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51.
52.
The dynamic scaling functions for ferromagnets above and below the critical temperature are determined using mode coupling theory. Below the critical temperature we study isotropic ferromagnets taking into account the exchange interaction only and give the first numerical solution of the resulting mode coupling equations. In the paramagnetic phase we examine how the critical dynamics is modified by the addition of the dipoledipole interaction. On the basis of this theory we are able to explain in a unifying fashion the results of different experimental methods; i.e.: neutron scattering, hyperfine interaction and electron-spin resonance. Predictions for new experiments are made. 相似文献
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54.
Baranoff E Curchod BF Frey J Scopelliti R Kessler F Tavernelli I Rothlisberger U Grätzel M Nazeeruddin MK 《Inorganic chemistry》2012,51(1):215-224
Investigations of blue phosphorescent organic light emitting diodes (OLEDs) based on [Ir(2-(2,4-difluorophenyl)pyridine)(2)(picolinate)] (FIrPic) have pointed to the cleavage of the picolinate as a possible reason for device instability. We reproduced the loss of picolinate and acetylacetonate ancillary ligands in solution by the addition of Br?nsted or Lewis acids. When hydrochloric acid is added to a solution of a [Ir(C^N)(2)(X^O)] complex (C^N = 2-phenylpyridine (ppy) or 2-(2,4-difluorophenyl)pyridine (diFppy) and X^O = picolinate (pic) or acetylacetonate (acac)), the cleavage of the ancillary ligand results in the direct formation of the chloro-bridged iridium(III) dimer [{Ir(C^N)(2)(μ-Cl)}(2)]. When triflic acid or boron trifluoride are used, a source of chloride (here tetrabutylammonium chloride) is added to obtain the same chloro-bridged iridium(III) dimer. Then, we advantageously used this degradation reaction for the efficient synthesis of tris-heteroleptic cyclometalated iridium(III) complexes [Ir(C^N(1))(C^N(2))(L)], a family of cyclometalated complexes otherwise challenging to prepare. We used an iridium(I) complex, [{Ir(COD)(μ-Cl)}(2)], and a stoichiometric amount of two different C^N ligands (C^N(1) = ppy; C^N(2) = diFppy) as starting materials for the swift preparation of the chloro-bridged iridium(III) dimers. After reacting the mixture with acetylacetonate and subsequent purification, the tris-heteroleptic complex [Ir(ppy)(diFppy)(acac)] could be isolated with good yield from the crude containing as well the bis-heteroleptic complexes [Ir(ppy)(2)(acac)] and [Ir(diFppy)(2)(acac)]. Reaction of the tris-heteroleptic acac complex with hydrochloric acid gives pure heteroleptic chloro-bridged iridium dimer [{Ir(ppy)(diFppy)(μ-Cl)}(2)], which can be used as starting material for the preparation of a new tris-heteroleptic iridium(III) complex based on these two C^N ligands. Finally, we use DFT/LR-TDDFT to rationalize the impact of the two different C^N ligands on the observed photophysical and electrochemical properties. 相似文献
55.
Egbert Müller Judith Vajda Djuro Josic Tim Schröder Romain Dabre Tim Frey 《Journal of separation science》2013,36(8):1327-1334
An essential part of the modulation of protein‐binding capacity in hydrophobic interaction chromatography is the buffer‐salt system. Besides using “single” electrolytes, multicomponent electrolyte mixtures may be used as an additional tool. Both the protein solubility and the binding capacity depend on the position of a salt in the so‐called Hofmeister series. Specific interactions are observed for an individual protein‐salt combination. For salt mixtures, selectivity, recovery, and binding capacity do not behave like for the single salts that are positioned in between the two mixed components in the Hofmeister series, as the continuous correlation would suggest. Thus, finding strategies for mixed salts could potentially lead to improved capacities in hydrophobic interaction chromatography. Mixtures of ammonium sulfate, sodium citrate, sodium sulfate, sodium chloride, sodium acetate, and glycine were used to investigate the binding capacities for lysozyme and a monoclonal antibody on various hydrophobic resins. Resin capacity for two investigated proteins increases when mixtures consisting of a chaotropic and a kosmotropic salt are applied. It seems to be related to the rather basic isoelectric points of the proteins. 相似文献
56.
