dimensional phase diagram. Such controlled death and revival of second-order phase transition sheds new insight into the nature of ubiquitous second-order phase transition. Our theory and experiment show that the single threshold second-order phase transition is only a special case of the more general multi-threshold second-order phase transition, which is an even richer phenomenon.Comment: 5 pages, 3 figure

    A Recombination Hotspot in a Schizophrenia-Associated Region of GABRB2

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    Background: Schizophrenia is a major disorder with complex genetic mechanisms. Earlier, population genetic studies revealed the occurrence of strong positive selection in the GABRB2 gene encoding the β2 subunit of GABAA receptors, within a segment of 3,551 bp harboring twenty-nine single nucleotide polymorphisms (SNPs) and containing schizophrenia-associated SNPs and haplotypes. Methodology/Principal Findings:In the present study, the possible occurrence of recombination in this 'S1-S29' segment was assessed. The occurrence of hotspot recombination was indicated by high resolution recombination rate estimation, haplotype diversity, abundance of rare haplotypes, recurrent mutations and torsos in haplotype networks, and experimental haplotyping of somatic and sperm DNA. The sub-segment distribution of relative recombination strength, measured by the ratio of haplotype diversity (Hd) over mutation rate (θ), was indicative of a human specific Alu-Yi6 insertion serving as a central recombining sequence facilitating homologous recombination. Local anomalous DNA conformation attributable to the Alu-Yi6 element, as suggested by enhanced DNase I sensitivity and obstruction to DNA sequencing, could be a contributing factor of the increased sequence diversity. Linkage disequilibrium (LD) analysis yielded prominent low LD points that supported ongoing recombination. LD contrast revealed significant dissimilarity between control and schizophrenic cohorts. Among the large array of inferred haplotypes, H26 and H73 were identified to be protective, and H19 and H81 risk-conferring, toward the development of schizophrenia. Conclusions/Significance: The co-occurrence of hotspot recombination and positive selection in the S1-S29 segment of GABRB2 has provided a plausible contribution to the molecular genetics mechanisms for schizophrenia. The present findings therefore suggest that genome regions characterized by the co-occurrence of positive selection and hotspot recombination, two interacting factors both affecting genetic diversity, merit close scrutiny with respect to the etiology of common complex disorders. © 2010 Ng et al
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