• 文献检索
  • 文档翻译
  • 深度研究
  • 学术资讯
  • Suppr Zotero 插件Zotero 插件
  • 邀请有礼
  • 套餐&价格
  • 历史记录
应用&插件
Suppr Zotero 插件Zotero 插件浏览器插件Mac 客户端Windows 客户端微信小程序
定价
高级版会员购买积分包购买API积分包
服务
文献检索文档翻译深度研究API 文档MCP 服务
关于我们
关于 Suppr公司介绍联系我们用户协议隐私条款
关注我们

Suppr 超能文献

核心技术专利：CN118964589B侵权必究
粤ICP备2023148730 号-1Suppr @ 2026

文献检索

告别复杂PubMed语法，用中文像聊天一样搜索，搜遍4000万医学文献。AI智能推荐，让科研检索更轻松。

立即免费搜索

文件翻译

保留排版，准确专业，支持PDF/Word/PPT等文件格式，支持 12+语言互译。

免费翻译文档

深度研究

AI帮你快速写综述，25分钟生成高质量综述，智能提取关键信息，辅助科研写作。

立即免费体验

向光蛋白LOV1形成半醌自由基时吸收光谱的红移：重建轨道结构

Red Shift in the Absorption Spectrum of Phototropin LOV1 upon the Formation of a Semiquinone Radical: Reconstructing the Orbital Architecture.

作者信息

Kurle-Tucholski Patrick, Wiebeler Christian, Köhler Lisa, Qin Ruonan, Zhao Ziyue, Šimėnas Mantas, Pöppl Andreas, Matysik Jörg

机构信息

Institut für Analytische Chemie, Universität Leipzig, Linnéstraße 3, D-04103 Leipzig, Germany.

Institut für Physik, Universität Augsburg, Universitätsstraße 1, D-86159 Augsburg, Germany.

出版信息

J Phys Chem B. 2024 May 9;128(18):4344-4353. doi: 10.1021/acs.jpcb.4c00397. Epub 2024 Apr 30.

DOI:10.1021/acs.jpcb.4c00397
PMID:38688080
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11089501/
Abstract

Flavin mononucleotide (FMN) is a ubiquitous blue-light pigment due to its ability to drive one- and two-electron transfer reactions. In both light-oxygen-voltage (LOV) domains of phototropin from the green algae , FMN is noncovalently bound. In the LOV1 cysteine-to-serine mutant (C57S), light-induced electron transfer from a nearby tryptophan occurs, and a transient spin-correlated radical pair (SCRP) is formed. Within this photocycle, nuclear hyperpolarization is created by the solid-state photochemically induced dynamic nuclear polarization (photo-CIDNP) effect. In a side reaction, a stable protonated semiquinone radical (FMNH) forms undergoing a significant bathochromic shift of the first electronic transition from 445 to 591 nm. The incorporation of phototropin LOV1-C57S into an amorphous trehalose matrix, stabilizing the radical, allows for application of various magnetic resonance experiments at ambient temperatures, which are combined with quantum-chemical calculations. As a result, the bathochromic shift of the first absorption band is explained by lifting the degeneracy of the molecular orbital energy levels for electrons with alpha and beta spins in FMNH due to the additional electron.

