解决钼依赖型蛋氨酸亚砜还原酶中的配体相关氧化还原问题。
Addressing Ligand-Based Redox in Molybdenum-Dependent Methionine Sulfoxide Reductase.
机构信息
Department of Chemistry and Chemical Biology , The University of New Mexico , MSC03 2060, 1 University of New Mexico , Albuquerque , New Mexico 87131-0001 , United States.
Department of Chemistry Biochemistry , University of Arizona , Tucson , Arizona 85721 , United States.
出版信息
J Am Chem Soc. 2020 Feb 12;142(6):2721-2725. doi: 10.1021/jacs.9b11762. Epub 2020 Jan 28.
Abstract
A combination of pulsed EPR, CW EPR, and X-ray absorption spectroscopies has been employed to probe the geometric and electronic structure of the periplasmic molybdenum-dependent methionine sulfoxide reductase (MsrP). O and H pulsed EPR spectra show that the Mo(V) enzyme form does not possess an exchangeable HO/OH ligand bound to Mo as found in the sulfite oxidizing enzymes of the same family. The nature of the unusual CW EPR spectrum has been re-evaluated in light of new data on the MsrP-N45R variant and related small-molecule analogues of the active site. These data point to a novel "thiol-blocked" [(PDT)MoO(S)(thiolate)] structure, which is supported by new EXAFS data. We discuss these new results in the context of ligand-based and metal-based redox chemistry in the enzymatic oxygen atom transfer reaction.
摘要
采用脉冲电子顺磁共振（EPR）、连续波 EPR 和 X 射线吸收光谱学相结合的方法，研究了周质钼依赖型蛋氨酸亚砜还原酶（MsrP）的几何和电子结构。O 和 H 脉冲 EPR 谱表明，Mo(V)酶形式不具有与亚硫酸氧化酶家族相同的可交换的 HO/OH 配体结合到 Mo 上。根据 MsrP-N45R 变体和相关活性位点小分子类似物的新数据，重新评估了异常连续波 EPR 谱的性质。这些数据指向一种新的“硫醇封锁”[(PDT)MoO(S)(硫醇盐)]结构，新的 EXAFS 数据支持这一结构。我们在酶促氧原子转移反应中基于配体和基于金属的氧化还原化学的背景下讨论了这些新结果。
相似文献
1
Addressing Ligand-Based Redox in Molybdenum-Dependent Methionine Sulfoxide Reductase.解决钼依赖型蛋氨酸亚砜还原酶中的配体相关氧化还原问题。
J Am Chem Soc. 2020 Feb 12;142(6):2721-2725. doi: 10.1021/jacs.9b11762. Epub 2020 Jan 28.
2
Investigation of the coordination structures of the molybdenum(v) sites of sulfite oxidizing enzymes by pulsed EPR spectroscopy.利用脉冲电子顺磁共振光谱研究亚硫酸盐氧化酶中钼（Ⅴ）位点的配位结构。
Dalton Trans. 2006 Aug 7(29):3501-14. doi: 10.1039/b602919a. Epub 2006 Jun 22.
3
Models for molybdenum coordination during the catalytic cycle of periplasmic nitrate reductase from Paracoccus denitrificans derived from EPR and EXAFS spectroscopy.基于电子顺磁共振（EPR）和扩展X射线吸收精细结构（EXAFS）光谱推导的反硝化副球菌周质硝酸还原酶催化循环中钼配位模型。
Biochemistry. 1999 Jul 13;38(28):9000-12. doi: 10.1021/bi990402n.
4
Structure of the molybdenum site in YedY, a sulfite oxidase homologue from Escherichia coli.YedY 中钼位点的结构，一种来自大肠杆菌的亚硫酸盐氧化酶同源物。
Inorg Chem. 2011 Feb 7;50(3):741-8. doi: 10.1021/ic101291j. Epub 2010 Dec 29.
5
Protonation and Non-Innocent Ligand Behavior in Pyranopterin Dithiolene Molybdenum Complexes.吡喃并蝶呤二硫醇钼配合物中的质子化和非非亲核配体行为。
Inorg Chem. 2022 Sep 5;61(35):13728-13742. doi: 10.1021/acs.inorgchem.2c01234. Epub 2022 Aug 24.
