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1
Arai, Kosuke, Satoshi Murata, Taifeng Wang, Wataru Yoshimura, Mayumi Oda-Tokuhisa, Tadashi Matsunaga, David Kisailus, and Atsushi Arakaki. "Adsorption of Biomineralization Protein Mms6 on Magnetite (Fe3O4) Nanoparticles." International Journal of Molecular Sciences 23, no. 10 (May 16, 2022): 5554. http://dx.doi.org/10.3390/ijms23105554.
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Biomineralization is an elaborate process that controls the deposition of inorganic materials in living organisms with the aid of associated proteins. Magnetotactic bacteria mineralize magnetite (Fe3O4) nanoparticles with finely tuned morphologies in their cells. Mms6, a magnetosome membrane specific (Mms) protein isolated from the surfaces of bacterial magnetite nanoparticles, plays an important role in regulating the magnetite crystal morphology. Although the binding ability of Mms6 to magnetite nanoparticles has been speculated, the interactions between Mms6 and magnetite crystals have not been elucidated thus far. Here, we show a direct adsorption ability of Mms6 on magnetite nanoparticles in vitro. An adsorption isotherm indicates that Mms6 has a high adsorption affinity (Kd = 9.52 µM) to magnetite nanoparticles. In addition, Mms6 also demonstrated adsorption on other inorganic nanoparticles such as titanium oxide, zinc oxide, and hydroxyapatite. Therefore, Mms6 can potentially be utilized for the bioconjugation of functional proteins to inorganic material surfaces to modulate inorganic nanoparticles for biomedical and medicinal applications.
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Chernov, A. A., J. J. De Yoreo, L. N. Rashkovich, and P. G. Vekilov. "Step and Kink Dynamics in Inorganic and Protein Crystallization." MRS Bulletin 29, no. 12 (December 2004): 927–34. http://dx.doi.org/10.1557/mrs2004.262.
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AbstractRevived interest in crystal growth from solutions is driven by a variety of demands, including the need to develop an understanding of biomineralization processes in bones, teeth, and shells;and efforts to characterize large optically nonlinear crystals, perfect crystals of proteins, nucleic acids, and complexes such as viruses. Producing and purifying drugs, food, paint, fertilizers, and other polycrystalline materials in industry are other expanding areas that rely on crystal growth from solution. These general practical incentives have activated in-depth studies that revealed new phenomena and raised new fundamental questions: Are thermal fluctuations of steps on a crystal face always fast enough to assure the step propagation at the rate controlled just by molecular incorporation at kinks? Is the Gibbs–Thomson capillarity shift of thermodynamic equilibrium always applicable to evaluate the crystallization driving force of polygonized steps? Is it possible to eliminate the step bunching on a growing crystal face that compromises crystal homogeneity, or at least to mitigate it? In this overview, we will discuss experimental findings and provide state-of-the-art answers to these questions.
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Becker, Wilhelm, Julia Marxen, Matthias Epple, and Oliver Reelsen. "Influence of microgravity on crystal formation in biomineralization." Journal of Applied Physiology 89, no. 4 (October 1, 2000): 1601–7. http://dx.doi.org/10.1152/jappl.2000.89.4.1601.
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Biomineralized tissues are widespread in animals. They are essential elements in skeletons and in statocysts. The function of both can only be understood with respect to gravitational force, which has always been present. Therefore, it is not astonishing to identify microgravity as a factor influencing biomineralization, normally resulting in the reduction of biomineralized materials. All known biominerals are composite materials, in which the organic matrix and the inorganic materials, organized in crystals, interact. If, during remodeling and turnover processes under microgravity, a defective organization of these crystals occurs, a reduction in biomineralized materials could be the result. To understand the influence of microgravity on the formation of biocrystals, we studied the shell-building process of the snail Biomphalaria glabrataas a model system. We show that, under microgravity (space shuttle flights STS-89 and STS-90), shell material is built in a regular way in both adult snails and snail embryos during the beginning of shell development. Microgravity does not influence crystal formation. Because gravity has constantly influenced evolution, the organization of biominerals with densities near 3 must have gained independence from gravitational forces, possibly early in evolution.
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Rimer, Jeffrey D. "Inorganic ions regulate amorphous-to-crystal shape preservation in biomineralization." Proceedings of the National Academy of Sciences 117, no. 7 (February 5, 2020): 3360–62. http://dx.doi.org/10.1073/pnas.1922923117.
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Heywood, Brigid R. "Crystal tectonics: Novel routes to the ordered aggregation and self assembly of inorganic solids." Proceedings, annual meeting, Electron Microscopy Society of America 52 (1994): 424–25. http://dx.doi.org/10.1017/s0424820100169857.
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Oriented materials attract considerable attention since thay have the potential to exhibit collective properties which exceed those of the isotropic species by several orders of magnitude. Much success has already been achieved with organic materials, e.g. liquid crystals, conducting polymers, but reliable protocols for the construction of organised crystal micro-architectures from inorganic solids have yet to be established. Given the potential advantages of translating molecular properties (optical, piezoelectric, catalytic) to the macroscopic scale strategies for the construction of hierarchical crystal assemblies, crystal tectonics, merit particular consideration.This crystal tectonics route to the synthesis of anisotropic inorganic materials remains entirely untested, but draws much of its inspiration from the study of deterministic self-organisation in biological systems. Such self-organisation relies on a series of highly specific “host-guest”, ligandreceptor type interactions (more typically cited examples of such include, enzyme-substrate-cofactor binding, antibody-antigen complexation, and triplet/base matching during polypeptide synthesis). The biogenic formation of hierarchical inorganic arrays, biomineralization, is remarkable not only for its control of crystallisation to yield solids of uniform size and unusual habit, but equally for the construction of elaborate functional micro-architectures from these biosolids.
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Ma, Wen Jie, and Xue Wu Wang. "Effect of Variety and Morphology of Substrate on the Crystal Form of Calcium Carbonate Crystal." Applied Mechanics and Materials 127 (October 2011): 168–71. http://dx.doi.org/10.4028/www.scientific.net/amm.127.168.
