Photoelectrochemical complexes for solar energy conversion that chemically and autonomously regenerate.

Naturally occurring photosynthetic systems use elaborate pathways of self-repair to limit the impact of photo-damage. Here, we demonstrate a complex consisting of two recombinant proteins, phospholipids and a carbon nanotube that mimics this process. The components self-assemble into a configuration in which an array of lipid bilayers aggregate on the surface of the carbon nanotube, creating a platform for the attachment of light-converting proteins. The system can disassemble upon the addition of a surfactant and reassemble upon its removal over an indefinite number of cycles. The assembly is thermodynamically metastable and can only transition reversibly if the rate of surfactant removal exceeds a threshold value. Only in the assembled state do the complexes exhibit photoelectrochemical activity. We demonstrate a regeneration cycle that uses surfactant to switch between assembled and disassembled states, resulting in an increased photoconversion efficiency of more than 300% over 168 hours and an indefinite extension of the system lifetime.

Hybridization kinetics and thermodynamics of DNA adsorbed to individually dispersed single-walled carbon nanotubes.

Hybridization of DNA adsorbed to single-walled carbon nanotubes in solution has much slower kinetics than free solution DNA, and can be detected through a blue shift in the near-infrared nanotube fluorescence. Adsorption of the receptor DNA strand to the nanotube surface is consistent with models of polyelectrolyte adsorption on charged surfaces, introducing both entropic (46.8 cal mol(-1) K(-1)) and activation energy (20.4 kcal mol(-1)) barriers to the hybridization, which are greater than free solution values (31.9 cal mol(-1) K(-1) and 12.9 kcal mol(-1)) at 25 degrees C. The increased hybridization barriers on the nanotube result in exceedingly slow kinetics for hybridization with t(1/2)=3.4 h, compared to the free solution value of t(1/2)=4 min. These results have significant implications for nanotube and nanowire biosensors.

Detection of DNA hybridization using the near-infrared band-gap fluorescence of single-walled carbon nanotubes.

We demonstrate the optical detection of DNA hybridization on the surface of solution suspended single-walled carbon nanotubes (SWNTs) through a SWNT band gap fluorescence modulation. Hybridization of a 24-mer oligonucleotide sequence with its complement produces a hypsochromic shift of 2 meV, with a detection sensitivity of 6 nM. The energy shift is modeled by correlating the surface coverage of DNA on SWNT to the exciton binding energy, yielding an estimated initial fractional coverage of 0.25 and a final coverage of 0.5. Hybridization on the nanotube surface is confirmed using Forster resonance energy transfer of fluorophore-labeled DNA oligonucleotides. This detection is enabled through a new technique to suspend SWNTs using adsorption of single-stranded DNA and subsequent removal of free DNA from solution. While the kinetics of free DNA hybridization are relatively fast (<10 min), the kinetics of the process on SWNTs are slower under comparable conditions, reaching steady state after 13 h at 25 degrees C. A second-order kinetic model yields a rate constant of k = 4.33 x 10(5) (M h)(-1). This optical, selective detection of specific DNA sequences may have applications in the life sciences and medicine as in vitro or in vivo detectors of oligonucleotides.

Optical detection of DNA conformational polymorphism on single-walled carbon nanotubes.

The transition of DNA secondary structure from an analogous B to Z conformation modulates the dielectric environment of the single-walled carbon nanotube (SWNT) around which it is adsorbed. The SWNT band-gap fluorescence undergoes a red shift when an encapsulating 30-nucleotide oligomer is exposed to counter ions that screen the charged backbone. The transition is thermodynamically identical for DNA on and off the nanotube, except that the propagation length of the former is shorter by five-sixths. The magnitude of the energy shift is described by using an effective medium model and the DNA geometry on the nanotube sidewall. We demonstrate the detection of the B-Z change in whole blood, tissue, and from within living mammalian cells.