6
Characterization of the redox centers in dimethyl sulfide dehydrogenase from Rhodovulum sulfidophilum.嗜硫红假单胞菌二甲基硫化物脱氢酶中氧化还原中心的表征
Biochemistry. 2002 Dec 24;41(51):15234-44. doi: 10.1021/bi026221u.
7
Reversible dissociation of thiolate ligands from molybdenum in an enzyme of the dimethyl sulfoxide reductase family.在二甲基亚砜还原酶家族的一种酶中，硫醇盐配体与钼的可逆解离。
Biochemistry. 2000 Sep 19;39(37):11258-69. doi: 10.1021/bi0000521.
8
Structures of the Mo(V) forms of sulfite oxidase from Arabidopsis thaliana by pulsed EPR spectroscopy.利用脉冲电子顺磁共振光谱法解析拟南芥亚硫酸盐氧化酶钼（V）形式的结构
Biochemistry. 2005 Oct 11;44(40):13274-81. doi: 10.1021/bi051220y.
9
Periplasmic nitrate reductase revisited: a sulfur atom completes the sixth coordination of the catalytic molybdenum.周质硝酸还原酶再探讨：一个硫原子完成了催化钼的第六配位。
J Biol Inorg Chem. 2008 Jun;13(5):737-53. doi: 10.1007/s00775-008-0359-6. Epub 2008 Mar 8.
10
Characterisation of the periplasmic methionine sulfoxide reductase (MsrP) from Salmonella Typhimurium.鼠伤寒沙门氏菌周质甲硫氨酸亚砜还原酶（MsrP）的特性。
Free Radic Biol Med. 2020 Nov 20;160:506-512. doi: 10.1016/j.freeradbiomed.2020.06.031. Epub 2020 Aug 1.
引用本文的文献
1
Molybdenum Cofactor Model Reveals Remarkable Redox Activity at Both Molybdenum and the Pyranopterin Dithiolene Ligand.钼辅因子模型揭示了钼和吡喃蝶呤二硫烯配体处显著的氧化还原活性。
J Am Chem Soc. 2025 May 7;147(18):15088-15099. doi: 10.1021/jacs.4c17577. Epub 2025 Apr 27.
2
Insights into periplasmic nitrate reductase function under single turnover.单周转条件下对周质硝酸还原酶功能的深入了解。
J Biol Inorg Chem. 2024 Dec;29(7-8):811-819. doi: 10.1007/s00775-024-02087-5. Epub 2024 Dec 4.
3
Active Site Characterization of a Nitrate Reductase Variant Provides Insight into the Enzyme Mechanism.硝酸盐还原酶变体的活性位点表征为深入了解酶的机制提供了线索。
Inorg Chem. 2024 Jul 22;63(29):13191-13196. doi: 10.1021/acs.inorgchem.4c01991. Epub 2024 Jul 10.
4
Advancing Our Understanding of Pyranopterin-Dithiolene Contributions to Moco Enzyme Catalysis.推进我们对吡喃并二硫醇对钼辅因子酶催化贡献的理解。
Molecules. 2023 Nov 7;28(22):7456. doi: 10.3390/molecules28227456.
5
Active Site Structures of the -Hydroxylaminopurine Resistance Molybdoenzyme YcbX.-羟氨基嘌呤耐药钼酶 YcbX 的活性位点结构。
Inorg Chem. 2023 Apr 10;62(14):5315-5319. doi: 10.1021/acs.inorgchem.3c00342. Epub 2023 Mar 27.
6
Protonation and Non-Innocent Ligand Behavior in Pyranopterin Dithiolene Molybdenum Complexes.吡喃并蝶呤二硫醇钼配合物中的质子化和非非亲核配体行为。
Inorg Chem. 2022 Sep 5;61(35):13728-13742. doi: 10.1021/acs.inorgchem.2c01234. Epub 2022 Aug 24.
7
Spectroscopic Studies of Mononuclear Molybdenum Enzyme Centers.单核钼酶中心的光谱研究。
Molecules. 2022 Jul 27;27(15):4802. doi: 10.3390/molecules27154802.