摘要

黄素单核苷酸（FMN）是一种普遍存在的蓝光色素，因为它能够驱动单电子和双电子转移反应。在绿藻向光蛋白的两个光-氧-电压（LOV）结构域中，FMN是非共价结合的。在LOV1半胱氨酸到丝氨酸突变体（C57S）中，会发生光诱导的电子从附近色氨酸转移，形成一个瞬态自旋相关自由基对（SCRP）。在这个光循环中，通过固态光化学诱导动态核极化（光-CIDNP）效应产生核超极化。在一个副反应中，会形成一个稳定的质子化半醌自由基（FMNH），其第一个电子跃迁发生了显著的红移，从445 nm移至591 nm。将向光蛋白LOV1-C57S掺入无定形海藻糖基质中，使自由基稳定，从而能够在环境温度下进行各种磁共振实验，并与量子化学计算相结合。结果表明，由于额外的电子，FMNH中α和β自旋电子的分子轨道能级简并性被消除，从而解释了第一个吸收带的红移。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/923516351d42/jp4c00397_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/d33c8efd4ec0/jp4c00397_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/e2ae26d5c436/jp4c00397_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/6ff3a44b1731/jp4c00397_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/59b98f9bc941/jp4c00397_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/05284c76b74f/jp4c00397_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/922a04f663d3/jp4c00397_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/923516351d42/jp4c00397_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/d33c8efd4ec0/jp4c00397_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/e2ae26d5c436/jp4c00397_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/6ff3a44b1731/jp4c00397_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/59b98f9bc941/jp4c00397_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/05284c76b74f/jp4c00397_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/922a04f663d3/jp4c00397_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8a4a/11089501/923516351d42/jp4c00397_0007.jpg

相似文献

1
Red Shift in the Absorption Spectrum of Phototropin LOV1 upon the Formation of a Semiquinone Radical: Reconstructing the Orbital Architecture.向光蛋白LOV1形成半醌自由基时吸收光谱的红移：重建轨道结构
J Phys Chem B. 2024 May 9;128(18):4344-4353. doi: 10.1021/acs.jpcb.4c00397. Epub 2024 Apr 30.
2
Nuclear spin-hyperpolarization generated in a flavoprotein under illumination: experimental field-dependence and theoretical level crossing analysis.光照下黄素蛋白中产生的核自旋超极化：实验场依赖性和理论能级交叉分析。
Sci Rep. 2019 Dec 5;9(1):18436. doi: 10.1038/s41598-019-54671-4.
3
Photo-reduction of flavin mononucleotide to semiquinone form in LOV domain mutants of blue-light receptor phot from Chlamydomonas reinhardtii.莱茵衣藻蓝光受体光趋蛋白（phot）的LOV结构域突变体中黄素单核苷酸光还原为半醌形式。
J Photochem Photobiol B. 2007 Apr 2;87(1):37-48. doi: 10.1016/j.jphotobiol.2006.12.007. Epub 2007 Jan 10.
4
A search for radical intermediates in the photocycle of LOV domains.对光氧电压感受结构域光循环中自由基中间体的研究。
Photochem Photobiol Sci. 2015 Feb;14(2):288-99. doi: 10.1039/c4pp00155a.
5
Stabilization of a flavoprotein for solid-state photo-CIDNP MAS NMR at room temperature by embedding in a glassy sugar matrix.通过嵌入玻璃态糖基质在室温下实现用于固态光化学诱导动态核极化（photo-CIDNP）核磁共振（MAS NMR）的黄素蛋白的稳定化。
J Magn Reson. 2023 Aug;353:107497. doi: 10.1016/j.jmr.2023.107497. Epub 2023 Jun 3.
6
Tailored flavoproteins acting as light-driven spin machines pump nuclear hyperpolarization.定制的黄素蛋白作为光驱动的自旋机器，可实现核超极化。
Sci Rep. 2020 Oct 29;10(1):18658. doi: 10.1038/s41598-020-75627-z.
7
Spectroscopic characterization of flavin mononucleotide bound to the LOV1 domain of Phot1 from Chlamydomonas reinhardtii.莱茵衣藻光受体1（Phot1）的LOV1结构域结合的黄素单核苷酸的光谱表征
Photochem Photobiol. 2002 May;75(5):479-87. doi: 10.1562/0031-8655(2002)075<0479:scofmb>2.0.co;2.
8
On the reaction mechanism of adduct formation in LOV domains of the plant blue-light receptor phototropin.关于植物蓝光受体向光素LOV结构域中加合物形成的反应机制
J Am Chem Soc. 2004 Sep 8;126(35):11067-76. doi: 10.1021/ja049553q.
9
Detecting a new source for photochemically induced dynamic nuclear polarization in the LOV2 domain of phototropin by magnetic-field dependent (13)C NMR spectroscopy.通过磁场依赖性（13）C核磁共振光谱法检测向光素LOV2结构域中光化学诱导动态核极化的新来源。
J Phys Chem B. 2014 Oct 9;118(40):11622-32. doi: 10.1021/jp507134y. Epub 2014 Sep 26.
10
Photoreaction of mutated LOV photoreceptor domains from Chlamydomonas reinhardtii with aliphatic mercaptans: implications for the mechanism of wild type LOV.莱茵衣藻突变 LOV 光受体结构域与脂肪族巯基的光化学反应：对野生型 LOV 机制的启示。
Phys Chem Chem Phys. 2010 Jul 7;12(25):6594-604. doi: 10.1039/b922408d. Epub 2010 May 6.

