DOI: 10.1073/pnas.1600525113. Valence tautomerism in synthetic models of cytochrome P450

Valence tautomerism in synthetic models of cytochrome P450

10.1073/pnas.1600525113

Crossref journal-article

Proceedings of the National Academy of Sciences

Proceedings of the National Academy of Sciences (341)

Abstract

Significance Cytochrome P450 is a mammalian enzyme responsible for the catabolism of organic molecules (food, drug, etc.) as well as biosynthesis of hormones and cholesterol. Unfortunately, in stark contrast to the stability of the enzyme, its synthetic mimics rapidly degrade on being exposed to oxygen impeding erstwhile efforts of the scientific community to understand its chemistry in detail. Here the discovery of a valence tautomerism between a ferric thiolate and an arcane ferrous-thiyl species in synthetic models at room temperature is proposed to be at the root of this three-decade-old mystery. Hydrogen bonding to the thiolate sulfur, also present in the enzyme active site, restrains the system to the ferric thiolate form imparting its stability in the presence of oxygen.

Bibliography

Das, P. K., Samanta, S., McQuarters, A. B., Lehnert, N., & Dey, A. (2016). Valence tautomerism in synthetic models of cytochrome P450. Proceedings of the National Academy of Sciences, 113(24), 6611â6616.

Authors 5

Pradip Kumar Das (first)
Subhra Samanta (additional)
Ashley B. McQuarters (additional)
Nicolai Lehnert (additional)
Abhishek Dey (additional)

References 44 Referenced 37

10.1021/cr0307143
10.1021/cr9500500
10.1039/C1CS15192D
10.1021/cr00081a015
10.1021/cr020443g
10.1021/ja00175a044
10.1021/ja00837a052
10.1021/ja00847a046
10.1021/ja8044986
10.1073/pnas.0704191104
10.1021/ic302369v
10.1021/es501912d
10.1021/acs.accounts.5b00167
10.1021/ar600059h
10.1021/ic049110n
10.1021/ar950048v
10.1021/ja0549695
10.1021/bi035260i
10.1021/cr020619e
10.1021/ja00487a018
10.1016/S0010-8545(99)00029-6
10.1021/ic00335a017
10.1021/j100192a031
10.1016/0162-0134(95)00153-0
10.1021/ja004305p
10.1073/pnas.1109931108
RM Buchanan, CG Pierpont, Tautomeric catecholate-semiquinone interconversion via metal-ligand electron transfer. Structural, spectral, and magnetic properties of (3,5-di-tert-butylcatecholato)(3,5-di-tert-butylsemiquinone)(bipyridyl)cobalt(III), a complex containing mixed-valence organic ligands. J Am Chem Soc 102, 4951–4957 (1980). (10.1021/ja00535a021) / J Am Chem Soc / Tautomeric catecholate-semiquinone interconversion via metal-ligand electron transfer. Structural, spectral, and magnetic properties of (3,5-di-tert-butylcatecholato)(3,5-di-tert-butylsemiquinone)(bipyridyl)cobalt(III), a complex containing mixed-valence organic ligands by Buchanan RM (1980)
10.1002/chem.201404925
10.1073/pnas.0900995106
10.1021/ic4020652
10.1021/ic5029959
10.1021/ja064167p
10.1021/ja0519031
10.1126/science.2111581
10.1021/cr020628n
10.1038/nsmb971
10.1126/science.1197881
10.1021/bi00112a008
10.1002/1521-3773(20020603)41:11<1947::AID-ANIE1947>3.0.CO;2-W
10.1021/bi101911y
10.1021/ja9915504
10.1021/ja005619f
10.1021/ic3016035
10.1021/ic401022z

Dates

Type	When
Created	9 years, 2 months ago (June 2, 2016, 11:33 p.m.)
Deposited	3 years, 4 months ago (April 13, 2022, 1:04 a.m.)
Indexed	16 hours, 15 minutes ago (Aug. 24, 2025, 7:05 p.m.)
Issued	9 years, 2 months ago (June 2, 2016)
Published	9 years, 2 months ago (June 2, 2016)
Published Online	9 years, 2 months ago (June 2, 2016)
Published Print	9 years, 2 months ago (June 14, 2016)

Funders 2

Department of Science and Technology, Ministry of Science and Technology 10.13039/501100001409 Department of Science and Technology, Ministry of Science and Technology, India
Region: Asia
gov (National government)
Labels12
1. Department Of Science & Technology | विज्ञान एवं प्रौद्योगिकी
2. Department of Science and Technology
3. विज्ञान और प्रौद्योगिकी विभाग
4. विज्ञान और प्रौद्योगिकी विभाग, विज्ञान और प्रौद्योगिकी मंत्रालय, भारत
5. Department of Science & Technology, Ministry of Science and Technology, India
6. Department of Science & Technology
7. Department of Science and Technology (India)
8. DSTIndia
9. IndiaDST
10. Department of Science and Technology, Government of India
11. DST
12. डीएसटी
Awards1
1. SB/S1/IC-25/2013
National Science Foundation 10.13039/100000001
Region: Americas
gov (National government)
Labels4
1. U.S. National Science Foundation
2. NSF
3. US NSF
4. USA NSF
Awards1
1. CHE-1464696

