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341.
Sobolev O Cuello GJ Román-Ross G Skipper NT Charlet L 《The journal of physical chemistry. A》2007,111(24):5123-5125
The structural parameters of Hg2+ hydration were studied in 0.225 mol/L solutions of Hg2+ in DNO3/D2O by means of neutron diffraction with isotopic substitution of 199Hg for natHg. It was found that Hg2+ is hydrated by a first solvation shell of six water molecules. The observed Hg-O and Hg-H distances are equal to 2.48+/-0.05 and 3.08+/-0.05 A, respectively. The angle phi between the plane of the water molecule and the cation-water oxygen axis is approximately 35 degrees . The solvation of Hg2+ therefore mimics very closely that of Ca2+ (the Ca-O and Ca-H distances are 2.40 and 3.03 A, respectively) and helps to account for the extreme toxicity of mercury(II). We note also that the Hg-O distance obtained in the neutron diffraction experiment is larger by approximately 0.1 A than that obtained by X-ray diffraction. This difference is consistent with a shift of the oxygen electron density toward the mercury cation due to the covalency of the Hg-O interaction. 相似文献
342.
We analyze numerically the violation of the fluctuation-dissipation theorem (FDT) in the +/-J Edwards-Anderson (EA) spin-glass model. Using single spin probability densities we reveal the presence of strong dynamical heterogeneities, which correlate with ground-state information. The physical interpretation of the results shows that the spins can be divided into two sets. In 3D, one set forms a compact structure which presents a coarseninglike behavior with its characteristic violation of the FDT, while the other asymptotically follows the FDT. Finally, we compare the dynamical behavior observed in 3D with 2D. 相似文献
343.
Synthesis of new fluorinated Tebufenpyrad analogs with acaricidal activity through regioselective pyrazole formation 总被引:1,自引:0,他引:1
Fustero S Román R Sanz-Cervera JF Simón-Fuentes A Bueno J Villanova S 《The Journal of organic chemistry》2008,73(21):8545-8552
In previous studies, our group has shown that the use of fluorinated alcohols such as trifluoroethanol (TFE) and hexafluoroisopropanol (HFIP) as solvents dramatically increases the regioselectivity in the pyrazole formation from 1,3-diketone with methylhydrazine. We have now applied this synthetic method to the preparation of new fluorinated pyrazoles, which have then been used as synthetic intermediates in the preparation of fluorinated analogs of Tebufenpyrad, a commercial acaricide. These compounds display a strong acaricidal activity that is either comparable to or better than that of the commercial compound. 相似文献
344.
Gonzalez AZ Román JG Gonzalez E Martinez J Medina JR Matos K Soderquist JA 《Journal of the American Chemical Society》2008,130(29):9218-9219
The syntheses of the optically pure asymmetric hydroborating agents 1 (a, R = Ph; b, R = TMS) in both enantiomeric forms are reported. These reagents are effective for the hydroboration of cis-, trans- and trisubstituted alkenes. More significantly, they exhibit unprecedented levels of selectivity in the asymmetric hydroboration of 1,1-disubstituted alkenes (28-92% ee), a previously unanswered challenge in the nearly 50 year history of this reagent-controlled process. For example, the hydroboration of alpha-methylstyrene with 1a produces the corresponding alcohol 6f in 78% ee (cf., Ipc2BH, 5% ee). Suzuki coupling of the intermediate adducts 5 produces the nonracemic products 7 very effectively (50-84%) without loss of optical purity. 相似文献
345.
Noud?Aldenhoven Erik?Koelink Pablo?RománEmail authorView authors OrcID profile 《Algebras and Representation Theory》2017,20(4):821-842
We consider the quantum symmetric pair \((\mathcal {U}_{q}(\mathfrak {su}(3)), \mathcal {B})\) where \(\mathcal {B}\) is a right coideal subalgebra. We prove that all finite-dimensional irreducible representations of \(\mathcal {B}\) are weight representations and are characterised by their highest weight and dimension. We show that the restriction of a finite-dimensional irreducible representation of \(\mathcal {U}_{q}(\mathfrak {su}(3))\) to \(\mathcal {B}\) decomposes multiplicity free into irreducible representations of \(\mathcal {B}\). Furthermore we give explicit expressions for the highest weight vectors in this decomposition in terms of dual q-Krawtchouk polynomials. 相似文献
346.
