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排序方式: 共有620条查询结果,搜索用时 359 毫秒
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Markus Bödenler Ludovic de Rochefort P. James Ross Nicolas Chanet Geneviève Guillot Gareth R. Davies 《Molecular physics》2019,117(7-8):832-848
ABSTRACTFast field-cycling (FFC) nuclear magnetic resonance relaxometry is a well-established method to determine the relaxation rates as a function of magnetic field strength. This so-called nuclear magnetic relaxation dispersion gives insight into the underlying molecular dynamics of a wide range of complex systems and has gained interest especially in the characterisation of biological tissues and diseases. The combination of FFC techniques with magnetic resonance imaging (MRI) offers a high potential for new types of image contrast more specific to pathological molecular dynamics. This article reviews the progress in FFC-MRI over the last decade and gives an overview of the hardware systems currently in operation. We discuss limitations and error correction strategies specific to FFC-MRI such as field stability and homogeneity, signal-to-noise ratio, eddy currents and acquisition time. We also report potential applications with impact in biology and medicine. Finally, we discuss the challenges and future applications in transferring the underlying molecular dynamics into novel types of image contrast by exploiting the dispersive properties of biological tissue or MRI contrast agents. 相似文献
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Statisticians are accustomed to processing numerical, ordinal or nominal data. In many circumstances, such as socio-economic, epidemiologic sample surveys and documentary data bases, this data is juxtaposed with textual data (for example, responses to open questions in surveys). This article presents a series of language-independent procedures based upon applying multivariate techniques (such as correspondence analysis and clustering) to sets of generalized lexical profiles. The generalized lexical profile of a text is a vector whose components are the frequencies of each word (graphical form) or ‘repeated segment’ (sequence of words appearing with a significant frequency in the text). The processing of such large (and often sparse) vectors and matrices requires special algorithms. The main outputs are the following: (1) printouts of the characteristic words and characteristic responses for each category of respondent (these categories are generally derived from available nominal variables); (2) graphical displays of the proximities between words or segments and categories of respondents; (3) when analysing a combination of several texts: graphical displays of proximities between words or segments and each text, or between words or segments and groupings of texts. The systematic use of ‘repeated segments’ provides a valuable help in interpreting the results from a semantic point of view. 相似文献
5.
Francis Garnier Pierre Krausz Jacques-Emile Dubois 《Journal of organometallic chemistry》1979,170(2):195-201
The photoinduced metathesis [W(CO)6CCl4hν] of cis- and trans-RCH=CHMe gives 2-butene in a very high trans but low cis stereoselectivity. Propene behaves like a cis olefin. These results are consistent with the proposal of a dinuclear tungsten intermediate, which requires high steric constraints in the transalkylidenation step. 相似文献
6.
A method is presented to reduce the memory requirement of normal mode analysis applied to systems containing two or more large proteins when these systems exhibit symmetry properties. We use a rigid geometry model (i.e., only the dihedral angles of the polypeptide chain are considered as variables). This model allows a reduction by a factor of 8 on average of the number of variables with a concomitant freezing of the high-frequency modes. The symmetry properties of the system are used to reduce further the number of variables that must be considered in the computation. Application of group theory leads to a factorization of the matrices of interest (the coefficient and the Hessian matrices) into independent blocks along the diagonal. The initial, reducible representation is thus transformed into a number of irreducible representations of smaller dimensions. In the case of the C2 symmetry group, the method leads to a reduction of the size of the matrices that must be manipulated during the computation (coefficient matrix, Hessian matrix, and eigenvectors matrix) by a factor of 256 compared with the usual normal mode analysis in Cartesian coordinate space. The method is particularly well adapted to the study of the dynamics of oligomeric proteins because these proteins often display symmetry properties (e.g., virus coat proteins, immunoglobulins, hemoglobin, etc.). In favorable cases, in conjunction with X-ray diffuse scattering data, the study of systems showing allosteric properties might be considered. © 1994 by John Wiley & Sons, Inc. 相似文献
7.