BibTeX

@article{Das_2016, title={Valence tautomerism in synthetic models of cytochrome P450}, volume={113}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.1600525113}, DOI={10.1073/pnas.1600525113}, number={24}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Das, Pradip Kumar and Samanta, Subhra and McQuarters, Ashley B. and Lehnert, Nicolai and Dey, Abhishek}, year={2016}, month=jun, pages={6611–6616} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2025,
        8,
        24
      ]
    ],
    "date-time": "2025-08-24T23:05:33Z",
    "timestamp": 1756076733762,
    "version": "3.37.3"
  },
  "reference-count": 44,
  "publisher": "Proceedings of the National Academy of Sciences",
  "issue": "24",
  "license": [
    {
      "start": {
        "date-parts": [
          [
            2016,
            12,
            2
          ]
        ],
        "date-time": "2016-12-02T00:00:00Z",
        "timestamp": 1480636800000
      },
      "content-version": "vor",
      "delay-in-days": 183,
      "URL": "http://www.pnas.org/preview_site/misc/userlicense.xhtml"
    }
  ],
  "funder": [
    {
      "DOI": "10.13039/501100001409",
      "name": "Department of Science and Technology, Ministry of Science and Technology",
      "doi-asserted-by": "publisher",
      "award": [
        "SB/S1/IC-25/2013"
      ],
      "id": [
        {
          "id": "10.13039/501100001409",
          "id-type": "DOI",
          "asserted-by": "publisher"
        }
      ]
    },
    {
      "DOI": "10.13039/100000001",
      "name": "National Science Foundation",
      "doi-asserted-by": "publisher",
      "award": [
        "CHE-1464696"
      ],
      "id": [
        {
          "id": "10.13039/100000001",
          "id-type": "DOI",
          "asserted-by": "publisher"
        }
      ]
    }
  ],
  "content-domain": {
    "domain": [
      "www.pnas.org"
    ],
    "crossmark-restriction": true
  },
  "published-print": {
    "date-parts": [
      [
        2016,
        6,
        14
      ]
    ]
  },
  "abstract": "<jats:title>Significance</jats:title>\n          <jats:p>Cytochrome P450 is a mammalian enzyme responsible for the catabolism of organic molecules (food, drug, etc.) as well as biosynthesis of hormones and cholesterol. Unfortunately, in stark contrast to the stability of the enzyme, its synthetic mimics rapidly degrade on being exposed to oxygen impeding erstwhile efforts of the scientific community to understand its chemistry in detail. Here the discovery of a valence tautomerism between a ferric thiolate and an arcane ferrous-thiyl species in synthetic models at room temperature is proposed to be at the root of this three-decade-old mystery. Hydrogen bonding to the thiolate sulfur, also present in the enzyme active site, restrains the system to the ferric thiolate form imparting its stability in the presence of oxygen.</jats:p>",
  "DOI": "10.1073/pnas.1600525113",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2016,
        6,
        3
      ]
    ],
    "date-time": "2016-06-03T03:33:49Z",
    "timestamp": 1464924829000
  },
  "page": "6611-6616",
  "update-policy": "https://doi.org/10.1073/pnas.cm10313",
  "source": "Crossref",
  "is-referenced-by-count": 37,
  "title": "Valence tautomerism in synthetic models of cytochrome P450",
  "prefix": "10.1073",
  "volume": "113",
  "author": [
    {
      "given": "Pradip Kumar",
      "family": "Das",
      "sequence": "first",
      "affiliation": [
        {
          "name": "Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700032, India;"
        }
      ]
    },
    {
      "given": "Subhra",
      "family": "Samanta",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700032, India;"
        }
      ]
    },
    {
      "given": "Ashley B.",
      "family": "McQuarters",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry, University of Michigan, Ann Arbor, MI 48109"
        }
      ]
    },
    {
      "given": "Nicolai",
      "family": "Lehnert",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Chemistry, University of Michigan, Ann Arbor, MI 48109"
        }
      ]
    },
    {
      "ORCID": "https://orcid.org/0000-0002-9166-3349",
      "authenticated-orcid": false,
      "given": "Abhishek",
      "family": "Dey",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700032, India;"
        }
      ]
    }
  ],
  "member": "341",
  "published-online": {
    "date-parts": [
      [
        2016,
        6,
        2
      ]
    ]
  },
  "reference": [
    {
      "key": "e_1_3_3_1_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr0307143"
    },
    {
      "key": "e_1_3_3_2_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr9500500"
    },
    {
      "key": "e_1_3_3_3_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/C1CS15192D"
    },
    {
      "key": "e_1_3_3_4_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr00081a015"
    },
    {
      "key": "e_1_3_3_5_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr020443g"
    },
    {
      "key": "e_1_3_3_6_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja00175a044"
    },
    {
      "key": "e_1_3_3_7_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja00837a052"
    },
    {
      "key": "e_1_3_3_8_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja00847a046"
    },
    {
      "key": "e_1_3_3_9_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja8044986"
    },
    {
      "key": "e_1_3_3_10_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1073/pnas.0704191104"
    },
    {
      "key": "e_1_3_3_11_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic302369v"
    },
    {
      "key": "e_1_3_3_12_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/es501912d"
