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161.
162.
163.
Schwartz L Ekström J Lomoth R Ott S 《Chemical communications (Cambridge, England)》2006,(40):4206-4208
The first model of the iron hydrogenase active site has been prepared in which an amine ligand is loosely coordinated to an Fe(i) centre, and can be replaced by a solvent molecule; irrespective of the ligand set, the one electron reduction of both complexes is chemically reversible and is shown to proceed through the same species which features a bridging CO ligand. 相似文献
164.
The aqueous phase behavior of a series of complex salts, containing cationic surfactants with polymeric counterions, has been investigated by visual inspection and small-angle X-ray scattering (SAXS). The salts were alkyltrimethylammonium polyacrylates, CxTAPAy, based on all combinations of five surfactant chain lengths (C6, C8, C10, C12, and C16) and two lengths of the polyacrylate chain (30 and 6 000 repeating units). At low water contents, all complex salts except C6TAPA6000 formed hexagonal and/or cubic Pm3n phases, with the hexagonal phase being favored by lower water contents. The aggregate dimensions in the liquid crystalline phases changed with the surfactant chain length. The determined micellar aggregation numbers of the cubic phases indicated that the micelles were only slightly aspherical. At high water contents, the C6TAPAy salts were miscible with water, whereas the other complex salts featured wide miscibility gaps with a concentrated phase in equilibrium with a (sometimes very) dilute aqueous solution. Thus, the attraction between oppositely charged surfactant aggregates and polyions decreases with decreasing surfactant chain length, and with decreasing polyion length, resulting in an increased miscibility with water. The complex salt with the longest surfactant chains and polyions gave the widest miscibility gap, with a concentrated hexagonal phase in equilibrium with almost pure water. A decrease in the attraction led to cubic-micellar and micellar-micellar coexistence in the miscibility gap and to an increasing concentration of the complex salt in the dilute phase. For each polyion length, the mixtures for the various surfactant chain lengths were found to conform to a global phase diagram, where the surfactant chain length played the role of an interaction parameter. 相似文献
165.
Olofsson M Kalinin S Zdunek J Oliveberg M Johansson LB 《Physical chemistry chemical physics : PCCP》2006,8(26):3130-3140
We demonstrate that Tryptophan (Trp) and N-(4,4-difluoro-5,7-dimethyl-4-bora-3a,4a-diaza-s-indacene-3-yl)methyl iodoacetamide (BODIPY) is a suitable donor-acceptor (D-A) pair for intraprotein distance measurements, applicable to the study of protein folding. The suitability of the Trp-BODIPY electronic energy transfer is exemplified on the extensively-characterised two-state protein, S6, from Thermus thermophilus. This protein has proved to be useful for the elucidation of folding cooperativity and nucleation, as well as the changes upon induction of structural transitions. For a comprehensive structural coverage, BODIPY molecules were anchored by Cys insertions at four different positions on the S6 surface. Trp residues at position 33 or 62 acted as donors of electronic energy to the BODIPY groups. None of the D-A pairs show any detectable difference in the folding kinetics (or protein stability), which supports the notion that the two-state transition of S6 is a highly concerted process. Similar results are obtained for mutants affecting the N- and C-terminus. The kinetic analyses indicate that changes of the transition state occur through local unfolding of the native state, rather than by a decrease of the folding cooperativity. The distances obtained from the analysis of the time-resolved fluorescence experiments in the native state were compared to those calculated from X-ray structure. As an additional measure, molecular dynamics simulations of the different protein constructs were performed to account for variability in the BODIPY location on the protein surface. The agreement between fluorescence and X-ray data is quite convincing, and shows that energy transfer measurements between Trp and BODIPY can probe distances between ca. 17 to 34 A, with an error better than 10%. 相似文献
166.
Anna Holmberg Lennart Piculell Peter Schurtenberger Ulf Olsson 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):325-336
Polymer–droplet interactions have been studied in AOT/water/isooctane oil-continuous microemulsions mixed with an amphiphilic graft copolymer, or with the parent homopolymer (AOT = sodium bis(2-ethylhexyl) sulfosuccinate). The graft copolymer has an oil-soluble poly(dodecyl methacrylate) backbone and water-soluble poly(ethylene glycol) side chains. Pseudo-ternary polymer/droplet/isooctane phase diagrams have been established for both the parent homopolymer and the graft copolymer, and the two types of mixture display entirely different phase behavior. The homopolymer–droplet interaction is repulsive, and a segregative phase separation occurs at high droplet concentrations. By contrast, the graft copolymer–droplet interaction is attractive: the polymer is insoluble in the pure oil, but dissolves in the microemulsion. A comparatively high concentration of droplets is required to solubilize even small amounts of polymer. Static and dynamic light scattering has been performed in order to obtain information on structure and dynamics in the two types of mixture. For optically matched microemulsions, with a vanishing excess polarizability of the droplets, the polymer dominates the intensity of scattered light. The absolute intensity of scattered light increases as phase separation is approached owing to large-scale concentration fluctuations. Dynamic light scattering shows two populations of diffusion coefficients; one population originates from “free” microemulsion droplets and the other from the polymer (for homopolymer mixtures) or from polymer–droplet aggregates (for mixtures with the graft copolymer). The graft copolymer forms large polymer–droplet aggregates with a broad size distribution, which coexist with a significant fraction of free droplets. 相似文献
167.
