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101.
M Ehde L Pettersson J Glaser 《Acta chemica Scandinavica (Copenhagen, Denmark : 1989)》1991,45(10):998-1005
The two complexes formed in the aqueous vanadooxalate system, V(Ox)- and V(Ox)2(3-), have been characterized using 51V, 13C and 17O NMR. For the V(Ox)2(3-) complex, two peaks are observed in 13C NMR and four in 17O NMR. This leads to the conclusion that each oxalate ligand has two different distances to the VO2 group. This fact, together with the peak integrals and the chemical shifts, indicates strongly that the hexacoordinate complex [VO2(C2O4)2]3- found in single-crystal X-ray structure determinations persists in aqueous solution. The dependence of the 13C NMR linewidths upon temperature reveals two types of dynamic processes: (1) a rearrangement in which the two different V-Oox switch places and (2) an exchange of the oxalate ligands in the [VO2(C2O4)2]3- complex with free oxalate, probably through a dissociative process. Rate constants and activation parameters for the two dynamic processes involving [VO2(C2O4)2]3- have been calculated from the shape of the 13C NMR signals. For the V(Ox)- complex, only one relatively narrow peak is obtained in 13C NMR and three peaks in 17O. This fact, as well as the relative positions of these peaks, is in accordance with a pentacoordinate complex [VO2(C2O4)H2O]-, where the two V-O distances to the oxalate ligand are equal. We also show that, in the pH range 0.8-6.6, there is no protonation of the studied complexes, in agreement with previous potentiometric results. 相似文献
102.
Methods for estimation of dispersion effects in two‐level unreplicated factorial designs are studied. The consequences of non‐constant variance are discussed. A natural assumption concerning the form of the covariance of location effects leads to a particular normal model. Some linear combinations of the response variables are constructed in order to make a simple structure for inference. The precision of point estimators of dispersion effects, where one is based on experiments with replicates, are compared. A numerical example is given as an illustration of a test. Finally, estimations in fractional designs are described and discussed. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
103.
Structural Revision and Elucidation of the Biosynthesis of Hypodoratoxide by 13C,13C COSY NMR Spectroscopy 下载免费PDF全文
Lena Barra Dr. Kerstin Ibrom Prof. Dr. Jeroen S. Dickschat 《Angewandte Chemie (International ed. in English)》2015,54(22):6637-6640
Feeding of (2,3,4,5,6‐13C5)mevalonolactone to the fungus Hypomyces odoratus resulted in a completely labeled sesquiterpene ether. The connectivity of the carbon atoms was easily deduced from a 13C,13C COSY spectrum, revealing a structure that was different from the previously reported structure of hypodoratoxide, even though the reported 13C NMR data matched. A structural revision of hypodoratoxide is thus presented. Its absolute configuration was tentatively assigned from its co‐metabolite cis‐dihydroagarofuran. Its biosynthesis was investigated by feeding of (3‐13C)‐ and (4,6‐13C2)mevalonolactone, which gave insights into the complex rearrangement of the carbon skeleton during terpene cyclization by analysis of the 13C,13C couplings. 相似文献
104.
105.
Anuradha Ramoji Kerstin Galler Uwe Glaser Thomas Henkel Günter Mayer Jan Dellith Michael Bauer Jürgen Popp Ute Neugebauer 《Journal of Raman spectroscopy : JRS》2016,47(7):773-786
For Raman spectroscopic analyses of the cells and other biological samples, the choice of the right substrate material is very important to avoid loss of information in characteristic spectral features because of competing background signals. In the current study, Raman spectroscopy is used to characterize several potential Raman substrates. Raman vibrational bands of the substrate material are discussed. The surface topography is analyzed by atomic force microscopy, and the root mean square surface roughness values are reported. Biocompatibility of the substrates is tested with Hep G2 cells evaluating cellular morphology as well as live/dead staining. Calcium fluoride, silicon, fused silica, borofloat glass, and silicon nitride membranes support cell growth and adherence. Silicon, borofloat glass, and fused silica give rise to Raman signals in the region of interest. Calcium fluoride substrate (UV grade) is suitable for Raman spectroscopic investigation of living cells. Nickel foil is suitable substrate for Raman spectroscopic investigation but cellular adherence and viability depend on the quality of the foil. Silicon nitride membranes coated with nickel chrome is a suitable Raman substrate in closed microfluidic systems. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
106.
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108.
Towards a simple and robust model for void-based fatigue prediction, we investigate the interaction of voids with its surrounding by using a multi-field method. We couple the concentration fields of tin c1 and lead c2 with an additional field c3, where the latter is assigned with a void field. The interaction potential manifests three stable states. Two are obtained by experimental results of tin-lead (SnPb) and the void stable state is postulated by construction. The logarithmic form of the thermodynamically consistent configurational entropy is approximated within this study by a fourth order polynom. It has been shown that the interfacial energy coefficient is independent of void's size, but rather depends numerically on the mesh size, which is used in the model presented here. Both governing equations follows a Cahn-Hilliard-type equation to mimic the microstructural changes. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
109.
M. K. Pham M. Betti P. P. Povinec M. Benmansour V. B��nger J. Drefvelin C. Engeler J. M. Flemal C. Gasc�� J. Guillevic R. Gurriaran M. Groening J. D. Happel J. Herrmann S. Klemola M. Kloster G. Kanisch K. Leonard S. Long S. Nielsen J.-S. Oh P. U. Rieth I. ?stergren H. Pettersson N. Pinhao L. Pujol K. Sato J. Schikowski Z. Varga V. P. Vartti J. Zheng 《Journal of Radioanalytical and Nuclear Chemistry》2011,288(2):603-611
A new certified reference material (CRM) for radionuclides in sea water from the Irish sea (IAEA-443) is described and the results of the certification process are presented. Ten radionuclides (3H, 40K, 90Sr, 137Cs, 234U, 235U, 238U, 238Pu, 239+240Pu and 241Am) have been certified, and information values on massic activities with 95% confidence intervals are given for four radionuclides (230Th, 232Th, 239Pu and 240Pu). Results for less frequently reported radionuclides (99Tc, 228Th, 237Np and 241Pu) are also reported. The CRM can be used for quality assurance/quality control of the analysis of radionuclides in water samples, for the development and validation of analytical methods and for training purposes. The material is available in 5 L units from IAEA (http://nucleus.iaea.org/rpst/index.htm). 相似文献
110.
Rendl M Bönisch A Mader A Schuh K Prucker O Brandstetter T Rühe J 《Langmuir : the ACS journal of surfaces and colloids》2011,27(10):6116-6123
For the miniaturization of biological assays, especially for the fabrication of microarrays, immobilization of biomolecules at the surfaces of the chips is the decisive factor. Accordingly, a variety of binding techniques have been developed over the years to immobilize DNA or proteins onto such substrates. Most of them require rather complex fabrication processes and sophisticated surface chemistry. Here, a comparatively simple immobilization technique is presented, which is based on the local generation of small spots of surface attached polymer networks. Immobilization is achieved in a one-step procedure: probe molecules are mixed with a photoactive copolymer in aqueous buffer, spotted onto a solid support, and cross-linked as well as bound to the substrate during brief flood exposure to UV light. The described procedure permits spatially confined surface functionalization and allows reliable binding of biological species to conventional substrates such as glass microscope slides as well as various types of plastic substrates with comparable performance. The latter also permits immobilization on structured, thermoformed substrates resulting in an all-plastic biochip platform, which is simple and cheap and seems to be promising for a variety of microdiagnostic applications. 相似文献