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151.
Marius A. Wünsche Tim Witteler Dr. Fabian Dielmann 《Angewandte Chemie (International ed. in English)》2018,57(24):7234-7239
Oxophosphonium ions (R2P=O)+ are fascinating chemical intermediates related to the well‐known acylium cations (RC=O)+, and comprise a tricoordinate phosphorus(V) center with a phosphorus–oxygen double bond. Here, we report the synthesis of two oxophosphonium ions stabilized by bulky imidazolin‐2‐imine and imidazolin‐2‐olefin substituents attached to phosphorus. The novel species were characterized by NMR spectroscopy and single‐crystal X‐ray diffraction analysis, and the bonding situation was probed by DFT calculations. Determination of the acceptor number and the fluoride ion affinity revealed that the choice of the substituents has a strong influence on the electrophilicity of the phosphorus center. Additionally, the formation of Lewis base adducts with pyridine derivatives and the reactivity with isopropyl alcohol was explored. 相似文献
152.
We extend classical volume formulas for ellipsoids and zonoids to p-sums of segments $${vol}\left( {\sum\limits_{i=1}^m { \oplus_p } [ -x_i ,x_i ]} \right)^{1/n} \sim_{c_p} n^{ - \frac{1}{{p'}}} \left( {\sum\limits_{card(I) = n} {|\det (x_i)_i |^p}} \right)^{\frac{1}{{pn}}}$$ where x1,...,xm are m vectors in $\mathbb{R}^n ,\frac{1}{p} + \frac{1}{{p\prime }} = 1$ . According to the definition of Firey, the Minkowski p-sum of segments is given by $$\sum\limits_{i = 1}^m { \oplus _p [ - x_{i,} x_i ]} = \left\{ {\sum\limits_{i = 1}^m {\alpha _i } x_i \left| {\left( {\sum\limits_{i = 1}^m {|\alpha _i |^{p^\prime } } } \right)} \right.^{\frac{1}{{p^\prime }}} \leqslant 1} \right\}.$$ We describe related geometric properties of the Lewis maps associated to classical operator norms. 相似文献
153.
Marius B. Stefan 《Proceedings of the American Mathematical Society》1998,126(8):2299-2307
In this paper we prove that any II-subfactor of finite index in the interpolated free group factor is prime for any i.e., it is not isomorphic to tensor products of II-factors.
154.
V. Henriques L. de Jager S. P. L. Sörensen H. Jessen-Hansen H. Malfatti O. v. Spindler H. Björn-Andersen Marius Laritzen T. Yoshida W. Frey und A. Gigon 《Fresenius' Journal of Analytical Chemistry》1911,50(8):528-534
Ohne ZusammenfassungVergl. auch diese Zeitschrift47, 547;49, 66. 相似文献
155.
Wanko M Hoffmann M Frauenheim T Elstner M 《The journal of physical chemistry. B》2008,112(37):11462-11467
The optical and IR-spectroscopic properties of the protonated Schiff base of retinal are highly sensitive to the electrostatic environment. This feature makes retinal a useful probe to study structural differences and changes in rhodopsins. It also raises an interest to theoretically predict the spectroscopic response to mutation and structural evolution. Computational models appropriate for this purpose usually combine sophisticated quantum mechanical (QM) methods with molecular mechanics (MM) force fields. In an effort to test and improve the accuracy of these QM/MM models, we consider in this article the effects of polarization and inter-residual charge transfer within the binding pocket of bacteriorhodopsin (bR) and pharaonis sensory rhodopsin II (psRII, also called pharaonis phoborhodopsin, ppR) on the excitation energy using an ab initio QM/QM/MM approach. The results will serve as reference for assessing empirical polarization models in a consecutive article. 相似文献
156.
157.
