Charge-Transfer Dynamics at the α/β Subunit Interface of a Photochemical Ribonucleotide Reductase

United States. National Institutes of Health (GM 29595

2007 Renewable Energy: Solar Fuels Gordon Research Conference - January 21-26

This Gordon Research Conference seeks to brings together chemists, physicists, materials scientists and biologists to address perhaps the outstanding technical problem of the 21st Century - the efficient, and ultimately economical, storage of energy from carbon-neutral sources. Such an advance would deliver a renewable, environmentally benign energy source for the future. A great technological challenge facing our global future is energy. The generation of energy, the security of its supply, and the environmental consequences of its use are among the world's foremost geopolitical concerns. Fossil fuels - coal, natural gas, and petroleum - supply approximately 90% of the energy consumed today by industrialized nations. An increase in energy supply is vitally needed to bring electric power to the 25% of the world's population that lacks it, to support the industrialization of developing nations, and to sustain economic growth in developed countries. On the geopolitical front, insuring an adequate energy supply is a major security issue for the world, and its importance will grow in proportion to the singular dependence on oil as a primary energy source. Yet, the current approach to energy supply, that of increased fossil fuel exploration coupled with energy conservation, is not scaleable to meet future demands. Rising living standards of a growing world population will cause global energy consumption to increase significantly. Estimates indicate that energy consumption will increase at least two-fold, from our current burn rate of 12.8 TW to 28 - 35 TW by 2050. - U.N. projections indicate that meeting global energy demand in a sustainable fashion by the year 2050 will require a significant fraction of the energy supply to come carbon free sources to stabilize atmospheric carbon dioxide levels at twice the pre-anthropogenic levels. External factors of economy, environment, and security dictate that this global energy need be met by renewable and sustainable sources from a carbon-neutral source. Sunlight is by far the most abundant global carbon-neutral energy resource. More solar energy strikes the surface of the earth in one hour than is obtained from all of the fossil fuels consumed globally in a year. Sunlight may be used to power the planet. However, it is intermittent, and therefore it must be converted to electricity or stored chemical fuel to be used on a large scale. The ''grand challenge'' of using the sun as a future energy source faces daunting challenges - large expanses of fundamental science and technology await discovery. A viable solar energy conversion scheme must result in a 10-50 fold decrease in the cost-to-efficiency ratio for the production of stored fuels, and must be stable and robust for a 20-30 year period. To reduce the cost of installed solar energy conversion systems to $0.20/peak watt of solar radiation, a cost level that would make them economically attractive in today's energy market, will require revolutionary technologies. This GRC seeks to present a forum for the underlying science needed to permit future generations to use the sun as a renewable and sustainable primary energy source

Reversible, Long-Range Radical Transfer in E. coli Class Ia Ribonucleotide Reductase

Ribonucleotide reductases (RNRs) catalyze the conversion of nucleotides (NDPs or NTPs where N = C, U, G, or A) to 2′-deoxynucleotides (dNDPs or dNTPs)[superscript 1] and are responsible for controlling the relative ratios and absolute concentrations of cellular dNTP pools. For this reason, RNRs play a major role in ensuring the fidelity of DNA replication and repair. RNRs are found in all organisms and are classified based on the metallocofactor used to initiate catalysis,[superscript 1] with the class Ia RNRs requiring a diferric-tyrosyl radical (Y•) cofactor.National Institutes of Health (U.S.) (GM47274)National Institutes of Health (U.S.) (GM29595

Photochemical tyrosine oxidation with a hydrogen-bonded proton acceptor by bidirectional proton-coupled electron transfer

Amino acid radical generation and transport are fundamentally important to numerous essential biological processes to which small molecule models lend valuable mechanistic insights. Pyridyl-amino acid-methyl esters are appended to a rhenium(I) tricarbonyl 1,10-phenanthroline core to yield rhenium–amino acid complexes with tyrosine ([Re]–Y–OH) and phenylalanine ([Re]–F). The emission from the [Re] center is more significantly quenched for [Re]–Y–OH upon addition of base. Time-resolved studies establish that excited-state quenching occurs by a combination of static and dynamic mechanisms. The degree of quenching depends on the strength of the base, consistent with a proton-coupled electron transfer (PCET) quenching mechanism. Comparative studies of [Re]–Y–OH and [Re]–F enable a detailed mechanistic analysis of a bidirectional PCET process.National Institutes of Health (U.S.) (GM47274

Ten-percent solar-to-fuel conversion with nonprecious materials

Direct solar-to-fuels conversion can be achieved by coupling a photovoltaic device with water-splitting catalysts. We demonstrate that a solar-to-fuels efficiency (SFE) > 10% can be achieved with nonprecious, low-cost, and commercially ready materials. We present a systems design of a modular photovoltaic (PV)–electrochemical device comprising a crystalline silicon PV minimodule and low-cost hydrogen-evolution reaction and oxygen-evolution reaction catalysts, without power electronics. This approach allows for facile optimization en route to addressing lower-cost devices relying on crystalline silicon at high SFEs for direct solar-to-fuels conversion.National Science Foundation (U.S.). Faculty Early Career Development Program (ECCS-1150878)Singapore. National Research Foundation (Singapore-MIT Alliance for Research and Technology. Low Energy Electronic Systems Research Program)Chesonis Family Foundatio

Modulation of Phenol Oxidation in Cofacial Dyads

The presentation of two phenols on a xanthene backbone is akin to the tyrosine dyad (Y[subscript 730] and Y[subscript 731]) of ribonucleotide reductase. X-ray crystallography reveals that the two phenol moieties are cofacially disposed at 4.35 Å. Cyclic voltammetry reveals that phenol oxidation is modulated within the dyad, which exhibits a splitting of one-electron waves with the second oxidation of the phenol dyad occurring at larger positive potential than that of a typical phenol. In contrast, a single phenol appended to a xanthene exhibits a two-electron process, consistent with reported oxidation pathways of phenols in acetonitrile. The perturbation of the phenol potential by stacking is reminiscent of a similar effect for guanines stacked within DNA base pairs.National Institutes of Health (U.S.) (GM5R01

Photochemical Generation of a Tryptophan Radical within the Subunit Interface of Ribonucleotide Reductase

United States. National Institutes of Health (GM029595