Pigmentation Chemistry and Radical-Based Collagen Degradation in Alkaptonuria and Osteoarthritic Cartilage.


Journal

Angewandte Chemie (International ed. in English)
ISSN: 1521-3773
Titre abrégé: Angew Chem Int Ed Engl
Pays: Germany
ID NLM: 0370543

Informations de publication

Date de publication:
13 07 2020
Historique:
received: 15 01 2020
pubmed: 29 3 2020
medline: 26 3 2021
entrez: 29 3 2020
Statut: ppublish

Résumé

Alkaptonuria (AKU) is a rare disease characterized by high levels of homogentisic acid (HGA); patients suffer from tissue ochronosis: dark brown pigmentation, especially of joint cartilage, leading to severe early osteoarthropathy. No molecular mechanism links elevated HGA to ochronosis; the pigment's chemical identity is still not known, nor how it induces joint cartilage degradation. Here we give key insight on HGA-derived pigment composition and collagen disruption in AKU cartilage. Synthetic pigment and pigmented human cartilage tissue both showed hydroquinone-resembling NMR signals. EPR spectroscopy showed that the synthetic pigment contains radicals. Moreover, we observed intrastrand disruption of collagen triple helix in pigmented AKU human cartilage, and in cartilage from patients with osteoarthritis. We propose that collagen degradation can occur via transient glycyl radicals, the formation of which is enhanced in AKU due to the redox environment generated by pigmentation.

Identifiants

pubmed: 32219972
doi: 10.1002/anie.202000618
pmc: PMC7383862
doi:

Substances chimiques

Pigments, Biological 0
Homogentisic Acid NP8UE6VF08

Types de publication

Journal Article Research Support, Non-U.S. Gov't

Langues

eng

Sous-ensembles de citation

IM

Pagination

11937-11942

Subventions

Organisme : Medical Research Council
ID : MR/M01066X/1
Pays : United Kingdom

Informations de copyright

© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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Auteurs

Wing Ying Chow (WY)

Leibniz-Forschungsinstitut für Molekulare Pharmakologie, im Forschungsverbund Berlin e.V. (FMP), Campus Berlin-Buch, Robert-Rössle-Str. 10, 13125, Berlin, Germany.

Brendan P Norman (BP)

Department of Musculoskeletal Biology, Institute of Ageing & Chronic Disease, William Henry Duncan Building, University of Liverpool, Liverpool, L7 8TX, UK.

Norman B Roberts (NB)

Departments of Clinical Biochemistry and Metabolic Medicine, Royal Liverpool and Broadgreen University Hospitals Trust, Liverpool, L7 8XP, UK.

Lakshminarayan R Ranganath (LR)

Department of Musculoskeletal Biology, Institute of Ageing & Chronic Disease, William Henry Duncan Building, University of Liverpool, Liverpool, L7 8TX, UK.
Departments of Clinical Biochemistry and Metabolic Medicine, Royal Liverpool and Broadgreen University Hospitals Trust, Liverpool, L7 8XP, UK.

Christian Teutloff (C)

Freie Universität Berlin, Fachbereich Physik, Berlin Joint EPR Lab, Arnimallee 14, 14195, Berlin, Germany.

Robert Bittl (R)

Freie Universität Berlin, Fachbereich Physik, Berlin Joint EPR Lab, Arnimallee 14, 14195, Berlin, Germany.

Melinda J Duer (MJ)

Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.

James A Gallagher (JA)

Department of Musculoskeletal Biology, Institute of Ageing & Chronic Disease, William Henry Duncan Building, University of Liverpool, Liverpool, L7 8TX, UK.

Hartmut Oschkinat (H)

Leibniz-Forschungsinstitut für Molekulare Pharmakologie, im Forschungsverbund Berlin e.V. (FMP), Campus Berlin-Buch, Robert-Rössle-Str. 10, 13125, Berlin, Germany.
Freie Universität Berlin, Fachbereich Biologie, Chemie und Pharmazie, Takustraße 3, 14195, Berlin, Germany.

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