    },
    {
      "key": "e_1_3_3_13_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/acs.accounts.5b00167"
    },
    {
      "key": "e_1_3_3_14_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ar600059h"
    },
    {
      "key": "e_1_3_3_15_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic049110n"
    },
    {
      "key": "e_1_3_3_16_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ar950048v"
    },
    {
      "key": "e_1_3_3_17_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja0549695"
    },
    {
      "key": "e_1_3_3_18_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/bi035260i"
    },
    {
      "key": "e_1_3_3_19_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr020619e"
    },
    {
      "key": "e_1_3_3_20_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja00487a018"
    },
    {
      "key": "e_1_3_3_21_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/S0010-8545(99)00029-6"
    },
    {
      "key": "e_1_3_3_22_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic00335a017"
    },
    {
      "key": "e_1_3_3_23_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/j100192a031"
    },
    {
      "key": "e_1_3_3_24_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/0162-0134(95)00153-0"
    },
    {
      "key": "e_1_3_3_25_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja004305p"
    },
    {
      "key": "e_1_3_3_26_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1073/pnas.1109931108"
    },
    {
      "key": "e_1_3_3_27_2",
      "doi-asserted-by": "crossref",
      "first-page": "4951",
      "DOI": "10.1021/ja00535a021",
      "article-title": "Tautomeric catecholate-semiquinone interconversion via metal-ligand electron transfer. Structural, spectral, and magnetic properties of (3,5-di-tert-butylcatecholato)(3,5-di-tert-butylsemiquinone)(bipyridyl)cobalt(III), a complex containing mixed-valence organic ligands",
      "volume": "102",
      "author": "Buchanan RM",
      "year": "1980",
      "unstructured": "RM Buchanan, CG Pierpont, Tautomeric catecholate-semiquinone interconversion via metal-ligand electron transfer. Structural, spectral, and magnetic properties of (3,5-di-tert-butylcatecholato)(3,5-di-tert-butylsemiquinone)(bipyridyl)cobalt(III), a complex containing mixed-valence organic ligands. J Am Chem Soc 102, 4951\u20134957 (1980).",
      "journal-title": "J Am Chem Soc"
    },
    {
      "key": "e_1_3_3_28_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/chem.201404925"
    },
    {
      "key": "e_1_3_3_29_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1073/pnas.0900995106"
    },
    {
      "key": "e_1_3_3_30_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic4020652"
    },
    {
      "key": "e_1_3_3_31_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic5029959"
    },
    {
      "key": "e_1_3_3_32_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja064167p"
    },
    {
      "key": "e_1_3_3_33_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja0519031"
    },
    {
      "key": "e_1_3_3_34_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1126/science.2111581"
    },
    {
      "key": "e_1_3_3_35_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr020628n"
    },
    {
      "key": "e_1_3_3_36_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1038/nsmb971"
    },
    {
      "key": "e_1_3_3_37_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1126/science.1197881"
    },
    {
      "key": "e_1_3_3_38_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/bi00112a008"
    },
    {
      "key": "e_1_3_3_39_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/1521-3773(20020603)41:11<1947::AID-ANIE1947>3.0.CO;2-W"
    },
    {
      "key": "e_1_3_3_40_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/bi101911y"
    },
    {
      "key": "e_1_3_3_41_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja9915504"
    },
    {
      "key": "e_1_3_3_42_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja005619f"
    },
    {
      "key": "e_1_3_3_43_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic3016035"
    },
    {
      "key": "e_1_3_3_44_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic401022z"
    }
  ],
  "container-title": "Proceedings of the National Academy of Sciences",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "http://www.pnas.org/syndication/doi/10.1073/pnas.1600525113",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "syndication"
    },
    {
      "URL": "https://pnas.org/doi/pdf/10.1073/pnas.1600525113",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2022,
        4,
        13
      ]
    ],
    "date-time": "2022-04-13T05:04:51Z",
    "timestamp": 1649826291000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://pnas.org/doi/full/10.1073/pnas.1600525113"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        2016,
        6,
        2
      ]
    ]
  },
  "references-count": 44,
  "journal-issue": {
    "issue": "24",
    "published-print": {
      "date-parts": [
        [
          2016,
          6,
          14
        ]
      ]
    }
  },
  "alternative-id": [
    "10.1073/pnas.1600525113"
  ],
  "URL": "http://dx.doi.org/10.1073/pnas.1600525113",
  "relation": {},
  "ISSN": [
    "0027-8424",
    "1091-6490"
  ],
  "subject": [],
  "container-title-short": "Proc. Natl. Acad. Sci. U.S.A.",
  "published": {
    "date-parts": [
      [
        2016,
        6,
        2
      ]
    ]
  },
  "assertion": [
    {
      "value": "2016-06-02",
      "order": 2,
      "name": "published",
      "label": "Published",
      "group": {
        "name": "publication_history",
        "label": "Publication History"
      }
    }
  ]
}