Bionano Donor–Acceptor Hybrids of Porphyrin, ssDNA, and Semiconductive Single-Wall Carbon Nanotubes for Electron Transfer via Porphyrin Excitation

Abstract

Photoinduced electron transfer in self-assemblies of porphyrins ion-paired with ssDNA wrapped around single-wall carbon nanotubes (SWCNTs) has been reported. To accomplish the three-component hybrids, two kinds of diameter-sorted semiconducting SWCNT(n,m)s of different diameter ((n,m) = (6,5) and (7,6)) and free-base or zinc porphyrin bearing peripheral positive charges ((TMPyP(+))M (tetrakis(4-N-methylpyridyl)porphyrin); M = Zn and H(2)) serving as light-absorbing photoactive materials are utilized. The donor-acceptor hybrids are held by ion-pairing between the negatively charged phosphate groups of ssDNA on the surface of the SWCNT and the positively charged at the ring periphery porphyrin macrocycle. The newly assembled bionano donor-acceptor hybrids have been characterized by transmission electron microscopy (TEM) and spectroscopic methods. Photoinduced electron transfer from the excited singlet porphyrin to the SWCNTs directly and/or via ssDNA as an electron mediator has been established by performing systematic studies involving the steady-state and time-resolved emission as well as the transient absorption studies. Higher charge-separation efficiency has been successfully demonstrated by the selection of the appropriate semiconductive SWCNTs with the right band gap, in addition to the aid of ssDNA as the electron mediator.

Photon induced separation of bio-nano hybrid complex based on carbon nanotubes and optically active bacteriorhodopsin

“…Bio-nano hybrid complex are materials of active interest due to its immense potential in diverse applications such as bio-mimic devices, sensors, electro-optics, biotechnology, cancer therapy and diagnostics etc [1][2][3][4]. Biomolecules, specifically optically active purple membrane (PM) have long been studied for photonic and electro-optic applications.…”

“…Here, we attempt to provide theoretical frame work for our experimental observations. According to the theory, total interaction potential (V tot ) of two interacting spheres with radius R 1 , R 2 >>D, the inter-particle distance is given by 1 …”

Controlling the crystalline three-dimensional order in bulk materials by single-wall carbon nanotubes

“…In light of the latter, CNTs are suitable candidates for emerging nanotechnological applications [16][17][18][19][20][21] . In fact, numerous ways of dispersing CNTs in matrices such as surfactants 22 , polymers [23][24][25] , biopolymers [26][27][28] , supramolecular organic gels 29,30 and liquid crystals [31][32][33][34][35][36] were meant to order structures. The use of any of the aforementioned matrices has resulted in hybrid materials, in which both morphology and order are mainly controlled by the matrix components, while CNTs lack any significant role.…”

Functionalized Nanocarbons for Artificial Photosynthesis: From Fullerene to SWCNT, Carbon Nanohorn, and Graphene

“…Thus, ssDNA acts as an electron mediator from SWCNT to the outsidebound porphyrin [ 53 ]. To accomplish the three-component hybrids, chirality-sorted semiconducting SWCNT( n , m )s and zinc porphyrin bearing peripheral positive charges ((TMPyP + )Zn (tetrakis(4-N -methylpyridyl)porphyrin)Zn) serving as lightabsorbing photoactive materials are utilized.…”