A [3+2] annulation procedure for methylenecyclopentanes

A two step sequence converts certain cyclic enones to fused methylenecyclopentanes using the annulation reagent 2-chloromethyl-3-trimethylsilylpropene.     

求解复杂湍流的非线性涡黏性系数模型和代数应力模型

非线性涡黏性系数模型和代数应力模型联系了线性涡黏性系数湍流模型和完整的微分 雷诺应力模型.随着它们受到日益关注,其形式也越来越多样化.本篇综述的目的是对这些模 型加以总结并比较它们之间的共同点及不同之处,指出它们与完整微分雷诺应力模型之间的 关系,以及相对于线性涡黏性系数模型而言它们在预报流场上所具有的优势.     

Photoelastic stress freezing analysis of total shoulder replacement systems

Photoelastic stress freezing analyses in the orthopaedic literature have, in the past, been limited to studies where bone-on-bone, bone-on-metal or ultra-high molecular weight polyethylene (UHMWPE)-on-metal constructs are modeled. In these cases photoelastic plastics are used to simulate either bone or UHMWPE as it interacts with a metal implant. In joints such as the shoulder, a UHMWPE component is often cemented directly into the scapula's glenoid concavity using polymethylmethacrylate (PMMA). While a photoelastic material can be used to simulate bone with proper load scaling, UHMWPE and PMMA have very different mechanical properties at elevated stress freezing temperatures as compared within vivo body temperature. In this study, materials were identified such that proper scaling of elastic properties at elevated temperatures was utilized to simulate the metal-UHMWPE-PMMA-bone construct. Stresses on orthogonal planes throughout the glenoid were compared for two different UHMWPE component anchoring geometries (keeled and pegged). High stresses were found at the neck of the glenoid and also at the component-bone interface beneath simulated PMMA inclusions.     

The cultural Red King effect

Why do minority groups tend to be discriminated against when it comes to situations of bargaining and resource division? In this article, I explore an explanation for this disadvantage that appeals solely to the dynamics of social interaction between minority and majority groups—the cultural Red King effect (Bruner, 2017). As I show, in agent-based models of bargaining between groups, the minority group will tend to get less as a direct result of the fact that they frequently interact with majority group members, while majority group members meet them only rarely. This effect is strengthened by certain psychological phenomenon—risk aversion and in-group preference—is robust on network models, and is strengthened in cases where preexisting norms are discriminatory. I will also discuss how this effect unifies previous results on the impacts of institutional memory on bargaining between groups.     

Structural Heterogeneity of Doubly-Charged Peptide b-Ions

Performing collisionally activated dissociation (CAD) and electron capture dissociation (ECD) in tandem has shown great promise in providing comprehensive sequence information that was otherwise unobtainable by using either fragmentation method alone or in duet. However, the general applicability of this MS³ approach in peptide sequencing may be undermined by the formation of non-direct sequence ions, as sometimes observed under CAD, particularly when multiple stages of CAD are involved. In this study, varied-sized doubly-charged b-ions from three tachykinin peptides were investigated by ECD. Sequence scrambling was observed in ECD of all b-ions from neurokinin A (HKTDSFVGLM-NH₂), suggesting the presence of N- and C-termini linked macro-cyclic conformers. On the contrary, none of the b-ions from eledoisin (pEPSKDAFIGLM-NH₂) produced non-direct sequence ions under ECD, as it does not contain a free N-terminal amino group. ECD of several b-ions from Substance P (RPKPQQFFGLM-NH₂) showed series of c_m-Lys fragment ions which suggested that the macro-cyclic structure may also be formed by connecting the C-terminal carbonyl group and the ε-amino group of the lysine side chain. Theoretical investigation of selected Substance P b-ions revealed several low energy conformers, including both linear oxazolones and macro-ring structures, in corroboration with the experimental observation. This study showed that a b-ion may exist as a mixture of several forms, with their propensities influenced by its N-terminus, length, and certain side-chain groups. Further, the presence of several macro-cyclic structures may result in erroneous sequence assignment when the combined CAD and ECD methods are used in peptide sequencing.     

Kinetic discrimination in recognition of DNA quadruplex targets by guanine-rich heteroquadruplex-forming PNA probes

Guanine-rich peptide nucleic acid probes hybridize to DNA G quadruplex targets with high affinity, forming PNA-DNA heteroquadruplexes. We report a surprising degree of kinetic discrimination for PNA heteroquadruplex formation with a series of DNA targets. The fastest hybridization is observed for targets folded into parallel morphologies.     

Rainbows and glories in the angular scattering of the state-to-state F + H2 reaction at E(trans)=0.04088 eV

State-of-the-art differential cross sections (DCSs) have been reported by Wang et al. [Proc. Nat. Acad. Sci. (U.S.), 2008, 105, 6227] for the state-to-state F + H(2)→ FH + H reaction using fully quantum-state-selected crossed molecular beams. We theoretically analyze the angular scattering of this reaction, in order to quantitatively understand the physical content of structure in the DCSs. Three transitions are studied, v(i)=0, j(i)=0, m(i)=0 → v(f)=3, j(f)=0, 1, 2, m(f)=0 at a translational energy of 0.04088 eV, where v, j, m are the vibrational, rotational and helicity quantum numbers respectively for the initial and final states. The input to our analyses consists of accurate quantum scattering (S) matrix elements computed for the Fu-Xu-Zhang potential energy surface, as used by Wang et al. in a computational simulation of their experimental DCSs. We prove that the pronounced peak at forward angles observed in the experimental and simulated DCSs for all three transitions is a glory. At larger angles, it is demonstrated that the 000 → 300 and 000 → 310 DCSs both possess a broad farside rainbow, which is accompanied by diffraction oscillations. We confirm the conjecture of Wang et al. that these diffraction oscillations arise from nearside-farside (NF) interference. We find that the reaction is N dominant for all three transitions. The theoretical techniques used to analyze the angular scattering include uniform semiclassical theories of glory and of rainbow scattering. We also make the first application of a semiclassical formula that is uniform for both glory + rainbow scattering. In addition, structure in the DCSs is analyzed using NF theory and local angular momentum theory, in both cases with three resummations of the partial wave series for the scattering amplitude. We make the first explicit application of the Thiele rational interpolation formula to extract the position and residue of the leading Regge pole from a set of S matrix elements, thereby making contact with complex angular momentum theories of DCSs, which interpret the angular scattering in terms of Regge resonances. Our calculations complement the exit-valley vibrationally-adiabatic analysis of Wang et al.     

Semiclassical theory of molecular collisions: Real and complex-valued classical trajectories for collinear atom Morse oscillator collisions

Real and complex-valued classical trajectories have been calculated for the collinear collision of an atom with a Morse oscillator. They are used in three semiclassical approximations for the transition probability: a Bessel uniform approximation, an Airy uniform approximation and a primitive semiclassical approximation. Comparison with exact quantum results shows that the Bessel uniform approximation is accurate even for near elastic collisions where the Airy and primitive approximations break down. The Airy and Bessel approximations agree quite closely for inelastic collisions however. The primitive semiclassical approximation is less accurate than either the Airy or Bessel approximation.     

Evaluation of multidimensional canonical integrals in semiclassical collision theory

The evaluation of the multidimensional canonical integrals that occur in the uniform asymptotic representations of the S matrix in the semiclassical theory of inelastic and reactive molecular collisions is considered. For the non-separable two-dimensional canonical integral considered earlier, an exact series expansion is obtained with the help of convergence factors. This method avoids the complex variable techniques used previously. The uniform asymptotic formulae derived by Miller and Marcus are discussed, and compared with the approach adopted in the present paper.