The reversible, optical switching of individual polymer molecules was observed using molecular force spectroscopy. We synthesized a polypeptide with multiple photoactive azobenzene groups incorporated in the backbone. The contour length of the polymer could be selectively lengthened or shortened by switching between the trans- and cis-azo configurations with 420 and 365 nm wavelength light, respectively. This cis- to trans-azo configurational transition induced by ultraviolet light resulted in a measurable change in polymer contour length. The contour length change was observed at low force and under external loads of up to 400 pN using a modified force spectrometer, in which the sample could be irradiated in total internal reflectance. The ability to shorten the polymer against an external load is the first demonstration of photomechanical energy conversion in an individual molecule. This is a significant milestone in the road toward molecular level machines.

We investigated hydroxyalkylphosphonate monolayers as a novel platform for the biofunctionalization of silicon-based field effect sensor devices. This included a detailed study of the thin film properties of organophosphonate films on Si substrates using several surface analysis techniques, including AFM, ellipsometry, contact angle, X-ray photoelectron spectroscopy (XPS), X-ray reflectivity, and current-voltage characteristics in electrolyte solution. Our results indicate the formation of a dense monolayer on the native silicon oxide that has excellent passivation properties. The monolayer was biofunctionalized with 12 mer peptide nucleic acid (PNA) receptor molecules in a two-step procedure using the heterobifunctional linker, 3-maleimidopropionic-acid-N-hydroxysuccinimidester. Successful surface modification with the probe PNA was verified by XPS and contact angle measurements, and hybridization with DNA was determined by fluorescence measurements. Finally, the PNA functionalization protocol was translated to 2 microm long, 100 nm wide Si nanowire field effect devices, which were successfully used for label-free DNA/PNA hybridization detection.

Optimization of interfaces in inorganic-organic device systems depends strongly on understanding both the molecular processes that are involved in surface modification and the effects that such modifications have on the electronic states of the material. In particular, the last several years have seen passivation and functionalization of semiconductor surfaces to be strategies by which to realize devices with superior function by controlling Fermi level energies, band-gap magnitudes, and work functions of semiconducting substrates. Among all of the synthetic routes and deposition methods available for the optimization of functional interfaces in hybrid systems, organophosphonate chemistry has been found to be a powerful tool to control at the molecular level the properties of materials in many different applications. In this Review, we focus on the relevance of organophosphonate chemistry in nanotechnology, giving an overview about some recent advances in surface modification, interface engineering, nanostructure optimization, and biointegration.

The synthesis and characterization of two types of silicon-based biofunctional interfaces are reported; each interface bonds a dense layer of poly(ethylene glycol) (PEG(n)) and peptide nucleic acid (PNA) probes. Phosphonate self-assembled monolayers were derivatized with PNA using a maleimido-terminated PEG(45). Similarly, siloxane monolayers were functionalized with PNA using a maleimido-terminated PEG(45) spacer and were subsequently modified with a shorter methoxy-terminated PEG(12) ("back-filling"). The long PEG(45) spacer was used to distance the PNA probe from the surface and to minimize undesirable nonspecific adsorption of DNA analyte. The short PEG(12) "back-filler" was used to provide additional passivation of the surface against nonspecific DNA adsorption. X-ray photoelectron spectroscopic (XPS) analysis near the C 1s and N 1s ionization edges was done to characterize chemical groups formed in the near-surface region, which confirmed binding of PEG and PNA to the phosphonate and silane films. XPS also indicated that additional PEG chains were tethered to the surface during the back-filling process. Fluorescence hybridization experiments were carried out with complementary and noncDNA strands; both phosphonate and siloxane biofunctional surfaces were effective for hybridization of cDNA strands and significantly reduced nonspecific adsorption of the analyte. Spatial patterns were prepared by polydimethylsiloxane (PDMS) micromolding on the PNA-functionalized surfaces; selective hybridization of fluorescently labeled DNA was shown at the PNA functionalized regions, and physisorption at the probe-less PEG-functionalized regions was dramatically reduced. These results show that PNA-PEG derivatized phosphonate monolayers hold promise for the smooth integration of device surface chemistry with semiconductor technology for the fabrication of DNA biosensors. In addition, our results confirm that PNA-PEG derivatized self-assembled carboxyalkylsiloxane films are promising substrates for DNA microarray applications.