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Based on the basic principles of biomineralization, calcium carbonate (CaCO3) which has specific shapes can be synthesized by the biomimetic synthesis, using three-dimensional (3D) photonic crystals self-assembled by polystyrene spheres as the matrix (Ps film).The effects of variety and morphology of substrate on the crystal form and morphologies of CaCO3 were investigated. It was found that variety of substrates has great influence on the phase of calcium carbonate. On the Ps film, large amount of calcite and aragonite can be observed. SEM of the gold surface shows aragonite needles and vaterite. On the glass surface, large amount of vaterite can be observed. Ps films self-assembled by different diameters of polystyrene spheres have different morphologies and surface roughness, which have deep effects on the crystal form of calcium carbonate.This simple route might open opportunity to synthesis and the study of other novel inorganic materials.
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Han, Yu, Bin Sun, Huaxiao Yan, Maurice E. Tucker, Yanhong Zhao, Jingxuan Zhou, Yifan Zhao, and Hui Zhao. "Biomineralization of Carbonate Minerals Induced by The Moderate Halophile Staphylococcus Warneri YXY2." Crystals 10, no. 2 (January 22, 2020): 58. http://dx.doi.org/10.3390/cryst10020058.
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Although biomineralization of minerals induced by microorganisms has been widely reported, the mechanisms of biomineralization and the characteristics of the biominerals precipitated needs to be studied further. In this study, Staphylococcus warneri YXY2, a moderate halophile, was used to induce the precipitation of carbonate minerals at various Mg/Ca molar ratios. To investigate the biomineralization mechanism, the growth curve, pH changes, ammonia test, the concentration of bicarbonate and carbonate ions, and the activity of carbonic anhydrase (CA) and alkaline phosphatase (ALP) were determined. X-ray powder diffraction (XRD), scanning electron microscopy - energy disperse spectroscopy (SEM-EDS), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and stable carbon isotope analyses were used to characterize the minerals. The obtained biotic minerals were calcite, vaterite, Mg-rich calcite, and aragonite crystals. The crystallinity of aragonite decreased with increasing Mg/Ca ratios. The preferred orientation, diverse morphologies, organic substances, and more negative stable carbon isotope values proved the biogenesis of these carbonate minerals. The presence of Mg in the biotic aragonite crystals was likely related to the acidic amino acids which also facilitated the nucleation of minerals on/in the extracellular polymeric substances (EPS). Mg2+ and Ca2+ ions were able to enter into the YXY2 bacteria to induce intracellular biomineralization. Dynamics simulation using Material Studio software proved that different adsorption energies of Glutamic acid (Glu) adsorbed onto different crystal planes of aragonite led to the preferred orientation of aragonite. This study helps to deepen our understanding of biomineralization mechanisms and may be helpful to distinguish biotic minerals from abiotic minerals.
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Wolff, Annalena, Walid Hetaba, Marco Wißbrock, Stefan Löffler, Nadine Mill, Katrin Eckstädt, Axel Dreyer, et al. "Oriented attachment explains cobalt ferrite nanoparticle growth in bioinspired syntheses." Beilstein Journal of Nanotechnology 5 (February 28, 2014): 210–18. http://dx.doi.org/10.3762/bjnano.5.23.
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Oriented attachment has created a great debate about the description of crystal growth throughout the last decade. This aggregation-based model has successfully described biomineralization processes as well as forms of inorganic crystal growth, which could not be explained by classical crystal growth theory. Understanding the nanoparticle growth is essential since physical properties, such as the magnetic behavior, are highly dependent on the microstructure, morphology and composition of the inorganic crystals. In this work, the underlying nanoparticle growth of cobalt ferrite nanoparticles in a bioinspired synthesis was studied. Bioinspired syntheses have sparked great interest in recent years due to their ability to influence and alter inorganic crystal growth and therefore tailor properties of nanoparticles. In this synthesis, a short synthetic version of the protein MMS6, involved in nanoparticle formation within magnetotactic bacteria, was used to alter the growth of cobalt ferrite. We demonstrate that the bioinspired nanoparticle growth can be described by the oriented attachment model. The intermediate stages proposed in the theoretical model, including primary-building-block-like substructures as well as mesocrystal-like structures, were observed in HRTEM measurements. These structures display regions of substantial orientation and possess the same shape and size as the resulting discs. An increase in orientation with time was observed in electron diffraction measurements. The change of particle diameter with time agrees with the recently proposed kinetic model for oriented attachment.
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Jiang, Wenge, Xiaobin Chu, Ben Wang, Haihua Pan, Xurong Xu, and Ruikang Tang. "Biomimetically Triggered Inorganic Crystal Transformation by Biomolecules: A New Understanding of Biomineralization." Journal of Physical Chemistry B 113, no. 31 (August 6, 2009): 10838–44. http://dx.doi.org/10.1021/jp904633f.
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Heywood, Brigid R. "Biomineralization:New directions in crystal science." Proceedings, annual meeting, Electron Microscopy Society of America 50, no. 2 (August 1992): 1026–27. http://dx.doi.org/10.1017/s0424820100129760.
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The development of effective protocols for the reproducible control of crystal structure, size and morphology is attracting considerable interest given the requirement for particles of modal size and shape in many areas of materials fabrication and the importance of crystallochemical selectivity in determining the exploitable properties (eg. optical, magnetic, electrokinetic) of inorganic solids. In biological systems their are many examples of advanced “crystal engineering” in which inorganic solids are deposited in a highly controlled manner to produce mineral phases that are unique with respect to their structure, habit, and uniformity of size (Figures 1 & 2). The crystallochemical specificity of such biogenic solids (eg. calcium phosphates, calcium carbonates, iron oxides, barium and strontium sulphates) is tailored to a wide variety of both structural (eg. bones and teeth) and non-structural roles. Examples of the latter include pH homeostasis, the transduction of magnetic signals and inertial detection.A review of biomineralization will show that while a complex array of strategies have evolved for regulating the formation of crystalline phases, one feature is common to the continuum of mechanisms; interactions between organized biopolymeric assemblies and the nascent inorganic solids play a fundamental role in controlling the deposition of the biomineral.
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Wang, Yihua, Zhaoming Liu, Haihua Pan, and Ruikang Tang. "Biomineralization inspired crystal growth for biomimetic materials preparation." Journal of Crystal Growth 603 (February 2023): 127029. http://dx.doi.org/10.1016/j.jcrysgro.2022.127029.
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Arias, José L., Karla Silva, Andrónico Neira-Carrillo, Liliana Ortiz, José Ignacio Arias, Nicole Butto, and María Soledad Fernández. "Polycarboxylated Eggshell Membrane Scaffold as Template for Calcium Carbonate Mineralization." Crystals 10, no. 9 (September 9, 2020): 797. http://dx.doi.org/10.3390/cryst10090797.
