Editorial

3 pages, 158 KiB

Open AccessEditorial

Biominerals: Formation, Function, Properties

by Helmut Cölfen, Erika Griesshaber and Wolfgang W. Schmahl

Crystals 2021, 11(3), 299; https://0-doi-org.brum.beds.ac.uk/10.3390/cryst11030299 - 17 Mar 2021

Cited by 3 | Viewed by 1562

Triggered by geochemical cycles, large-scale terrestrial processes and evolution, a tremendous biodiversity evolved over the geological record and produced proto- and metazoa with biomineralized hard tissue, characterized by unique structural designs and exquisite performance [...] Full article

(This article belongs to the Special Issue Biominerals: Formation, Function, Properties)

Research

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24 pages, 5443 KiB

Open AccessEditor’s ChoiceArticle

Anatomical Variation of Human Bone Bioapatite Crystallography

by Brittany Foley, Martina Greiner, George McGlynn and Wolfgang W. Schmahl

Crystals 2020, 10(10), 859; https://0-doi-org.brum.beds.ac.uk/10.3390/cryst10100859 - 24 Sep 2020

Cited by 9 | Viewed by 3667

Abstract

This systematic investigation of bioapatite, the mineral component of human bone, aims to characterize its crystallographic state, including lattice parameters and average crystallite size, and correlate these values with respect to anatomical position (bone function), physicality, and bone chemical composition. In sample sets [...] Read more.

This systematic investigation of bioapatite, the mineral component of human bone, aims to characterize its crystallographic state, including lattice parameters and average crystallite size, and correlate these values with respect to anatomical position (bone function), physicality, and bone chemical composition. In sample sets of buried bone from three different human adult skeletons, anatomical variation of crystallographic parameters and correlation to chemical composition were indeed observed. In general, the observed bioapatite a unit-cell edge-length among all analyzed human bones in this study was larger by 0.1–0.2% compared to that of stoichiometric hydroxylapatite (HAp), and substantially larger than that of fluorapatite (FAp). Across all analyzed samples, the a (=b) lattice parameter (unit cell edge-length) varies more than does the c lattice parameter. Average crystallite size (average coherent diffracting domain size) in the c-direction was equal to approximately 25 nm, ranging among the analyzed 18 bone samples from about 20–32 nm, and varying more than crystallite size in the a,b-direction (~8–10 nm). Neither lattice parameters nor average bioapatite crystallite sizes appeared to be correlated with bone mechanical function. The relative chemical composition of the bone material, however, was shown to correlate with the a (=b) lattice parameter. To our knowledge, this research provides, for the first time, the systematic study of the crystallographic parameters of human bone bioapatite in the context of anatomical position, physical constitution, and bone chemical composition using X-ray powder diffraction (XRPD) and Fourier transform infrared spectroscopy (FTIR). Full article

(This article belongs to the Special Issue Biominerals: Formation, Function, Properties)

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32 pages, 4946 KiB

Open AccessArticle

A Nature’s Curiosity: The Argonaut “Shell” and Its Organic Content

by Morgane Oudot, Ira Ben Shir, Asher Schmidt, Laurent Plasseraud, Cédric Broussard, Pascal Neige and Frédéric Marin

Crystals 2020, 10(9), 839; https://0-doi-org.brum.beds.ac.uk/10.3390/cryst10090839 - 19 Sep 2020

Cited by 9 | Viewed by 3640

Abstract

Molluscs are known for their ability to produce a calcified shell resulting from a genetically controlled and matrix-mediated process, performed extracellularly. The occluded organic matrix consists of a complex mixture of proteins, glycoproteins and polysaccharides that are in most cases secreted by the [...] Read more.

