Theoretical studies on the influence of metallic cations on ring opening of propylene oxide catalyzed by metal-salen complexes

We studied the ring opening of propylene oxide (PO) by salen-M coordinated OH⁻ group [M = Al(III), Sc(III), Cr(III), Mn(III), Fe(III), Co(II), Co(III), Ni(II), Cu(II), Zn(II), Ru(III) and Rh(III)]. The results show that the ring-opening energy barriers for M(II) complexes are much lower than those with M(III) complexes in the gas phase, and the barriers correlate linearly with the negative charges on the OH⁻ group and the Fukui function condensed on the OH⁻ group. The nucleophilicity ordering in the gas phase can be rationalized by the ratio of formal positive charges/radius of M cations. Solvent effect greatly increases the barriers of M(II) complexes but slightly changes the results of M(III) ones, making the barriers similar. Analysis indicates that the reaction heats are linearly proportional to the reverse reaction barriers. The relationships established here can be used to estimate the ring-opening barriers and to screen epoxide ring-opening catalysts.     

Maximal Subrings and Covering Numbers of Finite Semisimple Rings

We classify the maximal subrings of the ring of n×n matrices over a finite field, and show that these subrings may be divided into three types. We also describe all of the maximal subrings of a finite semisimple ring, and categorize them into two classes. As an application of these results, we calculate the covering number of a finite semisimple ring.     

Potts models with magnetic field: Arithmetic,geometry, and computation

We give a sheaf theoretic interpretation of Potts models with external magnetic field, in terms of constructible sheaves and their Euler characteristics. We show that the polynomial countability question for the hypersurfaces defined by the vanishing of the partition function is affected by changes in the magnetic field: elementary examples suffice to see non-polynomially countable cases that become polynomially countable after a perturbation of the magnetic field. The same recursive formula for the Grothendieck classes, under edge-doubling operations, holds as in the case without magnetic field, but the closed formulae for specific examples like banana graphs differ in the presence of magnetic field. We give examples of computation of the Euler characteristic with compact support, for the set of real zeros, and find a similar exponential growth with the size of the graph. This can be viewed as a measure of topological and algorithmic complexity. We also consider the computational complexity question for evaluations of the polynomial, and show both tractable and NP-hard examples, using dynamic programming.     

Pentapnictogen heterocyclic monoanions: Structure,stability, and aromaticity

Inorganic planar ring-shape molecules with 4n + 2 π electrons are always the focus of experimental synthesis and theoretical research due to their potential aromaticity and stability. In this work, the whole series of five-membered heterocycle monoanions X _nY_5-n⁻ (X, Y = group 15 elements; n = 1-4) were thoroughly investigated by means of density functional theory calculations. They all have large formation energies and HOMO-LUMO gap energies, suggesting the potential thermodynamic and kinetic stability. Their aromaticities are comparable to that of typical aromatic hydrocarbons. Their thermal stabilities were firmly established by the ab initio molecular dynamics simulations. As most of them are predicted for the first time, their various spectra were simulated for experimental characterization. Furthermore, we demonstrate that these five-membered cyclic anions can be employed as η⁵-ligand to construct novel all-inorganic metallocenes, which may serve as the building blocks of low-dimensional nanomaterials.     

Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters

Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.     

合肥光源高亮度模式Lattice设计

介绍了一组合肥光源新高亮度模式的Lattice. 新的设计维持了储存环上所有元件和光束线位置不变,也没有加入新的元件. 取得了较低发射度. 所有直线节处的垂直方向β函数值都很小，适合插入件的运行. 跟踪计算表明新Lattice具有足够大的动力学孔径用于注入和储存粒子.     

硬X射线磁圆二色实验方法的建立

在北京同步辐射装置(BSRF)1W1B光束线和XAFS实验站上国内首次建立了硬X射线波段的磁圆二色实验(XMCD)方法. 以单晶金刚石作为相位延迟片, 在透射劳埃(Laue)模式下, 利用衍射双折射效应, 将入射的单色线偏振光转变为相应的左旋和右旋圆偏振光, 测量磁化样品对左旋和右旋圆偏振光吸收的差异, 获得了XMCD信号. 本实验使用透射方法测量了Pt-Fe合金Pt L_2,3边的XMCD, 获得了XMCD信号. XMCD实验方法的建立, 为研究磁性材料尤其是磁性薄膜材料的电子结构和磁结构提供了实验基础.     

推广的奇轮的圆色数

图G的圆色数(又称"星色数")xc(G)是Vince在1988年提出的,它是图的色数 的自然推广.本文由奇轮出发构造了一族平面图,并证明了此类图的圆色数恰恰介于2和 3之间,填补了该领域的空白.     

Circular perfect graphs

For 1 ≤ d ≤ k, let K_k/d be the graph with vertices 0, 1, …, k ? 1, in which i ～j if d ≤ |i ? j| ≤ k ? d. The circular chromatic number χ_c(G) of a graph G is the minimum of those k/d for which G admits a homomorphism to K_k/d. The circular clique number ω_c(G) of G is the maximum of those k/d for which K_k/d admits a homomorphism to G. A graph G is circular perfect if for every induced subgraph H of G, we have χ_c(H) = ω_c(H). In this paper, we prove that if G is circular perfect then for every vertex x of G, N_G[x] is a perfect graph. Conversely, we prove that if for every vertex x of G, N_G[x] is a perfect graph and G ? N[x] is a bipartite graph with no induced P₅ (the path with five vertices), then G is a circular perfect graph. In a companion paper, we apply the main result of this paper to prove an analog of Haj?os theorem for circular chromatic number for k/d ≥ 3. Namely, we shall design a few graph operations and prove that for any k/d ≥ 3, starting from the graph K_k/d, one can construct all graphs of circular chromatic number at least k/d by repeatedly applying these graph operations. © 2005 Wiley Periodicals, Inc. J Graph Theory 48: 186–209, 2005