本文引用的文献

1
Photocycle of a cyanobacteriochrome: a charge defect on ring impairs conjugation in chromophore.蓝细菌视紫红质的光循环：环上的电荷缺陷会损害生色团中的共轭作用。
Chem Sci. 2023 May 11;14(23):6295-6308. doi: 10.1039/d3sc00636k. eCollection 2023 Jun 14.
2
Stabilization of a flavoprotein for solid-state photo-CIDNP MAS NMR at room temperature by embedding in a glassy sugar matrix.通过嵌入玻璃态糖基质在室温下实现用于固态光化学诱导动态核极化（photo-CIDNP）核磁共振（MAS NMR）的黄素蛋白的稳定化。
J Magn Reson. 2023 Aug;353:107497. doi: 10.1016/j.jmr.2023.107497. Epub 2023 Jun 3.
3
Spin Dynamics of Flavoproteins.
flavoproteins 的自旋动力学。
Int J Mol Sci. 2023 May 4;24(9):8218. doi: 10.3390/ijms24098218.
4
Riboflavin-binding proteins for singlet oxygen production.产生单线态氧的核黄素结合蛋白。
Photochem Photobiol Sci. 2022 Sep;21(9):1545-1555. doi: 10.1007/s43630-021-00156-1. Epub 2022 Jan 18.
5
UV-visible absorption spectrum of FAD and its reduced forms embedded in a cryptochrome protein.黄素腺嘌呤二核苷酸（FAD）及其在隐色体蛋白中的还原形式的紫外-可见吸收光谱。
Phys Chem Chem Phys. 2020 Jun 10;22(22):12447-12455. doi: 10.1039/d0cp01714k.
6
Nuclear spin-hyperpolarization generated in a flavoprotein under illumination: experimental field-dependence and theoretical level crossing analysis.光照下黄素蛋白中产生的核自旋超极化：实验场依赖性和理论能级交叉分析。
Sci Rep. 2019 Dec 5;9(1):18436. doi: 10.1038/s41598-019-54671-4.
7
Probing basis set requirements for calculating hyperfine coupling constants.探究计算超精细耦合常数的基组需求。
J Chem Phys. 2019 Nov 7;151(17):174107. doi: 10.1063/1.5128286.
8
New Basis Set Exchange: An Open, Up-to-Date Resource for the Molecular Sciences Community.新基组交换：分子科学领域的开放、最新资源。
J Chem Inf Model. 2019 Nov 25;59(11):4814-4820. doi: 10.1021/acs.jcim.9b00725. Epub 2019 Oct 24.
9
Studying hydrogen bonding and dynamics of the acetylate groups of the Special Pair of Rhodobacter sphaeroides WT.研究 Rhodobacter sphaeroides WT 特殊对乙酰基基团的氢键和动力学。
Sci Rep. 2019 Jul 19;9(1):10528. doi: 10.1038/s41598-019-46903-4.
10
ssNake: A cross-platform open-source NMR data processing and fitting application.ssNake：一款跨平台的开源核磁共振数据处理与拟合应用程序。
J Magn Reson. 2019 Apr;301:56-66. doi: 10.1016/j.jmr.2019.02.006. Epub 2019 Mar 1.