Laurance G. Beauvais
Laurance G. Beauvais
- Phone: (619) 849-3251
- B.S., University of Houston, 1994. Advisor: Prof. C. W. Paul Chu
- Ph.D., University of California, Berkeley, 2002. Advisor: Prof. Jeffrey R. Long
- Postdoc, Massachusetts Institute of Technology, 2002-2006. Advisor: Prof. Stephen J. Lippard Research Interests
Our research is focused on the preparation of functional solids that act as (i) mimics of enzyme active sites, (ii) oxidation and reduction catalysts, and (iii) electronic and magnetic materials. We are especially interested in low temperature solid synthesis so that we can rationally design materials via the incorporation of specific functional building units.
(i) Solid Materials that Mimic Heme and P450 Active sites.
Nature uses iron-porphyrin active sites for a wide range of biological functions, from oxygen transport to substrate oxidation. Synthetic models of heme and cytochrome P450 active sites must be protected by sterically encumbering .organic shrubbery. to authentically model the protein function. We are interested in protecting the iron-porphyrin site by using it as a building block for microporous solids, in which the iron-porphyrin units will be well separated to prevent bimolecular reactions. After the solid has been prepared, we will add N- and S-donor ligands to mimic the function of heme and P450 proteins. The ultimate goal is the development of new oxidation catalysts based on P450 analogues.
(ii) Rationally Designed Heterogeneous Catalysts
Small molecule homogeneous catalysts have been developed for a wide range of oxidation and reduction reactions, ranging from the reduction of dinitrogen by Mo(tren) complexes to the oxidation of organic substrates by metal-porphyrin and metal-salen complexes. This project focuses on translating the reactivity of these homogeneous systems to microporous solids and studying the effect of the solid framework on the active sites reactivity.
(iii) Electronic and Magnetic Materials
Work by Yaghi, Suslick, and others has demonstrated the effectiveness of using carboxylate building units to prepare microporous solids. However, carboxylate linkers are not ideal for preparing conducting and magnetic materials. This project will focus on the use of alternate linkers, such as dithiolene, to prepare solids and probe their electronic and magnetic properties.
This work exposes students to almost all areas of chemistry.from inorganic to biochemistry and physical techniques to organic synthesis. Organic and inorganic synthesis will be required to prepare the building blocks and the solids. Much of this work will require an inert-gas atmosphere, and be conducted using Schlenck techniques or in a glovebox. Physical inorganic methods, such as NMR, EPR, crystallography, magnetic measurements, thermal analysis, gas sorption analysis, etc, will be used to probe the molecular building blocks and the solids. Finally, the biochemistry and kinetics experiments will be used to interrogate the heme and P450 mimics to ascertain their authenticity.
Smythe, Nathan C.; Butler, Derek P.; Moore, Curtis E.; McGowan, William R.; Rheingold, Arnold L.; Beauvais, Laurance G. "A heterobimetallic metal-organic framework with tunable reactive metal sites: synthesis, characterization, and reactivity." Dalton Trans. 2012, 41, 7855-7858.
Beauvais, L. G.; Long, J. R. "Synthesis and Characterization of Prussian Blue Analogues Incorporating the Edge-Bridged Octahedral [Zr6BCl12]2+ Cluster Core." Inorg. Chem. 2006, 45, 236-243.
Beauvais, L. G.; Lippard, S. J. "Reactions of the Diiron(IV) Intermediate Q in Soluble Methane Monooxygenase with Fluoromethanes." Biochem. Biophys. Res. Commun. 2005, 338, 262-266.
Beauvais, L. G.; Lippard, S. J. "Reactions of the Peroxo Intermediate of Soluble Methane Monooxygenase Hydroxylase with Ether Substrates." J. Am. Chem. Soc. 2005, 127, 7370-7378.
Beauvais, L. G.; Long, J. R. "Co3[Co(CN)5]2: A Microporous Magnet with an Ordering Temperature of 38 K." J. Am. Chem. Soc. 2002, 124, 12096-12097.
