Tailored Degradation and Dye Release from Poly(ester amides)

Poly(ester amides) based on L-valine and adipic acid with different aliphatic and aromatic diols were synthesized by interfacial polymerization. Four different diols such as ethylene glycol, 1,5-pentanediol, resorcinol, and catechol were used to systematically vary the chain lengths and position of the hydroxyl groups. The chemical structures, thermal properties, degradation, and dye release of these polymers were investigated. This study demonstrates that the release kinetics can be tailored through the control of the chain length of the diol and the position of the hydroxyl groups. These findings have important implications for designing biodegradable polymers for tailored release.     

Strong Reactivity Enhancement through Molecular Traffic Control in Zeolites

In the past, the investigation of catalytic reactivity enhancement through molecular traffic control (MTC) by means of dynamical Monte Carlo simulations of catalysis was initiated in simple, idealized zeolite channel networks. These results are reviewed here and, emphasizing more recent work, the conditions of reactivity enhancement through MTC are examined for a realistic channel topology based on the pore structure of the zeolite TNU‐9. For a wide range of reaction rates a very strong MTC effect can be found that increases with grain size. This effect is argued to be a generic feature of a certain class of zeolite pore topologies.     

0.40% Bipolar Strain in Lead Free BNT–KNN System Modified with Li,Ta and Sb

In this work we demonstrate a large electric field‐induced bipolar strain ~0.40% in Li, Ta and Sb modified BNT–KNN ((1?x) Bi_0.5Na_0.5TiO₃–xK_0.47Na_0.47Li_0.06 Nb_0.74Sb_0.06Ta_0.2O₃) system. The morphotropic phase boundary (MPB) of the system between rhombohedral and tetragonal phases lies in the range 0.02 ≤ x ≤ 0.06, beyond which all compositions (up to x < 0.15) were found to be tetragonal. A clear trade‐off between the large strain values and achievable d₃₃, k_p for a particular composition was noted. It is shown that while for x = 0.03, d₃₃ 169 pC/N, k_p 49% and strain ~0.13% were obtained, for x = 0.08 with 0.40% strain, d₃₃ and k_p values decreased drastically.     

The fast reaction asymptote of the coalescence-redispersion model

The coalescence-redispersion (CRD) model is examined in the fast chemistry limit for the single bimolecular reaction A+B M R and the series parallel reactions A+B M R;B+R M S occurring in a plug flow reactor with unmixed feed streams. For the single bimolecular reaction it is shown that in this limit the CRD model is asymptotically equivalent to the 3E fast closure as t M 0. For the series parallel reactions the CRD model predictions tend to be bracketed by the 3E slow and fast closure formulations. Representative results are presented for the variance decay of the individual reactants, and it is seen that even in the fast reaction limit where mixing is controlling, the shape of the feed stream PDFs has negligible influence on the progress of the reaction.     

Vinylogous Organocatalytic Triple Cascade Reaction: Forging Six Stereocenters in Complex Spiro‐Oxindolic Cyclohexanes

We report a triple vinylogous cascade reaction, yielding valuable spiro‐oxindolic cyclohexane derivatives. The three‐component domino process proceeds by way of a catalyzed Michael/1,6‐addition/vinylogous aldol sequence affording the products with six stereogenic centers and very high control over the stereochemistry. The chemistry is based on a rare example of asymmetric 1,6‐addition to linear 2,4‐dienals proceeding with complete δ‐site selectivity. Key to the reaction development was a directing group positioned at the β‐dienal position, which was essential for achieving highly predictable reaction outcomes.

     

The beneficial effect of small amount of water in the ambient temperature atom transfer radical homo and block co-polymerization of methacrylates

ATRP of several methacrylates viz. methyl methacrylate (MMA), ethyl methacrylate (EMA), n-butyl methacrylate (nBMA), t-butyl methacrylate (tBMA), benzyl methacrylate (BzMA) and (N,N-dimethylamino)ethyl methacrylate (DMAEMA) has been studied in neat as well as aqueous (up to 12 vol% water) acetone at 35 °C using CuCl/bipyridine (bpy) catalyst and ethyl 2-bromoisobutyrate as the initiator. Addition of water significantly enhances the rate of polymerization without losing control. Unlike CuCl/bpy the CuBr/bpy catalyst gives poor control which is attributed to the lower solubility and consequent heterogeneity in the latter case. Of the other ligands used with the CuCl catalyst viz. o-phenanthroline (o-phen), 1,1,4,7,7-pentamethyldiethylenetriamine (PMDETA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA), Me₆TREN only o-phen offers reasonably good control. The CuCl/bpy catalyst system has been used also in preparing some di- and tri-block copolymers with reasonably low polydispersity index (PDI) at ambient temperature (35 °C) using aqueous acetone as the solvent. The following block copolymers have been prepared PMMA-tBMA, PMMA-b-tBMA-b-MMA, PMMA-DMAEMA, by this method.     

