Bivalve shells are extensively used as bioarchives for paleoclimate and paleoenvironmental reconstructions. Proxy calibrations in recent shells are the basis for sclerochronology and the applications of geochemistry data to fossils. Shell geochemical information, however, could be altered with the disappearance of intercrystalline organic matrix components, including those linked to shell growth increments, during early diagenesis. Thus, an evaluation of the chemistry of such organics is needed for the correct use of sclerochronological records in fossil shells. Here, we use atom probe tomography (APT) for in situ geochemical characterization of the insoluble organic matrix in shell growth increments in the Antarctic scallop, Adamussium colbecki. We confirm the presence of carboxylated S-rich proteoglycans, possibly involved in calcite nucleation and growth in these scallops, with significant concentrations of magnesium and calcium. Diagenetic modification of these organic components could impact proxy data based on Mg/Ca ratios, but more importantly the use of the δ15N proxy, since most of the shell nitrogen is likely bound to the amide groups of proteins. Overall, our findings reinforce the idea that shell organics need to be accounted for in the understanding of geochemical proxies.
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Atom Probe Tomography (APT) Characterization of Organics Occluded in Single Calcite Crystals: Implications for Biomineralization Studies
Occlusion of organic components in synthetic calcite crystals has been recently used as a model to understand the role of intra-crystalline organics in biominerals. However, the characterization of the distribution of both types of organics inside these calcite crystals is very challenging. Here, we discuss the potential of using the technique of atom probe tomography (APT) for such characterization, focusing on the analysis of chitin incorporation in single crystals. Additionally, APT has at least the same spatial resolution as TEM tomography, yet with the advantage of obtaining quantitative chemical data. Results show that chitin, either after degradation with yatalase or in the form of nanofibers, forms discrete clusters (2 to 5 nm) in association to water and hydronium molecules, rather than forming a 3D network inside crystals. Overall findings indicate that APT can be an ideal technique to characterize intra-crystalline organic components in abiogenic and biogenic carbonates to further advance our understanding of biomineralization.
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- Award ID(s):
- 1647012
- PAR ID:
- 10176557
- Date Published:
- Journal Name:
- C — Journal of Carbon Research
- Volume:
- 5
- Issue:
- 3
- ISSN:
- 2311-5629
- Page Range / eLocation ID:
- 50
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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null (Ed.)Bivalve shells are extensively used as bioarchives for paleoclimate and paleoenvironmental reconstructions. Proxy calibrations in recent shells are the basis for sclerochronology and the applications of geochemistry data to fossils. Shell geochemical information, however, could be altered with the disappearance of intercrystalline organic matrix components, including those linked to shell growth increments, during early diagenesis. Thus, an evaluation of the chemistry of such organics is needed for the correct use of sclerochronological records in fossil shells. Here, we use atom probe tomography (APT) for in situ geochemical characterization of the insoluble organic matrix in shell growth increments in the Antarctic scallop, Adamussium colbecki. We confirm the presence of carboxylated S-rich proteoglycans, possibly involved in calcite nucleation and growth in these scallops, with significant concentrations of magnesium and calcium. Diagenetic modification of these organic components could impact proxy data based on Mg/Ca ratios, but more importantly the use of the 15N proxy, since most of the shell nitrogen is likely bound to the amide groups of proteins. Overall, our findings reinforce the idea that shell organics need to be accounted for in the understanding of geochemical proxies.more » « less
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Abstract Hydroxyapatite nanoparticles (HAP NPs) are important for medicine, bioengineering, catalysis, and water treatment. However, current understanding of the nanoscale phenomena that confer HAP NPs their many useful properties is limited by a lack of information about the distribution of the atoms within the particles. Atom probe tomography (APT) has the spatial resolution and chemical sensitivity for HAP NP characterization, but difficulties in preparing the required needle‐shaped samples make the design of these experiments challenging. Herein, two techniques are developed to encapsulate HAP NPs and prepare them into APT tips. By sputter‐coating gold or the atomic layer deposition of alumina for encapsulation, partially fluoridated HAP NPs are successfully characterized by voltage‐ or laser‐pulsing APT, respectively. Analyses reveal that significant tradeoffs exist between encapsulant methods/materials for HAP characterization and that selection of a more robust approach will require additional technique development. This work serves as an essential starting point for advancing knowledge about the nanoscale spatiochemistry of HAP NPs.
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Abstract Laser-assisted atom probe tomography (APT) is a relatively new, powerful technique for sub-nanometric mineral and biomineral analysis. However, the laser-assisted APT analysis of highly anisotropic and chemically diverse minerals, such as phyllosilicates, may prove especially challenging due to the complex interaction between the crystal structure and the laser pulse upon applying a high electric field. Micas are a representative group of nonswelling clay minerals of relevance to a number of scientific and technological fields. In this study, a Mg-rich biotite was analyzed by APT to generate preliminary data on nonisotropic minerals and to investigate the effect of the crystallographic orientation on mica chemical composition and structure estimation. The difference in results obtained for specimens extracted from the (001) and (hk0) mica surfaces indicate the importance of both experimental parameters and the crystallography. Anisotropy of mica has a strong influence on the physicochemical properties of the mineral during field evaporation and the interpretation of APT data. The promising results obtained in the present study open the way to future innovative APT applications on mica and clay minerals and contribute to the general discussion on the challenges for the analysis of geomaterials by atom probe tomography.
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Chitin, one of the most abundant natural amino polysaccharides, is obtained primarily from the exoskeletons of crustaceans, crabs and shrimp. Chitin and its derivative chitosan have gained much attention in the field of biomedical research due to attractive properties such as biocompatibility, non-toxicity, biodegradability, low immunogenicity, and ease of availability. While work has been done on the use of chitin and chitosan as functional biomaterials by imparting specific properties, the potential of chitin as a biomaterial is somewhat limited owing to its intractable processing. In this work, we propose a facile reaction to modify the chitin chain with photoactive moieties for the realization of photocrosslinkable chitin. This chitin derivative is easily usable with a benign solvent formic acid to be able to form mechanically robust, optically transparent sheets. These films exhibit comparable tensile properties to that of native chitin and chitosan and better surface wettability. Most importantly, this material can be used to form precise, high resolution microarchitectures on both rigid and flexible substrates using a facile bench top photolithography technique. These flexible micropatterned 2D sheets of chitin were demonstrated as a dynamic cell culture substrate for the adhesion and proliferation of fibroblasts, wherein the chitin micropatterns act as a template for spatial guidance of cells. This chitin-based biopolymer can find diverse uses in tissue engineering as well as to form components for degradable bioelectronics.more » « less
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/c5030050
