Preparation, characterization, surface modification and redox reactions of silver nanoparticles in the presence of tryptophan

The synthesis and characterization of water-soluble dispersions of Ag nanoparticles by the reduction of AgNO(3) using tryptophan under alkaline synthesis conditions are reported. The Ag nanoparticle formation was very slow at low concentration and rapid at extremes. For surface modification and redox reactions, manipulating the interparticles interaction controlled the size of Ag nanoparticles aggregates. Our results suggest that the replacement of the BH(4)(-) ions adsorbed on the nanoparticle surface by tryptophan destabilizes the particles and further caused aggregation. A mechanism is proposed for the formation of silver nanoparticles by tryptophan. The experimental results are supported by theoretical calculations. The Ag nanoparticles were characterized by UV-vis absorption, dynamic light scattering and transmission electron microscopy techniques.     

Electron transfer (oxidation) of complexes between bifunctional phenols and DMSO in non-polar surroundings

Pulse-radiolysis reactions were performed to study the effect of hydrogen bonding to dimethyl sulfoxide (DMSO) on the oxidation of dihydroxy benzene and biphenyl diols to phenoxyl radicals. It was observed that with DMSO as the hydrogen-bond acceptor, the oxidation process proceeds via proton-coupled electron transfer in the case of hydroquinone. For resorcinol, DMSO acts in a similar way as in the case of hydroquinone. For other biphenols, viz., 2,2′- and 4,4′-biphenyl diols, it was found that DMSO had no effect on the electron transfer. The results are explained based on the ionization potential and structure of the phenol derivatives which probably depends on the rotation of the OH bond causing different electron distribution in the transient conformation.     

Effective chemical route for the synthesis of silver nanostructures in formamide

Poly(N-vinyl-2-pyrrolidone) (PVP) and gelatin protected silver nanostructures are prepared in formamide by simple chemical route. Both PVP and gelatin stabilized silver nanoparticles in formamide lead to the formation of nanostructures of various definite geometric shapes and sizes. The effect of anisotropy on the surface plasmon absorption band is analyzed by monitoring the UV-Visible absorption spectra of gelatin stabilized silver nanoparticles. The particles were characterized by UV-Visible absorption spectra and TEM.     

Growth and reactivity of silver clusters in amino polycarboxylic acid solutions

Reduction and subsequent aggregation of silver ions in the presence of various chelating agents such as trans-1,2-diaminocyclohexanetetraacetic acid (DCTA) 1,2-propylenediaminetetraacetic acid (PDTA), diethylenetriaminepentaacetic acid (DTPA), and triethylenetetraaminehexaacetic acid (TTHA) have been studied by pulse radiolysis. Rate constants of formation and transient absorption spectra for the ligand-complexed Ag(0) and Ag(2)(+) have been determined. The redox potential of Ag(+)(L)/Ag(0)(L) becomes more negative than that of Ag(+)/Ag(0). Growth and reactivity of silver clusters were also studied in the presence of methyl viologen (MV(2+)). The kinetics of formation of the MV(+*) radical, produced by the same pulse as in the case of silver atoms, confirms the catalytic electron transfer toward super critical silver clusters in the presence of ligands. The results suggest that catalytic electron transfer activity of silver clusters depends on the ligand.     

Oleic acid-assisted phase transfer of nanosized silver colloids

In this study, it is demonstrated that silver nanoparticles can be transferred from formamide to chloroform using oleic acid as a phase transfer agent with a transfer efficiency of 90–95%. The silver nanoparticles are initially formed as an organosol by the reduction of silver ions with formamide. On aging the complex, the particles self-assemble to form an ordered close-packed two-dimensional array of silver nanocrystals when dissolved in CHCl₃. The size distribution of the colloidal silver particles after transfer in different solvents remains almost the same. On the basis of IR spectroscopy, we discuss the adsorption of oleic acid over the silver particles.     

Theory of Frequency-Dependent Polarization of General Planar Electrodes with Zeta Potentials of Arbitrary Magnitude in Ionic Media: 2. Applications and Results from Homogeneous and Array Systems of Electrodes

The expressions obtained in the previous paper for electrode polarization are applied to a homogeneous planar electrode and a planar array of electrodes used in the generation of nonuniform fields. The effective far field experienced outside the double layer is computed for both electrodes, and sample spectra are provided. The effective far field expression contains the electrode impedance and the effects of concentration polarization due to the static double layer on the electrode generated by the ζ potential. The effective far field results are compact and contain simple integrals that can be evaluated numerically.     

Five coordinate complexes of N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamide with copper Crystal and molecular structures of dichloro(N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamido)copper(II) and chloro(perchlorato)(N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamido)copper(II)

The title compound N,N,N′,N′-tetraethylpyridine-2,6-dicarboxamide (DEAP) forms a 1:1 complex with anhydrous CuCl₂, [Cu(DEAP)Cl₂], (1) which was crystallized from EtOH solution in the monoclinic space group P2_{1/ n} with cell constant, a = 10.024(1); b = 13.122(1); c = 14.404(1) Å β = 101.31(1)° V = 1857.8(3) ų and Z = 4. The chloro-perchlorato complex, [Cu(DEAP)Cl(ClO₄)], (2) obtained in near quantitative yield by reacting (1) with an excess of NaClO₄ in EtOH, crystallized in the monoclinic space group P2_{1/ n} with cell constants, a = 7.965(1); b = 25.827(2); c = 10.046(1) Å β = 98.81(1)° V = 2042.2(4) ų and Z = 4. Both (1) and (2) contain 5-coordinated copper linked to DEAP through O～N～O donor set of atoms with covalently bonded chlorine atoms in (1) and chlorine and perchlorate groups in (2). The coordination geometry is intermediate between square pyramidal and trigonal bipyramidal, and is probably best described as a trigonally distorted rectangular pyramid.     

Sulfuric acid-functionalized mesoporous benzene-silica with a molecular-scale periodicity in the walls

Novel sulfuric acid-functionalized mesoporous benzene-silicas with a molecular-scale periodicity in the walls were derived from the mesoporous benzene-silica possessing mercaptopropyl groups by the oxidative transformation of -SH into -SO3H.     

Role of PVA in synthesis of nano Co3O4‐decorated graphene oxide

Polymeric materials have been found to be ideal candidates for the synthesis of organic–inorganic nanomaterials. We have obtained Co₃O₄‐decorated graphene oxide (GO) nanocomposites by a simple polymer combustion method. Polyvinyl alcohol (PVA) of two different molecular weights, 14,000 and 125,000, was used for the synthesis. The pristine sample was annealed at 300, 500, and 800°C. PVA has played an important role in the formation of GO and Co₃O₄ nanoparticles. Synthesized Co₃O₄–GO nanocomposites were characterized by X‐ray diffraction, Fourier transform infrared, Raman, electron paramagnetic resonance, transmission electron microscopy, and vibrating sample magnetometry. Reflection peaks at 12° and 37° in an X‐ray study confirm the formation of Co₃O₄–GO. Raman study validates the presence of GO in nanocomposites of Co₃O₄–GO. Room temperature ferromagnetism was observed in all annealed samples. The highest coercivity of 462 G was observed for 300°C annealed samples as compared with bulk Co₃O₄. On the basis of the results obtained, a mechanism of formation is proposed. Copyright © 2015 John Wiley & Sons, Ltd.