Enhanced chemical reworkability of DGEBA thermosets cured with rare earth triflates using aromatic hyperbranched polyesters (HBP) and multiarm star HBP‐b‐poly(ε‐caprolactone) as modifiers

A hyperbranched aromatic polyester (HBPOH) has been synthesized, and poly(ε‐caprolactone) arms have been grown on some of its end hydroxyl groups (HBPCL). These modifiers have been used in cationic diglycidyl ether of bisphenol A formulations cured with ytterbium triflate as cationic initiator. The effect of HBPOH and HBPCL on the curing kinetics has been studied using differential scanning calorimetry (DSC). The obtained materials have been characterized by dynamomechanical analysis, DSC, thermogravimetric analysis and mechanical tests. The modifiers are incorporated into the thermosetting network because of the participation of the end hydroxyl groups in the cationic curing of epoxides by the activated monomer mechanism. Homogeneous thermosets have been obtained with a remarkable increase in impact strength without sacrificing elastic modulus or hardness. A compromise between the rigid structure of the aromatic hyperbranched core and the flexibilizing effect of the poly(ε‐caprolactone) arms is believed to be responsible for the overall thermal and mechanical properties of the materials. The use of these polymeric modifiers increases the thermal stability of the resulting materials because of the low degradability of the aromatic ester groups in the hyperbranched core and the incorporation of the modifier into the network structure. However, the presence of such ester groups makes them reworkable by hydrolysis or alcoholysis in an alkaline medium, thus opening a way for recovery of valuable substrates. Copyright © 2013 John Wiley & Sons, Ltd.     

Simulation of mesogenic diruthenium tetracarboxylates: Development of a force field for coordination polymers of the MMX type

A classical molecular mechanics force field, able to simulate coordination polymers (CP) based on ruthenium carboxylates (Ru₂(O₂CR_eq)₄L_ax) (eq = equatorial group containing aliphatic chains, L_ax= axial ligand), has been developed. New parameters extracted from experimental data and quantum calculations on short aliphatic chains model systems were included in the generalized AMBER force field. The proposed parametrization was evaluated using model systems with known structure, containing either short or long aliphatic chains; experimental results were reproduced satisfactorily. This modified force field, although in a preliminary stage, could then be applied to long chain liquid crystalline compounds. The resulting atomistic simulations allowed assessing the relative influence of the factors determining the CP conformation, determinant for the physical properties of these materials. © 2013 Wiley Periodicals, Inc.     

Reaction of N-(Benzyloxycarbonyl)aminobenzyl-phosphonous Acid with Ethyl Orthoformate

Reaction of N-(benzyloxycarbonyl)aminobenzylphosphonous acid with ethyl orthoformate afforded two major products diethyl N-(benzyloxycarbonyl)aminobenzylphosphhite and ethyl (diethoxymethyl)[N-(benzyloxy-carbonyl)aminobenzyl]phosphmate, a product of addition of phosphonous acid to orthoformate.     

Relation between structure and enthalpy for stacking interactions of aromatic molecules

An approximately linear correlation has been found between the enthalpy of complexation and the area of overlap of the chromophores using published structural and thermodynamical data on the self- and hetero-association of aromatic molecules measured under similar solution conditions. This finding is consistent with the assumption that short-range van-der-Waals forces dominate over other contributions to the enthalpy of stacking of aromatic molecules. It provides a ‘model-independent’ approach for a priori estimation of the enthalpy of aromatic–aromatic stacking interactions from knowledge of the structural properties or vice versa.     

Derivatives of Some 2-Chloroethylphosphonic Acid Esters,with Plant Growth Regulating Activity

Abstract

A method for the synthesis of esters of 2-(dimethylsulfonium)ethylphos-phonic acid and the results of some trials showing the plant growth regulating activity of these compounds are presented. For the synthesis of the mentioned compounds, dimethyl sulphide is reacted with 2-chloroethylphosphonic acid esters; these esters are obtained through the complex[1] of AlCl₃, PCl₃ and 1,2-dichloroethan (1). Using the optimum reaction conditions, very good yields were obtained (96–99%). This complex is reacted with different alcohols to give 2-chloroethylphosphonic acid esters (2) (R?Me, Et, Pr, i-Pr, Bu, i-Bu, Pe). Using the optimum reaction conditions, in the case of methanol the maximum obtained yield was 50%. In the case of the other alcohols, the obtained yields were between 76 and 83%. An exception is i-propanol. whose ester was obtained with low yields and the reaction parameters modification have little influence on the yield. The reaction of the esters with dimethyl sulphide gives, in good yields (between 69 and 79%). esters of 2-(dimethylsulfonium)ethylphosphonic acid (3). substances with plant growth regulating activity.     

Biomedical Implications of Polyphosphates

Abstract

The polyphosphates have the capacity of forming chelates with most of that metal cations[l]. Polyphosphatic complexes with trace- and macroelements art used as fodder additives for animals. In our experiments we studied the effect 01pyrophosphate (PP), tripolyphosphate (TPP) and hexametaphosphate (HMP), at different concentrations (0.909 mM, 1.8 I8 mM and 2.727 mM), on the enzymatic activity of carbonic anhydrase (CA), and the effect of polyphosphate chelates or the enzymatic activity of alkaline phosphatase (AP), both zincenzymes. The meta; ion, which can be dissociated in the presence of a chelating agent, is essential foi their catalytic activity 121. The presence of metal atoms as essential constituents of some enzymes, and the metal requirements of others for maximum activity, provide an obvious link between enzymatic reaction and coordination chemistry.     

Morphology and molecular organisation of liquid-crystalline perylene-3,4,9,10-tetra-(n-hexylester) deposited on a solid substrate

Liquid-crystalline perylene-3,4,9,10-tetra-(n-hexylester) forms characteristic dendritic or flower-like structures at room temperature when it is deposited on a hydrophilic glass substrate using the zone-casting technique. It was found that such unique structures were not possible to be created simply by recrystallisation of this dye from a liquid-crystalline columnar phase. On the basis of the observations using a confocal microscope and the study of wide angle X-ray scattering (WAXS) as well as the analysis of the absorption and fluorescence spectra, some conclusions, concerning the molecular organisation in the dendritic structure, are drawn. Based on the research, one can assume that the dendrites are formed by columnar molecular aggregates with the column axes parallel to the substrate. Such an organisation of the molecules can be interesting from the point of view of organic electronics.