163657-00-9Relevant academic research and scientific papers
Communication of electronic information over nanometer distances with supramolecular transduction. An experimental and density functional investigation
Deans, Robert,Cuello, Alejandro O.,Galow, Trent H.,Ober, Matthias,Rotello, Vincent M.
, p. 1309 - 1313 (2007/10/03)
We have synthesized a family of conjugated diaminotriazine-functionalized receptors. Variation of distal functionality modulated the affinity of these receptors for flavin, demonstrating efficient electronic communication over a distance of 11 A. The origin of this communication was explored using DFT methodology. These calculations demonstrate that modulation of recognition in these systems is derived from a complex push-pull type mechanism.
Model Systems for Flavoenzyme Activity. Regulation of Flavin Recognition via Modulation of Receptor Hydrogen-Bond Donor-Acceptor Properties
Deans, Robert,Cooke, Graeme,Rotello, Vincent M.
, p. 836 - 839 (2007/10/03)
We have synthesized a new family of receptors for flavins based on 6-aryl-2,4-(acyldiamino)-s-triazines. In these synthetic hosts, systematic variation of the spatially remote substituents on the 6-aryl ring alters the hydrogen-bond-donating abilities of the amide functionality and the hydrogen-bond-accepting properties of the triazine N(3). This variation results in a strong modulation of the efficiency of flavin binding, with association constants for the receptor flavin complexes ranging over an 8-fold range.
Model systems for flavoenzyme activity: One- and two-electron reduction of flavins in aprotic hydrophobic environments
Niemz, Angelika,Imbriglio, Jason,Rotello, Vincent M.
, p. 887 - 892 (2007/10/03)
The processes occurring during the electrochemically irreversible reduction of flavins in aprotic organic medium have been the cause of considerable controversy. To provide insight into these events we have investigated the reduction of flavins alkylated at N(3). We have demonstrated that the reversible reduction of N(3)-methylated flavin can be converted to the irreversible reduction observed with unalkylated flavins through addition of the weak external proton donor phthalimide. Proton transfer to the flavin radical anion generated at the electrode leads to partial formation of the neutral flavin radical, which is instantaneously further reduced to the fully reduced flavin anion. This mirrors the reduction of unalkylated flavins, where the proton source is the imide proton at N(3) of fully oxidized flavin in bulk solution. Simultaneous electrochemistry and EPR experiments confirm the disappearance of electrogenerated flavin radical anion both methylated and non-methylated at N(3), upon addition of phthalimide. UV/vis spectroelectrochemistry likewise confirmed the generation of the radical anion in the absence of proton donors and fully reduced flavin in the presence of proton donors.