H. K. Barrenscheen Margarete Frey F. Feigl L. T. Fairhall M. Settimj D. Ganassini A. Necke H. Müller Ch. Badham H. B. Taylor G. Moillère F. Weyrauch St. Litzner F. Grendel N. Schoorl H. Begemann A. Berat G. Widmark B. Vahlquist E. M. P. Widmar S. L. Oerskov J. P. Gregersen P. Iversen H. W. Mook D. D. van Sluke W. M. Kirjan W. C. Stadie E. C. Ross K. Lang H. Waelsch Gertrud Klepetar I. St. Lorant L. Kopetz J. W. Heim W. W. Práwdicz-Neminski Z. Babitsch J. F. Reith Th. von Fellenberg R. G. Turner Mina Z. Weeks A. Castille V. Henri 《Analytical and bioanalytical chemistry》1934,98(3-4):147-160
57.
M. Sc. Frederik Kramm M. Sc. Johannes Teske M. Sc. Franziska Ullwer Wolfgang Frey Prof. Dr. Bernd Plietker 《Angewandte Chemie (International ed. in English)》2018,57(40):13335-13338
Cationic Fe complexes of the general type [(Ph3P)2Fe(CO)(NO)]X (X=BF4, BArF4) catalyze the redox‐neutral cycloisomerization of 1,6‐ and 1,7‐enyneacetates to afford bicyclic cyclobutanes under mild conditions in good yields and diastereoselectivities. 相似文献
58.
Frey PA 《Chemical record (New York, N.Y.)》2001,1(4):277-289
Research on the mechanism of action of coenzyme B12, adenosylcobalamin, as a graduate student introduced the author to the field of organic free radicals in enzymology. Twenty years later, related work on S-adenosylmethionine (SAM) as a "poor man's coenzyme B12" was initiated in a detailed analysis of the mechanism of action of lysine 2,3-aminomutase (LAM). The interconversion of L-lysine and L-beta-lysine is catalyzed by LAM, which requires SAM, pyridoxal-5'-phosphate (PLP), and a [4Fe-4S] cluster as coenzymes. The mechanism of this reaction has been delineated as a radical isomerization, in which radical formation is initiated by the [4Fe-4S]-dependent cleavage of the SAM into methionine and the 5'-deoxyadenosyl radical. The mechanism of this process is discussed, together with the role of this radical in hydrogen abstraction from lysine to initiate the substrate radical isomerization. The chemistry underlying the functions of SAM, PLP, and [4Fe-4S] in the action of LAM is novel in all respects, except for the formation of a lysine-PLP aldimine at the active site. Of the four free radicals in the mechanism, three have been characterized by EPR spectroscopy. In the suicide inactivation of adenosylcobalamin-dependent dioldehydrase (DDH) by glycolaldehyde, the formation of cob(II)alamin and 5'-deoxyadenosine is accompanied by the conversion of glycolaldehyde to cis-ethanesemidione radical at the active site. The cis-ethanesemidione radical has been characterized by EPR spectroscopy. Its exceptional stability at the active site is the basis for the inactivation of DDH by glycolaldehyde. 相似文献
59.
60.
Frey M Harris SG Holmes JM Nation DA Parsons S Tasker PA Winpenny RE 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(8):1407-1415
Two polymetallic iron(III) complexes 1 and 2 have been synthesised from the known corrosion inhibitor 3-(4-methylbenzoyl)-propionic acid HL1 and their crystal structures determined. Coordination geometries extracted from these structures have been used as the basis for molecular modelling onto idealised iron(III) oxide surfaces as an aid to understanding the efficacy of inhibitors of the 4-keto acid type. The proposed mode of action involves 1,3-bridging didentate coordination of the carboxylate function of L1 to two FeIII ions, hydrogen-bond formation between the 4-keto group of L1 and a bridging surface hydroxy group, as well as close packing of the aromatic end groups, which should generate a hydrophobic barrier on the surface. Adsorption isotherm experiments have been used to compare the strengths of binding of related carboxylic acids onto iron(III) oxide surfaces and indicate that the presence of the 4-keto function leads to the formation of significantly more stable surface complexes. 相似文献