Ferrous-bromate redox as initiator of aqueous vinyl polymerization

Ferrous-bromate redox is a very efficient initiator for the aqueous polymerization of a number of vinyl monomers. With methylmethacrylate, polymerization takes place in dark and at temperatures starting from 0 °C onwards. Bromate, ferrous and monomer exponents are respectively 0.51, 0.43 and 1.32 and the overall activation energy is 7.47 Kcal/mole. Neutral salts depress the polymerization rate, while an emulsifier increases it. p_H of the medium has not much influence on the polymerization rate upto the value of 2.32. However, at p_H 1.39, rate is somewhat depressed. Endgroups incorporated are hydroxyl and bromine totalling to an average of one per chain. Based upon these findings suitable mechanisms of initiation and termination have been proposed.     

Study of theS-matrix near bound states in the continuum

The behaviour ofS-matrix for potentials generating bound states in continuum in the neighbourhood of the positive bound state energies is studied. It is shown that unlike the case of usual negative energy bound states, theS-matrix does not have a pole at the positive bound state energy but becomes unity at the energy corresponding to bound states in continuum. Calculations ofS-waveS-matrix for a local potential constructed by Stillinger and Herrick and a separable nonlocal potential constructed by the present authors verify these results. Our results indicate that the bound states embedded in continuum constructedvia the von Neumann and Wigner procedure cannot be interpreted as resonances with zero width.     

Evaluation of carbonic anhydrase and paraoxonase inhibition activities and molecular docking studies of highly water-soluble sulfonated phthalocyanines

The investigation of carbonic anhydrase and paraoxonase enzyme inhibition properties of water-soluble zinc and gallium phthalocyanine complexes ( 1 and 2 ) are reported for the first time. The binding of p-sulfonylphenoxy moieties to the phthalocyanine structure favors excellent solubilities in water, as well as providing an inhibition effect on carbonic anhydrase (CA) I and II isoenzymes and paraoxonase (PON1) enzyme. According to biological activity results, both complexes inhibited hCA I, hCA II, and PON1. Whereas 1 and 2 showed moderate hCA I and hCA II (off-target cytosolic isoforms) inhibitory activity (Ki values of 26.09 µM and 43.11 µM for hCA I and 30.95 µM and 33.19 µM for hCA II, respectively), they exhibited strong PON1 (associated with high-density lipoprotein [HDL]) inhibitory activity (Ki values of 0.37 µM and 0.27 µM, respectively). The inhibition kinetics were analyzed by Lineweaver–Burk double reciprocal plots. It revealed that 1 and 2 were noncompetitive inhibitors against PON1, hCA I, and hCA II. These complexes can be more advantageous than other synthetic CA and PON inhibitors due to their water solubility. Docking studies were carried out to examine the interactions between hCA I, hCA II, and PON1 inhibitors and metal complexes at a molecular level and to predict binding energies.     

Highly improved electrocatalytic oxidation of dimethylamine borane on silver nanoparticles modified polymer composite electrode

Dimethylamine borane (DMAB) is a promising fuel alternative for fuel cell applications. In this work cyclic voltammetric behavior of DMAB was investigated on the polymerized aminophenol film decorated with Ag nanoparticles in alkaline media. The polymer film was formed on the glassy carbon electrode by electrochemical technique and then, the surface was modified with Ag nanoparticles. The surface of the modified electrode was identified by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy techniques. The developed electrode has displayed high electrocatalytic activity for DMAB oxidation in alkaline media depending on the supporting electrolyte concentration. Experimental parameters such as cycle number used in electropolymerization of p-aminophenol, deposition of Ag nanoparticles and supporting electrolyte were optimized.     

The development of information storage materials — How microscopy can help?

The response of giant magnetoresistance (GMR) devices depends critically on the film microstructure, with parameters such as layer thickness and interfacial abruptness being crucial. This paper presents results obtained using high resolution electron microscopy (HREM), chemical mapping and atom probe microanalysis. Local variations in the magnetic properties are induced by the microstructure and also when the films are patterned to form small elements. These lead to changes in the magnetization reversal mechanism. Some results of the studies of the magnetization reversal carried out using in situ in Lorentz transmission electron microscopy (LTEM) magnetizing experiments are also included.     

Peak effect studies in single crystals CeRu2 and 2H-NbS2

We have studied the peak effect (PE) phenomenon in single crystals of weakly pinned superconductors CeRu₂ and 2H-NbS₂. 2H-NbS₂ is iso-structural and iso-electronic to 2H-NbSe₂, whose similarity with CeRu₂ as regards the PE representing the order-to-disorder transformation of the flux line lattice was claimed some time ago. We report on the step change in equilibrium magnetization across the peak effect in CeRu₂. We also present the vortex phase diagram of 2H-NbS₂ obtained from the magnetization data, and compare the PE phenomenon in 2H-NbS₂ and 2H-NbSe₂.     

