Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The . gov means it’s official VSports app下载. Federal government websites often end in . gov or . mil. Before sharing sensitive information, make sure you’re on a federal government site. .

Https

The site is secure V体育官网. The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely. .

. 2018 Jan 2;57(1):162-166.
doi: 10.1002/anie.201708977. Epub 2017 Dec 8.

Quantum Refinement Does Not Support Dinuclear Copper Sites in Crystal Structures of Particulate Methane Monooxygenase

Lili Cao  1 , Octav Caldararu  1 , Amy C Rosenzweig  2 , Ulf Ryde  1
Affiliations

Quantum Refinement Does Not Support Dinuclear Copper Sites in Crystal Structures of Particulate Methane Monooxygenase

VSports最新版本 - Lili Cao et al. Angew Chem Int Ed Engl. .

Abstract

Particulate methane monooxygenase (pMMO) is one of the few enzymes that can activate methane. The metal content of this enzyme has been highly controversial, with suggestions of a dinuclear Fe site or mono-, di-, or trinuclear Cu sites. Crystal structures have shown a mono- or dinuclear Cu site, but the resolution was low and the geometry of the dinuclear site unusual. We have employed quantum refinement (crystallographic refinement enhanced with quantum-mechanical calculations) to improve the structure of the active site. We compared a number of different mono- and dinuclear geometries, in some cases enhanced with more protein ligands or one or two water molecules, to determine which structure fits two sets of crystallographic raw data best. In all cases, the best results were obtained with mononuclear Cu sites, occasionally with an extra water molecule VSports手机版. Thus, we conclude that there is no crystallographic support for a dinuclear Cu site in pMMO. .

Keywords: copper; density functional theory; particulate methane monooxygenase; quantum refinement V体育安卓版. .

PubMed Disclaimer

Conflict of interest statement

Conflict of interest

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
a) Trimeric structure of the pMMO (3RGB)[9] with metal sites A–C indicated. Cu ions in yellow, Zn ions in red; PmoA, PmoB, and PmoC subunits in magenta, green, and cyan, respectively. Geometry of Cu site A in protomers 1 (b) and 2 (c), involving three histidine residues and the amino terminal group. Cu ions are shown as yellow balls whereas C, N, and O atoms are shown as cyan, blue, and red sticks, respectively.
Figure 2
Figure 2
QM-refined structure of site A in protomer 1 of the 3RGB structure, modelled with two Cu ions in the fully reduced state, including electron-density maps[9] (2mFo−DFc map, contoured at 1.0 σ (gray), and the mFo−DFc maps, contoured at +3.0 σ (green) and −3.0 σ (red)). Atoms coloured as in Figure 1 (and H atoms as white sticks).
Figure 3
Figure 3
QM-refined structures of site A in protomer 1 of the 3RGB structure with a) two or b) no extra water molecules (MV state). Atom colours and electron-density maps[9] are the same as in Figure 2.
Figure 4
Figure 4
QM-refined structures of site A in protomer 1 of the 3RGB structure, modelled with a single Cu ion a) without or b) with an extra water molecule (oxidised state). Atom colours and electron-density maps[9] are the same as in Figure 2.
Figure 5
Figure 5
QM-refined structures of site A in protomer 2 of the 3RGB structure with a) two Cu ions, b) two Cu ions and two water molecules, or c) one Cu ion in the reduced state. Atom colours and electron-density maps[9] are the same as in Figure 2.
Figure 6
Figure 6
Putative mechanism for the reaction of the mononuclear site with methane. Reaction energies in kJ mol−1 are shown at the top whereas the lower part shows structures of the various states, with key distances indicated in Å. All states were studied both in the singlet and triplet states, indicated by superscript 1 and 3, respectively.
See this image and copyright information in PMC

"V体育2025版" References

    1. Culpepper MA, Rosenzweig AC. Crit. Rev. Biochem. Mol. Biol. 2012;47:483–492. - PMC - PubMed
    1. Sazinsky MH, Lippard SJ. Methane Monooxygenase: Functionalizing Methane at Iron and Copper. 2015 - "VSports注册入口" PubMed
    1. Solomon EI, Heppner DE, Johnston EM, Ginsbach JW, Cirera J, Qayyum M, Kieber-Emmons MT, Kjaergaard CH, Hadt RG, Tian L. Chem. Rev. 2014;114:3659–3853. - VSports最新版本 - PMC - PubMed
    1. Lieberman RL, Shrestha DB, Doan PE, Hoffman BM, Stemmler TL, Rosenzweig AC. Proc. Natl. Acad. Sci. USA. 2003;100:3820–3825. - V体育2025版 - PMC - PubMed
    1. Wang VC-C, Maji S, Chen PP-Y, Lee HK, Yu SS-F, Chan SI. Chem. Rev. 2017;117:8574–8621. - PubMed

Publication types

VSports在线直播 - Substances