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Biomineralization is a process in which specialized cells secrete and deliver inorganic ions into confined spaces limited by organic matrices or scaffolds. Chicken eggshell is the fastest biomineralization system on earth, and therefore, it is a good experimental model for the study of biomineralization. Eggshell mineralization starts on specialized dispersed sites of the soft fibrillar eggshell membranes referred to as negatively charged keratan sulfate mammillae. However, the rest of the fibrillar eggshell membranes never mineralizes, although 21% of their amino acids are acidic. We hypothesized that, relative to the mammillae, the negatively charged amino acids of the fibrillar eggshell membranes are not competitive enough to promote calcite nucleation and growth. To test this hypothesis, we experimentally increased the number of negatively charged carboxylate groups on the eggshell membrane fibers and compared it with in vitro calcite deposition of isolated intact eggshell membranes. We conclude that the addition of poly-carboxylated groups onto eggshell membranes increases the number of surface nucleation sites but not the crystal size.
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Mann, S., B. R. Heywood, S. Rajam, J. B. A. Walker, and J. Didymus. "Crystal engineering of inorganic materials at organized organic surfaces: In vitro modelling of biomineralization." Journal of Inorganic Biochemistry 36, no. 3-4 (August 1989): 201. http://dx.doi.org/10.1016/0162-0134(89)84160-1.
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Wang, Zhengjiang, Yang Yang, Qi Jiang, Dalong Hu, Jiawei Li, Yan Su, Jing Wang, et al. "The Effect of Crystal Seeds on Calcium Carbonate Ion Pair Formation in Aqueous Solution: A ReaxFF Molecular Dynamics Study." Crystals 12, no. 11 (October 29, 2022): 1547. http://dx.doi.org/10.3390/cryst12111547.
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The effect of crystal seeds on calcium carbonate (CaCO3) cluster formation in aqueous solution is of interest in the fields of geochemistry, inorganic chemistry, atmospheric science, biomedicine, biomineralization, and tissue engineering. Due to an instantaneous and microscopic process, it is still experimentally challenging to directly capture the CaCO3 pre-nucleation. This study employed reactive force field (ReaxFF) molecular dynamics simulations to explore the variation among CaCO3 ion pairs in an aqueous solution with or without crystal seeds. The results show that the addition of crystal seeds can improve CaCO3 ion pair formation. We found that the surface of the calcite phase, compared with the metastable vaterite phase, prefers to attach the ion pairs from solution via proton transfer. This work sheds light on the effect of different crystal seeds on CaCO3 ion pair formation as a precursor of pre-nucleation clusters.
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Evans, John Spencer. "Glycosylation: A “Last Word” in the Protein-Mediated Biomineralization Process." Crystals 10, no. 9 (September 16, 2020): 818. http://dx.doi.org/10.3390/cryst10090818.
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Post-translational modifications are one way that biomineral-associated cells control the function and fate of proteins. Of the ten different types of post-translational modifications, one of the most interesting and complex is glycosylation, or the covalent attachment of carbohydrates to amino acid sidechains Asn, Ser, and Thr of proteins. In this review the author surveys some of the known biomineral-associated glycoproteins and summarizes recent in vitro recombinant protein experiments which test the impact of glycosylation on biomineralization protein functions, such as nucleation, crystal growth, and matrix assembly. These in vitro studies show that glycosylation does not alter the inherent function of the polypeptide chain; rather, it either accentuates or attenuates functionality. In essence, glycosylation gives the cell the “last word” as to what degree a biomineralization protein will participate in the biomineralization process.
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Yao, Nan, Alexander K. Epstein, Wendy W. Liu, Franz Sauer, and Ning Yang. "Organic–inorganic interfaces and spiral growth in nacre." Journal of The Royal Society Interface 6, no. 33 (August 26, 2008): 367–76. http://dx.doi.org/10.1098/rsif.2008.0316.
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Nacre, the crown jewel of natural materials, has been extensively studied owing to its remarkable physical properties for over 160 years. Yet, the precise structural features governing its extraordinary strength and its growth mechanism remain elusive. In this paper, we present a series of observations pertaining to the red abalone ( Haliotis rufescens ) shell's organic–inorganic interface, organic interlayer morphology and properties, large-area crystal domain orientations and nacre growth. In particular, we describe unique lateral nano-growths and paired screw dislocations in the aragonite layers, and demonstrate that the organic material sandwiched between aragonite platelets consists of multiple organic layers of varying nano-mechanical resilience. Based on these novel observations and analysis, we propose a spiral growth model that accounts for both [001] vertical propagation via helices that surround numerous screw dislocation cores and simultaneous 〈010〉 lateral growth of aragonite sheet structure. These new findings may aid in creating novel organic–inorganic micro/nano composites through synthetic or biomineralization pathways.
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Ogawa, Tomohisa, Rie Sato, Takako Naganuma, Kayeu Liu, Saho Sato, Shizuka Sakaue, Makoto Osada, Kyosuke Yoshimi, and Koji Muramoto. "Diversified Biomineralization Roles of Pteria penguin Pearl Shell Lectins as Matrix Proteins." International Journal of Molecular Sciences 22, no. 3 (January 22, 2021): 1081. http://dx.doi.org/10.3390/ijms22031081.
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Previously, we isolated jacalin-related lectins termed PPL2, PPL3 (PPL3A, 3B and 3C) and PPL4 from the mantle secretory fluid of Pteria penguin (Mabe) pearl shell. They showed the sequence homology with the plant lectin family, jacalin-related β-prism fold lectins (JRLs). While PPL3s and PPL4 shared only 35%–50% homology to PPL2A, respectively, they exhibited unique carbohydrate binding properties based on the multiple glycan-binding profiling data sets from frontal affinity chromatography analysis. In this paper, we investigated biomineralization properties of these lectins and compared their biomineral functions. It was found that these lectins showed different effects on CaCO3 crystalization, respectively, although PPL3 and PPL2A showed similar carbohydrate binding specificities. PPL3 suppressed the crystal growth of CaCO3 calcite, while PPL2A increased the number of contact polycrystalline calcite composed of more than one crystal with various orientations. Furthermore, PPL4 alone showed no effect on CaCO3 crystalization; however, PPL4 regulated the size of crystals collaborated with N-acetyl-D-glucosamine and chitin oligomer, which are specific in recognizing carbohydrates for PPL4. These observations highlight the unique functions and molecular evolution of this lectin family involved in the mollusk shell formation.