Buse C Altmann F Amann B Hauck SM Poulsen Nautrup C Ueffing M Stangassinger M Deeg CA 《Electrophoresis》2008,29(6):1325-1332
There is increasing evidence that a large proportion of dilated cardiomyopathy (DCM) cases are mediated by autoimmune processes. Since DCM is a fatal disorder with rapid aggravation and is the leading cause of heart transplantation, further insights into disease pathogenesis are needed. Recent studies have separated the pathogenic capacity of autoantibodies and initial clinical trials removing such autoantibodies via immunoadsorption have been promising. In order to elucidate the full autoantibody repertoire involved in DCM, we applied an autoantibody screening test using ventricular and atrial proteomes as autoantigenic sources and subsequently tested the autoantibody-binding patterns of sera from dogs with spontaneous DCM. With this method, we detected five potentially DCM-related autoantigens which were identified by MS as being: myosin heavy chain cardiac muscle alpha isoform, alpha cardiac actin, mitochondrial aconitate hydratase, glyceraldehyde-3-phosphate dehydrogenase (GAPDH), and brain glycogen phosphorylase (GPBB). The recovery of two known DCM autoantigens (myosin heavy chain and alpha cardiac actin) and the discovery of three novel autoantigens (mitochondrial aconitate hydratase, GADPH, and GPBB) underscore the efficacy of this experimental method and the significance of the spontaneous canine DCM model. 相似文献
158.
Miroslaw Pluta Marius Murariu Michaël Alexandre Andrzej Galeski Philippe Dubois 《Polymer Degradation and Stability》2008,93(5):925-931
High-performance composites prepared by melt-blending polylactide (PLA, l/d isomer ratio of 96/4) with various amounts of β-anhydrite II (AII), the dehydrated form of calcium sulfate hemihydrate obtained by a specific thermal treatment at 500 °C, have been aged to study the evolution of their physical and mechanical properties with time. The effect of 1-year ageing under ambient conditions (below Tg of PLA) for selected composites, i.e., filled with 20 and 40 wt% AII, was determined and compared to unfilled PLA with the same processing and ageing history. Samples with an initial amorphous PLA matrix, obtained by fast quenching from the melt, were characterized before and during ageing. The changes in physical parameters have been studied using dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and density measurements. Surprisingly, for all the samples, an increase of the storage modulus (E′) was recorded, as a result of ageing. This improvement was ascribed to the reorganization of the PLA structure induced by ageing. The structural reorganization was also reflected by a slight increase of PLA density and changes in thermal behaviour. The X-ray investigations showed unchanged crystallographic structure of AII both during blending with molten PLA and in the composite systems after ageing. The surprising stability of the thermo-mechanical properties of PLA and PLA/AII composites is in agreement with the results of size exclusion chromatography analysis (SEC) which did not show significant changes of PLA molecular weights brought out by ageing. 相似文献
159.
Jan Sietmann Marius Tenberge Prof. Dr. Johannes M. Wahl 《Angewandte Chemie (International ed. in English)》2023,62(7):e202215381
Methylenecyclobutanes are found to undergo Wacker oxidation via a semi-pinacol-type rearrangement. Key to a successful process is the use of tert-butyl nitrite as oxidant, which not only enables efficient catalyst turn-over but also ensures high Markovnikov-selectivity under mild conditions. Thus, cyclopentanones (26 examples) can be accessed in an overall good yield and excellent selectivity (up to 97 % yield, generally >99 : 1 ketone:aldehyde ratio). Stereochemical analysis of the reaction sequence reveals migration aptitudes in line with related 1,2-shifts. By introducing a pyox ligand to palladium, prochiral methylenecyclobutanes can be desymmetrized, thus realizing the first enantioselective Wacker oxidation. 相似文献
160.
A bimetallic coordination polymer, infinity (2)[{LNi (II)Co (II)}(dca) 2], has been constructed from heterobinuclear [Ni (II)Co (II)] nodes and dicyanamido spacers [L (2-) is the dianion of the Schiff base resulting from the 2:1 condensation of 3-methoxysalicyladehyde with 1,3-propanediamine; L (2-) = N, N'-propylenebis(3-methoxysalycilideneiminato)]. The intranode Co (II)-Ni (II) interaction was found to be ferromagnetic because of the orthogonality of the magnetic orbitals. Below 12 K, the onset of the canted ferromagnetic ordering is observed. 相似文献