100442-89-5Relevant articles and documents
A non-covalent strategy for the assembly of supramolecular photocurrent-generating systems
Soto, Ernesto,MacDonald, John C.,Cooper, Christopher G. F.,McGimpsey, W. Grant
, p. 2838 - 2839 (2003)
Three photocurrent-generating thin films were assembled on gold surfaces. SAM I was constructed from molecules consisting of an alkyl disulfide group linked covalently to a 12-residue helical peptide and terminated with an alanine residue containing a pyrene chromophore. SAM I served as a benchmark for multilayered films II and III in photocurrent generation experiments. Films II and III were assembled from several components that were linked noncovalently by metal-ligand complexation. Cyclic voltammetry and contact angle measurements suggest that the films consist of ordered layers with relatively few defects. Photoexcitation of SAM I by the output of a 350 nm lamp (~0.2 mW power incident on the sample) results in current generation in the range 5-10 nA/cm2. Photoexcitation of II and III yields higher current in the range 10-30 nA/cm2, representing a quantum efficiency of ~1%. The observation of comparable or higher current from noncovalently assembled multicomponent films indicates that this method of assembly may obviate the problems associated with the covalent assembly of devices from large molecules. Copyright
Photoinduced Electron Transfer on a Single α-Helical Polypeptide Chain
Sisido, Masahiko,Tanaka, Ryo,Inai, Yoshihito,Imanishi, Yukio
, p. 6790 - 6796 (2007/10/02)
Electron transfer on an α-helical polypeptide carrying the sequence L-p-(dimethylamino)phenylalanine (dmaPhe)-L-alanine-L-1-pyrenylalanine (pyrAla) at the midpoint of an α-helical poly(γ-benzyl L-glutamate) chain was studied.Conformational energy calculation for the side-chain orientations predicted that only one type of orientation is allowed for both the dmaPhe and the pyrAla units.The center-to-center (edge-to-edge) distance between the two chromophores was estimated to be 13.2 (9.4) Angstroem.The fluorescence spectrum showed no exciplex emission in thepolypeptide, in contrast to the strong exciplex observed for a model tripeptide having the same dmaPhe-Ala-pyrAla sequence.The rate of electron transfer was calculated from the decay times of pyrenyl fluorescence of the polypeptide in trimethyl phosphate and in tetrahydrofuran solutions.The ket was on the order of 1E5 (s-1).The activation enthalpy was 1.4 kcal mol-1 in trimethyl phosphate and smaller than 1 kcal mol-1 in less polar solvents near room temperature.It was even smaller at lower temperatures.The activation entropy was less than -25 eu, suggesting a nonadiabatic electron transfer.In contrast to the slow electron transfer in the polypeptide, the rate constant for the model tripeptide was on the order of 1E7-1E8 (s-1) around room temperature, and the activation enthalpy was higher than that in the polypeptide case.