Chemical bonding in representative astrophysically relevant neutral,cation, and anion HCnH chains

Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths. Building on our recent work, in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis. Presently reported results include atomic charges, natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC_2k/2k+1H chain family. They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes, e.g., electron removal from or electron attachment to a neutral chain. Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC_2k/2k+1H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study.     

Morphology and microphase separation of star copolymers

Star copolymers have attracted significant interest due to their different characteristics compared with diblock copolymers, including higher critical micelle concentration, lower viscosity, unique spatial shape, or morphologies. Development of synthetic skills such as anionic polymerization and controlled radical polymerization have made it possible to make diverse architectures of polymers. Depending on the molecular architecture of the copolymer, numerous morphologies are possible, for instance, Archimedean tiling patterns and cylindrical microdomains at symmetric volume fraction for miktoarm star copolymers as well as asymmetric lamellar microdomains for star‐shaped copolymers, which have not been reported for linear block copolymers. In this review, we focus on morphologies and microphase separations of miktoarm (A_mB_n and ABC miktoarm) star copolymers and star‐shaped [(A‐b‐B)_n] copolymers with nonlinear architecture. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1–21     

Synthesis of partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions

Partially fluorinated poly(arylene ether sulfone) multiblock copolymers bearing perfluorosulfonic functions (ps‐PES‐FPES), with ionic exchange capacity (IEC) ranging between 0.9 and 1.5 meq H⁺/g, are synthesized by regioselective bromination of partially fluorinated poly(arylene ether sulfone) multiblock copolymers (PES‐FPES), followed by Ullman coupling reaction with lithium 1,1,2,2‐tetrafluoro‐2‐(1,1,2,2‐tetrafluoro‐2‐iodoethoxy)ethanesulfonate. The PES‐FPES are prepared by aromatic nucleophilic substitution reaction by an original approach, that is, “one pot two reactions synthesis.” The chemical structures of polymers are analyzed by ¹H and ¹⁹F NMR spectroscopy. The resulted ionomers present two distinct glass transitions and α relaxations revealing phase separation between the hydrophilic and the hydrophobic domains. The phase separation is observed at much lower block lengths of ps‐PES‐FPES as compared with the literature. AFM and SANS observations supported the phase separation, the hydrophilic domains are well dispersed but the connectivity to each other depends on the ps‐PES block lengths. The thermomechanical behavior, the water up‐take, and the conductivity of the ps‐PES‐FPES membranes are compared with those of Nafion 117^® and randomly functionalized polysulfone (ps‐PES). Conductivities close or higher to those of Nafion 117^® are obtained. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1941–1956     

13C NMR investigations of molecular order of rod-like,bent-core,and thiophene mesogens

In this review, methods to obtain the orientational order of topologically variant molecular mesogens using by one- and two-dimensional (2D) solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy are described. Besides ¹³C chemical shifts, the ¹³C─¹H dipolar couplings measured from 2D-separated local field (SLF) technique are used for computing the order parameters of a variety of mesogens. The investigated molecules are composed of a variable number of rings in the core, that is, core ranging from simply one ring to five rings. Among the mesogens investigated, a special focus has been placed on mesogens with thiophene rings, which are gaining popularity as liquid crystalline organic semiconductors. The replacement of a phenyl ring by thiophene in the core has a dramatic influence on molecular topology, as observed from the measured order parameters. The review highlights the advantages of the 2D SLF method for understanding the local dynamics and for mapping the topology of mesogens through the measured order parameters. SLF NMR studies of as many as 24 molecular mesogens that vary in terms of the molecular structure as well as topology are covered in the review. Order parameters of the rings have been estimated from the ¹³C─¹H dipolar couplings in the nematic, smectic A, smectic C, and tilted hexatic phases as well as in B₁ and B₂ mesophases of various mesogens. It is anticipated that, in the years to come, the 2D SLF method would provide advanced molecular information on structurally complex mesogens that are emerging in liquid crystal science through the incessant efforts of synthetic chemists. The mini review covers the orientational order of topologically variant molecular mesogens determined by 1D and 2D solid-state ¹³C NMR spectroscopy. Accordingly, rod-like, bent-core, and thiophene mesogens were subjected to 2D SLF measurements to get the order parameters from which the topology was established. The replacement of phenyl ring by thiophene and its influence on order parameters as well as on molecular topology is also discussed.     