8
Active site architecture reveals coordination sphere flexibility and specificity determinants in a group of closely related molybdoenzymes.活性位点结构揭示了一组密切相关的钼酶中配位球灵活性和特异性决定因素。
J Biol Chem. 2021 Jan-Jun;296:100672. doi: 10.1016/j.jbc.2021.100672. Epub 2021 Apr 20.
9
Kβ X-Ray Emission Spectroscopic Study of a Second-Row Transition Metal (Mo) and Its Application to Nitrogenase-Related Model Complexes.Kβ 射线发射光谱法研究第二过渡金属（钼）及其在氮酶相关模型配合物中的应用。
Angew Chem Int Ed Engl. 2020 Jul 27;59(31):12965-12975. doi: 10.1002/anie.202003621. Epub 2020 May 29.
本文引用的文献
1
methionine sulfoxide reductase P reduces - and -diastereomers of methionine sulfoxide from a broad-spectrum of protein substrates.甲硫氨酸亚砜还原酶 P 还原 - 和 - 甲硫氨酸亚砜对映异构体从广泛的蛋白质底物。
Biochem J. 2018 Dec 6;475(23):3779-3795. doi: 10.1042/BCJ20180706.
2
Consensus structures of the Mo(v) sites of sulfite-oxidizing enzymes derived from variable frequency pulsed EPR spectroscopy, isotopic labelling and DFT calculations.源自可变频率脉冲电子顺磁共振光谱、同位素标记和密度泛函理论计算的亚硫酸盐氧化酶钼（Ⅴ）位点的共识结构。
Dalton Trans. 2017 Oct 10;46(39):13202-13210. doi: 10.1039/c7dt01731f.
3
Oxidative stress, protein damage and repair in bacteria.细菌中的氧化应激、蛋白质损伤与修复。
Nat Rev Microbiol. 2017 Jul;15(7):385-396. doi: 10.1038/nrmicro.2017.26. Epub 2017 Apr 19.
4
A Two-component NADPH Oxidase (NOX)-like System in Bacteria Is Involved in the Electron Transfer Chain to the Methionine Sulfoxide Reductase MsrP.细菌中的双组分烟酰胺腺嘌呤二核苷酸磷酸氧化酶（NOX）样系统参与向甲硫氨酸亚砜还原酶MsrP的电子传递链。
J Biol Chem. 2017 Feb 10;292(6):2485-2494. doi: 10.1074/jbc.M116.752014. Epub 2016 Dec 27.
5
Repairing oxidized proteins in the bacterial envelope using respiratory chain electrons.利用呼吸链电子修复细菌包膜中的氧化蛋白。
Nature. 2015 Dec 17;528(7582):409-412. doi: 10.1038/nature15764. Epub 2015 Dec 7.
6
Pyranopterin Coordination Controls Molybdenum Electrochemistry in Escherichia coli Nitrate Reductase.吡喃蝶呤配位调控大肠杆菌硝酸还原酶中的钼电化学。
J Biol Chem. 2015 Oct 9;290(41):25164-73. doi: 10.1074/jbc.M115.665422. Epub 2015 Aug 21.
7
Novel mechanism for scavenging of hypochlorite involving a periplasmic methionine-rich Peptide and methionine sulfoxide reductase.涉及一种富含周质甲硫氨酸的肽和甲硫氨酸亚砜还原酶的次氯酸盐清除新机制。
mBio. 2015 May 12;6(3):e00233-15. doi: 10.1128/mBio.00233-15.
8
Oxyl and hydroxyl radical transfer in mitochondrial amidoxime reducing component-catalyzed nitrite reduction.线粒体偕胺肟还原成分催化亚硝酸盐还原过程中的氧自由基和羟基自由基转移
J Am Chem Soc. 2015 Apr 29;137(16):5276-9. doi: 10.1021/jacs.5b01112. Epub 2015 Apr 21.
9
Molybdenum site structure of MOSC family proteins.MOSC家族蛋白的钼位点结构
Inorg Chem. 2014 Sep 15;53(18):9460-2. doi: 10.1021/ic5015863. Epub 2014 Aug 28.
10
The mononuclear molybdenum enzymes.单核钼酶。
Chem Rev. 2014 Apr 9;114(7):3963-4038. doi: 10.1021/cr400443z. Epub 2014 Jan 28.
Zotero 插件