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91.
Janine Will Lars Schneider Dr. Jonathan Becker Jun.-Prof. Dr. Sabine Becker Andreas Miska Christopher Gawlig Prof. Dr. Siegfried Schindler 《Israel journal of chemistry》2020,60(10-11):999-1003
A new tripodal imine ligand tris(2-(propan-2-ylideneamino)ethyl)amine (imine3tren) was prepared in order to stabilize high valent iron-oxido complexes. Iron complexes were synthesized in template reactions from iron(II) salts, tris(2-aminoethyl)amine (tren) and acetone. Due to the reversibility of the imine formation, complexes with different ligands were obtained depending on the reaction conditions. Three complexes, [Fe(imine3tren)(OAc)2] ( 1 ), [Fe(imine3tren)(OAc)]OTf ( 2 ) and [(imine3tren)2Fe2(F)2](SbF6)2 ( 3 ), could be synthesized and structurally characterized. However, reactions with hydrogen peroxide, iodosobenzene or ozone did not lead to any kind of “oxygen adduct” complex that could be spectroscopically observed. 相似文献
92.
Pengfei Liu Kacper Januchta Lars R. Jensen Mathieu Bauchy Morten M. Smedskjaer 《Journal of the American Ceramic Society》2020,103(2):944-954
Lithium aluminoborate glasses have recently been found to feature high resistance to crack initiation during indentation, but suffer from relatively low hardness and chemical durability. To further understand the mechanical properties of this glass family and their correlation with the network structure, we here study the effect of adding SiO2 to a 25Li2O–20Al2O3–55B2O3 glass on the structure and mechanical properties. Addition of silica increases the average network rigidity, but meanwhile its open tetrahedral structure decreases the atomic packing density. Consequently, we only observe a minor increase in hardness and glass transition temperature, and a decrease in Poisson's ratio. The addition of SiO2, and thus removal of Al2O3 and/or B2O3, also makes the network less structurally adaptive to applied stress, since Al and B easily increase their coordination number under pressure, while this is not the case for Si under modest pressures. As such, although the silica-containing networks have more free volume, they cannot densify more during indentation, which in turn leads to an overall decrease in crack resistance upon SiO2 addition. Our work shows that, although pure silica glass has very high glass transition temperature and relatively high hardness, its addition in oxide glasses does not necessarily lead to significant increase in these properties due to the complex structural interactions in mixed network former glasses and the competitive effects of free volume and network rigidity. 相似文献
93.
Lei Zhang Dr. Marina Toplak Raspudin Saleem-Batcha Lars Höing Dr. Roman Jakob Dr. Nico Jehmlich Prof. Dr. Martin von Bergen Prof. Timm Maier Prof. Robin Teufel 《Chembiochem : a European journal of chemical biology》2023,24(2):e202200632
Antimicrobial resistance represents a major threat to human health and knowledge of the underlying mechanisms is therefore vital. Here, we report the discovery and characterization of oxidoreductases that inactivate the broad-spectrum antibiotic chloramphenicol via dual oxidation of the C3-hydroxyl group. Accordingly, chloramphenicol oxidation either depends on standalone glucose-methanol-choline (GMC)-type flavoenzymes, or on additional aldehyde dehydrogenases that boost overall turnover. These enzymes also enable the inactivation of the chloramphenicol analogues thiamphenicol and azidamfenicol, but not of the C3-fluorinated florfenicol. Notably, distinct isofunctional enzymes can be found in Gram-positive (e. g., Streptomyces sp.) and Gram-negative (e. g., Sphingobium sp.) bacteria, which presumably evolved their selectivity for chloramphenicol independently based on phylogenetic analyses. Mechanistic and structural studies provide further insights into the catalytic mechanisms of these biotechnologically interesting enzymes, which, in sum, are both a curse and a blessing by contributing to the spread of antibiotic resistance as well as to the bioremediation of chloramphenicol. 相似文献
94.
Studies using both in vitro and in vivo techniques have repeatedly shown that endothelium-dependent vasodilation (EDV) is impaired in different forms of experimental
as well as human hypercholesterolemia. Clearly this impaired EDV can be reversed by lowering cholesterol levels by diet or
medical therapy. Competitive blocking of l-arginine, changes in nitric oxide synthase acitivity, increased release of endothelin-1, and inactivation of nitric oxide
due to superoxide ions all contribute to the impairment in EDV during dyslipidemia. The oxidation of low density lipoprotein,
with its compound lysophosphatidylcholine, plays a critical role in these events. However, data on the role of triglycerides
and fat-rich meals regarding EDV are not so consistent as data for cholesterol, although a view that the compositions of individual
fatty acids and antioxidants are of major importance is emerging. Thus, this review shows that while impaired FDV is a general
feature of hypercholesterolemia, the mechanisms involved and the therapeutic opportunities available still have to be investigated.
Furthermore, discrepancies regarding the role of triglycerides and fat content in food may be explained by divergent effects
of different fatty acids on the endothelium. 相似文献
95.