Molluscs are known for their ability to produce a calcified shell resulting from a genetically controlled and matrix-mediated process, performed extracellularly. The occluded organic matrix consists of a complex mixture of proteins, glycoproteins and polysaccharides that are in most cases secreted by the mantle epithelium. To our knowledge, the model studied here—the argonaut, also called paper nautilus—represents the single mollusc example where this general scheme is not valid: the shell of this cephalopod is indeed formed by its first dorsal arms pair and it functions as an eggcase, secreted by females only; furthermore, this coiled structure is fully calcitic and the organization of its layered microstructures is unique. Thus, the argonautid shell appears as an apomorphy of this restricted family, not homologous to other cephalopod shells. In the present study, we investigated the physical and biochemical properties of the shell of Argonauta hians, the winged argonaut. We show that the shell matrix contains unusual proportions of soluble and insoluble components, and that it is mostly proteinaceous, with a low proportion of sugars that appear to be mostly sulfated glycosaminoglycans. Proteomics performed on different shell fractions generated several peptide sequences and identified a number of protein hits, not shared with other molluscan shell matrices. This may suggest the recruitment of unique molecular tools for mineralizing the argonaut’s shell, a finding that has some implications on the evolution of cephalopod shell matrices. Full article

(This article belongs to the Special Issue Biominerals: Formation, Function, Properties)

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10 pages, 2895 KiB

Open AccessArticle

Relation between Fish Habitat and the Periodicity of Incremental Lines in the Fossil Otoliths

by Hiroyuki Mishima, Yasuo Kondo, Fumio Ohe, Yasuo Miake and Tohru Hayakawa

Crystals 2020, 10(9), 820; https://0-doi-org.brum.beds.ac.uk/10.3390/cryst10090820 - 16 Sep 2020

Cited by 2 | Viewed by 1836

Abstract

There are few research reports on the relationship between fish habitats and the periodicity of the fishes’ incremental lines of otolith fossils. The present study examines this relationship through histological and analytical studies on otolith fossils from Nobori Formation, Pliocene, Japan. The specimens [...] Read more.

There are few research reports on the relationship between fish habitats and the periodicity of the fishes’ incremental lines of otolith fossils. The present study examines this relationship through histological and analytical studies on otolith fossils from Nobori Formation, Pliocene, Japan. The specimens were observed and analyzed using light microscopy, polarizing microscopy, Miniscopy, Scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS) analysis, electron probe X-ray microanalyzer (EPMA), Raman spectroscopy, and XRD. The otolith crystals were aragonite according to XRD and Raman analysis. The incremental lines contained C, O, and Ca, with Si as a trace element. In the layer between the incremental lines, Si was not detected. The circadian incremental lines were unclear and irregularly observed in both Lobianchia gemellarii and Diaphus gigas. Their behavioral pattern included a diurnal vertical movement. By comparison, for Cetonurus noboriensis, Ventrifossa sp., Sebastes scythropus, and Congriscus megastomus, the circadian incremental lines were evident. The habitat of the fishes that live exclusively on the continental slope is kept constant, and the circadian incremental lines are formed regularly. However, for fishes that spend the day in the deep sea and ascend to the shallow sea at night, the ecosystem, such as seawater temperature and pressure, fluctuates, and the circadian incremental lines become unclear and irregular. The period of the circadian incremental lines of otolith may vary due to differences in the ecosystems. Full article

(This article belongs to the Special Issue Biominerals: Formation, Function, Properties)

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18 pages, 5152 KiB

Open AccessArticle

Molecular Spectroscopic Imaging Offers a Systematic Assessment of Pathological Aortic Valve and Prosthesis Tissue in Biomineralization

by Claudia Dittfeld, Alice Mieting, Cindy Welzel, Anett Jannasch, Klaus Matschke, Sems-Malte Tugtekin and Gerald Steiner

Crystals 2020, 10(9), 763; https://0-doi-org.brum.beds.ac.uk/10.3390/cryst10090763 - 28 Aug 2020

Cited by 4 | Viewed by 2642

Abstract

Pathological ECM remodelling and biomineralization in human aortic valve and bioprosthesis tissue were investigated by Fourier transformed infrared (FT-IR) spectroscopic imaging and multivariate data analysis. Results of histological von Kossa staining to monitor hydroxyapatite biomineralization correlated to the definition of mineralized tissue using [...] Read more.

