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201.
Stähler J Mehlhorn M Bovensiepen U Meyer M Kusmierek DO Morgenstern K Wolf M 《Physical review letters》2007,98(20):206105
The structure of D2O clusters on a Cu(111) surface and the femtosecond dynamics of photoexcited excess electrons are investigated by low-temperature scanning tunneling microscopy and two-photon photoemission spectroscopy. Two types of amorphous ice clusters, porous and compact, which exhibit characteristic differences in electron dynamics, are identified. By titration with Xe we show that in both structures solvated electrons preferentially bind on the cluster surface. 相似文献
202.
Christian Schneider Dr. Serhiy Demeshko Prof. Dr. Franc Meyer Dr. C. Gunnar Werncke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(20):6348-6353
A [Fe-S-Fe] subunit with a single sulfide bridging two low-coordinate iron ions is the supposed active site of the iron-molybdenum co-factor (FeMoco) of nitrogenase. Here we report a dinuclear monosulfido bridged diiron(II) complex with a similar complex geometry that can be oxidized stepwise to diiron(II/III) and diiron(III/III) complexes while retaining the [Fe-S-Fe] core. The series of complexes has been characterized crystallographically, and electronic structures have been studied using, inter alia, 57Fe Mössbauer spectroscopy and SQUID magnetometry. Further, cleavage of the [Fe-S-Fe] unit by CS2 is presented. 相似文献
203.
Dr. Gabriele Hierlmeier Dr. Peter Coburger Dr. Daniel J. Scott Dr. Thomas M. Maier Dr. Stefan Pelties Prof. Dr. Robert Wolf Daniel M. Pividori Prof. Dr. Karsten Meyer Dr. Nicolaas P. van Leest Prof. Dr. Bas de Bruin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(60):14936-14946
Reactions of di-tert-butyldiphosphatetrahedrane ( 1 ) with cycloocta-1,5-diene- or anthracene-stabilised metalate anions of iron and cobalt consistently afford complexes of the rarely encountered 1,2-diphosphacyclobutadiene ligand, which have previously been very challenging synthetic targets. The subsequent reactivity of 1,2-diphosphacyclobutadiene cobaltates toward various electrophiles has also been investigated and is compared to reactions of related 1,3-diphosphacyclobutadiene complexes. The results highlight the distinct reactivity of such isomeric species, showing that the 1,2-isomers can act as precursors for previously unknown triphospholium ligands. The electronic structures of the new complexes were investigated by several methods, including NMR, EPR and Mößbauer spectroscopies as well as quantum chemical calculations. 相似文献
204.
C. Amsler F. H. Heinsius H. Koch B. Kopf U. Kurilla C. A. Meyer K. Peters J. Pychy M. Steinke U. Wiedner 《The European Physical Journal C - Particles and Fields》2015,75(3):124
The spin density matrix of the \(\omega \) has been determined for the reaction \({\bar{p}p}\,\rightarrow \,\omega \pi ^0\) with unpolarized in-flight data measured by the Crystal Barrel LEAR experiment at CERN. The two main decay modes of the \(\omega \) into \(\pi ^0 \gamma \) and \(\pi ^+ \pi ^- \pi ^0\) have been separately analyzed for various \({\bar{p}}\)momenta between 600 and 1940 MeV/c. The results obtained with the usual method by extracting the matrix elements via the \(\omega \) decay angular distributions and with the more sophisticated method via a full partial wave analysis are in good agreement. A strong spin alignment of the \(\omega \) is clearly visible in this energy regime and all individual spin density matrix elements exhibit an oscillatory dependence on the production angle. In addition, the largest contributing orbital angular momentum of the \({\bar{p}p~}\)system has been identified for the different beam momenta. It increases from \(L^{max}_{{\bar{p}p~}}\) \(=\) 2 at 600 MeV/c to \(L^{max}_{{\bar{p}p~}}\) \(=\) 5 at 1940 MeV/c. 相似文献
205.
