Following fungal melanin biosynthesis with solid-state NMR: Biopolymer molecular structures and possible connections to cell-wall polysaccharides

Junyan Zhong, Susana Frases, Hsin Wang, Arturo Casadevall, Ruth E. Stark

Research output: Contribution to journalArticle

Abstract

Melanins serve a variety of protective functions in plants and animals, but in fungi such as Cryptococcus neoformans they are also associated with virulence. A recently developed solid-state nuclear magnetic resonance (NMR) strategy, based on the incorporation of site-specific 13C-enriched precursors into melanin, followed by spectroscopy of both powdered and solvent-swelled melanin ghosts, was used to provide new molecular-level insights into fungal melanin biosynthesis. The side chain of an L-dopa precursor was shown to cyclize and form a proposed indole structure in C. neoformans melanin, and modification of the aromatic rings revealed possible patterns of polymer chain elongation and cross-linking within the biopolymer. Mannose supplied in the growth medium was retained as a β-pyranose moiety in the melanin ghosts even after exhaustive degradative and dialysis treatments, suggesting the possibility of tight binding or covalent incorporation of the pigment into the polysaccharide fungal cell walls. In contrast, glucose was scrambled metabolically and incorporated into both polysaccharide cell walls and aliphatic chains present in the melanin ghosts, consistent with metabolic use as a cellular nutrient as well as covalent attachment to the pigment. The prominent aliphatic groups reported previously in several fungal melanins were identified as triglyceride structures that may have one or more sites of chain unsaturation. These results establish that fungal melanin contains chemical components derived from sources other than L-dopa polymerization and suggest that covalent linkages between L-dopa-derived products and polysaccharide components may serve to attach this pigment to cell wall structures.

Original languageEnglish (US)
Pages (from-to)4701-4710
Number of pages10
JournalBiochemistry®
Volume47
Issue number16
DOIs
StatePublished - Apr 22 2008
Externally publishedYes

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Biopolymers
Biosynthesis
Melanins
Molecular Structure
Cell Wall
Molecular structure
Polysaccharides
Magnetic Resonance Spectroscopy
Nuclear magnetic resonance
Levodopa
Pigments
Cryptococcus neoformans
Cells
Fungal Polysaccharides
Dialysis
Mannose
Polymerization
Fungi
Virulence
Spectrum Analysis

ASJC Scopus subject areas

  • Biochemistry

Cite this

Following fungal melanin biosynthesis with solid-state NMR : Biopolymer molecular structures and possible connections to cell-wall polysaccharides. / Zhong, Junyan; Frases, Susana; Wang, Hsin; Casadevall, Arturo; Stark, Ruth E.

In: Biochemistry®, Vol. 47, No. 16, 22.04.2008, p. 4701-4710.

Research output: Contribution to journalArticle

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