Pathological ECM remodelling and biomineralization in human aortic valve and bioprosthesis tissue were investigated by Fourier transformed infrared (FT-IR) spectroscopic imaging and multivariate data analysis. Results of histological von Kossa staining to monitor hydroxyapatite biomineralization correlated to the definition of mineralized tissue using FT-IR spectroscopic imaging. Spectra exhibit signals of carbonate and phosphate groups of hydroxyapatite. Proteins could be identified by the amide I and amide II bands. Proteins were detected in the calcified human aortic valve tissue, but no absorption signals of proteins were observed in the mineralized bioprosthesis sample region. A shift of the amide I band from 1654 cm⁻¹ to 1636 cm⁻¹ was assumed to result from β-sheet structures. This band shift was observed in regions where the mineralization process had been identified but also in non-mineralized bioprosthesis tissue independent of prior implantation. The increased occurrence of β-sheet conformation is hypothesized to be a promoter of the biomineralization process. FT-IR spectroscopic imaging offers a wealth of chemical information. For example, slight variations in band position and intensity allow investigation of heterogeneity across aortic valve tissue sections. The exact evaluation of these properties and correlation with conventional histological staining techniques give insights into aortic valve tissue remodelling and calcific pathogenesis. Full article

(This article belongs to the Special Issue Biominerals: Formation, Function, Properties)

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16 pages, 4074 KiB

Open AccessArticle

Carbonate and Oxalate Crystallization by Interaction of Calcite Marble with Bacillus subtilis and Bacillus subtilis–Aspergillus niger Association

by Katerina V. Sazanova (nee Barinova), Olga V. Frank-Kamenetskaya, Dmitry Yu. Vlasov, Marina S. Zelenskaya, Alexey D. Vlasov, Aleksei V. Rusakov and Maya A. Petrova

Crystals 2020, 10(9), 756; https://0-doi-org.brum.beds.ac.uk/10.3390/cryst10090756 - 27 Aug 2020

Cited by 19 | Viewed by 3490

Abstract

Rock surfaces in natural systems are inhabited by multispecies communities of microorganisms. The biochemical activity of microorganisms and the patterns of microbial crystallization in these communities are mostly unexplored. Patterns of calcium carbonate and calcium oxalate crystallization induced by bacteria Bacillus subtilis and [...] Read more.

Rock surfaces in natural systems are inhabited by multispecies communities of microorganisms. The biochemical activity of microorganisms and the patterns of microbial crystallization in these communities are mostly unexplored. Patterns of calcium carbonate and calcium oxalate crystallization induced by bacteria Bacillus subtilis and by B. subtilis together with Aspergillus niger on marble surface in vitro in liquid medium and in humidity chamber—were studied. Phase identification was supported by XRD, SEM, EDXS; metabolite composition was determined by GC–MS. It was found that the activity of B. subtilis–A. niger associations significantly differ from the activity of B. subtilis monocultures in the same trophic conditions. The phase composition and the morphology of the forming crystals are determined by the composition of the metabolites excreted by the microorganisms—particularly by the ratio of the concentrations of extracellular polymeric substances (EPS) and oxalic acid in the medium. The acidification activity of micromycetes may suppress the formation of bacterial EPS and prevent the formation of calcite. The present results can be used in the development of biotechnologies using microbial communities. Full article

(This article belongs to the Special Issue Biominerals: Formation, Function, Properties)

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12 pages, 1361 KiB

Open AccessArticle

About the Role of Fluorine-Bearing Apatite in the Formation of Oxalate Kidney Stones

by Anatolii V. Korneev, Olga V. Frank-Kamenetskaya and Alina R. Izatulina

Crystals 2020, 10(6), 486; https://0-doi-org.brum.beds.ac.uk/10.3390/cryst10060486 - 06 Jun 2020

Cited by 3 | Viewed by 2768

Abstract

Using electron microprobe analysis, 17 kidney stones containing apatite were studied. According to the results of the research, it was found that the apatite of all the oxalate kidney stones contained fluorine, while in the apatite of the phosphate kidney stones, fluorine was [...] Read more.

