Solution-Phase Supramolecular Chemistry
The interdependence between redox events and molecular recognition is a prevalent theme in biological systems. Enzymes containing redox-active organic molecules use specific enzyme-cofactor interactions to regulate the reactivity of the cofactor. Through hydrogen bonding, aromatic-stacking, and other electrostatic interactions, these enzymes selectively stabilize specific oxidation and protonation states of the cofactor.
In ongoing research, we are using host-guest complexes as model systems for flavoenzyme activity. In the course of these investigations, we have explored the effects of hydrogen bonding, aromatic stacking and dipolar interactions on flavin redox processes, using an interdisciplinary array of electrochemical and spectroelectrochemical techniques. We are continuing these investigations under NIH grant RO1 GM59249-01,synthesizing new model systems to explore issues of hydrogen bonding, and through-space field effects.
We are currently extending these studies to actual biomolecules, using a combination of synthetic and protein engineering techniques. This project is sponsored by the Chemistry-Biology Interface program, and is a collaboration between the Rotello and Gierasch groups.
Fundamental principles observed in biological systems are applicable for the design of novel man-made molecular devices. In recent studies, we have demonstrated the hydrogen bonding and aromatic stacking can be used to create a molecular switch. In current National Science Foundation andPRF-funded research, we are creating redox-active host molecules based on organometallic and inorganic redox units to provide more efficient and versatile devices.
Electronically-controlled Switch from: "Electrochemical Control of Recognition Processes. A Three-Component Molecular Switch" R. Deans, A. Niemz, E. Breinlinger, V. Rotello, J. Am. Chem. Soc., 1997, 119, 10863-10864.
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Group Publications on Solution-Phase Supramolecular Chemistry
"Communication of Electronic Information over Extended Distances. An Experimental and Density Functional Investigation" R. Deans, A. Cuello, T. Galow, M. Ober and V. Rotello, J. Chem. Soc. Perkin Trans., submitted for publication
"Model Systems for Flavoenzyme Activity. The Role of N(3)-H Hydrogen Bonding in Flavin Redox Processes" A. Cuello, C. McIntosh, V. Rotello, J. Am. Chem. Soc., submitted for publication.
"Electronic Communication in Structurally Constrained Cyclopenta-Fused Polyaromatics. An Experimental and Density Functional Investigation" A. Niemz, L. Steffen, B. Plummer, A. Cuello, V. Rotello, J. Am. Chem. Soc., submitted for publication.
"Redox Modulation by Molecular Recognition" V. Rotello, Electron Transfer in Chemistry, Wiley-VCH:Weinheim, V. Balzani, ed., invited submission.
"Encapsulation of an Electroactive Guest in a Dynamically Self-Assembled Polymer" F. Ilhan, T. Galow, G. Cooke J. Am. Chem. Soc., in press.
"The Plausible Aromaticity of 1,8 Naphthalimides: The Enthalpy of Formation of N-Methyl-1-8 Naphthalimide" M. Roux, P. Jimenez, J. Davalos, M. Martin-Luengo, V. Rotello, A. Cuello, J. Liebman, J. Struct Chem. in press.
"Synthetic Models of Flavoenzyme Activity" V. Rotello, Flavins and Flavoproteins 99, VCH:Berlin, in press.
"Supramolecular Models of Flavoenzyme Activity" C. McIntosh, A. Niemz, V. Rotello Flavins and Flavoproteins 99, VCH:Berlin, in press.
"Model Systems of Redox Cofactor Activity", V. Rotello, Curr. Opin. Chem. Biol. 1999, 3, 747-751.
"Fluorocarbonylferrocene. A Versatile Intermediate for Ferrocene Amides and Esters", T. Galow, J. Rodrigo, K. Clearey, G. Cooke, and V. Rotello, J. Org. Chem., 1999 64, 3745-3746.
"Control of One- Versus two-Electron Reduction of Ubiquinone Via Redox-Dependent Recognition" M. Greaves, V. Rotello, J. Am. Chem. Soc., 1999, 121, 266-267.
"From Enzyme to Molecular Device. The Interdependence of Recognition and Redox Processes" A. Niemz, V. Rotello, Accts. Chem. Res., 1999,32,44-53.