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Zhao, Peng, Guang Yan Li, and Yun Sheng Zhang. "Understanding and Assessment of Ancient Chinese Pig Blood–Lime Mortar." Advanced Materials Research 997 (August 2014): 446–49. http://dx.doi.org/10.4028/www.scientific.net/amr.997.446.
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Pig blood-lime mortar is one of the most representative formulations among the ancient Chinese organic-inorganic mortars. It was used primarily as binding material, lacquer and the ground layer of decorative oil paintings due to its good mechanical and waterproof preformance. Mortar in this work was fabricated according to the formulas of the ancient literature, and the mechanism of interaction between the key components of ancient mortar binding materials was analyzed via X-ray diffractometry. Results show that pig blood accelerates the formation of microstructure at early stage. A mechanism was suggested that biomineralization occurs during the carbonation of calcium hydroxide, where the pig blood functions as a template and controls the growth of calcium carbonate crystal.
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McLean, Robert J. C., and Erin T. Brown. "Potential Influences of Bacterial Cell Surfaces and Nano-Sized Cell Fragments on Struvite Biomineralization." Crystals 10, no. 8 (August 15, 2020): 706. http://dx.doi.org/10.3390/cryst10080706.
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Struvite (MgNH4PO4·6H2O) calculi are formed as a result of urinary tract infections by Proteus mirabilis and other urease-producing bacteria. During struvite formation, the bacteria grow as biofilms, and thus crystals are formed in close association with bacterial cell surfaces and biofilm matrix components. Small nano-sized objects (originally termed “nanobacteria”) have been described in association with urinary calculi including struvite calculi. A much more likely explanation of these nano-structures is outer membrane vesicles (OMVs) that can be produced by P. mirabilis and other Gram-negative bacteria. In this brief review, we describe the association of bacterial cell surfaces and biofilm matrix components with metal binding and the generation of chemical microenvironments during struvite formation; we propose potential mechanisms whereby OMVs can influence struvite crystal growth and biomineralization.
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Sorauf, James E. "Biocrystallization models and skeletal structure of Phanerozoic corals." Paleontological Society Papers 1 (October 1996): 159–85. http://dx.doi.org/10.1017/s1089332600000097.
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Modern understanding of skeletal microstructure in fossil corals builds on knowledge of structure and biomineralization in modern corals and diagenesis of carbonate skeletons. It is agreed that the skeleton of living stony corals, the Scleractinia, is made of fibrous aragonite, with growth of biocrystals generally according to rules of crystal growth as observed in inorganic aragonite, but here controlled by organic matrix. Fossil scleractinians all apparently fit the same model of biomineralization seen in living corals, although some early taxa (Triassic) lack septal trabeculae, rod-like framework structures typical of all living and most fossil septate corals.Paleozoic corals, both septate Rugosa and non-septate Tabulata, had a skeleton of calcite, most likely low-magnesium calcite, thus had diagenetic histories differing considerably from the aragonitic Scleractinia. Agreement is lacking as to whether a single structural motif can be defined for the calcitic corals, that is, whether the Rugosa and Tabulata originally had a calcitic skeleton built of fibrous biocrystals, analogous to the scleractinians, or whether some others originally had a non-fibrous, lamellar skeletal microstructure. The disagreement hinges on whether both of these basic configurations are biogenic, or whether the latter is sometimes or always diagenetic in origin. The presence of matrix control over biomineralization in Rugosa and Tabulata is yet to be proven, but will play an important role in models for biocrystallization in these older cnidarians. Details of diagenetic history and modification of structures in these calcitic corals likewise warrant investigation to improve our ability to interpret the Paleozoic corals.
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Gao, Ruohe, Rize Wang, Xin Feng, and Gangsheng Zhang. "Growth of Nacre Biocrystals by Self-Assembly of Aragonite Nanoparticles with Novel Subhedral Morphology." Crystals 10, no. 1 (December 18, 2019): 3. http://dx.doi.org/10.3390/cryst10010003.
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Nacre has long served as a research model in the field of biomineralization and biomimetic materials. It is widely accepted that its basic components, aragonite biocrystals, namely, tablets, are formed by the nanoparticle-attachment pathway. However, the details of the nanoparticle morphology and arrangement in the tablets are still a matter of debate. Here, using field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM), we observed the nanostructure of the growing tablets at different growth stages and found that: (1) the first detectable tablet looked like a rod; (2) tablets consisted of subhedral nanoparticles (i.e., partly bounded by crystal facets and partly by irregular non-crystal facets) that were made of aragonite single crystals with a width of 160–180 nm; and (3) these nanoparticles were ordered in orientation but disordered in position, resulting in unique subhedral and jigsaw-like patterns from the top and side views, respectively. In short, we directly observed the growth of nacre biocrystals by the self-assembly of aragonite nanoparticles with a novel subhedral morphology.
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Choudhary, Madhuresh K., Rishabh Jain, and Jeffrey D. Rimer. "In situ imaging of two-dimensional surface growth reveals the prevalence and role of defects in zeolite crystallization." Proceedings of the National Academy of Sciences 117, no. 46 (October 30, 2020): 28632–39. http://dx.doi.org/10.1073/pnas.2011806117.
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Zeolite crystallization predominantly occurs by nonclassical pathways involving the attachment of complex (alumino)silicate precursors to crystal surfaces, yet recurrent images of fully crystalline materials with layered surfaces are evidence of classical growth by molecule attachment. Here we use in situ atomic force microscopy to monitor three distinct mechanisms of two-dimensional (2D) growth of zeolite A where we show that layer nucleation from surface defects is the most common pathway. Direct observation of defects was made possible by the identification of conditions promoting layered growth, which correlates to the use of sodium as an inorganic structure-directing agent, whereas its replacement with an organic results in a nonclassical mode of growth that obscures 2D layers and markedly slows the rate of crystallization. In situ measurements of layered growth reveal that undissolved silica nanoparticles in the synthesis medium can incorporate into advancing steps on crystal surfaces to generate defects (i.e., amorphous silica occlusions) that largely go undetected in literature. Nanoparticle occlusion in natural and synthetic crystals is a topic of wide-ranging interest owing to its relevance in fields spanning from biomineralization to the rational design of functional nanocomposites. In this study, we provide unprecedented insight into zeolite surface growth by molecule addition through time-resolved microscopy that directly captures the occlusion of silica nanoparticles and highlights the prevalent role of defects in zeolite crystallization.
