Surface-attached peptide nucleic acids (PNA) are shown to retain their unique and efficient hybridization properties, reported in solution studies. PNA recognition layers thus offer significant advantages for sequence-specific DNA biosensors, compared to their DNA counterparts. These advantages include significantly higher sensitivity and specificity (including greater discrimination against single-base mismatches), faster hybridization at room and elevated temperatures, minimal dependence on ionic strength, and use of shorter (10−15-mer) probes. Such unique properties and advantages are illustrated in connection with electrochemical detection of the hybridization event using the Co(phen)3 3+ redox indicator and a carbon paste electrode transducer. The new capabilities and opportunities afforded by the use of PNA surface probes are discussed.

Articles you may be interested inMolecular and electronic structure of electroactive self-assembled monolayers

The attachment of redox-active molecules such as porphyrins to an electroactive surface provides an attractive approach for electrically addressable molecular-based information storage. Porphyrins are readily attached to a gold surface via thiol linkers. The rate of electron transfer between the electroactive surface and the porphyrin is one of the key factors that dictates suitability for molecular-based memory storage. This rate depends on the type and length of the linker connecting the thiol unit to the porphyrin. We have developed different routes for the preparation of thiol-derivatized porphyrins with eight different linkers. Two sets of linkers explore the effects of linker length and conjugation, with one set comprising phenylethyne units and one set comprising alkyl units. One electron-deficient linker has four fluorine atoms attached directly to a thiophenyl unit. To facilitate the synthesis of the porphyrins, convenient routes have been developed to a wide range of aldehydes possessing a protected S-acetylthio group. An efficient synthesis of 1-(S-acetylthio)-4-iodobenzene also has been developed. A set of porphyrins, each bearing one S-acetyl-derivatized linker at one meso position and mesityl moieties at the three remaining meso positions, has been synthesized. Altogether seven new aldehydes, eight free base porphyrins and eight zinc porphyrins have been prepared. The zinc porphyrins bearing the different linkers all form self-assembled monolayers (SAMs) on gold via in situ cleavage of the S-acetyl protecting group. The SAM of each porphyrin is electrochemically robust and exhibits two reversible oxidation waves.