Hydrophilic Polymer Brush Layers on Stainless Steel Using Multilayered ATRP Initiator Layer.

Thin polymer coatings (in tens of nanometers to a micron thick) are desired on industrial surfaces such as stainless steel. In this thickness range coatings are difficult to produce using conventional methods. In this context, surface-initiated controlled polymerization method can offer a promising tool to produce thin polymer coatings via bottom-up approach.

Improved adhesion between PMMA and stainless steel modified with PMMA brushes.

In this work, various lengths and densities of poly(methyl methacrylate) (PMMA) brushes were synthesized on stainless steel (SS) surfaces via surface initiated atom transfer radical polymerization. Subsequently, the joints between the bulk PMMA and the PMMA brushed stainless steel were obtained by injection molding, and for these the degree of adhesion was assessed by tensile testing. Several conditions are required to facilitate the mixing between the brushes and the bulk polymer and to reduce the residual stress at the interface: preheating of the SS samples before the injection molding; a long packing time; and a mold temperature above the glass transition temperature (Tg) of PMMA during the injection molding.

Versatile transformations of alkylamine-derivatized glassy carbon electrodes using aryl isocyanates.

The reaction between a nucleophilic 4-(2-aminoethyl)phenyl-tethered glassy carbon surface and various para-substituted aryl isocyanates [ONC-PhX; X = NO(2), COPh, Cl, H, and NMe(2)] has been studied in toluene. It is demonstrated that the nucleophilic addition reaction is relatively fast occurring within two hours while providing an efficient and versatile route for derivatizing alkylamine-functionalized surfaces. An often overlooked issue in surface reactions is the possibility for competing physisorption processes.

Electrochemical surface derivatization of glassy carbon by the reduction of triaryl- and alkyldiphenylsulfonium salts.

The range of materials susceptible to electrochemically assisted grafting onto carbon materials has been expanded to include a new group of compounds. This new approach is based on the reduction of symmetrical or unsymmetrical triarylsulfonium salts and alkyldiphenylsulfonium salts. Our findings suggest that it is possible to form layers of aryl moieties on the surface and that the unsymmetrical triarylsulfonium salts cleave upon reduction in a direction dictated by the substituent on the rings (i.

Covalent grafting of glassy carbon electrodes with diaryliodonium salts: new aspects.

The applicability and versatility of the recently communicated procedure for the grafting of conducting carbon substrates by diaryliodonium salts is expanded. We have found that several types of organic arylic layers can be formed on the carbon surface and that the chemical functionalities of the thus formed layers can be varied extensively over electron withdrawing (for example, -NO2) to electron donating (for example, -OMe) groups. A comparative study involving the grafting of aryldiazonium salts reveals that, despite the two approaches being similar, iodonium salts exhibit spontaneous grafting to a significantly lower extent.

Immobilization of aryl and alkynyl groups onto glassy carbon surfaces by electrochemical reduction of iodonium salts.

A new versatile method has been developed for the electrochemically assisted grafting of carbon materials. The approach is based on the reduction of iodonium salts and allows the immobilization not only of aryl groups, such as phenyl or nitrophenyl, but also of alkynyl groups under mild conditions. In particular, the immobilization of alkynyl groups is important because such grafting cannot be accomplished using any other known reductive procedure.

Elucidation of the thermochemical properties of triphenyl- or tributyl-substituted Si-, Ge-, and Sn-centered radicals by means of electrochemical approaches and computations.

Redox potentials of a number of triphenyl- or tributyl-substituted Si-, Ge-, or Sn-centered radicals, R(3)M(*), have been measured in acetonitrile, tetrahydrofuran, or dimethyl sulfoxide by photomodulated voltammetry or through a study of the oxidation process of the corresponding anions in linear sweep voltammetry. For the results pertaining to the Ph(3)M(*) series (including literature data for M = C), the order of reduction potentials follows Sn > Ge > C > Si, while for the two oxidation potentials, it is C > Si. The effect of the R group on the redox properties of R(3)Sn(*) is pronounced in that the reduction potential is more negative by 490 mV in tetrahydrofuran (390 mV in dimethyl sulfoxide) when R is a butyl rather than a phenyl group.

Thermochemistry of arylselanyl radicals and the pertinent ions in acetonitrile.

Reduction and oxidation potentials of a series of parasubstituted phenylselanyl radicals, XC(6)H(4)Se(*), have been measured using photomodulated voltammetry in acetonitrile. The thermodynamic significance of these data was substantiated through a study of the oxidation process of the pertinent selenolates in linear sweep voltammetry. Both the reduction and the oxidation potentials correlate linearly with the Hammett substituent coefficients sigma and sigma(+) leading in the latter case to slopes, rho(+), of 2.