Dr. Henry S. La Pierre Dr. Hajime Kameo MSc. Dominik P. Halter Dr. Frank W. Heinemann Prof. Dr. Karsten Meyer 《Angewandte Chemie (International ed. in English)》2014,53(28):7154-7157
Synthetic studies on the redox chemistry of trivalent uranium monoarene complexes were undertaken with a complex derived from the chelating tris(aryloxide)arene ligand (Ad,MeArO)3mes3?. Cyclic voltammetry of [{(Ad,MeArO)3mes}UIII] ( 1 ) revealed a nearly reversible and chemically accessible reduction at ?2.495 V vs. Fc/Fc+—the first electrochemical evidence for a formally divalent uranium complex. Chemical reduction of 1 indicates that reduction induces coordination and redox isomerization to form a uranium(IV) hydride, and addition of a crown ether results in hydride insertion into the coordinated arene to afford uranium(IV) complexes. This stoichiometric reaction sequence provides structural insight into the mechanism of arene functionalization at diuranium inverted sandwich complexes. 相似文献
206.
Inside Back Cover: Controlled Electropolymerization of Ruthenium(II) Vinylbipyridyl Complexes in Mesoporous Nanoparticle Films of TiO (Angew. Chem. Int. Ed. 19/2014) 下载免费PDF全文
207.
208.
Chien-Tai Tsai Ricardo Morales-Rodriguez Gürkan Sin Anne S. Meyer 《Applied biochemistry and biotechnology》2014,172(6):2815-2837
The objective of this study is to perform a comprehensive enzyme kinetics analysis in view of validating and consolidating a semimechanistic kinetic model consisting of homogeneous and heterogeneous reactions for enzymatic hydrolysis of lignocellulosic biomass proposed by the U.S. National Renewable Energy Laboratory (Kadam et al., Biotechnol Prog 20(3):698–705, 2004) and its variations proposed in this work. A number of dedicated experiments were carried out under a range of initial conditions (Avicel® versus pretreated barley straw as substrate, different enzyme loadings and different product inhibitors such as glucose, cellobiose and xylose) to test the hydrolysis and product inhibition mechanisms of the model. A nonlinear least squares method was used to identify the model and estimate kinetic parameters based on the experimental data. The suitable mathematical model for industrial application was selected among the proposed models based on statistical information (weighted sum of square errors). The analysis showed that transglycosylation plays a key role at high glucose levels. It also showed that the values of parameters depend on the selected experimental data used for parameter estimation. Therefore, the parameter values are not universal and should be used with caution. The model proposed by Kadam et al. (Biotechnol Prog 20(3):698–705, 2004) failed to predict the hydrolysis phenomena at high glucose levels, but when combined with transglycosylation reaction(s), the prediction of cellulose hydrolysis behaviour over a broad range of substrate concentrations (50–150 g/L) and enzyme loadings (15.8–31.6 and 1–5.9 mg protein/g cellulose for Celluclast and Novozyme 188, respectively) was possible. This is the first study introducing transglycosylation into the semimechanistic model. As long as these type of models are used within the boundary of their validity (substrate type, enzyme source and substrate concentration), they can support process design and technology improvement efforts at pilot and full-scale studies. 相似文献
209.
Solar energy is considered clean energy, and its use is predicted to increase in the near future. Most installed units today are crystalline solar cells, but the field is in constant development, and when the first dye sensitized solar cell was published by Grätzel and O'Reagan a new, third-generation, solar power was born. Highly toxic metals are used to produce the photovoltaic units today, and with the predicted increase in solar cell installation, the human health hazards of these panels could become an issue. Additionally, many of these materials are used in their nanoform, which is associated with an additional risk. In this article, we discuss the technology behind the third-generation solar cells with its valuable use of nanotechnology as well as the possible health hazard when such nanomaterials are used in solar power units. We will show that the main exposure will occur either during the development and production phases or at the end-of-life stage of the solar cells, where toxic material can leach into landfills, and subsequently into the environment and impact the ecosystem directly, or humans indirectly through edible plants or drinking water. 相似文献
210.
The new scandium(III) carbodiimides Sc2(CN2)3 and Sc2O2(CN2) were prepared by solid-state metathesis reactions between Li2(CN2) and ScCl3 and, regarding Sc2O2(CN2), Sc2O3 was added. The X-ray powder diffraction pattern refinements lead to a trigonal-rhombohedral (R3 c) crystal system for Sc2(CN2)3 and to an orthorhombic (Immm) crystal system for Sc2O2(CN2). The structure of Sc2(CN2)3 is isotypic to the well-known rare earth carbodiimides RE2(CN2)3 with the smaller cations RE = Tm, Yb, and Lu, whereas Sc2O2(CN2) is not isotypic to the known RE2O2(CN2) (RE = Y, La, Ce–Gd, except Pm) compounds. Both crystal structures are represented by layered arrangements of scandium, respectively scandium and oxide, alternating with carbodiimide layers. 相似文献