Beauvais, L. G.; Long, J. R. "Cyanide-Limited Complexation of Molybdenum(III): Synthesis of Octahedral [Mo(CN)6]3- and Cyano-Bridged [Mo2(CN)11]5-." J. Am. Chem. Soc 2002, 124, 2110-2111.
Bennett, M. V.; Beauvais, L. G.; Shores, M. P.; Long, J. R. "Expanded Prussian Blue Analogues Incorporating [Re6Se8(CN)6]3-/4- Clusters: Adjusting Porosity via Charge Balance." J. Am. Chem. Soc. 2001, 123, 8022-8032.
Wierczinski, B.; Gregorich, K. E.; Kadkhodayan, B.; Lee, D. M.; Beauvais, L. G.; Hendricks, M. B.; Kacher, C. D.; Lane, M. R.; Keeney-Shaughnessy, D. A.; Stoyer, N. J.; Strellis, D. A.; Sylwester, E. R.; Wilk, P. A.; Hoffman, D. C.; Malmbeck, R.; Skarnemark, G.; Alstad, J.; Omtvedt, J. P.; Eberhardt, K.; Mendel, M.; Nahler, A.; Trautmann, N. "First Chemical On-Line Separation and Detection of a Subsecond a-Decaying Nuclide, 224Pa." J. Radioanal. Nucl. Chem. 2001, 247, 57-60.
Bennett, M. V.; Shores, M. P.; Beauvais, L. G.; Long, J. R. "Expansion of the Porous Solid Na2Zn3[Fe(CN)6]2Â·9H2O: Enhanced Ion-Exchange Capacity in Na2Zn3[Re6Se8(CN)6]2Â·24H2O." J. Am. Chem. Soc. 2000, 122, 6664-6668.
Beauvais, L. G.; Shores, M. P.; Long, J. R. "Cyano-Bridged Re6Q8 (Q = S, Se) Cluster-Cobalt(II) Framework Materials: Versatile Solid Chemical Sensors." J. Am. Chem. Soc. 2000, 122, 2763-2772.
Shores, M. P.; Beauvais, L. G.; Long, J. R. "[Cd2(H2O)4][Re6S8(CN)6]Â·14H2O: A Cyano-Bridged Cluster-Cluster Framework Solid with Accessible Cubelike Cavities." Inorg. Chem. 1999, 38, 1648-1649.
Shores, M. P.; Beauvais, L. G.; Long, J. R. "Cluster-Expanded Prussian Blue Analogues." J. Am. Chem. Soc. 1999, 121, 775-779.
Beauvais, L. G.; Shores, M. P.; Long, J. R. "Cyano-Bridged Re6Q8 (Q = S, Se) Cluster-Metal Framework Solids: A New Class of Porous Materials." Chem. Mater. 1998, 10, 3783-3786.
Eggert, J. H.; Hu, J. Z.; Mao, H. K.; Beauvais, L.; Meng, R. L.; Chu, C. W. "Compressibility of the HgBa2Can-1CunOn+2+d (n = 1, 2, 3) High Temperature Superconductors." Phys. Rev. B 1994, 49, 15299-15304.
Xue, Y. Y.; Huang, Z. J.; Qui, X. D.; Beauvais, L.; Zhang, X. N.; Sun, Y. Y.; Meng, R.; Chu, C. W. "Pb-Doping Effects in Hg1-xPbxBa2Ca2Cu3O8+d." Mod. Phys. Lett. B 1993, 7, 1833-1842.
Meng, R. L.; Beauvais, L.; Zhang, X. N.; Huang, Z. J.; Sun, Y. Y.; Xue, Y. Y.; Chu, C. W. "Synthesis of the High-Temperature Superconductors HgBa2CaCu2O6+d and HgBa2Ca2Cu3O8+d." Physica C 1993, 216, 21-28.
Gao, L,; Huang, J. Z.; Meng, R. L.; Lin, G.; Chen, F.; Beauvais, L.; Sun, Y. Y.; Xue, Y. Y.; Chu, C. W. "Study of Superconductivity in the Hg-Ba-Ca-Cu-O System." Physica C 1993, 213, 261-265.