Hyper-aging dynamics of nanoclay suspension

Aqueous suspension of nanoclay Laponite undergoes structural evolution as a function of time, which enhances its elasticity and relaxation time. In this work, we employ an effective time approach to investigate long-term relaxation dynamics by carrying out creep experiments. Typically, we observe that the monotonic evolution of elastic modulus shifts to lower aging times, while maxima in viscous moduli get progressively broader for experiments carried out on a later date after preparation (idle time) of the nanoclay suspension. Application of effective time theory produces a superposition of all the creep curves irrespective of their initial state. The resulting dependence of the relaxation time on aging time shows very strong hyper-aging dynamics at short idle times, which progressively weakens to demonstrate a linear dependence in the limit of very long idle times. Remarkably, this behavior of nanoclay suspensions is akin to that observed for polymeric glasses. Consideration of aging as a first-order process suggests that continued hyper-aging dynamics causes cessation of aging. The dependence of relaxation time on aging time, therefore, must attenuate eventually producing linear or weaker dependence on time in order to approach a progressively low-energy state in the limit of very long times as observed experimentally. We also develop a simple scaling model based on a concept of aging of an energy well, which qualitatively captures various experimental observations very well, leading to profound insight into the hyper-aging dynamics of nanoclay suspensions.     

An efficient and general method for the Heck and Buchwald-Hartwig coupling reactions of aryl chlorides

The β-diketiminatophosphane Pd complex acted as a powerful catalyst for the Heck coupling of aryl chlorides with alkenes. Various aryl and heteroaryl chlorides were coupled efficiently under relatively mild conditions. Furthermore, this catalytic system also proved to be highly active in the Buchwald-Hartwig coupling of deactivated and sterically hindered aryl chlorides at room temperature.     

The Johari-Goldstein β-relaxation of glass-forming binary mixtures

The present paper shows, by means of broadband dielectric measurements, that the primary α- and the secondary Johari-Goldstein (JG) β-processes in binary mixtures are strongly correlated. This occurs for different polar rigid probes dissolved in apolar glass-forming solvents, over a wide temperature and pressure range.We found that the coupling parameter n = 1 − β_KWW and the ratio between α- and β-relaxation time reduce on increasing the size of the solute solved within the same apolar matrix. Moreover, such a ratio is invariant when calculated at different combinations of P and T maintaining either the primary or the JG relaxation times constant. Dielectric spectra measured at different T-P combinations but with an invariant α-relaxation time are well superposed in both the α- and β-frequency ranges. Experimental results can be rationalized by Coupling Model equation.     

An eco-compatible multicomponent strategy for the synthesis of new 2-amino-6-(1H-indol-3-yl)-4-arylpyridine-3,5-dicarbonitriles in aqueous micellar medium promoted by thiamine-hydrochloride

A thiamine hydrochloride (VB₁) accelerated, one-pot synthesis of 2-amino-6-(1H-indol-3-yl)-4-arylpyridine-3,5-dicarbonitriles was achieved via four-component reaction of 3-cyanoacetyl indole, aromatic aldehydes, ammonium acetate, and malononitrile in aqueous micellar conditions by a Knoevenagel condensation reaction followed by Michael-addition, which upon cyclization and dehydration yielded the corresponding product in excellent proportion.     

Simultaneous study of cure kinetics and rheology of montmorillonite/vinyl ester resin nanocomposites

In this work, the effect of quaternary ammonium salt containing nanoclay content (1–5 wt%) on phase morphology, rheology, cure kinetics, and mechanical properties of the vinyl ester resin (VER)‐based nanocomposites was studied. The morphological characterization including d‐spacing measurement, microscopy observation and phase‐height image processing were performed on the prepared nanocomposites using small angel X‐ray scattering (SAXS), transmission electron microscopy (TEM) and atomic force microscopy (AFM). According to the results obtained from these techniques, it was concluded that an intercalated morphology existed for all the nanocomposites. The kinetic analyses of the isothermal curing followed by storage modulus obtained from the rheometry experiments are shown to be an affective rheological characteristic to investigate the cure behavior of VER/clay nanocomposites. In addition, the most important finding regarding the effect of nanoclay on the cross‐linking behavior of VER systems lays on the chemisorption and physisorption of the reacting monomers and initiator molecules on the nanoclay platelets surface which is found to be responsible for the retardation of the cure reaction caused by organoclay. Eventually, the mechanical characterizations were performed through the tensile, flexural and impact analysis tests. In this case, a considerable improvement of the bulk mechanical responses such as tensile and flexural strengths and also the corresponding moduli were observed for the nanocomposites. Copyright © 2011 John Wiley & Sons, Ltd.     

Single meson photoproduction and IR renormalons

Single pseudoscalar and vector mesons hard semi-inclusive photoproductionγh → MX via higher twist mechanism is calculated using the QCD running coupling constant method. It is proved that in the context of this method a higher twist contribution to the photoproduction cross section cannot be normalized in terms of the meson electromagnetic form factor. The structure of infrared renormalon singularities of the higher twist subprocess cross section and the resummed expression (the Borel sum) for it are found. Comparisons are made with earlier results, as well as with leading twist cross section. Phenomenological effects of studied contributions for π,K,?-meson photoproduction are discussed.     

QSAR modeling of toxicities of ionic liquids toward Staphylococcus aureus using SMILES and graph invariants

Structural Chemistry - Ionic liquids (ILs) have been popular in many industrial and chemical processes, like antimicrobial properties, solvents, and synthesis of new compounds with antioxidant...     

Tris(dimethylsilyl)methyllithium: A Reagent for the Synthesis of Vinylbis(silanes) Containing Si–H Functional Groups

Reactions between a series of nonenolisable aldehydes and tris(dimethylsilyl)methyllithium, (HMe₂Si)₃CLi, are described. The Peterson reaction takes place readily to give vinylbis(silanes). Moreover, styrene and butyl acrylate 1:1 copolymer (P), prepared by use of α,α′-azobis(isobutyronitrile) (AIBN) as an initiator in toluene at 70 ± 1°C, was formylated via direct electophilic substitution by methyl dichloromethyl ether (Cl₂CHOMe) in the presence of tin(IV) chloride (SnCl₄) in nitrobenzene (PhNO₂) as solvent. The reaction of (HMe₂Si)₃CLi with formyl groups on the side chains of the copolymer led to new macromolecules bearing vinylbis(silane) functional groups.