The Effective Conjugation Length Is Responsible for the Red/Green Spectral Tuning in the Cyanobacteriochrome Slr1393g3

Christian Wiebeler; Aditya G. Rao; Wolfgang Gärtner; Igor Schapiro

doi:10.1002/anie.201810266

The Effective Conjugation Length Is Responsible for the Red/Green Spectral Tuning in the Cyanobacteriochrome Slr1393g3

Christian Wiebeler, Aditya G. Rao, Wolfgang Gärtner, Igor Schapiro^*

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

43 Scopus citations

Abstract

The origin of the spectral shift from a red- to a green-absorbing form in a cyanobacteriochrome, Slr1393g3, was identified by combined quantum mechanics/molecular mechanics simulations. This protein, related to classical phytochromes, carries the open-chain tetrapyrrole chromophore phycocyanobilin. Our calculations reveal that the effective conjugation length in the chromophore becomes shorter upon conversion from the red to the green form. This is related to the planarity of the entire chromophore. A large distortion was found for the terminal pyrrole rings A and D; however, the D ring contributes more strongly to the photoproduct tuning, despite a larger change in the twist of the A ring. Our findings implicate that the D ring twist can be exploited to regulate the absorption of the photoproduct. Hence, mutations that affect the D ring twist can lead to rational tuning of the photoproduct absorption, allowing the tailoring of cyanobacteriochromes for biotechnological applications such as optogenetics and bioimaging.

Original language	American English
Pages (from-to)	1934-1938
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	7
DOIs	https://doi.org/10.1002/anie.201810266
State	Published - 11 Feb 2019

Bibliographical note

Funding Information:
This project has received funding from the European Research Council (ERC) under the European Union≫s Horizon 2020 research and innovation programme (Grant Agreement No. 678169, ERC Starting Grant “PhotoMu-tant”). I.S. is grateful for the Mercator Fellowship and support from the DFG (Grant No. SFB 1078). C.W. acknowledges support by the German Research Foundation (DFG) via a research scholarship (reference number: WI 4853/1-1). The Turbomole calculations leading to the results presented here were conducted on resources provided by the Paderborn Center for Parallel Computing.

Funding Information:
This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (Grant Agreement No. 678169, ERC Starting Grant ?PhotoMutant?). I.S. is grateful for the Mercator Fellowship and support from the DFG (Grant No. SFB 1078). C.W. acknowledges support by the German Research Foundation (DFG) via a research scholarship (reference number: WI 4853/1-1). The Turbomole calculations leading to the results presented here were conducted on resources provided by the Paderborn Center for Parallel Computing.

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords

chromophores
cyanobacteriochromes
hybrid QM/MM
spectral tuning
tetrapyrroles

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10.1002/anie.201810266

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title = "The Effective Conjugation Length Is Responsible for the Red/Green Spectral Tuning in the Cyanobacteriochrome Slr1393g3",

abstract = "The origin of the spectral shift from a red- to a green-absorbing form in a cyanobacteriochrome, Slr1393g3, was identified by combined quantum mechanics/molecular mechanics simulations. This protein, related to classical phytochromes, carries the open-chain tetrapyrrole chromophore phycocyanobilin. Our calculations reveal that the effective conjugation length in the chromophore becomes shorter upon conversion from the red to the green form. This is related to the planarity of the entire chromophore. A large distortion was found for the terminal pyrrole rings A and D; however, the D ring contributes more strongly to the photoproduct tuning, despite a larger change in the twist of the A ring. Our findings implicate that the D ring twist can be exploited to regulate the absorption of the photoproduct. Hence, mutations that affect the D ring twist can lead to rational tuning of the photoproduct absorption, allowing the tailoring of cyanobacteriochromes for biotechnological applications such as optogenetics and bioimaging.",

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author = "Christian Wiebeler and Rao, {Aditya G.} and Wolfgang G{\"a}rtner and Igor Schapiro",

note = "Funding Information: This project has received funding from the European Research Council (ERC) under the European Union≫s Horizon 2020 research and innovation programme (Grant Agreement No. 678169, ERC Starting Grant “PhotoMu-tant”). I.S. is grateful for the Mercator Fellowship and support from the DFG (Grant No. SFB 1078). C.W. acknowledges support by the German Research Foundation (DFG) via a research scholarship (reference number: WI 4853/1-1). The Turbomole calculations leading to the results presented here were conducted on resources provided by the Paderborn Center for Parallel Computing. Funding Information: This project has received funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation programme (Grant Agreement No. 678169, ERC Starting Grant ?PhotoMutant?). I.S. is grateful for the Mercator Fellowship and support from the DFG (Grant No. SFB 1078). C.W. acknowledges support by the German Research Foundation (DFG) via a research scholarship (reference number: WI 4853/1-1). The Turbomole calculations leading to the results presented here were conducted on resources provided by the Paderborn Center for Parallel Computing. Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Schapiro, Igor

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N2 - The origin of the spectral shift from a red- to a green-absorbing form in a cyanobacteriochrome, Slr1393g3, was identified by combined quantum mechanics/molecular mechanics simulations. This protein, related to classical phytochromes, carries the open-chain tetrapyrrole chromophore phycocyanobilin. Our calculations reveal that the effective conjugation length in the chromophore becomes shorter upon conversion from the red to the green form. This is related to the planarity of the entire chromophore. A large distortion was found for the terminal pyrrole rings A and D; however, the D ring contributes more strongly to the photoproduct tuning, despite a larger change in the twist of the A ring. Our findings implicate that the D ring twist can be exploited to regulate the absorption of the photoproduct. Hence, mutations that affect the D ring twist can lead to rational tuning of the photoproduct absorption, allowing the tailoring of cyanobacteriochromes for biotechnological applications such as optogenetics and bioimaging.

AB - The origin of the spectral shift from a red- to a green-absorbing form in a cyanobacteriochrome, Slr1393g3, was identified by combined quantum mechanics/molecular mechanics simulations. This protein, related to classical phytochromes, carries the open-chain tetrapyrrole chromophore phycocyanobilin. Our calculations reveal that the effective conjugation length in the chromophore becomes shorter upon conversion from the red to the green form. This is related to the planarity of the entire chromophore. A large distortion was found for the terminal pyrrole rings A and D; however, the D ring contributes more strongly to the photoproduct tuning, despite a larger change in the twist of the A ring. Our findings implicate that the D ring twist can be exploited to regulate the absorption of the photoproduct. Hence, mutations that affect the D ring twist can lead to rational tuning of the photoproduct absorption, allowing the tailoring of cyanobacteriochromes for biotechnological applications such as optogenetics and bioimaging.

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The Effective Conjugation Length Is Responsible for the Red/Green Spectral Tuning in the Cyanobacteriochrome Slr1393g3

Abstract

Bibliographical note

Keywords

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