Permanent electric dipole moments of carboxyamides in condensed media: what are the limitations of theory and experiment?

Electrostatic properties of proteins are crucial for their functionality. Carboxyamides are small polar groups that, as peptide bonds, are principal structural components of proteins that govern their electrostatic properties. We investigated the medium dependence of the molar polarization and of the permanent dipole moments of amides with different state of alkylation. The experimentally measured and theoretically calculated dipole moments manifested a solvent dependence that increased with the increase in the media polarity. We ascribed the observed enhancement of the amide polarization to the reaction fields in the solvated cavities. Chloroform, for example, caused about a 25% increase in the amide dipole moments determined for vacuum, as the experimental and theoretical results demonstrated. Another chlorinated solvent, 1,1,2,2-tetrachloroethane, however, caused an "abnormal" increase in the experimentally measured amide dipoles, which the theoretical approaches we used could not readily quantify. We showed and discussed alternatives for addressing such discrepancies between theory and experiment.

Heterogeneous graphene nanostructures: ZnO nanostructures grown on large-area graphene layers.

In this work, the synthesis and characterization of three-dimensional hetergeneous graphene nanostructures (HGN) comprising continuous large-area graphene layers and ZnO nanostructures, fabricated via chemical vapor deposition, are reported. Characterization of large-area HGN demonstrates that it consists of 1-5 layers of graphene, and exhibits high optical transmittance and enhanced electrical conductivity. Electron microscopy investigation of the three-dimensional heterostructures shows that the morphology of ZnO nanostructures is highly dependent on the growth temperature. It is observed that ordered crystalline ZnO nanostructures are preferably grown along the <0001> direction. Ultraviolet spectroscopy and photoluminescence spectroscopy indicates that the CVD-grown HGN layers has excellent optical properties. A combination of electrical and optical properties of graphene and ZnO building blocks in ZnO-based HGN provides unique characteristics for opportunities in future optoelectronic devices.

Gating of single-layer graphene with single-stranded deoxyribonucleic acids.

Patterning of biomolecules on graphene layers could provide new avenues to modulate their electrical properties for novel electronic devices. Single-stranded deoxyribonucleic acids (ssDNAs) are found to act as negative-potential gating agents that increase the hole density in single-layer graphene. Current-voltage measurements of the hybrid ssDNA/graphene system indicate a shift in the Dirac point and "intrinsic" conductance after ssDNA is patterned. The effect of ssDNA is to increase the hole density in the graphene layer, which is calculated to be on the order of 1.8 x 10(12) cm(-2). This increased density is consistent with the Raman frequency shifts in the G-peak and 2D band positions and the corresponding changes in the G-peak full width at half maximum. Ab initio calculations using density functional theory rule out significant charge transfer or modification of the graphene band structure in the presence of ssDNA fragments.

Study of a single InSb nanowire fabricated via DC electrodeposition in porous templates.

InSb nanowire arrays have been fabricated by direct current electrodeposition inside the nanochannels of anodic alumina membranes without subsequent annealing. After Au contacts were patterned to the nanowires using electron beam lithography, photoresponse studies were conducted. Absorbance peaks were also recorded from free suspending nanowires. A significant response was observed when the wires were exposed to visible light and infrared absorption peaks were observed during absorption experiment. Comparisons were also made between single and multiple nanowires' responses. The nanowires also conduct almost no current in the dark, but when hit with light, they conduct 10,000 times more current. This photoconducting property could lead to a variety of tiny optoelectronic devices potentially useful in future generations of nanoelectronics and chemical sensors.

Microtubule-based gold nanowires and nanowire arrays.

Biological structures are attractive as templates to form nanoscale architectures for electronics because of their dimensions and the ability to interact with inorganic materials. In this study, we report the fabrication and electrical properties of microtubule (MT)-templated Au nanowires, and methods for assembling Au nanowire arrays based on these templates. The adsorption of MTs on silicon substrates is an effective means for preserving the conformation of the MT and provides a convenient platform for electrical measurements. To improve the metallization of MTs, a photochemical route for gold reduction is adapted, which leads to continuous coverage. The conductivity values measured on micrometer-long nanowires are similar to those reported for other biotemplated gold nanowires. A protocol for fabricating arrays of MT-templated gold nanowires is demonstrated.

Carbon nanotube-DNA nanoarchitectures and electronic functionality.

Biological molecules such as deoxyribonucleic acid (DNA) possess inherent recognition and self-assembly capabilities, and are attractive templates for constructing functional hierarchical material structures as building blocks for nanoelectronics. Here we report the assembly and electronic functionality of nanoarchitectures based on conjugates of single-walled carbon nanotubes (SWNTs) functionalized with carboxylic groups and single-stranded DNA (ssDNA) sequences possessing terminal amino groups on both ends, hybridized together through amide linkages by adopting a straightforward synthetic route. Morphological and chemical-functional characterization of the nanoarchitectures are investigated using scanning electron microscopy, transmission electron microscopy, atomic force microscopy, energy-dispersive X-ray spectroscopy, Raman spectroscopy, and Fourier-transform infrared spectroscopy. Electrical measurements (I-V characterization) of the nanoarchitectures demonstrate negative differential resistance in the presence of SWNT/ssDNA interfaces, which indicates a biomimetic route to fabricating resonant tunneling diodes. I-V characterization on platinum-metallized SWNT-ssDNA nanoarchitectures via salt reduction indicates modulation of their electrical properties, with effects ranging from those of a resonant tunneling diode to a resistor, depending on the amount of metallization. Electron transport through the nanoarchitectures has been analyzed by density functional theory calculations. Our studies illustrate the great promise of biomimetic assembly of functional nanosystems based on biotemplated materials and present new avenues toward exciting future opportunities in nanoelectronics and nanobiotechnology.