Enhancement of the Electrical Properties of DNA Molecular Wires through Incorporation of Perylenediimide DNA Base Surrogates.

DNA has long been viewed as a promising material for nanoscale electronics, in part due to its well-ordered arrangement of stacked, pi-conjugated base pairs. Within this context, a number of studies have investigated how structural changes, backbone modifications, or artificial base substitutions affect the conductivity of DNA. Herein, we present a comparative study of the electrical properties of both well-matched and perylene-3,4,9,10-tetracarboxylic diimide (PTCDI)-containing DNA molecular wires that bridge nanoscale gold electrodes. By performing current-voltage measurements for such devices, we find that the incorporation of PTCDI DNA base surrogates within our macromolecular constructs leads to an approximately 6-fold enhancement in the observed current levels. Together, these findings suggest that PTCDI DNA base surrogates may enable the preparation of designer DNA-based nanoscale electronic components.

Length-Independent Charge Transport in Chimeric Molecular Wires.

Advanced molecular electronic components remain vital for the next generation of miniaturized integrated circuits. Thus, much research effort has been devoted to the discovery of lossless molecular wires, for which the charge transport rate or conductivity is not attenuated with length in the tunneling regime. Herein, we report the synthesis and electrochemical interrogation of DNA-like molecular wires. We determine that the rate of electron transfer through these constructs is independent of their length and propose a plausible mechanism to explain our findings. The reported approach holds relevance for the development of high-performance molecular electronic components and the fundamental study of charge transport phenomena in organic semiconductors.

Molecular Dynamics Simulations of Perylenediimide DNA Base Surrogates.

Perylene-3,4,9,10-tetracarboxylic diimides (PTCDIs) are a well-known class of organic materials. Recently, these molecules have been incorporated within DNA as base surrogates, finding ready applications as probes of DNA structure and function. However, the assembly dynamics and kinetics of PTCDI DNA base surrogates have received little attention to date. Herein, we employ constant temperature molecular dynamics simulations to gain an improved understanding of the assembly of PTCDI dimers and trimers. We also use replica-exchange molecular dynamics simulations to elucidate the energetic landscape dictating the formation of stacked PTCDI structures. Our studies provide insight into the equilibrium configurations of multimeric PTCDIs and hold implications for the construction of DNA-inspired systems from perylene-derived organic semiconductor building blocks.

Sequence specific detection of restriction enzymes at DNA-modified carbon nanotube field effect transistors.

Protein-DNA interactions play a central role in many cellular processes, and their misregulation has been implicated in a number of human diseases. Thus, there is a pressing need for the development of analytical strategies for interrogating the binding of proteins to DNA. Herein, we report the electrical monitoring of a prototypical DNA-binding protein, the PvuII restriction enzyme, at microfluidic-encapsulated, DNA-modified carbon nanotube field effect transistors. Our integrated platform enables the sensitive, sequence specific detection of PvuII at concentrations as low as 0.5 pM in a volume of 0.025 µL (corresponding to ~7500 proteins). These figures of merit compare favorably to state of the art values reported for alternative fluorescent and electrical assays. The overall detection strategy represents a step toward the massively parallel electrical monitoring, identification, and quantification of protein-DNA interactions at arrayed nanoscale devices.

Bulk protonic conductivity in a cephalopod structural protein.

Proton-conducting materials play a central role in many renewable energy and bioelectronics technologies, including fuel cells, batteries and sensors. Thus, much research effort has been expended to develop improved proton-conducting materials, such as ceramic oxides, solid acids, polymers and metal-organic frameworks. Within this context, bulk proton conductors from naturally occurring proteins have received somewhat less attention than other materials, which is surprising given the potential modularity, tunability and processability of protein-based materials. Here, we report proton conductivity for thin films composed of reflectin, a cephalopod structural protein. Bulk reflectin has a proton conductivity of ~2.6 × 10(-3) S cm(-1) at 65 °C, a proton transport activation energy of ~0.2 eV and a proton mobility of ~7 × 10(-3) cm(2) V(-1) s(-1). These figures of merit are similar to those reported for state-of-the-art artificial proton conductors and make it possible to use reflectin in protein-based protonic transistors. Our findings may hold implications for the next generation of biocompatible proton-conducting materials and protonic devices.

Reconfigurable infrared camouflage coatings from a cephalopod protein.

In nature, cephalopods employ unique dynamic camouflage mechanisms. Herein, we draw inspiration from self-assembled structures found in cephalopods to fabricate tunable biomimetic camouflage coatings. The reflectance of these coatings is dynamically modulated between the visible and infrared regions of the electromagnetic spectrum in situ. Our studies represent a crucial step towards reconfigurable and disposable infrared camouflage for stealth applications.