Electrocatalytic reactions mediated by N,N,N',N'-Tetraalkyl-1,4-phenylenediamine redox liquid microdroplet-modified electrodes: chemical and photochemical reactions In, and At the surface of, femtoliter droplets.

The electro-oxidation of electrolytically unsupported ensembles of N,N-diethyl-N',N'-dialkyl-para-phenylenediamine (DEDRPD, R = n-butyl, n-hexyl, and n-heptyl) redox liquid femtoliter volume droplets immobilized on a basal plane pyrolytic graphite electrode is reported in the presence of aqueous electrolytes. Electron transfer at these redox liquid modified electrodes is initiated at the microdroplet-electrode-electrolyte three-phase boundary. Dependent on both the lipophilicity of the redox oil and that of the aqueous electrolyte, ion uptake into or expulsion from the organic deposits is induced electrolytically.

Graphite powder and multiwalled carbon nanotubes chemically modified with 4-nitrobenzylamine.

We demonstrate that graphite powder and multiwalled carbon nanotubes (MWCNTs) can be derivatised by 4-nitrobenzylamine (4-NBA) simply by stirring the graphite powder or MWCNTs in a solution of acetonitrile containing 10 mM 4-NBA. We propose that 4-NBA partially intercalates at localised edge-plane or edge-plane-like defect sites and this hypothesis with a range of experimental data provided by electrochemistry in both aqueous and nonaqueous media, electron microscopy and X-ray powder diffraction.

Selective electrochemical glycosylation by reactivity tuning.

Electrochemical glycosylation of a selenoglycoside donor proceeds efficiently in an undivided cell in acetonitrile to yield beta-glycosides. Measurement of cyclic voltammograms for a selection of seleno-, thio-, and O-glycosides indicates the dependence of oxidation potential on the anomeric substituent allowing the possibility for the rapid construction of oligosaccharides by selective electrochemical activation utilising variable cell potentials in combination with reactivity tuning of the glycosyl donor. A variety of disaccharides are readily synthesised in high yield, but limitations of the use of selenoglycosides as glycosyl donors for selective glycosylation of thioglycoside acceptors are exposed.

Selective activation of glycosyl donors utilising electrochemical techniques: a study of the thermodynamic oxidation potentials of a range of chalcoglycosides.

A series of six chalcoglycosides (phenyl-2,3,4,6-tetra-O-benzoyl-1-seleno-beta-D-glucopyranoside, phenyl-2,3,4,6-tetra-O-benzyl-1-seleno-beta-D-glucopyranoside, phenyl-2,3,4,6-tetra-O-benzyl-1-thio-beta-D-glucopyranoside, p-tolyl-2,3,4,6-O-benzoyl-1-thio-beta-D-glucopyranoside, p-tolyl-2,3,4,6-O-benzyl-1-thio-beta-D-glucopyranoside, and phenyl-2,3,4,6-O-benzyl-beta-D-glucopyranoside) are voltammetrically interrogated in dimethyl sulfoxide, so as to determine their formal (i.e. thermodynamic) redox potentials.

Synthesis of fluorescence-labelled disaccharide substrates of glucosidase II.

The fluorescence-labelled disaccharides Glcalpha(1-->3)GlcalphaOR and Glcalpha(1-->3)ManalphaOR, both substrates for the glycoprotein-processing enzyme glucosidase II, were synthesised via the use of a n-pentenyl-derived linker at the anomeric position. This allowed incorporation of a pyrenebutyric acid label, via a sequence of oxidative hydroboration, mesylation, azide displacement, reduction with concomitant global deprotection, and peptide coupling. Selective activation of a fully armed thioglycoside in the presence of n-pentenyl glycosides was readily achieved by the use of methyl triflate as promoter.