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951.
Martin Walter Dr. Walter D. C. Schenkeveld Assoc. Prof. Michael Reissner Assoc. Prof. Lars Gille Prof. Stephan M. Kraemer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3286-3300
Chrysotile asbestos is a soil pollutant in many countries. It is a carcinogenic mineral, partly due to its surface chemistry. In chrysotile, FeII and FeIII substitute Mg octahedra (Fe[6]), and FeIII substitutes Si tetrahedra (Fe[4]). Fe on fiber surfaces can generate hydroxyl radicals (HO.) in Fenton reactions, which damage biomolecules. To better understand chrysotile weathering in soils, net Mg and Si dissolution rates over the pH range 3.0–11.5 were determined in the presence and absence of biogenic ligands. Also, HO. generation and Fe bulk speciation of pristine and weathered fibers were examined by EPR and Mössbauer spectroscopy. Dissolution rates were increased by ligands and inversely related to pH with complete inhibition at cement pH (11.5). Surface-exposed Mg layers readily dissolved at low pH, but only after days at neutral pH. On longer timescales, the slow dissolution of Si layers became rate-determining. In the absence of ligands, Fe[6] precipitated as Fenton-inactive Fe phases, whereas Fe[4] (7 % of bulk Fe) remained redox-active throughout two-week experiments and at pH 7.5 generated 50±10 % of the HO. yield of Fe[6] at pristine fiber surfaces. Ligand-promoted dissolution of Fe[4] (and potentially Al[4]) labilized exposed Si layers. This increased Si and Mg dissolution rates and lowered HO. generation to near-background level. It is concluded that Fe[4] surface species control long-term HO. generation and dissolution rates of chrysotile at natural soil pH. 相似文献
952.
Tim-Oliver Kindler Christoph Alberti Jannis Sundermeier Dr. Stephan Enthaler 《ChemistryOpen》2019,8(12):1410-1412
The valorization of waste to valuable chemicals can contribute to a more resource-efficient and circular chemistry. In this regard, the selective degradation of end-of-life polymers/plastics to produce useful chemical building blocks can be a promising target. We have investigated the hydrogenative depolymerization of end-of-life poly(bisphenol A carbonate). Applying catalytic amounts of the commercial available Ruthenium-MACHO-BH complex the end-of-life polycarbonate was converted to bisphenol A and methanol. Importantly, bisphenol A can be reprocessed for the manufacture of new poly-(bisphenol A carbonate) and methanol can be utilized as energy storage material. 相似文献
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Bernd Trathnigg Muhammad Imran Malik Nicole Pircher Stephan Hayden 《Journal of separation science》2010,33(14):2052-2059
In ternary mobile phases consisting of acetone, methanol, and water, the retention of PEG on reversed‐phase columns is independent on molar mass at certain compositions of the mobile phase. Along this critical adsorption line, the retention of polypropylene glycol varies quite strongly, which can be utilized in the separation of block copolymers. Gradient elution along the critical line allows a baseline separation of all oligomers in polypropylene glycol up to approximately 25 propylene oxide units. The same resolution can be achieved in the separation of ethylene oxide‐propylene oxide block copolymers, regardless of the length of the ethylene oxide block. 相似文献
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Stephan Labsch Shute Ye Andreas Adler Jörg-Martin Neudörfl Hans-Günther Schmalz 《Tetrahedron: Asymmetry》2010,21(13-14):1745-1751
The stereospecificity of the Au(I)-catalyzed reaction of 1-alkynyl-bicyclo[4.1.0]-heptan-2-ones with nucleophiles was investigated. The substrates were prepared in non-racemic form (up to 88% ee) through parallel kinetic resolution (CBS reduction) and reoxidation of the separated diastereomeric alcohols. The key Au-catalyzed reaction was then found to proceed without significant loss of absolute stereochemical information; this way, an achiral carbocationic intermediate could be excluded. Thus, a bicyclobutonium-type intermediate seems to be attacked in a SN2-type fashion by the nucleophile in accordance with computational predictions. 相似文献
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Salah Bouhroum Joseph A. Grondin Stephan Houdier Hassan Lazrek Mohamed Rhazi Abdelouahad Tolaimate 《Journal of carbohydrate chemistry》2013,32(3):309-314
ABSTRACT Hydrazine acetate is shown to effect selective deacetylation on peracetylated glycals like D-xylal, D-glucal, D-galactal and L-rhamnal. It is demonstrated that the observed selectivity on the -4 position cannot be explained by acetyl migration during the reaction. 相似文献