Multistep Photoinduced Electron Transfer in a de Novo Helix Bundle:  Multimer Self-Assembly of Peptide Chains Including a Chromophore Special Pair<sup>1</sup>

Jones, Guilford; Vullev, Valentine I.; Braswell, Emory H.; Zhu, Dan

doi:10.1021/ja981936z

Cited by 48 publications

(56 citation statements)

References 18 publications

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“…Proteins and polypeptides (composed of native α-amino acids and their derivatives) mediate ET solely via tunneling, the efficiency of which is limited to about 2 nm. [41][42][43][44][45][46] Conversely, arrays of cofactors and redox-active residues, such as tryptophan or tyrosine, make it possible to attain long-range ET. 47,48 That is, multiple short and efficient "electron hopping" steps along arrays of redox moieties allow ET to exceed the 2-nm tunneling limit.…”

Section: Ct Molecular Electrets: Practical Ideas From Structural Biologymentioning

confidence: 99%

Bioinspired molecular electrets: bottom-up approach to energy materials and applications

2015

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Abstract. The diversity of life on Earth is made possible through an immense variety of proteins that stems from less than a couple of dozen native amino acids. Is it possible to achieve similar engineering freedom and precision to design electronic materials? What if a handful of nonnative residues with a wide range of characteristics could be rationally placed in sequences to form organic macromolecules with specifically targeted properties and functionalities? Referred to as molecular electrets, dipolar oligomers and polymers composed of non-native aromatic beta-amino acids, anthranilamides (Aa) provide venues for pursuing such possibilities. The electret molecular dipoles play a crucial role in rectifying charge transfer, e.g., enhancing charge separation and suppressing undesired charge recombination, which is essential for photovoltaics, photocatalysis, and other solar-energy applications. A set of a few Aa residues can serve as building blocks for molecular electrets with widely diverse electronic properties, presenting venues for bottom-up designs. We demonstrate how three substituents and structural permutations within an Aa residue widely alter its reduction potential. Paradigms of diversity in electronic properties, originating from a few changes within a basic molecular structure, illustrate the promising potentials of biological inspiration for energy science and engineering.

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Section: Ct Molecular Electrets: Practical Ideas From Structural Biologymentioning

confidence: 99%

Bioinspired molecular electrets: bottom-up approach to energy materials and applications

2015

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“…Free-moving charges in the electret or in the surrounding media would screen the dipolegenerated fields eliminating the dipole effect. Hence, electron tunneling is representative of the prevalent mechanism of CT mediated by biological and biomimetic polypeptide structures [37][38][39][40][41][42][43]. Tunneling, however, limits the distance of efficient CT to about 2 nm [37,38].…”

Section: Introductionmentioning

confidence: 99%

Building blocks for bioinspired electrets: molecular-level approach to materials for energy and electronics

Larsen

Espinoza

Hartman

et al. 2015

Pure and Applied Chemistry

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In biology, an immense diversity of protein structural and functional motifs originates from only 20 common proteinogenic native amino acids arranged in various sequences. Is it possible to attain the same diversity in electronic materials based on organic macromolecules composed of non-native residues with different characteristics? This publication describes the design, preparation and characterization of non-native aromatic β-amino acid residues, i.e. derivatives of anthranilic acid, for polyamides that can efficiently mediate hole transfer. Chemical derivatization with three types of substituents at two positions of the aromatic ring allows for adjusting the energy levels of the frontier orbitals of the anthranilamide residues over a range of about one electronvolt. Most importantly, the anthranilamide residues possess permanent electric dipoles, adding to the electronic properties of the bioinspired conjugates they compose, making them molecular electrets.

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“…Upon photoexcitation of the acceptor, an electron moves from the HOMO of the donor to fill the newly generated vacancy in the acceptor "HOMO." (Strictly speaking, after photoexcitation, the HOMO becomes a singly occupied MO; and because the transfer is along the HOMOs of the CT species following the excitation of the acceptor [120][121][122][123][124], it can be viewed as hole transfer rather than electron transfer). The rates of CT are up to about 30 times larger when the acceptor is positioned close to the N-terminus than to the C-terminus of the helices [117].…”

Section: Dipole Effects On Charge Transfermentioning

confidence: 99%

Bioinspired approach toward molecular electrets: synthetic proteome for materials

Espinoza

Larsen-Clinton

Krzeszewski

et al. 2017

Pure and Applied Chemistry

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Molecular-level control of charge transfer (CT) is essential for both, organic electronics and solarenergy conversion, as well as for a wide range of biological processes. This article provides an overview of the utility of local electric fields originating from molecular dipoles for directing CT processes. Systems with ordered dipoles, i.e. molecular electrets, are the centerpiece of the discussion. The conceptual evolution from biomimicry to biomimesis, and then to biological inspiration, paves the roads leading from testing the understanding of how natural living systems function to implementing these lessons into optimal paradigms for specific applications. This progression of the evolving structure-function relationships allows for the development of bioinspired electrets composed of non-native aromatic amino acids. A set of such non-native residues that are electron-rich can be viewed as a synthetic proteome for hole-transfer electrets. Detailed considerations of the electronic structure of an individual residue prove of key importance for designating the points for optimal injection of holes (i.e. extraction of electrons) in electret oligomers. This multifaceted bioinspired approach for the design of CT molecular systems provides unexplored paradigms for electronic and energy science and engineering.

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Multistep Photoinduced Electron Transfer in a de Novo Helix Bundle: Multimer Self-Assembly of Peptide Chains Including a Chromophore Special Pair¹

Cited by 48 publications

References 18 publications

Bioinspired molecular electrets: bottom-up approach to energy materials and applications

Bioinspired molecular electrets: bottom-up approach to energy materials and applications

Building blocks for bioinspired electrets: molecular-level approach to materials for energy and electronics

Bioinspired approach toward molecular electrets: synthetic proteome for materials

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Multistep Photoinduced Electron Transfer in a de Novo Helix Bundle: Multimer Self-Assembly of Peptide Chains Including a Chromophore Special Pair1

Cited by 48 publications

References 18 publications

Bioinspired molecular electrets: bottom-up approach to energy materials and applications

Bioinspired molecular electrets: bottom-up approach to energy materials and applications

Building blocks for bioinspired electrets: molecular-level approach to materials for energy and electronics

Bioinspired approach toward molecular electrets: synthetic proteome for materials

Contact Info

Product

Resources

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Multistep Photoinduced Electron Transfer in a de Novo Helix Bundle: Multimer Self-Assembly of Peptide Chains Including a Chromophore Special Pair¹