Stress-Induced Domain Wall Motion in a Ferroelastic Mn3+ Spin Crossover Complex

Domain wall motion is detected for the first time during the transition to a ferroelastic and spin state ordered phase of a spin crossover complex. Single-crystal X-ray diffraction and resonant ultrasound spectroscopy (RUS) revealed two distinct symmetry-breaking phase transitions in the mononuclear Mn³⁺ compound [Mn(3,5-diBr-sal₂(323))]BPh₄, 1. The first at 250 K, involves the space group change Cc→Pc and is thermodynamically continuous, while the second, Pc→P1 at 85 K, is discontinuous and related to spin crossover and spin state ordering. Stress-induced domain wall mobility was interpreted on the basis of a steep increase in acoustic loss immediately below the the Pc-P1 transition     

Stereoselective Palladium‐Catalyzed C−F Bond Alkynylation of Tetrasubstituted gem‐Difluoroalkenes

A stereoselective Pd(PPh₃)₄‐catalyzed C?F bond alkynylation of tetrasubstituted gem‐difluoroalkenes with terminal alkynes has been developed. This method gives access to a great variety of conjugated monofluoroenynes bearing a tetrasubstituted alkene moiety with well‐defined stereochemistry. Chelation‐assisted oxidative addition of Pd to the C?F bond is proposed to account for the high level of stereocontrol. An X‐ray crystal structure of a key monofluorovinyl Pd^II intermediate has been obtained for the first time as evidence for the proposed mechanism.     

Unusual Behavior of Nanocrystalline Strontium Oxide Toward Hydrogen Sulfide

The thermodynamically favored reaction of solid strontium oxide with gaseous hydrogen sulfide is kinetically enhanced to a large degree by the use of higher surface area nanocrystalline SrO in the form of brush-like collections of metal oxide fibers. An unusual feature is that the reaction SrO + H₂S SrS + H₂O proceeds stoichiometrically at room temperature, but at higher temperatures the reaction efficiency goes down, apparently due to rapid temperature induced crystal growth of the nanocrystalline SrO. The samples studied vary in crystallite size from 20 to 27nm, while average particle size (nanocrystal aggregates) varies in the following order; aerogel prepared SrO (100nm) 相似文献   

Higgs boson searches at the Tevatron

This article reviews the Higgs searches at the Tevatron, as presented over the summer of 2012; both standard model (SM) and beyond the standard model (BSM) results are discussed as detailed (arXiv: 1207.0449; Phys. Rev. Lett., 2012, 109: 071804; Phys. Rev. D, 2012, 85: 032005). We discuss the combination of searches by the CDF and D0 Collaborations for the standard model Higgs boson in the mass range 100–200 GeV/c ² produced in the the gg → H, WH, ZH, t{ie27-1}H, and vector boson fusion production modes, and decaying in the H → b{ie27-2}, H → W ⁺ W ^?, H → ZZ, H → τ ⁺ τ ^?, and H → γγ modes. The data, collected at the Fermilab Tevatron collider in p{ie27-3} collisions at {ie27-4} TeV, correspond to integrated luminosities of up to 10 fb^?1. In the absence of signal, we expect to exclude the regions 100<m _H < 120 GeV/c ² and 139<m _H < 184 GeV/c ². We exclude, at the 95% C.L., two regions: 100<m _H < 103 GeV/c ², and 147<m _H < 180 GeV/c ². We observe a significant excess of events in the mass range between 115 and 140 GeV/c ². The local significance corresponds to 3.0 standard deviations at m _H = 120 GeV/c ²; the global significance (incorporating the look-elsewhere effect) for such an excess anywhere in the full mass range investigated is approximately 2.5 standard deviations. Furthermore, we separately combine searches for H → b{ie27-5}, H → W+W ^? and H → γγ. We find that the excess is concentrated in the H → b{ie27-6} channel, appearing in the searches over a broad range of m _H ; the maximum local significance of 3.3 standard deviations corresponds to a global significance of approximately 3.1 standard deviations. The observed signal strengths in all channels are consistent with the expectation for a standard model Higgs boson at m _H = 125 GeV/c ². The production of neutral Higgs bosons in association with b-quarks can be significantly enhanced in various beyond the standard model scenarios, including Supersymmetry. The recent combination of such searches from the two collaborations is discussed.     

