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排序方式: 共有331条查询结果,搜索用时 31 毫秒
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43.
Borel A Kang H Gateau C Mazzanti M Clarkson RB Belford RL 《The journal of physical chemistry. A》2006,110(45):12434-12438
We present an EPR study of two Gd(III) complexes in aqueous solution at multiple temperatures and EPR frequencies. These two complexes, [Gd(TPATCN)] and [Gd(DOTAM)(H(2)O)](3+), display remarkably sharp lines (i.e. slow transverse electron spin relaxation) in comparison with all complexes studied in the past, especially at X-band ( approximately 9.08 GHz). These unprecedented spectra even show, for the first time in solution, a distinct influence of hyperfine coupling to two magnetically active Gd isotopes ((155)Gd 14.8%, I = 3/2, gamma = -0.8273 x 10(7) s(-1) T(-1) and (157)Gd, 15.65%, I = 3/2, -1.0792 x 10(7) s(-1) T(-1)). The hyperfine coupling splitting in [Gd(TPATCN)] was determined accurately for a (157)Gd-enriched complex, and the value A((157)Gd)/gmu(B) = 5.67 G seems to be a good estimation for most chelates of interest. Consequently, we can safely assert that neglecting the Gd isotopes in line shape studies is not a significant source of error as long as the apparent peak-to-peak width is greater than 10-20 G. This is generally the case, except at very high EPR frequencies (>150 GHz). Analyzing the spectra within the physical model of Rast et al. we find that the slow electron spin relaxation is due to a nearly zero static ZFS. We discuss some structural features that might explain this interesting electron structure. 相似文献
44.
The kinetics of phase transitions of milk fat triacylglycerols, as model multicomponent lipid systems, were studied under
shear in a Couette cell at 17 °C, 17.5 °C and 20 °C under shear rates ranging from 0 to 2880s^-1 using synchrotron X-ray diffraction.
Two-dimensional diffraction patterns were captured during the crystallization process. No effect of shear on onset time for
phase α from the liquid was observed. Afterwards a two-regime crystallization process was observed. During the first regime,
as observed in other systems, shear reduced the onset time of the phase transition from phase α to 2880s−. The model previously developed for palm oil (ODE model) worked well to describe this regime, confirming the general value
of the proposed ODE model. However, the ODE model did not satisfactorily describe the second regime. We found that, as the
system gets closer to equilibrium, the growth regime becomes controlled by diffusion, manifested by the kinetics following
a dependence. This regime was found to be consistent with a mechanism combining step growth at a kink with progressive selection
of the crystallizing moieties. This mechanism is in agreement with the displacement of the diffraction peak positions, which
revealed how increased shear rate promotes the crystallization of the higher melting fraction affecting the composition of
the crystallites. 相似文献
45.
Lucile Chatelain Radmila Faizova Farzaneh Fadaei‐Tirani Jacques Pcaut Marinella Mazzanti 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(10):3053-3058
Herein we report the assembly of large uranium(IV) clusters with novel nuclearities and/or shapes from the controlled hydrolysis of UCl4 in organic solution and in the presence of the benzoate ligands. {U6}, {U13}, {U16}, {U24}, {U38} oxo and oxo/hydroxo clusters were isolated and crystallographically characterized. These structural snapshots indicate that larger clusters are slowly built from the condensation of octahedral {U6} building blocks. The uranium/benzoate ligand ratio, the reaction temperature and the presence of base play an important role in determining the structure of the final assembly. Moreover, the isolation of different size cluster {U6} (few hours), {U16} (3 days), {U24} (21 days) from the same solution in a chosen set of conditions shows that the assembly of uranium oxo clusters in hydrolytic conditions is time dependent. 相似文献
46.
A quantum Monte Carlo simulation of a system of bosonic hard rods in one dimension is presented and discussed. The calculation is exact since the analytical form of the wave function is known and is in excellent agreement with predictions obtained from asymptotic expansions valid at large distances. The analysis of the static structure factor and the pair distribution function indicates that a solidlike and a gaslike phases exist at high and low densities, respectively. The one-body density matrix decays following a power law at large distances and produces a divergence in the low density momentum distribution at k=0 which can be identified as a quasicondensate. 相似文献
47.
