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21.
C. H. Gast J. C. Kraak 《International journal of environmental analytical chemistry》2013,93(4):297-312
Abstract The suitability of HPLC (normal and reversed phase adsorption) with UV or post-column reaction detection for the analysis of organomercurials was investigated systematically. The separation of organomercurials is best carried out on a reversed phase system with a C-8 bonded phase material as the stationary phase and acetonitrile-aqueous sodium bromide mixtures as the mobile phase. The precision and detection limit of the method and the efficiency of the extraction procedure were established. For the alkylmercury compounds the lowest limit of detection (80ppb) was obtained with the dithizone reaction detection and for the phenylmercury compounds with UV detection (60ppb). A chromatogram of a spiked fish (2ppmHg) and a river water sample (50ppbHg) is shown. 相似文献
22.
Stable nitrogen isotopes in essential versus non-essential amino acids of different plankton size fractions 总被引:1,自引:0,他引:1
The stable nitrogen isotope values (delta(15)N) of the essential amino acid (EAA) leucine and the delta(15)N values of six non-essential amino acids (NEAAs) from plankton size fractions from the South China Sea (SCS) were analysed. Data from the SCS were collected during two cruises in July 2003 and 2004 onboard of RV Nghien Cuu Bien. The delta(15)N values of alanine, aspartic acid, glutamic acid and leucine increased with size at all sites. The delta(15)N of glycine did not increase with size, the delta(15)N of tyrosine increased with size only at offshore stations and the delta(15)N of proline increased with size only at inshore stations. We found highly significant correlations between the delta(15)N ratios of leucine to the delta(15)N ratios of glutamic acid, proline, alanine, tyrosine and aspartic acid at oligotrophic sites of enhanced nitrogen fixation. In contrast thereto these correlations were less distinct or absent at more eutrophic sites of low nitrogen fixation. A comparison with an independent data set from the tropical North Atlantic revealed intriguing similar patterns. We interpret these patterns as result of the connected metabolism of EAA and NEAA in zooplankton at sites of nitrogen limitation. 相似文献
23.
Julia Beerhues Maren Neubrand Dr. Sebastian Sobottka Dr. Nicolás I. Neuman Hannes Aberhan Shubhadeep Chandra Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(21):6557-6568
Carbene-based radicals are important for both fundamental and applied chemical research. Herein, extensive electrochemical investigations of nine different 1,2,3-triazolylidene selenium adducts are reported. It is found that the half-wave potentials of the first reduction of the selones correlate with their calculated LUMO levels and the LUMO levels of the corresponding triazolylidene-based mesoionic carbenes (MICs). Furthermore, unexpected quasi-reversibility of the reduction of two triazoline selones, exhibiting comparable reduction potentials, was discovered. Through UV/Vis/NIR and EPR spectroelectrochemical investigations supported by DFT calculations, the radical anion was unambiguously assigned to be triazoline centered. This electrochemical behavior was transferred to a triazolylidene-type MIC-gold phenyl complex resulting in a MIC-radical coordinated AuI species. Apart from UV-Vis-NIR and EPR spectroelectrochemical investigations of the reduction, the reduced gold-coordinated MIC radical complex was also formed in situ in the bulk through chemical reduction. This is the first report of a monodentate triazolylidene-based MIC ligand that can be reduced to its anion radical in a metal complex. The results presented here provide design principles for stabilizing radicals based on MICs. 相似文献
24.
Aamir Iqbal Waidha Humera Khatoon Siddiqui Dr. Yuji Ikeda Dr. Maren Lepple Dr. Sami Vasala Manuel Donzelli Dr. A. D. Fortes Dr. Peter Slater Dr. Blazej Grabowski Dr. Ulrike I. Kramm Dr. Oliver Clemens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(38):9763-9767
A new vacancy ordered, anion deficient perovskite modification with composition of BaCoO2.67 (Ba3Co3O8□1) has been prepared via a two-step heating process. Combined Rietveld analysis of neutron and X-ray powder diffraction data shows a novel ordering of oxygen vacancies not known before for barium cobaltates. A combination of neutron powder diffraction, magnetic measurements, and density functional theory (DFT) studies confirms G-type antiferromagnetic ordering. From impedance measurements, the electronic conductivity of the order of 10−4 S cm−1 is determined. Remarkably, the bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is found to be comparable to that of Ba0.5Sr0.5Co0.8Fe0.2O3–y, confirming that charge-ordered anion deficient non-cubic perovskites can be highly efficient catalysts. 相似文献
25.
