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June Cyriac Justin Paulose Mathai George Marupaka Ramesh Ragampeta Srinivas Daryl Giblin Michael L. Gross 《Journal of the American Society for Mass Spectrometry》2014,25(3):398-409
ESI-protonated 1,5-bis-(2-methoxyphenyl)-1,4-pentadien-3-one (1) undergoes a gas-phase Nazarov cyclization and dissociates via expulsions of ketene and anisole. The dissociations of the [M + D]+ ions are accompanied by limited HD scrambling that supports the proposed cyclization. Solution cyclization of 1 was effected to yield the cyclic ketone, 2,3-bis-(2-methoxyphenyl)-cyclopent-2-ene-1-one, (2) on a time scale that is significantly shorter than the time for cyclization of dibenzalacetone. The dissociation characteristics of the ESI-generated [M + H]+ ion of the synthetic cyclic ketone closely resemble those of 1, suggesting that gas-phase and solution cyclization products are the same. Additional mechanistic studies by density functional theory (DFT) methods of the gas-phase reaction reveals that the initial cyclization is followed by two sequential 1,2-aryl migrations that account for the observed structure of the cyclic product in the gas phase and solution. Furthermore, the DFT calculations show that the methoxy group serves as a catalyst for the proton migrations necessary for both cyclization and fragmentation after aryl migration. An isomer formed by moving the 2-methoxy to the 4-position requires relatively higher collision energy for the elimination of anisole, as is consistent with DFT calculations. Replacement of the 2-methoxy group with an OH shows that the cyclization followed by aryl migration and elimination of phenol occurs from the [M + H]+ ion at low energy similar to that for 1. Figure
The role of methoxy group in the Nazarov cyclization of 1,5-bis-(2-methoxyphenyl)-1,4-pentadien-3-one in the gas-phase and condensed phase by June Cyriac, Justin Paulose, M. George, Department of Chemistry, Sacred Heart College, Thevara, Cochin, Kerala, India-682013., M. Ramesh, R. Srinivas, National center for Mass Spectrometry, IICT, Hyderabad, India. Daryl Giblin and Michael L. Gross, Department of Chemistry, Washington University in St.Louis, St.Louis, USA, MO 63130. 相似文献
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Affine-Invariant Distances, Envelopes and Symmetry Sets 总被引:3,自引:0,他引:3
Affine invariant symmetry sets of planar curves are introduced and studied in this paper. Two different approaches are investigated. The first one is based on affine invariant distances, and defines the symmetry set as the closure of the locus of points on (at least) two affine normals and affine-equidistant from the corresponding points on the curve. The second approach is based on affine bitangent conics. In this case the symmetry set is defined as the closure of the locus of centers of conics with (at least) 3-point contact with the curve at two or more distinct points on the curve. This is equivalent to conic and curve having, at those points, the same affine tangent, or the same Euclidean tangent and curvature. Although the two analogous definitions for the classical Euclidean symmetry set are equivalent, this is not the case for the affine group. We present a number of properties of both affine symmetry sets, showing their similarities with and differences from the Euclidean case. We conclude the paper with a discussion of possible extensions to higher dimensions and other transformation groups, as well as to invariant Voronoi diagrams. 相似文献
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Computer simulations based on Discrete Element Method have been performed in order to investigate the influence of interparticle interactions on the kinetics of self-assembly and the mechanical strength of nanoparticle aggregates.Three different systems have been considered.In the first system the interaction between particles has been simulated using the JKR (Johnson,Kendall and Roberts) contact theory,while in the second and third systems the interaction between particles has been simulated using van der Waals and electrostatic forces respectively.In order to compare the mechanical behaviour of the three systems,the magnitude of the maximum attractive force between particles has been kept the same in all cases.However,the relationship between force and separation distance differs from case to case and thus,the range of the interparticle force.The results clearly indicate that as the range of the interparticle force increases,the self-assembly process is faster and the work required to produce the mechanical failure of the assemblies increases by more than one order of magnitude. 相似文献
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Let M be a smooth surface in real affine 3-space. Consider the pairs of points of this surface at which the tangent planes are
parallel and in particular the chords (infinite lines) joining these pairs. We study in detail and classify the singularities
of the envelope of these chords, that is a (singular) surface tangent to all of them. This is called the Centre Symmetry Set
(CSS) of M. The study is local in character and is based upon a more general investigation by the authors of the n-dimensional case. The construction of the CSS is affinely invariant and generalises the focal set of a surface in euclidean
space and the affine focal set of a surface in affine space. Many standard and some unusual singularities occur in a natural
way as the singularities of the CSS. There are illustrations of the various cases by means of concrete examples.
相似文献
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在一系列H模放电条件下,建立了一个旨在研究等离子体温度分布剖面不变性的数据库。介绍了数据库建立过程中要解决的关键问题和所用软件,对等离子体温度分布剖面不变性及芯部约束与边缘参数的关系进行了研究。 相似文献
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A chord is a straight line joining two points of a pair of hypersurfaces in an affine space such that the tangent hyperplanes at these points are parallel. We classify the singularities of envelopes of the families of chords determined by generic pairs of plane curves and surfaces in three-space. The list contains all bifurcation diagrams of simple boundary singularities (of the corresponding multiplicity). 相似文献
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Goebl JA Black RW Puthussery J Giblin J Kosel TH Kuno M 《Journal of the American Chemical Society》2008,130(44):14822-14833
We demonstrate the solution-phase synthesis of CdS/CdSe, CdSe/CdS, and CdSe/ZnTe core/shell nanowires (NWs). On the basis of bulk band offsets, type-I and type-II heterostructures are made, contributing to the further development of low-dimensional heteroassemblies using solution-phase chemistry. Core/shell wires are prepared by slowly introducing shell precursors into a solution of premade core NWs dispersed in a noncoordinating solvent at moderate temperatures (215-250 degrees C). Resulting heterostructures are characterized through low- and high-resolution transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray analysis. From these experiments, initial shell growth appears to occur through either Stranski-Krastanov or Volmer-Weber island growth. However, beyond a critical shell thickness, nucleation of randomly oriented nanocrystals results in a polycrystalline coat. In cases where overcoating has been achieved, corresponding elemental analyses show spatially varying compositions along the NW radial direction in agreement with expected element ratios. Electronic interactions between the core and shell were subsequently probed through optical studies involving UV-vis extinction spectroscopy, photoluminescence experiments, and transient differential absorption spectroscopy. In particular, transient differential absorption studies reveal unexpected shell-induced changes in core NW Auger kinetics at high carrier densities. Previously seen three-carrier Auger kinetics in CdS (bimolecular in CdSe) NWs were suppressed by the presence of a CdSe (CdS) shell. These observations suggest the ability to influence NW optical/electrical properties by coating them with a surrounding shell, a method which could be important for future NW optical studies as well as for NW-based applications. 相似文献
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We consider gravitational wave production due to parametric resonance at the end of inflation, or "preheating." This leads to large inhomogeneities that source a stochastic background of gravitational waves at scales inside the comoving Hubble horizon at the end of inflation. We confirm that the present amplitude of these gravitational waves need not depend on the inflationary energy scale. We analyze an explicit model where the inflationary energy scale is approximately 10{9} GeV, yielding a signal close to the sensitivity of Advanced Laser Interferometer Gravitational Wave Observatory and Big Bang Observer. This signal highlights the possibility of a new observational "window" into inflationary physics and provides significant motivation for searches for stochastic backgrounds of gravitational waves in the Hz to GHz range, with an amplitude on the order of Omega_{gw}(k)h{2} approximately 10{-11}. 相似文献