Depalo N Mallardi A Comparelli R Striccoli M Agostiano A Curri ML 《Journal of colloid and interface science》2008,325(2):558-566
Organic capped luminescent CdSe@ZnS nanocrystals (NCs) have been incorporated in block copolymer micelles, formed by polyethylene glycol modified phospholipids (PEG lipids). The obtained water soluble NC including PEG lipid micelles have been conjugated with bovine serum albumine (BSA). The entire process has been investigated by using optical, structural and electrophoretic complementary techniques. Such an integrated approach has allowed to elucidate critical issues, such as the time and temperature effects on the phase behavior of the PEG lipid/NC aggregate structures, the emitting properties of the NCs before and after micelle formation and bio-conjugation and the effect of conjugation on the biological moiety. The overall results provide relevant insight on the fabrication of the bio-conjugates, on their stability and on preparative procedure reproducibility, in view of the use of the resulting protein decorated NCs as multifunctional hybrid building blocks for the fabrication of a variety of supramolecular assemblies to exploit in biological sensing and diagnostic applications. 相似文献
48.
Capriati V Florio S Luisi R Mazzanti A Musio B 《The Journal of organic chemistry》2008,73(8):3197-3204
The alpha-lithiation-trapping sequence of trans-N-alkyl-2,3-diphenylaziridines (s-BuLi or s-BuLi/TMEDA), taking place with a stereochemistry which dramatically depends on the solvent coordinating ability (inversion of configuration in THF and retention in toluene), has been carefully investigated. 1H,13C, and 7Li multinuclear NMR investigations at low temperature suggest that two differently configured lithiated aziridines (monomeric cis-1-Li in THF and dimeric trans-1-Li in toluene) are involved. 相似文献
49.
Marta Falcone Dr. Christos E. Kefalidis Rosario Scopelliti Prof. Laurent Maron Prof. Marinella Mazzanti 《Angewandte Chemie (International ed. in English)》2016,55(40):12290-12294
Uranium nitrides are important materials with potential for application as fuels for nuclear power generation, and as highly active catalysts. Molecular nitride compounds could provide important insight into the nature of the uranium–nitride bond, but currently little is known about their reactivity. In this study, we found that a complex containing a nitride bridging two uranium centers and a cesium cation readily cleaved the C≡O bond (one of the strongest bonds in nature) under ambient conditions. The product formed has a [CsU2(μ‐CN)(μ‐O)] core, thus indicating that the three cations cooperate to cleave CO. Moreover, the addition of MeOTf to the nitride complex led to an exceptional valence disproportionation of the CsUIV–N–UIV core to yield CsUIII(OTf) and [MeN=UV] fragments. The important role of multimetallic cooperativity in both reactions is illustrated by the computed reaction mechanisms. 相似文献
50.
Multiple-frequency EPR spectra of two aqueous Gd3+ polyamino polypyridine carboxylate complexes: a study of high field effects 总被引:1,自引:0,他引:1
Borel A Laus S Ozarowski A Gateau C Nonat A Mazzanti M Helm L 《The journal of physical chemistry. A》2007,111(25):5399-5407
In the search for highly efficient magnetic resonance imaging contrast agents, polyamino polypyridine carboxylate complexes of Gd3+ have shown unusual properties with both very rapid and very slow electron spin relaxation in solution observed by electron paramagnetic resonance. Since the relationship between the molecular structure and the electron spin properties remains quite obscure at this point, detailed studies of such complexes may offer useful clues for the design of Gd3+ compounds with tailored electronic features. Furthermore, the availability of very high-frequency EPR spectrometers based on quasi-optical components provides us with an opportunity to test the existing relaxation theories at increasingly high magnetic fields and observation frequencies. We present a detailed EPR study of two gadolinium polyamino polypyridine carboxylate complexes, [Gd(tpaen)]- and [Gd(bpatcn)(H2O)], in liquid aqueous solutions at multiple temperatures and frequencies between 9.5 and 325 GHz. We analyze the results using the model of random zero-field splitting modulations through Brownian rotation and molecular deformations. We consider the effect of concentration on the line width, as well as the possible existence of an additional g-tensor modulation relaxation mechanism and its possible impact on future experiments. We use (17)O NMR to characterize the water exchange rate on [Gd(bpatcn)(H2O)] and find it to be slow (approximately 0.6 x 10(6) s-1). 相似文献