NMR Structures of the Selenoproteins Sep15 and SelM Reveal ...
Craig A. Bayse Department of Chemistry and Biochemistry · ‘Conformational dynamics of redox...
Transcript of Craig A. Bayse Department of Chemistry and Biochemistry · ‘Conformational dynamics of redox...
Craig A. Bayse
Department of Chemistry and Biochemistry
www.gaussian.com
Electronic structure software package
Introduced by Nobel Laureate John Pople in 1970
Approximate solutions to Schrödinger’s Equation
H = E
Applications:
◦ Optimizing geometries of chemical structures
◦ Calculating chemical properties (IR, NMR, UV/Vis, etc)
◦ Modeling reaction mechanisms
What do you need to run a G09 job?◦ Structure
◦ Basis set – represents the wavefunction
◦ Method – represents the Hamiltonian
Inexpensive, but inaccurate (MM, semiempirical)
Expensive, state-of-the-art (CCSD(T))
Balanced (DFT, current favorite)
Wide range of functionals available
Fast on multiprocessor execution
GaussView - GUI
Lewisite/British Anti-Lewisite
L.K. Harper, S. Antony and C.A. Bayse. ‘Thiol reduction of arsenite and selenite: DFT modeling of the pathways to an As-Se bond.’ Chemical Research in Toxicology. Submitted.
C.A. Bayse, L.K. Harper, J.L. Ming and R.D. Pike. ‘The effect of amine and phosphine decoration on the photoluminescence of 1-D copper(I) and silver(I) cyanide coordination polymers.’ (invited) Dalton Transations. 43 (2014) 11243-11251.
F. Li, P.B. Lutz, Y. Pepelyayeva, E.S.J. Arnér, C.A. Bayse and S. Rozovsky. ‘Conformational dynamics of redox active motifs in selenoproteins.’ Proceedings of the National Academy of Sciences. 111 (2014) 6976-6981.
S. Antony and C.A. Bayse. ‘Density functional theory study of the attack of ebselen on a zinc finger model.’ Inorganic Chemistry. 52 (2013) 13803-13805.
C.A. Bayse and K.N. Ortwine. ‘Modeling the glutathione peroxidase-like activity of a cyclic seleninate by DFT and solvent-assisted proton exchange.’ European Journal of Inorganic Chemistry. (2013) 3680-3688.
P.B. Lutz and C.A. Bayse. ‘Orbital-based insights into parallel-displaced and twisted conformations in - interactions.’ Physical Chemistry Chemical Physics. 15 (2013) 9397-9406.
P.O. Atolagbe, K.N. Taylor, S.E. Wood, A.L. Rheingold, L.K. Harper, C.A. Bayse and T.J. Brunker. ‘Ruthenium(II) dichloride complexes of chiral, tetradentateaminosulfoxide ligands: Stereoisomerism and redox-induced linkage isomerism.’ Inorganic Chemistry. 52 (2013) 1170-1172.
J.P. Safko, J.E. Kuperstock, S.M. McCullough, A.M. Noviello, X. Li, J.P. Killarny, C. Murphy, H.H. Patterson, C.A. Bayse and P.D. Pike. ‘Network formation and photoluminescence in copper(I) halide complexes with substituted piperazineligands.’ Dalton Transactions. 41 (2012) 11663-11674.
S. Antony and C.A. Bayse. ‘Modeling the mechanism of the glutathione peroxidase mimic ebselen.’ Inorganic Chemistry. 50 (2011) 12075-12084.
C.A. Bayse and A. Pavlou. ‘The relationship between Se···N,O bond strength and the activity of glutathione peroxidase mimics: A DFT study incorporating solvent-assisted proton exchange (SAPE).’ Organic & Biomolecular Chemistry. 9(2011) 8006-8015.
C.A. Bayse, J.L. Ming, K.M. Miller, S.M. McCollough and R.D. Pike. ‘Photoluminescence of silver(I) and gold(I) cyanide 1D coordination polymers.’ Inorganica Chimica Acta. 375 (2011) 47-52.
Important non-bonding interaction◦ Petroleum science, nanotubes
◦ Biochemical recognition
◦ Crystal packing
We are developing new models
Turing allows us to handle larger systems
42 e150 bf 156 e
528 bf 270 e906 bf
374 e2448 bf
Healthy thyroid function requires Iodine andselenium!
Mechanism known, but how does it occur?◦ Protein structure was unknown until recently
Important to treat thyroid illnesses
Our novel mechanism modeledwith G09 with small models
Verified in prestige journals (JACS and PNAS)
Scale up with Turing!
Pre-Turing Turing And Beyond…
Pigments extracted from Stentor are photosensitive and potential photodynamic therapy agents
Compounds are difficult to characterize
Simulation of the UV/Vis spectrum using
TD-DFT
Model mechanisms
Images from eol.org