Topological “interfacial” polymer chemistry: Dependency of polymer “shape” on surface morphology and stability of layer structures when heating organized molecular films of cyclic and linear block copolymers of n‐butyl acrylate‐ethylene oxide

The “topological polymer chemistry” of amphiphilic linear and cyclic block copolymers at an air/water interface was investigated. A cyclic copolymer and two linear copolymers (AB‐type diblock and ABA‐type triblock copolymers) synthesized from the same monomers were used in this study. Relatively stable monolayers of these three copolymers were observed to form at an air/water interface. Similar condensed‐phase temperature‐dependent behaviors were observed in surface pressure–area isotherms for these three monolayers. Molecular orientations at the air/water interface for the two linear block copolymers were similar to that of the cyclic block copolymer. Atomic force microscopic observations of transferred films for the three polymer types revealed the formation of monolayers with very similar morphologies at the mesoscopic scale at room temperature and constant compression speed. ABA‐type triblock linear copolymers adopted a fiber‐like surface morphology via two‐dimensional crystallization at low compression speeds. In contrast, the cyclic block copolymer formed a shapeless domain. Temperature‐controlled out‐of‐plane X‐ray diffraction (XRD) analysis of Langmuir–Blodgett (LB) films fabricated from both amphiphilic linear and cyclic block copolymers was performed to estimate the layer regularity at higher temperatures. Excellent heat‐resistant properties of organized molecular films created from the cyclic copolymer were confirmed. Both copolymer types showed clear diffraction peaks at room temperature, indicating the formation of highly ordered layer structures. However, the layer structures of the linear copolymers gradually disordered when heated. Conversely, the regularity of cyclic copolymer LB multilayers did not change with heating up to 50 °C. Higher‐order reflections (d₀₀₂, d₀₀₃) in the XRD patterns were also unchanged, indicative of a highly ordered structure. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 486–498     

Experimental Charge Density Evidence for Pnicogen Bonding in a Crystal of Ammonium Chloride

Chemical binding in crystalline ammonium chloride, a simple inorganic salt with an unexpectedly complex bonding pattern, was studied by using a topological analysis of electron density function derived from high‐resolution X‐ray diffraction. Supported by periodic quantum chemical calculations, it provided experimental evidence for weak σ‐hole bonds (1.5 kcal mol^?1) that involve ammonium cations in a crystal. Our results show this type of supramolecular interaction to be more numerous than has been found to date by using gas‐phase calculations or statistical analysis of CSD.     

Electron Density Analysis of Hyperconjugation

Hyperconjugation is analyzed through the electron density of orbitals responsible for hyperconjugative interactions, which cannot be detected by means of conventional electron‐density‐based calculations. This interaction is detected through the π electron density topology, by excluding σ electron density from the total. As the presence of the hyperconjugation phenomenon in carbocation systems is well understood, several carbocations are benchmarked, and the results show that the positive carbon atom establishes a hyperconjugative critical point with the adjacent methyl group(s). Also, π localization and delocalization indices are employed to support the conclusions made by the topological analysis.     

Neumann problems with resonance in the first eigenvalue

The aim of this work is to present results of existence of solutions for a class of superlinear asymmetric elliptic systems with resonance in the first eigenvalue. The asymmetry that we consider has linear behavior on and superlinear on . To obtain these results we apply topological degree theory.     

Wedge Operations and Doubling Operations of Real Toric Manifolds

This paper deals with two things.First,the cohomology of canonical extensions of real topological toric manifolds is computed when coefficient ring G is a commutative ring in which 2 is unit in G.Second,the author focuses on a specific canonical extensions called doublings and presents their various properties.They include existence of infinitely many real topological toric manifolds admitting complex structures,and a way to construct infinitely many real toric manifolds which have an odd torsion in their cohomology groups.Moreover,some questions about real topological toric manifolds related to Halperin's toral rank conjecture are presented.     

A unifying theory of exactness of linear penalty functions II: parametric penalty functions

In this article, we develop a general theory of exact parametric penalty functions for constrained optimization problems. The main advantage of the method of parametric penalty functions is the fact that a parametric penalty function can be both smooth and exact unlike the standard (i.e. non-parametric) exact penalty functions that are always nonsmooth. We obtain several necessary and/or sufficient conditions for the exactness of parametric penalty functions, and for the zero duality gap property to hold true for these functions. We also prove some convergence results for the method of parametric penalty functions, and derive necessary and sufficient conditions for a parametric penalty function to not have any stationary points outside the set of feasible points of the constrained optimization problem under consideration. In the second part of the paper, we apply the general theory of exact parametric penalty functions to a class of parametric penalty functions introduced by Huyer and Neumaier, and to smoothing approximations of nonsmooth exact penalty functions. The general approach adopted in this article allowed us to unify and significantly sharpen many existing results on parametric penalty functions.     

内部算子生成的直觉I-Fuzzy拓扑空间

在直觉I-fuzzy拓扑空间中定义了内部度,并研究了它的一些性质,接着给出了直觉I-fuzzy拓扑空间内部算子的概念,最后得到了从拓扑的直觉I-Fuzzy内部算子I出发,得到一个直觉I-fuzzy拓扑r,再利用r定义的内部算子恰好回到了I等结论.     

半监督度量学习内蕴最速下降算法的收敛性分析

主要研究对称正定矩阵群上的内蕴最速下降算法的收敛性问题.首先针对一个可转化为对称正定矩阵群上无约束优化问题的半监督度量学习模型,提出对称正定矩阵群上一种自适应变步长的内蕴最速下降算法.然后利用李群上的光滑函数在任意一点处带积分余项的泰勒展开式,证明所提算法在对称正定矩阵群上是线性收敛的.最后通过在分类问题中的数值实验说明算法的有效性.     

On the vanishing of homology in random Čech complexes

We compute the homology of random ?ech complexes over a homogeneous Poisson process on the d‐dimensional torus, and show that there are, coarsely, two phase transitions. The first transition is analogous to the Erd?s ‐Rényi phase transition, where the ?ech complex becomes connected. The second transition is where all the other homology groups are computed correctly (almost simultaneously). Our calculations also suggest a finer measurement of scales, where there is a further refinement to this picture and separation between different homology groups. © 2016 Wiley Periodicals, Inc. Random Struct. Alg., 51, 14–51, 2017