Matrix-valued spherical functions related to the quantum symmetric pair for the quantum analogue of \((\mathrm{SU}(2) \times \mathrm{SU}(2), \mathrm{diag})\) are introduced and studied in detail. The quantum symmetric pair is given in terms of a quantised universal enveloping algebra with a coideal subalgebra. The matrix-valued spherical functions give rise to matrix-valued orthogonal polynomials, which are matrix-valued analogues of a subfamily of Askey–Wilson polynomials. For these matrix-valued orthogonal polynomials, a number of properties are derived using this quantum group interpretation: the orthogonality relations from the Schur orthogonality relations, the three-term recurrence relation and the structure of the weight matrix in terms of Chebyshev polynomials from tensor product decompositions, and the matrix-valued Askey–Wilson type q-difference operators from the action of the Casimir elements. A more analytic study of the weight gives an explicit LDU-decomposition in terms of continuous q-ultraspherical polynomials. The LDU-decomposition gives the possibility to find explicit expressions of the matrix entries of the matrix-valued orthogonal polynomials in terms of continuous q-ultraspherical polynomials and q-Racah polynomials. 相似文献
347.
Spontaneous CO Release from RuII(CO)2–Protein Complexes in Aqueous Solution,Cells, and Mice
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Dr. Miguel Chaves‐Ferreira Inês S. Albuquerque Dr. Dijana Matak‐Vinkovic Dr. Ana C. Coelho Dr. Sandra M. Carvalho Dr. Lígia M. Saraiva Prof. Carlos C. Romão Dr. Gonçalo J. L. Bernardes 《Angewandte Chemie (International ed. in English)》2015,54(4):1172-1175
We demonstrate that RuII(CO)2–protein complexes, formed by the reaction of the hydrolytic decomposition products of [fac‐RuCl(κ2‐H2NCH2CO2)(CO)3] (CORM‐3) with histidine residues exposed on the surface of proteins, spontaneously release CO in aqueous solution, cells, and mice. CO release was detected by mass spectrometry (MS) and confocal microscopy using a CO‐responsive turn‐on fluorescent probe. These findings support our hypothesis that plasma proteins act as CO carriers after in vivo administration of CORM‐3. CO released from a synthetic bovine serum albumin (BSA)–RuII(CO)2 complex leads to downregulation of the cytokines interleukin (IL)‐6, IL‐10, and tumor necrosis factor (TNF)‐α in cancer cells. Finally, administration of BSA–RuII(CO)2 in mice bearing a colon carcinoma tumor results in enhanced CO accumulation at the tumor. Our data suggest the use of RuII(CO)2–protein complexes as viable alternatives for the safe and spatially controlled delivery of therapeutic CO in vivo. 相似文献
348.
Dr. Stijn Van de Vyver Prof. Yuriy Román‐Leshkov 《Angewandte Chemie (International ed. in English)》2015,54(43):12554-12561
The use of metalloenzyme‐like zeolites as Lewis acid catalysts for C? C bond formation reactions has received increasing attention over the past few years. In particular, the observation of direct aldol condensation reactions enabled by hydrophobic zeolites with isolated framework metal sites has encouraged the development of catalytic approaches for producing chemicals from biomass‐derived compounds. The discovery of new Diels–Alder cycloaddition/dehydration routes and experimental and computational studies of Lewis acid catalyzed carbonyl–ene reactions have given a further boost to this rapidly evolving field. 相似文献
349.
Given a set of n black and n white points in general position in the plane, a line l determined by them is said to be balanced if each open half-plane bounded by l contains precisely the same number of black points as white points. It is proved that the number of balanced lines is at
least n . This settles a conjecture of George Baloglou.
Received August 1, 2000, and in revised form October 23, 2000. Online publication April 6, 2001. 相似文献
350.