Using electron microprobe analysis, 17 kidney stones containing apatite were studied. According to the results of the research, it was found that the apatite of all the oxalate kidney stones contained fluorine, while in the apatite of the phosphate kidney stones, fluorine was present in trace amounts or absent. Direct correlation between the amount of oxalate mineral phases and the fluorine content was observed. Ionic substitutions in the apatite of kidney stones have a multidirectional effect on the unit cell parameters. The fluorine content increases with the increase of a unit cell parameter, which is probably associated with a simultaneous increase in the amount of H₂O in the structure of apatite. The results of thermodynamic modeling show that fluorapatite is stable at lower pH values than hydroxylapatite, and therefore can be a precursor of calcium oxalates crystallization. Full article

(This article belongs to the Special Issue Biominerals: Formation, Function, Properties)

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Review

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20 pages, 1933 KiB

Open AccessReview

Synthesis of Metal Nanoparticles by Microorganisms

by Yugo Kato and Michio Suzuki

Crystals 2020, 10(7), 589; https://0-doi-org.brum.beds.ac.uk/10.3390/cryst10070589 - 08 Jul 2020

Cited by 27 | Viewed by 5102

Abstract

Metal nanoparticles (NPs), with sizes ranging from 1–100 nm, are of great scientific interest because their functions and features differ greatly from those of bulk metal. Chemical or physical methods are used to synthesize commercial quantities of NPs, and green, energy-efficient approaches generating [...] Read more.

Metal nanoparticles (NPs), with sizes ranging from 1–100 nm, are of great scientific interest because their functions and features differ greatly from those of bulk metal. Chemical or physical methods are used to synthesize commercial quantities of NPs, and green, energy-efficient approaches generating byproducts of low toxicity are desirable to minimize the environmental impact of the industrial methods. Some microorganisms synthesize metal NPs for detoxification and metabolic reasons at room temperature and pressure in aqueous solution. Metal NPs have been prepared via green methods by incubating microorganisms or cell-free extracts of microorganisms with dissolved metal ions for hours or days. Metal NPs are analyzed using various techniques, such as ultraviolet-visible spectroscopy, electron microscopy, X-ray diffraction, electron diffraction, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. Numerous publications have focused on microorganisms that synthesize various metal NPs. For example, Ag, Au, CdS, CdSe, Cu, CuO, Gd₂O₃, Fe₃O₄, PbS, Pd, Sb₂O₃, TiO₂, and ZrO₂ NPs have been reported. Herein, we review the synthesis of metal NPs by microorganisms. Although the molecular mechanisms of their synthesis have been investigated to some extent, experimental evidence for the mechanisms is limited. Understanding the mechanisms is crucial for industrial-scale development of microorganism-synthesized metal NPs. Full article

(This article belongs to the Special Issue Biominerals: Formation, Function, Properties)

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Other

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10 pages, 1606 KiB

Open AccessBrief Report

Bacterial Colonization on the Surface of Copper Sulfide Minerals Probed by Fourier Transform Infrared Micro-Spectroscopy

by Constantinos Varotsis, Marios Papageorgiou, Charalampos Tselios, Konstantinos A. Yiannakkos, Anastasia Adamou and Antonis Nicolaides

Crystals 2020, 10(11), 1002; https://0-doi-org.brum.beds.ac.uk/10.3390/cryst10111002 - 05 Nov 2020

Cited by 5 | Viewed by 2701

Abstract

Biofilm formation is a molecular assembly process occurring at interfaces, such as in bioleaching processes. The real time monitoring of the marker bands of amide I/amide II by FTIR microspectroscopy during Acidithiobacillus ferrooxidans colonization on chalcopyrite surfaces revealed the central role of lipids, [...] Read more.

Biofilm formation is a molecular assembly process occurring at interfaces, such as in bioleaching processes. The real time monitoring of the marker bands of amide I/amide II by FTIR microspectroscopy during Acidithiobacillus ferrooxidans colonization on chalcopyrite surfaces revealed the central role of lipids, proteins and nucleic acids in bacterial cell attachment to copper sulfide surfaces. The Raman and FTIR spectra of the interactions of Acidithiobacillus ferrooxidans with bornite are also reported. Full article

(This article belongs to the Special Issue Biominerals: Formation, Function, Properties)

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