• 제목/요약/키워드: proton-coupled electron transfer

검색결과 6건 처리시간 0.021초

Elucidation of photo-induced electron transfer in a loop-forming peptide: Dye-Ala-Gly-Gln-Tyr

  • Lee, Hwiin;Kim, Jeongyun;Kwon, Yong-Uk;Lee, Minyung
    • Rapid Communication in Photoscience
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    • 제4권3호
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    • pp.59-62
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    • 2015
  • We investigated photo-induced electron transfer (PET) in a dye-labeled peptide, fluorophore-Ala-Gly-Gln-Tyr, employing time-resolved fluorescence. As an effort to develop new functional dyes, we studied an acriflavine derivative for the electron-acceptor in the excited state from tyrosine, an electrondonor in the ground-state. The pH dependence of the fluorescence lifetime of the model peptide indicates that electron transfer between the excited dye and tyrosine occurs when the tyrosine is deprotonated. The proton-coupled electron transfer appears to be sequential rather than concerted. We also report direct time measurements on the end-to-end loop formation processes of the peptide in water.

Photoelectrochemical Water Oxidation and $CO_2$ Conversion for Artificial Photosynthesis

  • Park, Hyunwoong
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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    • pp.70-70
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    • 2013
  • As the costs of carbon-footprinetd fuels grow continuously and simultaneously atmospheric carbon dioxide concentration increases, solar fuels are receiving growing attention as alternative clean energy carriers. These fuels include molecular hydrogen and hydrogen peroxide produced from water, and hydrocarbons converted from carbon dioxide. For high efficiency solar fuel production, not only light absorbers (oxide semiconductors, Si, inorganic complexes, etc) should absorb most sunlight, but also charge separation and interfacial charge transfers need to occur efficiently. With this in mind, this talk will introduce the fundamentals of solar fuel production and artificial photosynthesis, and then discuss in detail on photoelectrochemical (PEC) water splitting and CO2 conversion. This talk largely divides into two section: PEC water oxidation and PEC CO2 reduction. The former is very important for proton-coupled electron transfer to CO2. For this oxidation, a variety of oxide semiconductors have been tested including TiO2, ZnO, WO3, BiVO4, and Fe2O3. Although they are essentially capable of oxidizing water into molecular oxygen, the efficiency is very low primarily because of high overpotentials and slow kinetics. This challenge has been overcome by coupling with oxygen evolving catalysts (OECs) and/or doping donor elements. In the latter, surface-modified p-Si electrodes are fabricated to absorb visible light and catalyze the CO2 reduction. For modification, metal nanoparticles are electrodeposited on the p-Si and their PEC performance is compared.

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Coordination chemistry of mitochondrial copper metalloenzymes: exploring implications for copper dyshomeostasis in cell death

  • Daeun Shim;Jiyeon Han
    • BMB Reports
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    • 제56권11호
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    • pp.575-583
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    • 2023
  • Mitochondria, fundamental cellular organelles that govern energy metabolism, hold a pivotal role in cellular vitality. While consuming dioxygen to produce adenosine triphosphate (ATP), the electron transfer process within mitochondria can engender the formation of reactive oxygen species that exert dual roles in endothelial homeostatic signaling and oxidative stress. In the context of the intricate electron transfer process, several metal ions that include copper, iron, zinc, and manganese serve as crucial cofactors in mitochondrial metalloenzymes to mediate the synthesis of ATP and antioxidant defense. In this mini review, we provide a comprehensive understanding of the coordination chemistry of mitochondrial cuproenzymes. In detail, cytochrome c oxidase (CcO) reduces dioxygen to water coupled with proton pumping to generate an electrochemical gradient, while superoxide dismutase 1 (SOD1) functions in detoxifying superoxide into hydrogen peroxide. With an emphasis on the catalytic reactions of the copper metalloenzymes and insights into their ligand environment, we also outline the metalation process of these enzymes throughout the copper trafficking system. The impairment of copper homeostasis can trigger mitochondrial dysfunction, and potentially lead to the development of copper-related disorders. We describe the current knowledge regarding copper-mediated toxicity mechanisms, thereby shedding light on prospective therapeutic strategies for pathologies intertwined with copper dyshomeostasis.

