Liquid crystalline epoxy resin with improved thermal conductivity by intermolecular dipole–dipole interactions

To address tremendous needs for developing efficiently heat dissipating materials with lightweights, a series of liquid crystalline epoxy resins (LCEs) are designed and synthesized as thermally conductive matrix. All prepared LCEs possess epoxies at the molecular side positions and cyanobiphenyl mesogenic end groups. Based on several experimental results such as differential scanning calorimetry, polarized optical microscopy, and X‐ray diffraction, it is found that the LCEs exhibited liquid crystalline mesophases. When LCE is cured with a diamine crosslinker, the cured LCE maintains the oriented LC domain formed in the uncured state, ascribing to a presence of dipole–diploe and π–π interactions between cyanobiphenyl mesogenic end groups. Due to the anisotropic molecular orientation, the cured LCE exhibits a high thermal conductivity of 0.46 W m^?1 K^?1, which is higher than those of commercially available crystalline or amorphous epoxy resins. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 708–715     

Push–Pull Porphyrins via β-Pyrrole Functionalization: Evidence of Excited State Events Leading to High-Potential Charge-Separated States

A new set of free-base and zinc(II)-metallated, β-pyrrole-functionalized unsymmetrical push–pull porphyrins were designed and synthesized via β-mono- and dibrominated tetraphenylporphyrins using Sonogashira cross-coupling reactions. The ability of donors and acceptors on the push–pull porphyrins to produce high-potential charge separated states was investigated. The porphyrins were functionalized at the opposite β,β′-pyrrole positions of porphyrin ring bearing triphenylamine push groups and naphthalimide pull groups. Systematic studies involving optical absorption, steady-state and time-resolved emission revealed existence of intramolecular type interactions both in the ground and excited states. The push–pull nature of the molecular systems was supported by frontier orbitals generated on optimized structures, wherein delocalization of HOMO over the push group and LUMO over the pull group connecting the porphyrin π-system was witnessed. Electrochemical studies were performed to visualize the effect of push and pull groups on the overall redox potentials of the porphyrins. Spectroelectrochemical studies combined with frontier orbitals helped in characterizing the one-electron oxidized and reduced porphyrins. Finally, by performing transient absorption studies in polar benzonitrile, the ability of push–pull porphyrins to produce charge-separated states upon photoexcitation was confirmed and the measured rates were in the range of 10⁹ s⁻¹. The lifetime of the final charge separated state was around 5 ns. This study ascertains the importance of push–pull porphyrins in solar energy conversion and diverse optoelectronic applications, for which high-potential charge-separated states are warranted.     

Cage motion of a probe atom in a vacancy complex in Pt

The perturbation function of a Cd probe atom bound in a hydrogen-decorated vacancy complex in Pt is found to exhibit dynamical relaxation at 294 K, as measured by the technique of perturbed γ-γ angular correlations. Based on other characteristics of the complex, a model is proposed for the structure of the complex. In the undecorated state, it consists of a probe atom at the center of a tetrahedron of vacancies in the fcc structure. In the decorated state at low temperature, the probe atom returns to one of the four vacant lattice sites. The relaxation at room temperature is attributed to motion of the probe atom in a cage formed by the four vacant sites.     

New interpretations for noncrossing partitions of classical types

We interpret noncrossing partitions of type B and type D in terms of noncrossing partitions of type A. As an application, we get type-preserving bijections between noncrossing and nonnesting partitions of type B, type C and type D which are different from those in the recent work of Fink and Giraldo. We also define Catalan tableaux of type B and type D, and find bijections between them and noncrossing partitions of type B and type D respectively.     