Anna Puig-Molina Lars Pleth Nielsen Alfons M. Molenbroek Konrad Herbst 《Catalysis Letters》2004,92(1-2):29-34
The chemical state of arsenic deposited on a NiMoP/Al2O3 hydrotreating catalyst exposed to ppb levels of arsenic over several years in a refinery reactor has been studied by in situ EXAFS. In the as-received As-NiMoP catalyst, arsenic is exclusively coordinated to oxygen atoms. Upon sulfiding the sample in 2%H2S/2%H2/96%He, the As atoms become surrounded by approximately two sulfur atoms. No evidence was found for Ni–As bond formation. A possible model for the As local environment is suggested on the basis of combined EXAFS results, STM data and FEFF8.0 simulations (program for ab initio calculations on multiple scattering XAFS and XANES). The FEFF8.0 simulations of the proposed model are in accord with the experimental data measured at the As K edge. In this model, an As atom is located at the edge of a hexagonally truncated Ni-MoS2 slab and is blocking the active NiMoS site. 相似文献
96.
Photoreduction of Shewanella oneidensis Extracellular Cytochromes by Organic Chromophores and Dye‐Sensitized TiO2 下载免费PDF全文
Emma V. Ainsworth Dr. Colin W. J. Lockwood Dr. Gaye F. White Dr. Ee Taek Hwang Dr. Tsubasa Sakai Manuela A. Gross Prof. David J. Richardson Dr. Thomas A. Clarke Dr. Lars J. C. Jeuken Dr. Erwin Reisner Prof. Julea N. Butt 《Chembiochem : a European journal of chemical biology》2016,17(24):2324-2333
The transfer of photoenergized electrons from extracellular photosensitizers across a bacterial cell envelope to drive intracellular chemical transformations represents an attractive way to harness nature's catalytic machinery for solar‐assisted chemical synthesis. In Shewanella oneidensis MR‐1 (MR‐1), trans‐outer‐membrane electron transfer is performed by the extracellular cytochromes MtrC and OmcA acting together with the outer‐membrane‐spanning porin ? cytochrome complex (MtrAB). Here we demonstrate photoreduction of solutions of MtrC, OmcA, and the MtrCAB complex by soluble photosensitizers: namely, eosin Y, fluorescein, proflavine, flavin, and adenine dinucleotide, as well as by riboflavin and flavin mononucleotide, two compounds secreted by MR‐1. We show photoreduction of MtrC and OmcA adsorbed on RuII‐dye‐sensitized TiO2 nanoparticles and that these protein‐coated particles perform photocatalytic reduction of solutions of MtrC, OmcA, and MtrCAB. These findings provide a framework for informed development of strategies for using the outer‐membrane‐associated cytochromes of MR‐1 for solar‐driven microbial synthesis in natural and engineered bacteria. 相似文献
97.
Hong?ZhangEmail author Lars?Saaby?Pedersen Dorther?Kristensen Jens?Adler-Nissen Hans?Christian Holm 《Journal of the American Oil Chemists' Society》2004,81(7):653-658
Lipozyme TL IM-catalyzed interesterification for the modification of margarine fats was carried out in a batch reactor at
70°C with a lipase dosage of 4%. Solid fat content (SFC) was used to monitor the reaction progress. Lipase-catalyzed interesterification,
which led to changes in the SFC, was assumed to be a first-order reversible reaction. Accordingly, the change in SFC vs. reaction
time was described by an exponential model. The model contained three parameters, each with a particular physical or chemical
meaning: (i) the initial SFC (SFC0), (ii) the change in SFC (ΔSFC) from the initial to the equilibrium state, and (iii) the reaction rate constant value (k). SFCo and ΔSFC were related to only the types of blends and the blend ratios. The rate constant k was related to lipase activity on a given oil blend. Evaluation of the model was carried out with two groups of oil blends,
i.e., palm stearin/coconut oil in weight ratios of 90∶10, 80∶20, and 70∶30, and soybean oil/fully hydrogenated soybean oil
in weight ratios of 80∶20, 65∶35, and 50∶50. Correlation coefficients higher than 0.99 between the experimental and predicted
values were observed for SFC at temperatures above 30°C. The model is useful for predicting changes in the SFC during lipase-catalyzed
interesterification with a selected group of oil blends. It also can be used to control the process when particular SFC values
are targeted. 相似文献
98.
99.
The variation of the brominated indole and diterpenoid content within single and different colonies of the bryozoan Flustra foliacea was investigated. The secondary metabolite profile and concentrations of individual components of F. foliacea samples were established using GC-MS. Samples from 17 different collecting sites were analyzed. The alkaloid and diterpene composition of F. foliacea varied greatly depending upon the site of collection. Investigation of F. foliacea samples from a single site (Helgoland, North Sea) over a period of time showed that the alkaloid and diterpenoid profile remained constant, however concentrations of individual components varied significantly. The alkaloid and diterpenoid composition of different segments of a single colony was found to be constant. Only small differences could be detected in the essential oil composition of different colonies and segments of single colonies of F. foliacea. Two of the F. foliacea alkaloids were found in the gastropods Hydrobia ulva and Gibbula cinerea, and one alkaloid in the common starfish Asteria rubens, all collected from the surface of the bryozoan. 相似文献
100.
Snyder JW Zebger I Gao Z Poulsen L Frederiksen PK Skovsen E McIlroy SP Klinger M Andersen LK Ogilby PR 《Accounts of chemical research》2004,37(11):894-901
The lowest excited electronic state of molecular oxygen, singlet molecular oxygen (a1Deltag), is an intermediate in many chemical and biological processes. Tools and methods have been developed to create singlet-oxygen-based optical images of heterogeneous samples that range from phase-separated polymers to biological cells. Such images provide unique insight into a variety of oxygen-dependent phenomena, including the photoinitiated death of cells. 相似文献