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1.
Guido Pintacuda Andrei Kaikkonen Gottfried Otting 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2004,171(2):387-243
Paramagnetic metal ions with fast-relaxing electronic spin and anisotropic susceptibility tensor provide a rich source of structural information that can be derived from pseudo-contact shifts, residual dipolar couplings, dipole-dipole Curie spin cross-correlation, and paramagnetic relaxation enhancements. The present study draws attention to a cross-correlation effect between nuclear relaxation due to anisotropic chemical shielding (CSA) and due to the anisotropic dipolar shielding (DSA) caused by the electronic Curie spin. This CSA x DSA cross-correlation contribution seems to have been overlooked in previous interpretations of paramagnetic relaxation enhancements. It is shown to be sufficiently large to compromise the 1/r6 distance dependence usually assumed. The effect cannot experimentally be separated from auto-correlated DSA relaxation. It can increase or decrease the observed paramagnetic relaxation enhancement. Under certain conditions, the effect can dominate the entire paramagnetic relaxation, resulting in nuclear resonances narrower than in the absence of the paramagnetic center. CSAxDSA cross-correlation becomes important when paramagnetic relaxation is predominantly due to the Curie rather than the Solomon mechanism. Therefore the effect is most pronounced for relaxation by metal ions with large magnetic susceptibility and fast-relaxing electron spin. It most strongly affects paramagnetic enhancements of transverse relaxation in macromolecules and of longitudinal relaxation in small molecules. 相似文献
2.
Gottfried Mayer Vitali Vogel Bas G. G. Lohmeijer Jean‐Franois Gohy Jacomina A. Van Den Broek Winfried Haase Ulrich S. Schubert Dieter Schubert 《Journal of polymer science. Part A, Polymer chemistry》2004,42(17):4458-4465
Micelles prepared from amphiphilic block copolymers in which a poly(styrene) segment is connected to a poly(ethylene oxide) block via a bis‐(2,2′:6′,2″‐terpyridine‐ruthenium) complex have been intensely studied. In most cases, the micelle populations were found to be strongly heterogeneous in size because of massive micelle/micelle aggregation. In the study reported in this article we tried to improve the homogeneity of the micelle population. The variant preparation procedure developed, which is described here, was used to prepare two “protomer”‐type micelles: PS20‐[Ru]‐PEO70 and PS20‐[Ru]‐PEO375. The dropwise addition of water to a solution of the compounds in dimethylformamide was replaced by the controlled addition of water by a syringe pump. The resulting micelles were characterized by sedimentation velocity and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission electron microscopy of negatively stained samples. Sedimentation analysis showed virtually unimodal size distributions, in contrast to the findings on micelles prepared previously. PS20‐[Ru]‐PEO70 micelles were found to have an average molar mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly less than after micelle preparation by the standard method) and an average hydrodynamic diameter (dh) of 18 nm. For PS20‐[Ru]‐PEO375 micelles, the corresponding values were M = 603,000 g/mol (31 protomers per micelle) and dh = 34 nm. The latter particles were found to be identical to the “equilibrium” micelles prepared in pure water. Both micelle types had a very narrow molar mass distribution but a much broader distribution of s values and thus of hydrodynamic diameters. This indicates a conformational heterogeneity that is stable on the time scale of sedimentation velocity analysis. The findings from electron microscopy were in disagreement with those from the sedimentation analysis both in average micelle diameter and in the width of the distributions, apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4458–4465, 2004 相似文献
3.
K. -J. Berg A. Berger H. Hofmeister 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,20(1):309-311
Small spherical silver particles in a surface layer of commercial flat glass were produced by means of sodium-silver ion exchange. In each volume element of the layer there is a Gaussian distribution of the particle diameters. The mean diameter increases with penetration depth. Within one individual sample it can vary from 4.5 nm immediately at the glass surface up to more than 50 nm at the end of the layer. Due to a special preparation technique the results were gained by microspectrophotometric measurements as well as by investigations carried out with the transmission electron microscope and the electron-probe microanalyzer on one and the same sample always as function of the penetration depth. 相似文献
4.
E.R. Berger M. Diehl B. Pire 《The European Physical Journal C - Particles and Fields》2002,23(4):675-689
We investigate the exclusive photoproduction of a heavy timelike photon which decays into a lepton pair, . This can be seen as the analog of deeply virtual Compton scattering, and we argue that the two processes are complementary
for studying generalized parton distributions in the nucleon. In an unpolarized experiment the angular distribution of the
leptons readily provides access to the real part of the Compton amplitude. We estimate the possible size of this effect in
kinematics where the Compton process should be dominated by quark exchange.
Received: 9 October 2001 / Published online: 5 April 2002 相似文献
5.
T. A. Berger 《Journal of separation science》1989,12(2):96-100
A model for restrictor flow produces accurate predictions of flow that can be used to optimize restrictor design. The relative amplitudes of restrictor and other flows and their effect on efficiency are discussed. 相似文献
6.
Gottfried Ortner 《Fresenius' Journal of Analytical Chemistry》1938,112(3-4):96-101
Ohne Zusammenfassung 相似文献
7.
We consider biased random walk on supercritical percolation clusters in ℤ2. We show that the random walk is transient and that there are two speed regimes: If the bias is large enough, the random
walk has speed zero, while if the bias is small enough, the speed of the random walk is positive.
Received: 20 November 2002 / Revised version: 17 January 2003
Published online: 15 April 2003
Research supported by Microsoft Research graduate fellowship.
Research partially supported by the DFG under grant SPP 1033.
Research partially supported by NSF grant #DMS-0104073 and by a Miller Professorship at UC Berkeley.
Mathematics Subject Classification (2000): 60K37; 60K35; 60G50
Key words or phrases: Percolation – Random walk 相似文献
8.
9.
The potential role of ultrasound in differentiating solid and cystic swellings of the true vocal fold 总被引:3,自引:0,他引:3
John S. Rubin Stuart Lee John McGuinness Ian Hore David Hill Leslie Berger 《Journal of voice》2004,18(2):231-235
This study was designed to investigate the potential role of ultrasound in the diagnosis of cysts of the true vocal fold. Materials and Methods: Grayscale ultrasound of the larynx was carried out in 29 patients with a swelling of the true vocal fold and dysphonia. The findings were then compared with those at subsequent microlaryngoscopy, in the majority of cases. Results and Conclusions: Whereas preoperative laryngeal ultrasound correctly predicted the surgical findings of a cystic lesion in only 5 of 11 cases, it correctly identified that no cyst was present in 15 of 16 instances when this had been queried. This study suggests that ultrasound may have some role in investigation of unilateral vocal fold pathology, but that further fine-tuning of the technique may be necessary. 相似文献