Morphological,Mechanical Property Analysis and Comparative Study over Structural Properties of CVD TiN Film Grown under Different Substrate Temperature in Nitrogen Gas Atmosphere

Silicon - Titanium Nitride (TiN) thin films were deposited by thermal chemical vapor deposition process (CVD) over Si (100) substrate under different substrate temperatures. Morphological,...     

Experimental study of paddy drying in a vortex chamber

The intensification of interfacial mass, heat, and momentum transfer makes vortex chambers potentially interesting for the efficient drying of paddy, allowing shorter drying times and/or more compact equipment. The presence of a shell introduces particular challenges. Intraparticle diffusion limitations are strong and may reduce the advantage from intensified interfacial mass and heat transfer and the efficiency of air usage. Furthermore, high shear and normal stresses in the fast rotating particle bed may cause damage to the paddy shell, posing problems for transport and storage. With these specific aspects in mind, the use of vortex chambers for paddy drying is experimentally evaluated.     

Sol–gel approach to near-net-shape oxide–oxide composites reinforced with short alumina fibres—The effect of crystallization

Near-net-shape (NNS) high alumina (alumina:silica = 96:4, in equivalent weight ratio) fibre reinforced ceramic matrix composites (CMCs) were prepared with single and bicomponent sols following sol–gel vacuum infiltration technique. The CMCs were characterized by X-ray diffraction (XRD), three-point bend test and scanning electron microscopy (SEM). Crystallization of tetragonal zirconia (t-ZrO₂) in the composite, CZY having zirconia–yttria matrix and that of gamma alumina (γ-Al₂O₃) in the composites, CAZ having alumina–zirconia matrix, CAS having alumina–silica matrix and CA having alumina matrix, enhanced the flexural strength values and pseudo-ductile character of CMCs.     

Oligosaccharide mimics containing galactose and fucose specifically label tumour cell surfaces and inhibit cell adhesion to fibronectin

With the aim of establishing a versatile and easy synthesis of branched saccharides for biological applications, we used molecular-dynamics simulations to model Lewis(y) to two classes of di- or triantennary saccharide mimetics. One set of mimetics was based on 1,3,5-tris(hydroxymethyl)cyclohexane (TMC) as the core, the other on furan, and both were derivatised with galactose and/or fucose. The TMC-based saccharides were biotinylated, while the furan disaccharides were treated with maleimide-activated biotin in a Diels-Alder fashion to yield oxazatricyclodecanes (OTDs). These were then assayed as cell-surface labels in human colon (SW480 and CaCo-2), liver (PLC), Glia (U333 CG 343) and ovary (SKOV-3) tumour cell lines. Discrete staining patterns were observed in all cells, usually at one or two poles of the cells, particularly with the asymmetric 3-beta-L-fucopyranosyloxymethyl-4-beta-D-galactopyranosyloxymethyl-OTD. Normal SV40-transformed fibroblasts (SV80) showed no staining. Adhesion of the highly metastatic mouse melanoma line B16 F10 to fibronectin was inhibited by 80 % by the TMC-digalactoside and by 30 % by 3,4-bis-(beta-D-galactopyranosyloxymethyl)furan. None of the saccharide mimetics inhibited the adhesion of the less metastatic B16 F1 line. Migration of B16 F10 cells through Matrigel was greatly inhibited by the TMC-digalactoside and weakly inhibited by the TMC-trigalactoside. The saccharide mimetics that had shown the best structural agreements with the terminal saccharides of Lewis(y) in the molecular dynamics simulation were also the most biologically potent compounds; this underlines the predictive nature of molecular dynamics simulations. The use of the non-saccharide cores enabled us to adapt spacer lengths and terminal saccharides to optimise the structures to bind more avidly to cell-surface lectins.