Photocatalytic Systems of Pt Nanoparticles and Molecular Co Complexes for NADH Regeneration and Enzyme-coupled CO2 Conversion

  • Kim, Ellen;Jeon, Minkyung;Kim, Soojin;Yadav, Paras Nath;Jeong, Kwang-Duk;Kim, Jinheung
    • Rapid Communication in Photoscience
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    • 제2권2호
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    • pp.42-45
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    • 2013
  • Natural photosynthesis utilizes solar energy to convert carbon dioxide and water to energy-rich carbohydrates. Substantial use of sunlight to meet world energy demands requires energy storage in useful fuels via chemical bonds because sunlight is intermittent. Artificial photosynthesis research focuses the fundamental natural process to design solar energy conversion systems. Nicotinamide adenine dinucleotide ($NAD^+$) and $NADP^+$ are ubiquitous as electron transporters in biological systems. Enzymatic, chemical, and electrochemical methods have been reported for NADH regeneration. As photochemical systems, visible light-driven catalytic activity of NADH regeneration was carried out using platinum nanoparticles, molecular rhodium and cobalt complexes in the presence of triethanolamine as a sacrificial electron donor. Pt nanoparticles showed photochemical NADH regeneration activity without additional visible light collector molecules, demonstrating that both photoactivating and catalytic activities exist together in Pt nanoparticles. The NADH regeneration of the Pt nanoparticle system was not interfered with the reduction of $O_2$. Molecular cobalt complexes containing dimethylglyoxime ligands also transfer their hydrides to $NAD^+$ with photoactivation of eosin Y in the presence of TEOA. In this photocatalytic reaction, the $NAD^+$ reduction process competed with a proton reduction.

Biological Inspiration toward Artificial Photostystem

  • Park, Jimin;Lee, Jung-Ho;Park, Yong-Sun;Jin, Kyoungsuk;Nam, Ki Tae
    • 한국진공학회:학술대회논문집
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    • 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
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    • pp.91-91
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    • 2013
  • Imagine a world where we could biomanufacture hybrid nanomaterials having atomic-scale resolution over functionality and architecture. Toward this vision, a fundamental challenge in materials science is how to design and synthesize protein-like material that can be fully self-assembled and exhibit information-specific process. In an ongoing effort to extend the fundamental understanding of protein structure to non-natural systems, we have designed a class of short peptides to fold like proteins and assemble into defined nanostructures. In this talk, I will talk about new strategies to drive the self-assembled structures designing sequence of peptide. I will also discuss about the specific interaction between proteins and inorganics that can be used for the development of new hybrid solar energy devices. Splitting water into hydrogen and oxygen is one of the promising pathways for solar to energy convertsion and storage system. The oxygen evolution reaction (OER) has been regarded as a major bottleneck in the overall water splitting process due to the slow transfer rate of four electrons and the high activation energy barrier for O-O bond formation. In nature, there is a water oxidation complex (WOC) in photosystem II (PSII) comprised of the earthabundant elements Mn and Ca. The WOC in photosystem II, in the form of a cubical CaMn4O5 cluster, efficiently catalyzes water oxidation under neutral conditions with extremely low overpotential (~160 mV) and a high TOF number. The cluster is stabilized by a surrounding redox-active peptide ligand, and undergo successive changes in oxidation state by PCET (proton-coupled electron transfer) reaction with the peptide ligand. It is fundamental challenge to achieve a level of structural complexity and functionality that rivals that seen in the cubane Mn4CaO5 cluster and surrounding peptide in nature. In this presentation, I will present a new strategy to mimic the natural photosystem. The approach is based on the atomically defined assembly based on the short redox-active peptide sequences. Additionally, I will show a newly identified manganese based compound that is very close to manganese clusters in photosystem II.

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Single-cathode와 Dual-cathode 미생물연료전지의 탄소원과 질산성질소의 전류발생 특성 (Electricity Production Performance of Single- and Dual-cathode Microbial Fuel Cells Coupled to Carbon Source and Nitrate)

  • 장재경;이은영;유영선;이성현;황지환;이형모;김종구;강연구;김영화
    • 한국미생물·생명공학회지
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    • 제39권4호
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    • pp.382-386
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    • 2011
  • 이 연구에서는 일반적인 음극부 한 개에 양극부 한 개로 구성된 single-cathode 미생물연료전지(SCMFC)와 음극부 한 개에 양극부 두 개로 이루어진 dual-cathode 미생물연료전지(DCMFC)를 이용하여 전류발생에 비치는 영향을 확인하였다. 이 결과 dual-cathode 미생물연료전지에서 single-cathode 미생물연료전지 보다 전류발생이 약 40% 높았으며 COD 제거율도 약 13% 더 높은 것으로 확인되었다. 이것은 양극부와 음극부의 접촉면적이 증가하여 양극반응속도가 향상된 것에 의한 것으로 판단되며 dual-cathode 미생물연료전지가 single-cathode보다 전류발생과 COD제거 측면서 더 효율이 높은것으로 나타났다. 음극부 전자수용체에 대한 영향 실험에서는 전자수용체로 사용된 질산성질소의 농도가 높아질수록 급격히 전류발생이 감소하는 것을 확인 할 수 있었으며, 이에 대한 적절한 처리가 필요한 것으로 나타났다.