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1.
Pengjin Qin Li-An Wang Prof. Joseph M. O'Connor Prof. Kim K. Baldridge Yifan Li Burak Tufekci Jiyue Chen Prof. Arnold L. Rheingold 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18114-18121
Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C5H5)Ru(NCMe)3]PF6 as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations. 相似文献
2.
Let
d−1{(x1,…,xd)
d:x21+···+x2d=1} be the unit sphere of the d-dimensional Euclidean space
d. For r>0, we denote by Brp (1p∞) the class of functions f on
d−1 representable in the formwhere dσ(y) denotes the usual Lebesgue measure on
d−1,
and Pλk(t) is the ultraspherical polynomial.For 1p,q∞, the Kolmogorov N-width of Brp in Lq(
d−1) is given bythe left-most infimum being taken over all N-dimensional subspaces XN of Lq(
d−1).The main result in this paper is that for r2(d−1)2,where ANBN means that there exists a positive constant C, independent of N, such that C−1ANBNCAN.This extends the well-known Kashin theorem on the asymptotic order of the Kolmogorov widths of the Sobolev class of the periodic functions. 相似文献
3.
4.
Gavin D. Henry Author Vitae 《Tetrahedron》2004,60(29):6043-6061
5.
We couple a morphological study of an immiscible binary AB mixture with a micromechanical simulation to determine how the spatial distribution of the A and B domains and the interfacial region (interphase) affects the mechanical behavior of the blend. The morphological studies are conducted through a three-dimensional Cahn-Hilliard (CH) simulation. Through the CH calculations, we obtain the size and structure of the domains for different blend compositions. The output of the CH model serves as the input to the Lattice Spring Model (LSM), which consists of a three-dimensional network of springs. In particular, the location of the different phases is mapped onto the LSM lattice and the appropriate force constants are assigned to the LSM sites. A stress is applied to the LSM lattice and we calculate the elastic response of the material. We find that the local stress and strain fields are highly dependent on the morphology of the system. By integrating the morphological and mechanical models, we can isolate how modifications in the composition of the mixture affect the macroscopic behavior. Thus, we can establish how choices made in the components affect the ultimate performance of the material. 相似文献
6.
Richard A. Cairncross Jeffrey G. Becker Shri Ramaswamy Ryan O'Connor 《Applied biochemistry and biotechnology》1996,131(1-3):774-785
Management of moisture penetration and hydrolytic degradation of polylactide (PLA) is extremely important during the manufacturing,
shipping, storage, and end-use of PLA products. Moisture transport, crystallization, and degradation, in PLA have been measured
through a variety of experimental techniques including size-exclusion chromatography, differential scanning calorimetry, and
X-ray diffraction. Quartz crystal microbalance and dynamic vapor sorption experiments have also been used to measure moisture
sorption isotherms in PLA films with varying crystallinity. A surprising result is that, within the accuracy of the experiments,
crystalline and amorphous PLA films exhibit identical sorption isotherms. 相似文献
7.
Using flow microcalorimetry, the ion association reaction M2+(aq)+Fe(CN)
6
4–
(aq)=MFe(CN)
6
2–
(aq) (M=Ca, Mg) has been studied at 25°C over the ionic strength range 0.02 to 0.08 mol-dm–3. Analyses of the data to obtain Ho, the enthalpy change at infinite dilution, are described. The value obtained for Ho is sensitive to the kind of functions used to correct for non-ideal behavior. 相似文献
8.
Kommareddi Nagesh S. Tata Murthy Karayigitoglu Cigdem John Vijay T. McPherson Gary L. Herman Michael F. O'Connor Charles J. Lee Young-Sook Akkara Joseph A. Kaplan David L. 《Applied biochemistry and biotechnology》1995,51(1):241-252
Applied Biochemistry and Biotechnology - Horseradish peroxidase has been used as a biocatalyst to synthesize a polymeric material from alkyl-substituted phenols. The synthesis is carried out in a... 相似文献
9.
10.
Caruntu D Remond Y Chou NH Jun MJ Caruntu G He J Goloverda G O'Connor C Kolesnichenko V 《Inorganic chemistry》2002,41(23):6137-6146
Study of the reactivity of 3d transition metal cations in diethylene glycol solutions revealed several key features that made it possible to develop a new method for synthesis of the nanocrystalline transition metal ferrites. The 3-7 nm particles of [MFe2O4]n[O2CR]m, where M = Mn, Fe, Co, Ni, and Zn, ligated on their surface with long-chain carboxylate anions, have been obtained in an isolated yield of 75-90%. The key features are the following. Complexation of the first-row transition metal cations with diethylene glycol at a presence of alkaline hydroxide is sufficient to enable control over the rate of their hydrolysis. The reaction of hydrolysis leads to the formation of metal oxide nanocrystals in colloidal solution. The nanoparticles growth is terminated by an added long-chain carboxylic acid, which binds to their surface and acts as a capping ligand. The isolated nanocrystalline powders are stable against agglomeration and highly soluble in nonpolar organic solvents. 相似文献