Second-Coordination Sphere Effects on Selectivity and Specificity of Heme and Nonheme Iron Enzymes

Mononuclear iron-containing enzymes are highly versatile oxidants that often react stereospecifically and/or regioselectively with substrates. Combined experimental and computational studies on heme monooxygenases, nonheme iron dioxygenases and halogenases have revealed the intricate details of the second-coordination sphere, which determine this specificity and selectivity. These second-coordination sphere effects originate from the positioning of the substrate and oxidant, which involve the binding of the co-factors and substrate into the active site of the protein. In addition, some enzymes affect the selectivity and reactivity through charge-stabilization from nearby bound cations/anions, an induced electric field or through the positioning of salt bridges and hydrogen-bonding interactions to first-coordination sphere iron ligands and/or the substrate. Examples of all of these second-coordination sphere effects in iron-containing enzymes and how these influence structure and reactivity are given.     

Theoretical Study on Photoisomerization Mechanisms of Diphenyl-Substituted N,C-Chelate Organoboron Compounds

N,C-chelate organoboron compounds are widely employed as photoresponsive and optoelectronic materials due to their efficient photochromic reactivity. It was found in experiments that two diphenyl-substituted organoboron compounds, namely B(ppy)Ph₂ (ppy=2-phenylpyridyl) and B(iba)Ph₂ (iba=N-isopropylbenzylideneamine), show distinct photochemical reactivity. B(ppy)Ph₂ is inert on irradiation, whereas B(iba)Ph₂ undergoes photoinduced transformations, yielding BN-cyclohepta-1,3,5-triene via a borirane intermediate. In this work, the complete active space self-consistent field and its second-order perturbation (CASPT2//CASSCF) methods were used to investigate the photoinduced reaction mechanisms of B(ppy)Ph₂ and B(iba)Ph₂. The calculations showed that the two compounds isomerize to borirane in the same way by passing a transition state in the S₁ state and a conical intersection between the S₁ and S₀ states. The energy barriers in the S₁ state of 0.54 and 0.26 eV for B(ppy)Ph₂ and B(iba)Ph₂, respectively, were explained by analyzing the charge distributions of minima in S₀ and S₁ states. The results provide helpful insights into the excited-state dynamics of organoboron compounds, which could assist in rational design of boron-based photoresponsive materials.     

Divergent Synthesis of Vinyl‐, Benzyl‐, and Borylsilanes: Aryl to Alkyl 1,5‐Palladium Migration/Coupling Sequences

Organosilicon compounds have been extensively utilized both in industry and academia. Studies on the syntheses of diverse organosilanes is highly appealing. Through‐space metal/hydrogen shifts allow functionalization of C?H bonds at a remote site, which are otherwise difficult to achieve. However, until now, an aryl to alkyl 1,5‐palladium migration process seems to have not been presented. Reported herein is the remote olefination, arylation, and borylation of a methyl group on silicon to access diverse vinyl‐, benzyl‐, and borylsilanes, constituting a unique C(sp³)?H transformation based on a 1,5‐palladium migration process.     

市场机制和政府调控下产学研联盟稳定性研究

为了促进产学研联盟的稳定发展,针对我国产学研联盟短期化行为严重问题,基于演化博弈理论从市场机制和政府调控两方面构建企业和学研机构联盟行为选择的决策模型,以及通过复制动态方程对策略选择进行稳定性分析,同时运用Matlab 7.0软件模拟仿真在不同程度的市场机制和政府调控下企业和学研机构在联盟创新中的演化行为。通过市场机制和政府调控两方面的深入剖析,对我国产学研联盟的稳定发展具有重要的理论指导意义。     

Evaluation of Charged Defect Energy in Two-Dimensional Semiconductors for Nanoelectronics: The WLZ Extrapolation Method

Defects play a central role in controlling the electronic properties of two-dimensional (2D) materials and realizing the industrialization of 2D electronics. However, the evaluation of charged defects in 2D materials within first-principles calculation is very challenging and has triggered a recent development of the WLZ (Wang, Li, Zhang) extrapolation method. This method lays the foundation of the theoretical evaluation of energies of charged defects in 2D materials within the first-principles framework. Herein, the vital role of defects for advancing 2D electronics is discussed, followed by an introduction of the fundamentals of the WLZ extrapolation method. The ionization energies (IEs) obtained by this method for defects in various 2D semiconductors are then reviewed and summarized. Finally, the unique defect physics in 2D dimensions including the dielectric environment effects, defect ionization process, and carrier transport mechanism captured with the WLZ extrapolation method are presented. As an efficient and reasonable evaluation of charged defects in 2D materials for nanoelectronics and other emerging applications, this work can be of benefit to the community.     