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Green, David W., Tazuko K. Goto, Kye-Seong Kim, and Han-Sung Jung. "Calcifying tissue regeneration via biomimetic materials chemistry." Journal of The Royal Society Interface 11, no. 101 (December 6, 2014): 20140537. http://dx.doi.org/10.1098/rsif.2014.0537.
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Materials chemistry is making a fundamental impact in regenerative sciences providing many platforms for tissue development. However, there is a surprising paucity of replacements that accurately mimic the structure and function of the structural fabric of tissues or promote faithful tissue reconstruction. Methodologies in biomimetic materials chemistry have shown promise in replicating morphologies, architectures and functional building blocks of acellular mineralized tissues dentine, enamel and bone or that can be used to fully regenerate them with integrated cell populations. Biomimetic materials chemistry encompasses the two processes of crystal formation and mineralization of crystals into inorganic formations on organic templates. This review will revisit the successes of biomimetics materials chemistry in regenerative medicine, including coccolithophore simulants able to promote in vivo bone formation. In-depth knowledge of biomineralization throughout evolution informs the biomimetic materials chemist of the most effective techniques for regenerative framework construction exemplified via exploitation of liquid crystals (LCs) and complex self-organizing media. Therefore, a new innovative direction would be to create chemical environments that perform reaction–diffusion exchanges as the basis for building complex biomimetic inorganic structures. This has evolved widely in biology, as have LCs, serving as self-organizing templates in pattern formation of structural biomaterials. For instance, a study is highlighted in which artificially fabricated chiral LCs, made from bacteriophages are transformed into a faithful copy of enamel. While chemical-based strategies are highly promising at creating new biomimetic structures there are limits to the degree of complexity that can be generated. Thus, there may be good reason to implement living or artificial cells in ‘morphosynthesis’ of complex inorganic constructs. In the future, cellular construction is probably key to instruct building of ultimate biomimetic hierarchies with a totality of functions.
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Cheng, Zhenzhen, Qingfeng Wang, Wenlong Ma, Ruibo Sun, Shaohui Wang, and Hongtao Tang. "Effect of Hydroxyapatite Composite Nano-Artificial Bone on Treatment and Rehabilitation of Patients with Ankle Joint Injury." Journal of Nanoscience and Nanotechnology 21, no. 2 (February 1, 2021): 1091–98. http://dx.doi.org/10.1166/jnn.2021.18650.
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The formation of natural bone tissue is the result of the joint regulation of multiple template molecules. Although its complex hierarchical structure has been studied for many years, the mechanism of biomineralization of hard bone tissue has not been fully clarified. In this paper, the nanocomposites obtained by mineralization were characterized and analyzed, and the effect of the template on the crystal formation of hydroxyapatite was studied. The characterization results show that the main phase of the inorganic mineral obtained by template mineralization is the hydroxyapatite phase. The nano-apatite composite particles with an inorganic component content of 90.2% have the highest loading efficiency, reaching 67.9 mg/g. By statistical analysis of the pain scores at 5 days, 10 days, and 15 days after ankle injury, it was found that the average pain score of the treatment group was smaller than that of the control group. Two weeks later, the clinical efficacy judgment standard statistics show that the treatment group has a 22.5% improvement in healing rate, a significant increase in 3.18%, and a total effective rate of 8.71%, which is significantly better than the control group.
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Volkmer, Dirk, Norbert Mayr, and Marc Fricke. "Crystal structure analysis of [Ca(O3SC18H37)2(DMSO)2], a lamellar coordination polymer and its relevance for model studies in biomineralization." Dalton Transactions, no. 41 (2006): 4889. http://dx.doi.org/10.1039/b608760d.
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Tan, Guo Xin, Cheng Yun Ning, and Shu Jiang Zhang. "Induction of Hydroxyapatite Particles Formation on PEGDA-Based Hydrogels by Nanobacteria." Advanced Materials Research 105-106 (April 2010): 569–71. http://dx.doi.org/10.4028/www.scientific.net/amr.105-106.569.
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Nanobacteria is a tiny structure with size varying 80 to 500nm, commonly occurring in clusters and producing a biofilm which contains carbonate or hydroxyl apatite. In this study, the bioactive synthetic hydrogel materials were prepared with polyethylene glycol diacrylate (PEGDA) and 2-hydroxyethyl mathacrylate (HEMA) by UV photo-polymerization. Bone marrow mesenchymal stem cells (BMSCs) were seeded onto hydrogel surface for five days. The BMSCs cell adhesion on hydrogels was confirmed by SEM to evaluate the biocompatibility of the materials. It was found groups of nanoparticles on the hydrogel surface and the particles were analyzed by SEM. The particles were analyzed for its inorganic chemical constituents using energy dispersive X-ray microanalysis (EDS). The predominant components were found to be calcium (24.40%) and phosphorus (13.98%). The most likely source of cell culture contamination by such organisms is bovine serum albumin (BSA) used as supplement in culture media. Nanobacteria in BSA may be the important factor which accelerated hydroxyapatite crystal growth on hydrogels. It is important to study the biomineralization in biological system and has potential application in biomaterials science and biotechnology.
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Katti, Kalpana S., Maoxu Qian, Daniel W. Frech, and Mehmet Sarikaya. "Low-loss Electron Energy-loss Spectroscopy and Dielectric Function of Biological and Geological Polymorphs of CaCO3." Microscopy and Microanalysis 5, no. 5 (September 1999): 358–64. http://dx.doi.org/10.1017/s1431927699000197.
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Previous work on microstructural characterization has shown variations in terms of defects and organization of nanostructures in the two polymorphs of calcium carbonate, calcite, and aragonite in mollusc shells. Large variations in mechanical properties are observed between these sections which have been attributed to variations in composite microstructure as well as intrinsic properties of the inorganic phases. Here we present local low-loss electron energy-loss spectroscopic (EELS) study of calcitic and aragonitic regions of abalone shell that were compared to geological (single-crystal) counterpart polymorphs to reveal intrinsic differences that could be related to organismal effects in biomineralization. In both sets of samples, local dielectric function is computed using Kramer-Kronig analysis. The electronic structures of biogenic and geological calcitic materials are not significantly different. On the other hand, electronic structure of biogenic aragonite is remarkably different from that of geological aragonite. This difference is attributed to the increased contribution from single electron excitations in biogenic aragonite as compared to that of geological aragonite. Implications of these changes are discussed in the context of macromolecular involvement in the making of the microstructures and properties in biogenic phases.