Cyclopropanols 5, 6 and 2 with substituent groups (-CH2OH, -CH2OTs, -CH2Br) in the 1-position, and oxaspiropentane 8, have been prepared from methylenecyclopropane. Cyclopropanols with vinyl groups in the 1-position (1-vinyl 12, 1-cyclopentenyl 13 and 1-cyclohexenyl 14) and 1-cyclopropylcyclopropanol 20 have been prepared from 1, 3-dichloroacetone.Each of the compounds readily undergoes ring expansion to the corresponding cyclobutanones. The reaction provides a simple route to cyclobutanones, the parent ketone itself being easily obtained from oxaspiropentane 8. 相似文献
8.
Ludovic Jean 《Tetrahedron letters》2006,47(13):2141-2145
The first systematic screening of chiral phosphines in the cycloaddition reaction between 2,3-butadienoates and arylimines has led to the identification of fairly efficient catalysts. 2-Aryl-3-pyrrolines have been obtained with enantiomeric excesses up to 64%. In one instance, the enantiomeric excess could be increased to 91% ee by combining the enantioselective cyclization reaction with a crystallization step. 相似文献
9.
Layer by layer buildup of polysaccharide films: physical chemistry and cellular adhesion aspects 总被引:7,自引:0,他引:7
Richert L Lavalle P Payan E Shu XZ Prestwich GD Stoltz JF Schaaf P Voegel JC Picart C 《Langmuir : the ACS journal of surfaces and colloids》2004,20(2):448-458
The formation ofpolysaccharide films based on the alternate deposition of chitosan (CHI) and hyaluronan (HA) was investigated by several techniques. The multilayer buildup takes place in two stages: during the first stage, the surface is covered by isolated islets that grow and coalesce as the construction goes on. After several deposition steps, a continuous film is formed and the second stage of the buildup process takes place. The whole process is characterized by an exponential increase of the mass and thickness of the film with the number of deposition steps. This exponential growth mechanism is related to the ability of the polycation to diffuse "in" and "out" of the whole film at each deposition step. Using confocal laser microscopy and fluorescently labeled CHI, we show that such a diffusion behavior, already observed with poly(L-lysine) as a polycation, is also found with CHI, a polycation presenting a large persistence length. We also analyze the effect of the molecular weight (MW) of the diffusing polyelectrolyte (CHI) on the buildup process and observe a faster growth for low MW chitosan. The influence of the salt concentration during buildup is also investigated. Whereas the CHI/HA films grow rapidly at high salt concentration (0.15 M NaCl) with the formation of a uniform film after only a few deposition steps, it is very difficult to build the film at 10(-4) M NaCl. In this latter case, the deposited mass increases linearly with the number of deposition steps and the first deposition stage, where the surface is covered by islets, lasts at least up to 50 bilayer deposition steps. However, even at these low salt concentrations and in the islet configuration, CHI chains seem to diffuse in and out of the CHI/HA complexes. The linear mass increase of the film with the number of deposition steps despite the CHI diffusion is explained by a partial redissolution of the CHI/HA complexes forming the film during different steps of the buildup process. Finally, the uniform films built at high salt concentrations were also found to be chondrocyte resistant and, more interestingly, bacterial resistant. Therefore, the (CHI/HA) films may be used as an antimicrobial coating. 相似文献
10.
Complexes [ML3]2+ of the bidentate ligand 2‐(1H‐imidazol‐2‐yl)pyridine were prepared with iron(II), cobalt(II), and ruthenium(II). The electronic spectra suggest the ligand to be a weaker σ‐donor and π‐acceptor than the closely related 2,2′‐bipyridine. The complexes are readily deprotonated by addition of base, and the effect of the deprotonation is to lower the MIII/MII redox potential by roughly 900 mV. This is roughly 75% of the drop observed for related complexes of 2,6‐di‐1H‐imidazol‐2‐ylpyridine, and suggests the effect to be largely coulombic in origin. 相似文献