Saioa Zorita Rikard Westbom Lars Th?rneby Erland Bj?rklund Lennart Mathiasson 《Analytical sciences》2006,22(11):1455-1459
A combined solid-phase extraction (SPE)-supercritical fluid extraction (SFE) procedure was developed for the analysis of polychlorinated biphenyls (PCBs) in wastewater. The importance of cleaning and drying the filters and SPE-disks prior to eluting PCBs with SFE was studied, leading to improved recoveries for all congeners investigated. The average PCB recovery of the final procedure, at a concentration of 18 ng/L in reagent water, was 101% with relative standard deviations ranging from 1 to 5% for the different congeners. Spiked leachate to a final concentration of 4 ng/L was extracted directly after spiking, or after 24 h of spiking. An average recovery of 112% was obtained in the direct extraction of spiked leachate. 相似文献
168.
A numerical method for fully-resolved particle simulations on adaptively-refined Cartesian meshes is presented. When the particle size is on the order of or smaller than the smallest scales of the carrier flow, fully resolving the particle surfaces on uniform Cartesian meshes results in a tremendous computational effort. This is circumvented by locally refining the mesh near the moving particle surfaces. A new dynamic load-balancing strategy is described which enables the application of this approach to particulate turbulent flows on high-performance computers. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
169.
Dr. Om Prakash Dr. Pavel Chábera Dr. Nils W. Rosemann Dr. Ping Huang Prof. Dr. Lennart Häggström Prof. Dr. Tore Ericsson Dr. Daniel Strand Prof. Dr. Petter Persson Prof. Dr. Jesper Bendix Dr. Reiner Lomoth Prof. Dr. Kenneth Wärnmark 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(56):12728-12732
A homoleptic organometallic FeIV complex that is stable in both solution and in the solid state at ambient conditions has been synthesized and isolated as [Fe(phtmeimb)2](PF6)2 (phtmeimb=[phenyl(tris(3-methylimidazolin-2-ylidene))borate]−). This FeIV N-heterocyclic carbene (NHC) complex was characterized by 1H NMR, HR-MS, elemental analysis, scXRD analysis, electrochemistry, Mößbauer spectroscopy, and magnetic susceptibility. The two latter techniques unequivocally demonstrate that [Fe(phtmeimb)2](PF6)2 is a triplet FeIV low-spin S=1 complex in the ground state, in agreement with quantum chemical calculations. The electronic absorption spectrum of [Fe(phtmeimb)2](PF6)2 in acetonitrile shows an intense absorption band in the red and near IR, due to LMCT (ligand-to-metal charge transfer) excitation. For the first time the excited state dynamics of a FeIV complex was studied and revealed a ≈0.8 ps lifetime of the 3LMCT excited state of [Fe(phtmeimb)2](PF6)2 in acetonitrile. 相似文献
170.
Staffan Bergström Britt-Marie Svensson Lennart Mårtensson Lennart Mathiasson 《International journal of environmental analytical chemistry》2013,93(1):1-15
A strategy is presented for evaluation of treatment procedures for landfill leachate with emphasis on organic pollutants. An analytical scheme, the LAQUA protocol, was developed as a guide for the analytical work. The protocol includes organic as well as metals, inorganic ions, water-quality parameters, and toxicity. The proposed strategy considers the behaviour of both polar and non-polar organic substances at trace levels. For polar substances, phenols were chosen as markers and determined with an automated supported liquid membrane extraction device, coupled on-line to HPLC with a diode-array detector. For non-polar substances, PCBs and 10 unidentified compounds were chosen as markers and analysed by solid-phase extraction combined with supercritical fluid extraction with GC analysis. The chosen measurement strategy, based on the use of marker substances, difference measurements, and versatile data-handling procedures, provided essential information about complex systems at relatively low cost. 相似文献