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van Dijk, Inge, Christine Barras, Lennart Jan de Nooijer, Aurélia Mouret, Esmee Geerken, Shai Oron, and Gert-Jan Reichart. "Coupled calcium and inorganic carbon uptake suggested by magnesium and sulfur incorporation in foraminiferal calcite." Biogeosciences 16, no. 10 (May 20, 2019): 2115–30. http://dx.doi.org/10.5194/bg-16-2115-2019.
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Abstract. Shell chemistry of foraminiferal carbonate proves to be useful in reconstructing past ocean conditions. A new addition to the proxy toolbox is the ratio of sulfur (S) to calcium (Ca) in foraminiferal shells, reflecting the ratio of SO42- to CO32- in seawater. When comparing species, the amount of SO42- incorporated, and therefore the S∕Ca of the shell, increases with increasing magnesium (Mg) content. The uptake of SO42- in foraminiferal calcite is likely connected to carbon uptake, while the incorporation of Mg is more likely related to Ca uptake since this element substitutes for Ca in the crystal lattice. The relation between S and Mg incorporation in foraminiferal calcite therefore offers the opportunity to investigate the timing of processes involved in Ca and carbon uptake. To understand how foraminiferal S∕Ca is related to Mg∕Ca, we analyzed the concentration and within-shell distribution of S∕Ca of three benthic species with different shell chemistry: Ammonia tepida, Bulimina marginata and Amphistegina lessonii. Furthermore, we investigated the link between Mg∕Ca and S∕Ca across species and the potential influence of temperature on foraminiferal S∕Ca. We observed that S∕Ca is positively correlated with Mg∕Ca on a microscale within specimens, as well as between and within species. In contrast, when shell Mg∕Ca increases with temperature, foraminiferal S∕Ca values remain similar. We evaluate our findings in the light of previously proposed biomineralization models and abiological processes involved during calcite precipitation. Although all kinds of processes, including crystal lattice distortion and element speciation at the site of calcification, may contribute to changes in either the amount of S or Mg that is ultimately incorporated in foraminiferal calcite, these processes do not explain the covariation between Mg∕Ca and S∕Ca values within specimens and between species. We observe that groups of foraminifera with different calcification pathways, e.g., hyaline versus porcelaneous species, show characteristic values for S∕Ca and Mg∕Ca, which might be linked to a different calcium and carbon uptake mechanism in porcelaneous and hyaline foraminifera. Whereas Mg incorporation might be controlled by Ca dilution at the site of calcification due to Ca pumping, S is linked to carbonate ion concentration via proton pumping. The fact that we observe a covariation of S and Mg within specimens and between species suggests that proton pumping and Ca pumping are intrinsically coupled across multiple scales.
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King, Helen E., Aleksandar Živković, and Nora H. de Leeuw. "Evaluating the Effect of 18O Incorporation on the Vibrational Spectra of Vaterite and Calcite." Crystals 13, no. 1 (December 27, 2022): 48. http://dx.doi.org/10.3390/cryst13010048.
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Calcium carbonates are critical in biomineralization processes and as functional materials. For many applications, isotope enrichment in these materials allows researchers to monitor reaction pathways and retrace environmental signatures. When using vibrational spectroscopy, isotopic composition is currently derived by summing the concentration of each isotopologue, assumed to be directly obtainable from the band intensity, divided by the content of the isotope within the different isotopologues (e.g., C16O3, C16O218O, C16O18O2 and C18O3). However, this approach relies on the assumption that each isotopologue band has an equivalent intensity when present at the same concentration within the crystal structure. Here, using a joint experimental and theoretical approach we test the spectral behavior of the O-isotopologues by examining the effect of a key isotopic tracer, 18O, on the vibrational spectra of the calcium carbonate phases calcite and vaterite. We demonstrate that isotopic substitution changes both band positions and band intensities to different extents, depending on the vibrational spectroscopy method used and the bands examined. For calcite, the υ1 symmetrical stretching Raman-active bands related to individual isotopologues are found to have very similar intensities and are not affected by changes in isotopologue distribution within the material. Fitting these bands resulted in a consistent underestimation of the isotopic enrichment of only 1%, thus they are expected to be useful for estimating 18O-enrichment extent in future experimental work. In contrast, vaterite vibrational bands change more extensively and thus cannot be used directly to determine the 18O concentration within the material. These results are expected to contribute to a deeper und less ambiguous understanding of evaluating isotopic enrichment effects in the vibrational spectra of calcium carbonates.
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Cuéllar-Cruz, Mayra, Karina Sandra Pérez, María Eugenia Mendoza, and Abel Moreno. "Biocrystals in Plants: A Short Review on Biomineralization Processes and the Role of Phototropins into the Uptake of Calcium." Crystals 10, no. 7 (July 9, 2020): 591. http://dx.doi.org/10.3390/cryst10070591.
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The biomineralization process is a mechanism inherent to all organisms of the Earth. Throughout the decades, diverse works have reported that the origin of life is tied to crystals, specifically to biominerals of silica that catalyzed RNA, and had some influence in the homochirality. Although the mechanism by which crystals surfaces (minerals) gave origin to life has not yet been proven, the truth is that, up to the present, biominerals are being synthetized by the organisms of different kingdoms in two basic ways: biologically induced and biologically controlled biomineralization. Paradoxically, this fact makes a fundamental difference between inorganic materials and those formed by living organisms, as the latter are associated with macromolecules that are bound to the mineral phase. Conserving growth and formation of these biogenic organic crystals inside cells is a fascinating subject that has been studied mainly in some of the kingdoms, like Monera (bacteria), Fungi (yeasts), and Animalia (Homo sapiens). Notwithstanding in the Plantae kingdom, the formation, conservation, and functions of crystals has not yet been completely elucidated and described, which is of particular relevance because life on Earth, as we know it, would not be possible without plants. The aim of the present work is to revise the different crystals of calcium oxalate synthetized inside the cells of plants, as well as to identify the mechanism of their formation and their possible functions in plants. The last part is related to the existence of certain proteins called phototropins, which not only work as the blue-light sensors, but they also play an important role on the accumulation of calcium in vacuoles. This new trend is shortly reviewed to explain the characteristics and their plausible role in the calcium uptake along with the biomineralization processes.
