Characterization of organophosphatic brachiopod shells: spectroscopic assessment of collagen matrix and biomineral components

Agbaje, Oluwatoosin B. A.; George, Simon C.; Zhang, Zhifei; Brock, Glenn A.; Holmer, Lars E.

doi:10.1039/d0ra07523j

Cited by 9 publications

(15 citation statements)

References 67 publications

(183 reference statements)

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“…A ~1003 cm -1 phenyl ring vibration is visible in the Raman spectra of the studzied brachiopod shells, and is commonly observed in the published spectra of collagen 27,28 . Recent analyses provide comprehensive data on D. tenuis and L. anatina shells, with identification of a collagen matrix as the primary protein motif within the inorganic matrix of phosphate-shelled brachiopods 29 .…”

Section: Discussionmentioning

confidence: 99%

“…The CH deformation of the β-glycosidic bond band at 897 cm -1 for D. tenuis and at ~902 cm -1 for L. anatina is present at 895 cm -1 in standard α-chitin. Bands at 1003 cm -1 in L. anatina and 1005 cm -1 in D. tenuis are not present in standard α-chitin and are attributed to the aromatic C-C stretch of fibrous insoluble protein [27][28][29] . The vibrational bands at ~856 cm -1 and ~820 cm -1 are assigned to a combination of C-C and C-O stretching, and appear in L. anatina only.…”

Section: Vibrational Spectroscopy -Microraman and Ftir Spectramentioning

confidence: 92%

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Chitin Matrix and Ultrastructure of Phosphate-Shelled Brachiopods

Agbaje

Brock

Zhang³

et al. 2020

Preprint

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Phosphate-shelled brachiopods differ in filter-feeding lifestyle, with Lingula anatina an active infaunal burrower, and Discinisca tenuis a shallow marine epibenthic animal. The shells of these biomineralized organisms are built of organophosphatic constituents, the organic fibres/sheets reinforced with calcium phosphate (Ca-phosphate) to provide a sophisticated ultrastructural robustness. This investigation studied the nature of organic fibres in order to improve our understanding of how design principles are relevant to biominerals. Unlike the powdered samples that were commonly used in previous studies, for the first time organic fibres were isolated and the shell fractions were purified, in order to study the content and nature of the biopolymer fibres. Ultrastructural analysis, thermal gravimetric analysis and spectroscopic analyses reveal that the core polysaccharide framework is composed of layers of β-chitin sheets that are coated with a fibrous protein matrix. The chitin matrix in Lingula shells, 26.6 wt.%, is about two-fold higher wt.% compared to Discinisca shells,12.9 wt.%. After thermal gravimetric analysis, skeletal imaging of these shells shows important differences. Discinisca contains just a single layer that is ~21.0 µm thick. In contrast, Lingula exhibits two separate layers: the thicknesses of the primary- and secondary-layers are ~20.3 µm and ~8.1 µm, respectively. Taken together, the data shows that the chitin matrix contributes to increased skeletal strength, making Lingula highly adapted for life as an active burrower. In comparison, Discinisca contains less chitin and lives as attached epibenthos in a shallow marine environment.

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Section: Discussionmentioning

confidence: 99%

Section: Vibrational Spectroscopy -Microraman and Ftir Spectramentioning

confidence: 92%

Chitin Matrix and Ultrastructure of Phosphate-Shelled Brachiopods

Agbaje

Brock

Zhang³

et al. 2020

Preprint

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“…FTIR measurements were conducted as described previously [1], with 64 accumulations and a resolution of 2 cm -1 . Background spectra were measured at the start of each analysis.…”

Section: Microraman and Fourier Transform Infrared Spectroscopymentioning

confidence: 99%

“…These biomaterials are inorganic-organic nanocomposites with exceptional structures and functions. Inorganic components comprise biominerals, that is, calcium carbonates and phosphates or silica [1][2][3], whereas organic macromolecules constitute a combination of soluble-and insoluble-organic components, primarily peptide-, protein-and polysaccharide-based layers which provide a scaffolding for the inorganic phase [4][5][6]. Water insoluble macromolecules are most frequently built from monomers-based either on sugars or peptides.…”

Section: Introductionmentioning

confidence: 99%

“…Craniiformea and Rhynchonelliformea utilize calcium carbonate and * 2% of an organic matrix to hierarchically assemble ultrastructures of the calcitic shells [29]. In contrast, linguliform brachiopods such as L. anatina and D. tenuis use organic biopolymers reinforced with calcium phosphate (Ca-phosphate) to produce the shells [1,30]. Linguliform brachiopods are an important ancestral animal group, with an unexcelled fossil record that originated some 530 million years ago in the early Cambrian as part of the emergence of biomineralization across disparate animal clades [28,31].…”

Section: Introductionmentioning

confidence: 99%

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Biomacromolecules in recent phosphate-shelled brachiopods: identification and characterization of chitin matrix

et al. 2021

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Phosphate-shelled brachiopods differ in filter-feeding lifestyle, with Lingula anatina an active infaunal burrower, and Discinisca tenuis a shallow marine epibenthic animal. The shells of these animals are built of organophosphatic constituents, the organic fibres/sheets reinforced with calcium phosphate to provide a sophisticated ultrastructural robustness. This investigation examined the nature of the organic fibres in order to improve understanding of how living organisms produce hierarchically structured biomaterials. Unlike powdered samples commonly used in previous studies, organic fibres were isolated for the first time and the shell fractions were purified, in order to study the content and nature of the biopolymer fibres. Biochemical methods including Calcofluor staining revealed a chitin matrix. Ultrastructural analysis, thermal gravimetric analysis, and spectroscopic analyses show that the core polysaccharide framework is composed of layers of β-chitin sheets and/or fibrils that are coated with a fibrous organic matrix. There is more chitin matrix in the L. anatina shells (26.6 wt.%) compared to the D. tenuis shells (12.9 wt.%). Taken together, the data show that the chitin matrix contributes to increased skeletal strength, making L. anatina highly adapted for life as an active burrower. In comparison, D. tenuis contains less chitin and lives as attached epibenthos in a shallow marine environment. Graphical abstract First spectroscopic evidence of β-chitin sheets in recent organophosphatic brachiopods

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Organic biopolymers of venus clams: Collagen-related matrix in the bivalve shells with crossed-lamellar ultrastructure

Agbaje

Dominguez

Jacob

2021

Biochemistry and Biophysics Reports

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Characterization of organophosphatic brachiopod shells: spectroscopic assessment of collagen matrix and biomineral components

Abstract: The shells of linguloid brachiopods such as Lingula and Discinisca are inorganic–organic nanocomposites with a mineral phase of calcium phosphate (Ca-phosphate).

Cited by 9 publications

References 67 publications

Chitin Matrix and Ultrastructure of Phosphate-Shelled Brachiopods

Chitin Matrix and Ultrastructure of Phosphate-Shelled Brachiopods

Biomacromolecules in recent phosphate-shelled brachiopods: identification and characterization of chitin matrix

Organic biopolymers of venus clams: Collagen-related matrix in the bivalve shells with crossed-lamellar ultrastructure

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