A discrete two-stage population model: continuous versus seasonal reproduction

A discrete two-stage model which describes the dynamics of a population where juveniles and adults compete for different resources is developed. A motivating example is the green tree frog (Hyla cinerea) where tadpoles and adult frogs feed on separate resources. First, continuous breeding is assumed and the asymptotic behavior of the resulting autonomous model is fully analyzed. It is shown that the unique interior equilibrium is globally asymptotically stable when the inherent net reproductive number is greater than one. However, when the inherent net reproductive number is less than one, the population becomes extinct. Then a seasonal breeding described by a periodic birth rate with period 2 is assumed. It is proved that for this nonautonomous model a period two solution is globally asymptotically stable when the inherent net reproductive number is greater than one and when the inherent net reproductive number is less than one the population becomes extinct. Finally, the advantage (in terms of maximizing the number of juveniles and adults in the population over a fixed time period) of having a seasonal breeding is studied by comparing the average of the juvenile and adult numbers of the periodic solution for the nonautonomous model to the equilibrium solution of the autonomous model. Our results indicate that for high birth rates the equilibrium of the autonomous model is higher than the average of the two cycle solution. Therefore, all other factors being equal, seasonal breeding appears to be deleterious to populations with high birth rates. However, for low birth rates seasonal breeding can be beneficial. It is also shown that for a range of birth rates the nonautnomous model is persistent while the solution to the autonomous model goes to extinction.     

A Criterion for Projective Modules

In case G is a finite group, there is a well-known criterion for projective modules: A ? G-module M is projective if and only if it is ? -free and has finite projective dimension. We first investigate whether only finite groups satisfy the above criterion. In the class of groups L H 𝔉, we conclude that this is true. Secondly, we consider the problem when a stably flat Γ-module is projective, where Γ is an arbitrary group. We show that if Γ is an L H 𝔉-group, then every stably flat cofibrant ? Γ-module is projective.     

Efficient preparation of UCl3 by ZnCl2 mediated chlorination

Journal of Radioanalytical and Nuclear Chemistry - U chlorination is demonstrated using electrochemical and chemical reactions with ZnCl2 in LiCl–KCl molten salts. Voltammetric studies...     

Template‐free anion‐controlled synthesis of Pd (II) nano‐aggregates for the antifouling polymerization of CO and ethylene

The reaction of [(domppp) Pd (OAc)₂] [domppp = 1,3‐bis (di‐o‐methoxyphenylphosphino)propane] and imidazolium‐functionalized carboxylic acids containing various anions (Br^?, PF₆^?, SbF₆^? and BF₄^?) resulted in the formation of nano‐sized Pd (II) aggregates under template‐free conditions. The rate of formation of aggregates can be modulated by changing the anion, affecting the rate of polymerization of CO and olefins without fouling. Herein, we describe the analysis of Pd (II) catalysts by dynamic light scattering, atomic force microscopy, X‐ray photoelectron spectroscopy and X‐ray crystallography, and co‐ and terpolymerization results including the catalytic activity, and bulk density and molecular weight of polymers.     

Carbohydrate-based nanostructured catalysts: applications in organic transformations

The requirement of green and sustainable materials to prepare heterogeneous catalysts has intensified for practical reasons over the past few decades. Carbohydrates are possibly the most plentiful and renewable organic materials in nature with inimitable physiochemical properties, plausible low-cost and large-scale production, and sustainability features could be exploited in the generation of nanostructured heterogeneous catalysts. This review article outlines the organic transformations catalyzed by diverse carbohydrate-based nanostructured catalysts in greener and environmentally friendly processes. Selected examples are highlighted for a variety of organic reactions exploiting the proposed catalysts’ reactivity and reusability, and interactions with the intrinsic nature of the applied carbohydrate supports; advantages and speculated challenges of the introduced catalysts are deliberated as well.     

Synthesis and curing of liquid crystalline epoxy resin based on naphthalene mesogen

Aromatic liquid crystalline epoxy resin (LCE) based on naphthalene mesogen was synthesized and cured with aromatic diamines to prepare heat‐resistant LCE networks. Diaminodiphenylester (DDE) and diaminodiphenylsulfone (DDS) were used as curing agents. The curing reaction and liquid crystalline phase of LCE were monitored, and mechanical and thermal properties of cured LCE network were also investigated. Curing and postcuring peaks were observed in dynamic DSC thermogram. LCE network cured with DDE displayed liquid crystalline phase in the curing temperature range between 183 and 260°C, while that cured with DDS formed one between 182 and 230°C. Glass transition temperature of cured LCE network was above 240°C, and crosslinked network was thermally stable up to 330°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 419–425, 1999