Formation of porous polymer morphology by microsyneresis during divinylbenzene polymerization

This article describes the investigation of the importance of various reaction conditions on microsyneretic pore formation during polymerization of divinylbenzene (DVB) under so‐called “solvothermal” conditions. To induce microsyneretic pore formation, the most important parameter is an unusually high dilution of monomers with a “good” porogen solvating the polymer chains. High dilution and solvation of the growing poly(DVB) chains promote the prolongation of the polymer chains rather than their interconnection by crosslinking. Consequently, when the polymer gel density reaches the point where syneresis starts, the polymer network is geometrically too extensive to be broken up into precipitating entities and, instead, porogen droplets are formed within the continuous polymer gel. The pore geometry created by microsyneresis offers high surface area in wide mesopores and hence, high capacity for supporting functional groups or reactions with much better accessibility than narrow pores between polymer microspheres produced by macrosyneresis in conventional styrenic polymer supports. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 774–781     

Effect of additive length and chemistry on the morphology of blends of conjugated thiophenes and fullerene derivative acceptor molecules

Small molecule additives have been shown to increase the device efficiency of conjugated polymer (donor) and fullerene derivative (acceptor) based organic solar cells by modifying the morphology of the device active layer. In this paper we conduct a systematic study of how additives affect the donor‐acceptor morphology using molecular dynamics simulations of blends of thiophene‐based oligomers, mimicking poly(3‐dodecylthiophene) (P3DDT) or poly(2,2′:5′,2”‐3,3”‐didocyl‐terthiophene) (PTTT), and fullerene derivatives with additives of varying length and chemical functionalization, mimicking experimentally used additives like methyl ester additives, diiodooctane, and alkanedithiols. We find that functionalization of additives with end groups that are attracted to acceptor molecules are necessary to induce increased donor‐acceptor macrophase separation. In blends where acceptors intercalate between oligomer alkyl side chains, functionalized additives decrease acceptor intercalation. Functionalized additives with shorter alkyl segments increase acceptor macrophase separation more than additives with same chemical functionalization but longer alkyl segments. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1046–1057     

一阶最优性条件研究

本对由Botsko的关于多变量函数取极值的一阶导数检验条件定理^[1]进行了分析研究，给出了更实用而简捷的差别条件。最后，举出若干例子予以说明。     

SINGULAR PERTURBATION OF BOUNDARY VALUE PROBLEM FOR NONLINEAR HIGHER ORDER ORDINARY DIFFERENTIAL EQUATIONS INVOLVING TWO SMALL PARAMETERS

The singularly perturbed boundary value problem for nonlinear higher order ordinary differential equation involving two small parameters has been considered. Under appropriate assumptions, for the three cases:ε/μ2→0(μ→0),μ2/ε→0 (ε→0) andε=μ2, the uniformly valid asymptotic solution is obtained by using the expansion method of two small parameters and the theory of differential inequality.     

Surface structures formed by individual adsorption and coadsorption of Mn and Bi on Cu(0 0 1), studied by LEED

We have studied the individual adsorption of Mn and Bi, and their coadsorption on Cu(0 0 1) by low-energy electron diffraction (LEED). For Mn, we have determined the c(2 × 2) structure formed at 300 K, whose structure had been determined by several methods. We reconfirmed by a tensor LEED analysis that it is a substitutional structure and that a previously reported large corrugation (0.30 Å) between substitutional Mn and remaining surface Cu atoms coincides perfectly with the present value. In the individual adsorption of Bi, we have found a c(4 × 2) structure, which is formed by cooling below ∼250 K a surface prepared by Bi deposition of ∼0.25 ML coverage at 300 K where streaky half-order LEED spots appear. The c(4 × 2) structure has been determined by the tensor LEED analysis at 130 K and it is a substitutional structure. In the coadsorption, we found a c(6 × 4) structure, which has been determined by the tensor LEED analysis. It is very similar to the previously determined structure of the c(6 × 4) formed by coadsorption of Mg and Bi, and embedded MnBi₄ clusters are arranged in the top Cu layer instead of MgBi₄. Large lateral displacements of Bi atoms in the c(6 × 4)-(Mn + Bi) suggest that the Mn atoms undergo the size-enhancement caused by their large magnetic moment.