Kolmogorov Width of Classes of Smooth Functions on the Sphere

Let ^d−1{(x₁,…,x_d) ^d:x²₁+···+x²_d=1} be the unit sphere of the d-dimensional Euclidean space ^d. For r>0, we denote by B^r_p (1p∞) the class of functions f on ^d−1 representable in the formwhere dσ(y) denotes the usual Lebesgue measure on ^d−1, and P^λ_k(t) is the ultraspherical polynomial.For 1p,q∞, the Kolmogorov N-width of B^r_p in L^q( ^d−1) is given bythe left-most infimum being taken over all N-dimensional subspaces X_N of L^q( ^d−1).The main result in this paper is that for r2(d−1)²,where A_NB_N means that there exists a positive constant C, independent of N, such that C⁻¹A_NB_NCA_N.This extends the well-known Kashin theorem on the asymptotic order of the Kolmogorov widths of the Sobolev class of the periodic functions.     

Near-equilibrium measurements of nonequilibrium free energy

A central endeavor of thermodynamics is the measurement of free energy changes. Regrettably, although we can measure the free energy of a system in thermodynamic equilibrium, typically all we can say about the free energy of a nonequilibrium ensemble is that it is larger than that of the same system at equilibrium. Herein, we derive a formally exact expression for the probability distribution of a driven system, which involves path ensemble averages of the work over trajectories of the time-reversed system. From this we find a simple near-equilibrium approximation for the free energy in terms of an excess mean time-reversed work, which can be experimentally measured on real systems. With analysis and computer simulation, we demonstrate the accuracy of our approximations for several simple models.     

Robustness of fat quantification using chemical shift imaging

The purpose of this study was to investigate the effect of parameter changes that can potentially lead to unreliable measurements in fat quantification. Chemical shift imaging was performed using spoiled gradient echo sequences with systematic variations in the following: two-dimensional/three-dimensional sequence, number of echoes, delta echo time, fractional echo factor, slice thickness, repetition time, flip angle, bandwidth, matrix size, flow compensation and field strength. Results indicated no significant (or significant but small) changes in fat fraction with parameter. The significant changes can be attributed to the known effects of T1 bias and two forms of noise bias.     

Contributions of quantum chemistry to the development of ring opening polymerizations and chemical recycling

Quantum chemistry has increasingly become an integral component for the development of homogeneous catalytic processes to form polymers and to break them down. This review examines how quantum chemistry has been utilized to gain insights on mechanisms and selectivities in polymerization and depolymerization reactions by homogeneous catalysts, from some of the earliest uses of theory to the most recent efforts. Key aspects of catalysis by transition-metal catalysts, organocatalytic bases and organic acids will be highlighted.     

Mechanisms for the selective gas-phase fragmentation reactions of methionine side chain fixed charge sulfonium ion containing peptides

To enable the development of improved tandem mass spectrometry based methods for selective proteome analysis, the mechanisms, product ion structures, and other factors influencing the gas-phase fragmentation reactions of methionine side-chain derivatized "fixed-charge" phenacylsulfonium ion containing peptide ions have been examined. Dissociation of these peptide ions results in the exclusive characteristic loss of the derivatized side chain, thereby enabling their selective identification. The resultant product ion(s) are then subjected to further dissociation to obtain sequence information for subsequent protein identification. Molecular orbital calculations (at the B3LYP/6-31 + G (d,p) level of theory) performed on a simple peptide model, together with experimental evidence obtained by multistage dissociation of a regioselectively deuterated methionine derivatized sulfonium ion containing tryptic peptide, indicate that fragmentation of the fixed charge containing peptide ions occurs via SN2 reactions involving the N- and C-terminal amide bonds adjacent to the methionine side chain, resulting in the formation of stable cyclic five- and six-membered iminohydrofuran and oxazine product ions, respectively. These studies further indicate that the rings formed via these neighboring group reactions are stable to further dissociation by MS3. As a consequence, the formation of b- or y-type sequence ions are "skipped" at the site of cyclization. Despite this, complete sequence information is still obtained because of the presence of both cyclic products.