ERROR ESTIMATES FOR TWO-SCALE COMPOSITE FINITE ELEMENT APPROXIMATIONS OF NONLINEAR PARABOLIC EQUATIONS

We study spatially semidiscrete and fully discrete two-scale composite finite element method for approximations of the nonlinear parabolic equations with homogeneous Dirich-let boundary conditions in a convex polygonal domain in the plane.This new class of finite elements,which is called composite finite elements,was first introduced by Hackbusch and Sauter[Numer.Math.,75(1997),pp.447-472]for the approximation of partial differential equations on domains with complicated geometry.The aim of this paper is to introduce an efficient numerical method which gives a lower dimensional approach for solving par-tial differential equations by domain discretization method.The composite finite element method introduces two-scale grid for discretization of the domain,the coarse-scale and the fine-scale grid with the degrees of freedom lies on the coarse-scale grid only.While the fine-scale grid is used to resolve the Dirichlet boundary condition,the dimension of the finite element space depends only on the coarse-scale grid.As a consequence,the resulting linear system will have a fewer number of unknowns.A continuous,piecewise linear composite finite element space is employed for the space discretization whereas the time discretization is based on both the backward Euler and the Crank-Nicolson methods.We have derived the error estimates in the L∞(L2)-norm for both semidiscrete and fully discrete schemes.Moreover,numerical simulations show that the proposed method is an efficient method to provide a good approximate solution.     

Size-selective Pt siderophores based on redox active azo-aromatic ligands

We demonstrate a strategy inspired by natural siderophores for the dissolution of platinum nanoparticles that could enable their size-selective synthesis, toxicological assessment, and the recycling of this precious metal. From the fabrication of electronics to biomedical diagnosis and therapy, PtNPs find increasing use. Mitigating concerns over potential human toxicity and the need to recover precious metal from industrial debris motivates the study of bio-friendly reagents to replace traditional harsh etchants. Herein, we report a family of redox-active siderophore-viz. π-acceptor azo aromatic ligands (L) that spontaneously ionize and chelate Pt atoms selectively from nanoparticles of size ≤6 nm. The reaction produces a monometallic diradical complex, Pt^II(L˙⁻)₂, isolated as a pure crystalline compound. Density functional theory provides fundamental insights on the size dependent PtNP chemical reactivity. The reported findings reveal a generalized platform for designing π-acceptor ligands to adjust the size threshold for dissolution of Pt or other noble metals NPs. Our approach may, for example, be used for the generation of Pt-based therapeutics or for reclamation of Pt nano debris formed in catalytic converters or electronic fabrication industries.

Biofriendly recycling of Pt is enabled by ligands that size-selectively dissolve nanoclusters.     

Mechanistic studies of thiol-dimethylsulfoxide initiated polymerization of methylmethacrylate from endgroup analysis

Summary Endgroup analysis of polymethylmethacrylate obtained by initiation with thiol-dimethyl sulfoxide systems has been carried out using dye-techniques developed in our laboratory. Thiols used are 2-mercaptoethylamine hydrochloride, 2-mercaptoethanol, thioglycolic acid and n-butane thiol. The first three thiols incorporated amine, hydroxyl and carboxyl endgroup respectively to the extent of about one per macromolecule, while the last one as expected produced none of the above functional endgroups in the polymer. In the light of endgroup results initiation through thiyl radicals has been suggested. Probable termination mechanism has also been discussed.

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Zusammenfassung Die Endgruppenanalyse von Polymethylmethacrylat, das durch Initiierung mit Thioldimethylsulfoxid-Systemen hergestellt war, wurde unter Anwendung unserer in unserem Labor entwickelten Färbungstechnik durchgeführt. Die verwendeten Thiole waren 2-Mercaptoäthylaminhydrochlorid, 2-Mercaptoäthanol, Thioglykolsäure und N-Butandiol. Die ersten drei Thiole fügten Amin-Hydroxyl- und Carboxyl-Endgruppen respektiv bis zum Betrag von etwa einer pro Makromolekül ein, während das letztere wie erwartet keine der oben genannten funktionalen Endgruppen im Polymer erzeugte. Aufgrund dieser EndgruppenResultate wird auf eine Initiierung durch Thiylradikale geschlossen. Der wahrscheinliche Abbruchmechanismus wird ebenfalls diskutiert.