Atomic structure and collision dynamics with highly charged ions

The research progresses on the investigations of atomic structure and collision dynamics with highly charged ions based on the heavy ion storage rings and electron ion beam traps in recent 20 years are reviewed. The structure part covers test of quantum electrodynamics and electron correlation in strong Coulomb field studied through dielectronic recombination spectroscopy and VUV/x-ray spectroscopy. The collision dynamics part includes charge exchange dynamics in ion-atom collisions mainly in Bohr velocity region, ion-induced fragmentation mechanisms of molecules, hydrogen-bound and van de Waals bound clusters, interference, and phase information observed in ion-atom/molecule collisions. With this achievements, two aspects of theoretical studies related to low energy and relativistic energy collisions are presented. The applications of data relevant to key atomic processes like dielectronic recombination and charge exchanges involving highly charged ions are discussed. At the end of this review, some future prospects of research related to highly charged ions are proposed.     

Dislocation glide through non-randomly distributed point obstacles

Abstract

Classical meso-scale models for dislocation–obstacle interactions have, by and large, assumed a random distribution of obstacles on the glide plane. While a good approximation in many situations, this does not represent materials where obstacles are clustered on the glide plane. In this work, we have investigated the statistical problem of a dislocation sampling a set of clustered point obstacles in the glide plane using a modified areal-glide model. The results of these simulations show two clear regimes. For weak obstacles, the spatial distribution does not matter and the critically resolved shear stress is found to be independent of the degree of clustering. In contrast, above a critical obstacle strength determined by the degree of clustering, the critical resolved shear strength becomes constant. It is shown that this behaviour can be explained semi-analytically by considering the probability of interaction between the dislocation line and obstacles at a given level of stress. The consequences for alloys exhibiting solute clustering are discussed.     

A production system with two job classes,changeover times and revisitation

This paper, motivated by the need to predict performance of production systems with random arrivals, setup times and revisitation, presents an imbedded Markov chain analysis of the underlyingM/G/1 queue with two customer classes, changeover times and instantaneous Bernoulli feedback. It is assumed that jobs are scheduled according to the exhaustive alternative priority queue discipline. Expressions for the mean waiting time and the nonsaturation condition are derived under two different priority assignments to the repeat customers. Sojourn times under these priority assignments are shown to possess a convex ordering. Results of the study are also applicable to data communication networks that operate under cyclic switching mechanisms. Research supported in part by Natural Sciences and Engineering Research Council of Canada.     

Nature of light scalars through photon-photon collisions

The surprising thing is that arising almost 50 years ago from the linear sigma model(LSM)with spontaneously broken chiral symmetry,the light scalar meson problem has become central in the nonperturbative quantum chromodynamics(QCD)for it has been made clear that LSM could be the low energy realization of QCD.First we review briefly signs of four-quark nature of light scalars.Then we show that the light scalars are produced in the two photon collisions via four-quark transitions in contrast to the classic P wave tensor q(q)mesons that are produced via two-quark transitions γγ→q(q).Thus we get new evidence of the four-quark nature of these states.     

Mechanisms of a Cyclobutane-Fused Lactone Hydrolysis in Alkaline and Acidic Conditions

Searching for functional polyesters with stability and degradability is important due to their potential applications in biomedical supplies, biomass fuel, and environmental protection. Recently, a cyclobutane-fused lactone (CBL) polymer was experimentally found to have superior stability and controllable degradability through hydrolysis reactions after activation by mechanical force. In order to provide a theoretical basis for developing new functional degradable polyesters, in this work, we performed a detailed quantum chemical study of the alkaline and acidic hydrolysis of CBL using dispersion-corrected density functional theory (DFT-D3) and mixed implicit/explicit solvent models. Various possible hydrolysis mechanisms were found: B_AC2 and B_AL2 in the alkaline condition and A_AC2, A_AL2, and A_AL1 in the acidic condition. Our calculations indicated that CBL favors the B_AC2 and A_AC2 mechanisms in alkaline and acidic conditions, respectively. In addition, we found that incorporating explicit water solvent molecules is highly necessary because of their strong hydrogen-bonding with reactant/intermediate/product molecules.