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511.
Roberto Terzano Tanja Mimmo Bart Vekemans Laszlo Vincze Gerald Falkenberg Nicola Tomasi Magali Schnell Ramos Roberto Pinton Stefano Cesco 《Analytical and bioanalytical chemistry》2013,405(16):5411-5419
The development of highly brilliant synchrotron facilities all around the world is opening the way to new research in biological sciences including speciation studies of trace elements in plants. In this paper, for the first time, iron (Fe) speciation in xylem sap has been assessed by X-ray absorption near-edge structure (XANES) spectroscopy at the highly brilliant synchrotron PETRA III, beamline P06. Both standard organic Fe-complexes and xylem sap samples of Fe-deficient tomato plants were analyzed. The high photon flux provided by this X-ray synchrotron source allows on one side to obtain good XANES spectra in a reasonable amount of time (approx. 15 min for 200 eV scan) at low Fe concentrations (sub parts-per-million), while on the other hand may cause radiation damage to the sample, despite the sample being cooled by a stream of liquid nitrogen vapor. Standard Fe-complexes such as Fe(III)-succinate, Fe(III)-α-ketoglutarate, and Fe(III)-nicotianamine are somehow degraded when irradiated with synchrotron X-rays and Fe(III) can undergo photoreduction. Degradation of the organic molecules was assessed by HPLC-UV/Vis analyses on the same samples investigated by X-ray absorption spectroscopy (XAS). Fe speciation in xylem sap samples revealed Fe(III) to be complexed by citrate and acetate. Nevertheless, artifacts created by radiation damage cannot be excluded. The use of highly brilliant synchrotrons as X-ray sources for XAS analyses can dramatically increase the sensitivity of the technique for trace elements thus allowing their speciation in xylem sap. However, great attention must be paid to radiation damage, which can lead to biased results. Figure
Instrumental set-up for XANES measurements; Fe K-edge XANES spectrum for a xylem sap sample showing the determined Fe-speciation; chromatographic profile of the xylem sap sample showing organic acid composition 相似文献
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Alexei Daletskii Yuri Kondratiev Yuri Kozitsky Tanja Pasurek 《Journal of statistical physics》2014,156(1):156-176
Quenched thermodynamic states of an amorphous ferromagnet are studied. The magnet is a countable collection of point particles chaotically distributed over \(\mathbb {R}^d\) , \(d\ge 2\) . Each particle bears a real-valued spin with symmetric a priori distribution; the spin-spin interaction is pair-wise and attractive. Two spins are supposed to interact if they are neighbors in the graph defined by a homogeneous Poisson point process. For this model, we prove that with probability one: (a) quenched thermodynamic states exist; (b) they are multiple if the intensity of the underlying point process and the inverse temperature are big enough; (c) there exist multiple quenched thermodynamic states which depend on the realizations of the underlying point process in a measurable way. 相似文献
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Methandiide as a Non‐Innocent Ligand in Carbene Complexes: From the Electronic Structure to Bond Activation Reactions and Cooperative Catalysis 下载免费PDF全文
Dipl.‐Chem. Julia Becker Tanja Modl Dr. Viktoria H. Gessner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(36):11295-11299
The synthesis of a ruthenium carbene complex based on a sulfonyl‐substituted methandiide and its application in bond activation reactions and cooperative catalysis is reported. In the complex, the metal–carbon interaction can be tuned between a Ru?C single bond with additional electrostatic interactions and a Ru?C double bond, thus allowing the control of the stability and reactivity of the complex. Hence, activation of polar and non‐polar bonds (O?H, H?H) as well as dehydrogenation reactions become possible. In these reactions the carbene acts as a non‐innocent ligand supporting the bond activation as nucleophilic center in the 1,2‐addition across the metal–carbon double bond. This metal–ligand cooperativity can be applied in the catalytic transfer hydrogenation for the reduction of ketones. This concept opens new ways for the application of carbene complexes in catalysis. 相似文献
518.
NMR Fingerprints of the Drug‐like Natural‐Product Space Identify Iotrochotazine A: A Chemical Probe to Study Parkinson’s Disease 下载免费PDF全文
Dr. Tanja Grkovic Dr. Rebecca H. Pouwer Marie‐Laure Vial Luca Gambini Alba Noël Dr. John N. A. Hooper Dr. Stephen A. Wood Dr. George D. Mellick Prof. Dr. Ronald J. Quinn 《Angewandte Chemie (International ed. in English)》2014,53(24):6070-6074
The NMR spectrum of a mixture of small molecules is a fingerprint of all of its components. Herein, we present an NMR fingerprint method that takes advantage of the fact that fractions contain simplified NMR profiles, with minimal signal overlap, to allow the identification of unique spectral patterns. The approach is exemplified in the identification of a novel natural product, iotrochotazine A ( 1 ), sourced from an Australian marine sponge Iotrochota sp. Compound 1 was used as a chemical probe in a phenotypic assay panel based on human olfactory neurosphere‐derived cells (hONS) from idiopathic Parkinson’s disease patients. Compound 1 at 1 μM was not cytotoxic but specifically affected the morphology and cellular distribution of lysosomes and early endosomes. 相似文献
519.
Voss CV Gruber CC Faber K Knaus T Macheroux P Kroutil W 《Journal of the American Chemical Society》2008,130(42):13969-13972
Black and white are opposites as are oxidation and reduction. Performing an oxidation, for example, of a sec-alcohol and a reduction of the corresponding ketone in the same vessel without separation of the reagents seems to be an impossible task. Here we show that oxidative cofactor recycling of NADP (+) and reductive regeneration of NADH can be performed simultaneously in the same compartment without significant interference. Regeneration cycles can be run in opposing directions beside each other enabling one-pot transformation of racemic alcohols to one enantiomer via concurrent enantioselective oxidation and asymmetric reduction employing defined alcohol dehydrogenases with opposite stereo- and cofactor-preference. Thus, by careful selection of appropriate enzymes, NADH recycling can be performed in the presence of NADP (+) recycling to achieve overall, for example, deracemisation of sec-alcohols or stereoinversion representing a possible concept for a "green" equivalent to the chemical-intensive Mitsunobu inversion. 相似文献
520.
Mladenovic M Fink RF Thiel W Schirmeister T Engels B 《Journal of the American Chemical Society》2008,130(27):8696-8705
Papain-like cysteine proteases are ubiquitous proteolytic enzymes. The protonated His199/deprotonated Cys29 ion pair (cathepsin B numbering) in the active site is essential for their proper functioning. The presence of this ion pair stands in contrast to the corresponding intrinsic residue p K a values, indicating a strong influence of the enzyme environment. In the present work we show by molecular dynamics simulations on quantum mechanical/molecular mechanical (QM/MM) potentials that the ion pair is stabilized by a complex hydrogen bond network which comprises several amino acids situated in the active site of the enzyme and 2-4 water molecules. QM/MM reaction path computations for the proton transfer from His199 to the thiolate of the Cys29 moiety indicate that the ion pair is about 32-36 kJ mol (-1) more stable than the neutral form if the whole hydrogen bonding network is active. Without any hydrogen bonding network the ion pair is predicted to be significantly less stable than the neutral form. QM/MM charge deletion analysis and QM model calculations are used to quantify the stabilizing effect of the active-site residues and the L1 helix in favor of the zwitterionic form. The active-site water molecules contribute about 30 kJ mol (-1) to the overall stabilization. Disruption of the hydrogen bonding network upon substrate binding is expected to enhance the nucleophilic reactivity of the thiolate. 相似文献