Evaluation of the performance of metameric indices

Forty three metameric pairs were obtained by comparison, shade-adjustment, and redyeing of 660 self shades dyed with direct, azoic, vat, and reactive dyes. The pairs were regrouped shadewise and ranked visually in increasing order of metamerism. Spearman's rank correlation coefficients were calculated between 11 measures of metamerism and the visual metameric ranking under three illuminants A, D65, and TL84 in pairs. The illuminant-independent general indices included the indices based on reflectance differences (Bridgeman), weighted reflectance differences (Nimeroff and Yurow), Cohen-Kappauf's residual differences (proposed) obtained from the spectral decompositions of the reflectance spectra of the metameric pair. Illuminant-specific special indices included color-differences under test illuminant, addition, subtraction, division, and multiplication of color-differences under test and reference illuminants, indices based on ΔL*, Δa*, Δb* differences under two illuminants, based on chromatic adapted ΔL*, Δa*, Δb* differences with multiplicative corrections for tristimulus differences under reference illuminant (Berns-Billmeyer), differences of the color constancy indices. The present work showed that indices based on ΔL*, Δa*, Δb* differences under two illuminants, both unmodified and modified by Berns-Billmeyer performed best among the existing indices. The differences of color constancy indices showed good correlation with the degree of metamerism in some cases, and this may be utilized for developing newer indices of metamerism. © 1996 John Wiley & Sons, Inc.     

Metal-containing intermacromolecular complexes: Electrochemical and viscometric studies in DMF-methanol mixture

Summary Multicomponent intermacromolecular complexes have been prepared from some typical phenolic copolymers with a non-ionic polymer (e.g. PVP), and a polyelectrolyte (e.g. PAA). Some transition metal ions (e.g. Cu(II) and Ni (II)) have been incorporated in the complex through its unreacted co-ordinating groups. The formation of these complexes has been studied by several techniques, such as viscometry, conductometry, potentiometry, IR and UV spectrophotometry. A scheme has been presented to explain the mode of interaction of the various components.     

Affinity Studies of Hemicyanine Derived Water Soluble Colorimetric Probes with Reactive Oxygen/Nitrogen/Sulfur Species

Peroxynitrite (ONOO^-) is an essential endogenous reactive oxygen species (ROS) generated in mitochondria under various pathological and physiological conditions. An increase in its level in mitochondria is related to numerous diseases. Herein, we report a series of hemicyanine-derived water-soluble colorimetric probes ( 1 – 4 ) and the reactivity of which was studied with various reactive oxygen, nitrogen, and sulfur species. Probes 1 – 4 are formed by conjugating 1,2,3,3-tetramethyl-3H-indolium iodide and 4-hydroxybenzaldehyde or its derivatives through an alkene linkage formed by the Knoevenagel reaction. Oxidative cleavage of the electron-rich double bond of the conjugated hemicyanine dye revealed a discerning affinity of probe 3 towards peroxynitrite among all reactive oxygen species. The rapid change in color of 3 provides a sensitive and selective method for detecting peroxynitrite with a low detection limit of 180 nM. Notably, the water solubility of the probe displays excellent performance for the selective detection of peroxynitrite among ROS and reactive nitrogen (RNS)/sulfur species (RSS). UV-vis, ¹H NMR, and ¹³C NMR spectroscopic data and results from theoretical calculations provide further information on the interaction of peroxynitrite with probe 3 .     

Nonwoven viscose fabric-polyvinyl alcohol based flexible composite

Development of ecofriendly packaging materials is still a challenging area. Researchers are continuously working to improve the mechanical and barrier properties of the different polymers which are used in the packaging industry. Selection of reinforcement and matrix for any composite are based upon end use applications. The novelty of the work is development of fully biodegradable, flexible, lightweight biocomposite by reinforcing needle punched flexible nonwoven viscose fabric to the PVA solution. The effect of PVA concentration and areal density of viscose fabric on the properties of prepared composite is examined. The composite thus prepared is assessed in terms of mechanical, thermal, breathability, and UV blocking properties. The nonwoven viscose-PVA composite shows excellent improvement in tensile strength of 100% to 300% with respect to PVA film of equivalent concentration for two different areal densities of viscose fabric. The composite also exhibits improved thermal stability and UV blocking property with respect to parent components. However, a reduction in flexibility (with respect to PVA film) as well as breathability (with respect to viscose fabric) of the composite is observed. Based upon the improved performance of the viscose-PVA composite in terms of mechanical properties, UV and water vapor permeability, it seems that the composite has a strong potential for application in the packaging sector as a flexible as well as biodegradable composite.     

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.     

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.     

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.     

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.

     

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.     

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.