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Rodriguez-Navarro, Carlos, Manuel Rodriguez-Gallego, Koutar Ben Chekroun, and Maria Teresa Gonzalez-Muñoz. "Conservation of Ornamental Stone by Myxococcus xanthus-Induced Carbonate Biomineralization." Applied and Environmental Microbiology 69, no. 4 (April 2003): 2182–93. http://dx.doi.org/10.1128/aem.69.4.2182-2193.2003.
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ABSTRACT Increasing environmental pollution in urban areas has been endangering the survival of carbonate stones in monuments and statuary for many decades. Numerous conservation treatments have been applied for the protection and consolidation of these works of art. Most of them, however, either release dangerous gases during curing or show very little efficacy. Bacterially induced carbonate mineralization has been proposed as a novel and environmentally friendly strategy for the conservation of deteriorated ornamental stone. However, the method appeared to display insufficient consolidation and plugging of pores. Here we report that Myxococcus xanthus-induced calcium carbonate precipitation efficiently protects and consolidates porous ornamental limestone. The newly formed carbonate cements calcite grains by depositing on the walls of the pores without plugging them. Sonication tests demonstrate that these new carbonate crystals are strongly attached to the substratum, mostly due to epitaxial growth on preexisting calcite grains. The new crystals are more stress resistant than the calcite grains of the original stone because they are organic-inorganic composites. Variations in the phosphate concentrations of the culture medium lead to changes in local pH and bacterial productivity. These affect the structure of the new cement and the type of precipitated CaCO3 polymorph (vaterite or calcite). The manipulation of culture medium composition creates new ways of controlling bacterial biomineralization that in the future could be applied to the conservation of ornamental stone.
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Crick, R. E., B. Burkart, J. A. Chamberlain, and K. O. Mann. "Chemistry of Calcified Portions of Nautilus Pompilius." Journal of the Marine Biological Association of the United Kingdom 65, no. 2 (May 1985): 415–20. http://dx.doi.org/10.1017/s0025315400050517.
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The Sr, Mg, and Ca chemistry and mineralogy of the shell, beaks, and inorganic compounds of the renal appendages of Nautilus pompilius Linné 1758 reveal a complex physiochemical system of biomineralization. The chemistry of the shell and septal aragonite is similar, and establish that N. pompilius discriminates against the concentration of Sr and Mg in sea water by 78% and more than 99% respectively. Beaks consist of high-Mg calcite (4.4% MgCO3). Renal appendages contain either aggregates of crystals (uroliths) of Mg-oxalate dihydrate with nuclei of hydroxyapatite or disassociated particles of hydroxyapatite or both. There is no evidence that uroliths or hydroxyapatite particles serve as temporary reservoirs of Ca during calcification of septa.
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Chen, Long, Yuhua Shen, Rong Jia, Anjian Xie, Bei Huang, Xiaobin Cheng, Qingfeng Zhang, and Ruiyong Guo. "The Role ofEscherichia coliform in the Biomineralization of Calcium Oxalate Crystals." European Journal of Inorganic Chemistry 2007, no. 20 (July 2007): 3201–7. http://dx.doi.org/10.1002/ejic.200700212.
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Sorrentino, Andrea, Emil Malucelli, Francesca Rossi, Concettina Cappadone, Giovanna Farruggia, Claudia Moscheni, Ana J. Perez-Berna, et al. "Calcite as a Precursor of Hydroxyapatite in the Early Biomineralization of Differentiating Human Bone-Marrow Mesenchymal Stem Cells." International Journal of Molecular Sciences 22, no. 9 (May 6, 2021): 4939. http://dx.doi.org/10.3390/ijms22094939.
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Biomineralization is the process by which living organisms generate organized mineral crystals. In human cells, this phenomenon culminates with the formation of hydroxyapatite, which is a naturally occurring mineral form of calcium apatite. The mechanism that explains the genesis within the cell and the propagation of the mineral in the extracellular matrix still remains largely unexplained, and its characterization is highly controversial, especially in humans. In fact, up to now, biomineralization core knowledge has been provided by investigations on the advanced phases of this process. In this study, we characterize the contents of calcium depositions in human bone mesenchymal stem cells exposed to an osteogenic cocktail for 4 and 10 days using synchrotron-based cryo-soft-X-ray tomography and cryo-XANES microscopy. The reported results suggest crystalline calcite as a precursor of hydroxyapatite depositions within the cells in the biomineralization process. In particular, both calcite and hydroxyapatite were detected within the cell during the early phase of osteogenic differentiation. This striking finding may redefine most of the biomineralization models published so far, taking into account that they have been formulated using murine samples while studies in human cell lines are still scarce.
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He, Zhong, Zengzilu Xia, Mengying Zhang, Jinbo Wu, and Weijia Wen. "Calcium Carbonate Mineralization in a Surface-Tension-Confined Droplets Array." Crystals 9, no. 6 (May 30, 2019): 284. http://dx.doi.org/10.3390/cryst9060284.
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Calcium carbonate biomimetic crystallization remains a topic of interest with respect to biomineralization areas in recent research. It is not easy to conduct high-throughput experiments with only a few macromolecule reagents using conventional experimental methods. However, the emergence of microdroplet array technology provides the possibility to solve these issues efficiently. In this article, surface-tension-confined droplet arrays were used to fabricate calcium carbonate. It was found that calcium carbonate crystallization can be conducted in surface-tension-confined droplets. Defects were found on the surface of some crystals, which were caused by liquid flow inside the droplet and the rapid drop in droplet height during the evaporation. The diameter and number of crystals were related to the droplet diameter. Polyacrylic acid (PAA), added as a modified organic molecule control, changed the CaCO3 morphology from calcite to vaterite. The material products of the above experiments were compared with bulk-synthesized calcium carbonate by scanning electron microscopy (SEM), Raman spectroscopy and other characterization methods. Our work proves the possibility of performing biomimetic crystallization and biomineralization experiments on surface-tension-confined microdroplet arrays.
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Suttiat, Kullapop, Wassanai Wattanutchariya, and Chawan Manaspon. "Preparation and Characterization of Porous Poly(Lactic Acid)/Poly(Butylene Adipate-Co-Terephthalate) (PLA/PBAT) Scaffold with Polydopamine-Assisted Biomineralization for Bone Regeneration." Materials 15, no. 21 (November 3, 2022): 7756. http://dx.doi.org/10.3390/ma15217756.
