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2012 PROGRAM . 8 ThIrty Elghth Annual
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8:00 a.m. Registration & Continental Breakfast doxin family that are involved in long-range electron transfers g 9 Q g .
Keeneland Room, W.T. Young Library in many important biological processes such as photosynthe- 2 a? < c r: C hem Istry
8:50 a.m. Welcome  Dr. Eli Capilouto sis, to span ~1 V through carefully design of hydrophobicity 5 vi - g
President, University of Kentucky and hydrogen bonding networks around the primary coordi- d; D .5 r1 &
9:00 a.m. Dr. Brian Crane nation sphere, and the use of these redox proteins to ad- 8 3.
Cornell University dress fundamental questions in biological electron transfers 2 M I I
How Metal, Nitric Oxide and Redox Chemistry such as reorganization energy and Marcus inverted region. In 0 ecu ar
Coordinate Cellular Responses in Microbes the second example, we have shown that the roles of two .
and Men conserved glutamate in converting myoglobin into nitric oxide B I Ology
reductase, one through binding to a non-heme iron and the
Nitric oxide (NO) is a small, reactive and diffusible agent other through hydrogen bonding interaction. Finally, we pre-
produced by the complex redox chemistry of the nitric ox- sent recent unpublished results that the presence of waters \. \
ide synthases (NOSs). In mammals, NOSs generate NO as part of a new hydrogen-bonding network in myoglobin is / '
as a second messenger for many purposes that include necessary to confer oxidase activity in reducing 02 to water _ l
' neuronal transmission, regulation of the vasculature and with minimum release of other reactive oxygen species and
release of hormones. In addition, immune cells produce with > 1,000 turnovers. //
NO as part of the oxidative burst to combat pathogens and I / V
tumor cells. Microbial NOSs are less understood but ap- 11:30 a.m. Lunch l
pear to involve NO in novel mechanisms that include toxin 1:30 pm. Poster Session, Gallery, W.T. Young Library 
biosynthesis, protection against oxidative damage and the 2:30 pm. Dr. Harry Gray
coordination of stress responses. A common theme in this California Institute of Technology .
broad spectrum of reactivity is the ability of NO to mediate Electron Flow through Metalloproteins Es,tab3hed by M' Benton Naff
redox reactions at metalloenzyme centers. The chemistry in memory 0f Anna 3- Naff
 of NO production and targeting will be discussed as well as Electron transfers in photosynthesis and respiration common-
emerging roles of this fascinating molecule. ly occur between metal-containing cofactors that are separat- . _
ed by large molecular distances. Understanding the underly- -
10:00 a.m. Break (refreshments available) ing physics and chemistry of these biological electron trans- D m
10:30 a.m. Dr. Yi Lu fer processes is the goal of much of the work in my laborato- Ln UJ
University of Illinois at Urbana-Champaign ry. Employing laser ash-quench triggering methods, we 3 8 '
Designing Functional Metalloproteins: have shown that 2nm, coupling-limited Fe(|l) to Ru(l|l) and E >,C.> a ' SPEAKERS
Exploring the Roles of Non-covalent Cu(l) to Ru(l|l) electron tunneling in Ru-modified cyto- E 6 8 3
Interactions in Conferring and Fine-tuning chromes and blue copper proteins can occur on the micro- g 3 L0 0 ,
Enzymatic Activities second timescale both in solutions and crystals. Redox o g g [5&1 Dr- Br'an Crane
. equivalents can be transferred even longer distances by mul- ~45 g >_ Dr_ Yi Lu
,Designing metalloproteins is an ultimate test of our tistep tunneling (hopping) through intervening tyrosines and H H x J
. . o 0 Dr. Harry Gray
knowledge about metalloproteins and can result In new tryptophans. In recent work, we have found that 2 to 3-nm g > c" S
biocatalysts for practical applications. In this presentation, hole hopping through one or more intervening tryptophans is E *5 9 m
we provide three examples to demonstrate that, while re- several orders of magnitude faster than single-step tunneling t 5 U) LIJ
producing the primary coordination sphere may be good in Remodied mutants of Pseudomonas aeruginosa azurin. 82 ->E< 0 Frid M 4th 2012
enough to make structural models of metalloproteins, care- The lessons we have learned about the control of electron 0) C a) 0 ay ay 
ful design of the non-covalent secondary coordination tunneling and hopping are now guiding the design and con- D D ' 
sphere interactions is required to create functional metallo- struction of sensitizermodied redox metalloenzymes and n: .
proteins. In the rst example, we demonstrate the ne- other molecular machines for the production of fuels and z D Department Of Chem'Stry
tuning of reduction potentials of azurin a member of cupre- oxygenated hydrocarbons from sunlight and water. = 2 University Of Kentucky
Lexington, KY 40506-0055
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