Enzymatic Conversion of Flavonoids using Bacterial Chalcone Isomerase and Enoate Reductase 下载免费PDF全文
Dipl.‐Biol. Mechthild Gall Dipl.‐Biochem. Maren Thomsen Dipl.‐Biochem. Christin Peters Dr. Ioannis V. Pavlidis M. Sc. Patrick Jonczyk M. Sc. Philipp P. Grünert Dr. Sascha Beutel Prof. Dr. Thomas Scheper Egon Gross Dr. Michael Backes Dr. Torsten Geißler Dr. Jakob P. Ley Dr. Jens‐Michael Hilmer Dr. Gerhard Krammer Dr. Gottfried J. Palm Prof. Dr. Winfried Hinrichs Prof. Dr. Uwe T. Bornscheuer 《Angewandte Chemie (International ed. in English)》2014,53(5):1439-1442
Flavonoids are a large group of plant secondary metabolites with a variety of biological properties and are therefore of interest to many scientists, as they can lead to industrially interesting intermediates. The anaerobic gut bacterium Eubacterium ramulus can catabolize flavonoids, but until now, the pathway has not been experimentally confirmed. In the present work, a chalcone isomerase (CHI) and an enoate reductase (ERED) could be identified through whole genome sequencing and gene motif search. These two enzymes were successfully cloned and expressed in Escherichia coli in their active form, even under aerobic conditions. The catabolic pathway of E. ramulus was confirmed by biotransformations of flavanones into dihydrochalcones. The engineered E. coli strain that expresses both enzymes was used for the conversion of several flavanones, underlining the applicability of this biocatalytic cascade reaction. 相似文献
26.
Dr. Christoph Kieninger Dr. Klaus Wurst Dr. Maren Podewitz Dr. Maria Stanley Dr. Evelyne Deery Dr. Andrew D. Lawrence Prof. Dr. Klaus R. Liedl Prof. Dr. Martin J. Warren Prof. Dr. Bernhard Kräutler 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):20304-20311
The (formal) replacement of Co in cobalamin ( Cbl ) by NiII generates nibalamin ( Nibl ), a new transition-metal analogue of vitamin B12. Described here is Nibl , synthesized by incorporation of a NiII ion into the metal-free B12 ligand hydrogenobalamin ( Hbl ), itself prepared from hydrogenobyric acid ( Hby ). The related NiII corrin nibyric acid ( Niby ) was similarly synthesized from Hby , the metal-free cobyric acid ligand. The solution structures of Hbl , and Niby and Nibl , were characterized by spectroscopic studies. Hbl features two inner protons bound at N2 and N4 of the corrin ligand, as discovered in Hby . X-ray analysis of Niby shows the structural adaptation of the corrin ligand to NiII ions and the coordination behavior of NiII. The diamagnetic Niby and Nibl , and corresponding isoelectronic CoI corrins, were deduced to be isostructural. Nibl is a structural mimic of four-coordinate base-off Cbls , as verified by its ability to act as a strong inhibitor of bacterial adenosyltransferase. 相似文献
27.
Maren Lorenzen Peter Bsecke Christian Riekel Karen Reynders Harry Reynaers Noel Overbergh 《Macromolecular rapid communications》1996,17(3):189-192
Small-angle X-ray scattering using synchrotron radiation at pressures up to 700 MPa has been performed on triblock-copolymer gels, polystyrene-rubber-polystyrene with poly(ethylene/butylene) as the rubber mid-blocks. A 2-stage pressure behaviour could be verified by comparison of the experimental data with the Tait-equation and a model of pressure screening. 相似文献
28.
29.
Chlorophyll‐Derived Yellow Phyllobilins of Higher Plants as Medium‐Responsive Chiral Photoswitches 下载免费PDF全文
Dr. Chengjie Li Dr. Klaus Wurst Dr. Steffen Jockusch Prof. Karl Gruber Dr. Maren Podewitz Prof. Klaus R. Liedl Prof. Bernhard Kräutler 《Angewandte Chemie (International ed. in English)》2016,55(51):15760-15765
The fall colors are signs of chlorophyll breakdown, the biological process in plants that generates phyllobilins. Most of the abundant natural phyllobilins are colorless, but yellow phyllobilins (phylloxanthobilins) also occur in fall leaves. As shown here, phylloxanthobilins are unique four‐stage photoswitches. Which switching mode is turned on is controlled by the molecular environment. In polar media, phylloxanthobilins are monomeric and undergo photoreversible Z/E isomerization, similar to that observed for bilirubin. Unlike bilirubin, however, the phylloxanthobilin Z isomers photodimerize in apolar solvents by regio‐ and stereospecific thermoreversible [2+2] cycloadditions from self‐assembled hydrogen‐bonded dimers. X‐ray analysis revealed the first stereostructure of a phylloxanthobilin and its hydrogen‐bonded self‐templating architecture, helping to rationalize its exceptional photoswitch features. The chemical behavior of phylloxanthobilins will play a seminal role in identifying biological roles of phyllobilins. 相似文献
30.
The 3 MnIV title compound has been prepared and characterized by X-ray crystallography and magnetochemistry; the complex contains a [Mn(mu-O)2Mn(mu-O)2Mn]4+ core and possesses an S = 3/2 ground state. 相似文献