Fischer carbene mediated covalent grafting of a peptide nucleic acid on gold surfaces and IR optical detection of DNA hybridization with a transition metalcarbonyl label

Amine-reactive surfaces comprising N-hydroxysuccinimide ester groups as well as much more unusual Fischer alkoxymetallocarbene groups were generated on gold-coated surfaces via self-assembled monolayers of carboxy- and azido-terminated thiolates, respectively. These functions were further used to immobilize homothymine peptide nucleic acid (PNA) decamer in a covalent fashion involving the primary amine located at its N-terminus. These stepwise processes were monitored by polarization modulation reflection - absorption infrared spectroscopy (PM-RAIRS) that gave useful information on the molecular composition of the organic layers. PNA grafting and hybridization with complementary DNA strand were successfully transduced by quartz crystal microbalance (QCM) measurements. Unfortunately, attempts to transduce the hybridization optically by IR in a label-free fashion were inconclusive. Therefore we undertook to introduce an IR reporter group, namely a transition metalcarbonyl (TMC) entity at the 5\u2032 terminus of complementary DNA. Evidence for the formation of PNA-DNA heteroduplex was brought by the presence of \u3bd(C 61O) bands in the 2000 cm-1 region of the IR spectrum of the gold surface owing to the metalcarbonyl label

Oxidation mechanism of flavanone taxifolin. Electrochemical and spectroelectrochemical investigation

The oxidation of taxifolin on glassy carbon electrode in acetonitrile was studied by cyclic voltammetry, UV-vis and IR spectroelectrochemistry. The oxidation products were identified using HPLC-ESI-MS/MS. The two-electron oxidation mechanism differs from that of flavonols (e.g. quercetin) due to the absence of the double bond between atoms C-2 and C-3. As confirmed by IR spectroelectrochemistry, quinone at ring B is formed as low stable intermediate. The oxidation pathway leads to the formation of hydroxylated derivative of taxifolin 2′,3,3′,4′,5,7-hexahydroxyflavone accompanied by the 2,3-desaturation