"The Donor Atom-_ Interaction of Sulfur with Flavin. A Density Functional Investigation", V. Rotello, Heteroatom Chem., 1998, 605-606.
"Model Systems for Flavoenzyme Activity. Redox-Induced Modulation of Flavin-Receptor Hydrogen Bonding" V. Rotello, Molecular Recognition and Inclusion, A. Coleman, ed., Kluwer:Amsterdam, 1998, 479-482.
"Modulation of Flavin Recognition and Redox Properties through Donor Atom-p Interactions" E. Breinlinger, C. Keenan, V. Rotello, J. Am. Chem. Soc., 1998, 120, 8606-8609.
"Stereoisomeric p-Quinodimethanes" W. Cheng, N. Jasoney, J. Nadeau, S. Rosenfeld, M. Rushing, J. Jasinski, V. Rotello, J. Org. Chem., 1998, 63, 379-382.
"Electrochemical Control of Recognition Processes. A Three-Component Molecular Switch" R. Deans, A. Niemz, E. Breinlinger, V. Rotello, J. Am. Chem. Soc., 1997, 119, 10863-10864.
"UV-Vis Spectroelectrochemistry of Flavins in Aprotic Organic Solvents" A. Niemz, V. Rotello, Flavins and Flavoproteins '96, Steveneson, K.; Massey, V.; Williams, C.; eds. Univ. of Calgary: Calgary, 1997, 159-162.
"Synthetic Models for Flavoenzyme Activity: Modification of Flavin Redox Properties Through Hydrogen Bonding" E. Breinlinger, A. Niemz and V. Rotello, Flavins and Flavoproteins '96, Steveneson, K.; Massey, V.; Williams, C.; eds. Univ. of Calgary: Calgary, 1997, 123-126.
"Modification of Spin Density Distribution via Specific Hydrogen Bond Interactions: an Experimental, UHF and Density Functional Study" A. Niemz, V.Rotello, J. Am. Chem. Soc., 1997, 119, 6833-6836.
"Model Systems for Flavoenzyme Activity. A Versatile Synthesis of N(3) Alkylated Flavins" J. Dutra, A. Cuello, V. Rotello, Tetrahedron Lett., 1997, 4003-4006.
"Model Systems for Flavoenzyme Activity. Regulation of Flavin Recognition via Modulation of Receptor Hydrogen Bond Donor-Acceptor Properties" R. Deans, G. Cooke, V. Rotello, J. Org. Chem., 1997, 62, 836-839.
"Model Systems for Flavoenzyme Activity. Modulation of Flavin Redox Potentials Through p-stacking Interactions" E. Breinlinger, V. Rotello, J. Am. Chem. Soc., 1997, 119, 1165-1166.
"Model Systems for Flavoenzyme Activity: One and Two Electron Reduction of Flavins in Aprotic Hydrophobic Environments" A. Niemz, J. Imbriglio, V. Rotello, J. Am. Chem. Soc., 1997, 119, 892-897.
"Model Systems for Cofactor Activity. Biomimetic Reduction of Vitamin K by 1,3-Propanedithiol" J. Imbriglio, P. Patel, V. Rotello, Heteroatom Chem., 1996, 7(5), 293-294.
"Model Systems for Flavoenzyme Activity. 2-Aminopyridines as Spectroscopic Models for Flavoenzyme Active Sites" R. Deans, V. Rotello, Tetrahedron Lett., 1996, 4335-4338.
"Model Systems for Flavoenzyme Activity. The Effects of Specific Hydrogen Bonds on the 13C and 1H NMR of Flavins" A. Niemz, V. Rotello, J. Mol. Rec., 1996, 9, 158-162.
"Selective and Efficient Transport of Riboflavin Through a Liquid Membrane" T. Lambert, E. Breinlinger, V. Rotello, J. Org. Chem., 1995, 60, 2646-2647.
"Covalent Attachment of C60 to a Furan-Substituted Resin" B. Nie, K. Hasan, M. Greaves, V. Rotello, Tetrahedron Letters, 1995, 3617-3620.
"Model Systems for Flavoenzyme Activity. Stabilization of the Flavin Radical Anion Through Specific Hydrogen Bond Interactions" E. Breinlinger, A. Niemz, V. Rotello, J. Am. Chem. Soc., 1995, 117, 5379-5380.