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The development of scaffolds that simultaneously provide porous architectures and osteogenic properties is the major challenge in tissue engineering. Herein, a scaffold with high porosity and well interconnected networks, namely poly(lactic acid)/poly(butylene adipate-co-terephthalate) (PLA/PBAT), was fabricated using the gas foaming/ammonium bicarbonate particulate leaching technique. Mussel-inspired polydopamine (PDA)-assisted biomineralization generated by two-step simple soaking in dopamine solution and 10× SBF-like solution was performed to improve the material’s osteogenicity. Highly porous scaffolds available in less organized opened cell structures with diameters ranging from 10 µm to 100 µm and 200 µm to 500 µm were successfully prepared. The well interconnected porous architectures were observed through the whole thickness of the scaffold. The even deposition of the organic–inorganic bioactive mineralized layer composed of PDA and nano-scale hydroxyapatite (HA) crystals on the scaffold surface was evidenced by scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The developed scaffold exhibited high total porosity (84.17 ± 1.29%), a lower surface contact angle (θ = 45.7 ± 5.9°), lower material degradation rate (7.63 ± 2.56%), and a high level of material biocompatibility. The MTT assay and Alizarin Red S staining (ARS) confirmed its osteogenic enhancement property toward human osteoblast-like cells (MG-63). These results clarified that the developed porous PLA/PBAT scaffold with PDA-assisted biomineralization exhibited good potential for application as a biomaterial for bone tissue regeneration and hard tissue engineering.
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Wang, Dan, Yu-xuan Feng, Ming Li, Shengdi Guo, and Yuan Jiang. "Seeded Mineralization in Silk Fibroin Hydrogel Matrices Leads to Continuous Rhombohedral CaCO3 Films." Crystals 10, no. 3 (March 3, 2020): 166. http://dx.doi.org/10.3390/cryst10030166.
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As many biominerals are formed in gel-like media, hydrogel-mediated mineralization is deemed as paradigms of biomineralization and ideal approaches to synthetic minerals with hierarchical architectures and related functions. Nevertheless, the long diffusion distance in hydrogels makes mineralization a diffusion-limited process, leading to isolated crystals instead of uniform hierarchical architectures. In the current study, seeded mineralization in silk fibroin hydrogel matrices is successful in delivering continuous rhombohedral CaCO3 films. Though the coverage of hydrogel matrices makes mineralization a diffusion-limited process, the presence of seed layers promotes the growth of uniform overlayers in proper conditions. The regulation of the solid content of hydrogels provides a rational route to rhombohedral architectures with tunable morphologies and thickness. In the course of mineralization, the hydrogel matrices are partially occluded in rhombohedral films as inter- and intra-crystalline constituents, as confirmed by scanning and transmission electron microscopy. Our study confirms the availability of synthesizing continuous mineralized films with hierarchical architectures and the structural gradient in hydrogel matrices via self-organized mineralization. These films with the occlusion of hydrogel constituents may exhibit significant strength and resilience, and their formation can deepen our mechanistic understanding of biomineralization proceeding in gel-like media.
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Danesi, Alexander L., Dimitra Athanasiadou, Ahmad Mansouri, Alina Phen, Mehrnoosh Neshatian, James Holcroft, Johan Bonde, Bernhard Ganss, and Karina M. M. Carneiro. "Uniaxial Hydroxyapatite Growth on a Self-Assembled Protein Scaffold." International Journal of Molecular Sciences 22, no. 22 (November 15, 2021): 12343. http://dx.doi.org/10.3390/ijms222212343.
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Biomineralization is a crucial process whereby organisms produce mineralized tissues such as teeth for mastication, bones for support, and shells for protection. Mineralized tissues are composed of hierarchically organized hydroxyapatite crystals, with a limited capacity to regenerate when demineralized or damaged past a critical size. Thus, the development of protein-based materials that act as artificial scaffolds to guide hydroxyapatite growth is an attractive goal both for the design of ordered nanomaterials and for tissue regeneration. In particular, amelogenin, which is the main protein that scaffolds the hierarchical organization of hydroxyapatite crystals in enamel, amelogenin recombinamers, and amelogenin-derived peptide scaffolds have all been investigated for in vitro mineral growth. Here, we describe uniaxial hydroxyapatite growth on a nanoengineered amelogenin scaffold in combination with amelotin, a mineral promoting protein present during enamel formation. This bio-inspired approach for hydroxyapatite growth may inform the molecular mechanism of hydroxyapatite formation in vitro as well as possible mechanisms at play during mineralized tissue formation.
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De Vincentiis, Sara, Alessandro Falconieri, Frank Mickoleit, Valentina Cappello, Dirk Schüler, and Vittoria Raffa. "Induction of Axonal Outgrowth in Mouse Hippocampal Neurons via Bacterial Magnetosomes." International Journal of Molecular Sciences 22, no. 8 (April 16, 2021): 4126. http://dx.doi.org/10.3390/ijms22084126.
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Magnetosomes are membrane-enclosed iron oxide crystals biosynthesized by magnetotactic bacteria. As the biomineralization of bacterial magnetosomes can be genetically controlled, they have become promising nanomaterials for bionanotechnological applications. In the present paper, we explore a novel application of magnetosomes as nanotool for manipulating axonal outgrowth via stretch-growth (SG). SG refers to the process of stimulation of axonal outgrowth through the application of mechanical forces. Thanks to their superior magnetic properties, magnetosomes have been used to magnetize mouse hippocampal neurons in order to stretch axons under the application of magnetic fields. We found that magnetosomes are avidly internalized by cells. They adhere to the cell membrane, are quickly internalized, and slowly degrade after a few days from the internalization process. Our data show that bacterial magnetosomes are more efficient than synthetic iron oxide nanoparticles in stimulating axonal outgrowth via SG.
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Cuéllar-Cruz, Mayra. "Synthesis of inorganic and organic crystals mediated by proteins in different biological organisms. A mechanism of biomineralization conserved throughout evolution in all living species." Progress in Crystal Growth and Characterization of Materials 63, no. 3 (September 2017): 94–103. http://dx.doi.org/10.1016/j.pcrysgrow.2017.07.001.
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Hollergschwandtner, Elena, Thomas Schwaha, Josef Neumüller, Ulrich Kaindl, Daniela Gruber, Margret Eckhard, Michael Stöger-Pollach, and Siegfried Reipert. "Novel mesostructured inclusions in the epidermal lining of Artemia franciscana ovisacs show optical activity." PeerJ 5 (October 27, 2017): e3923. http://dx.doi.org/10.7717/peerj.3923.
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Background Biomineralization, e.g., in sea urchins or mollusks, includes the assembly of mesoscopic superstructures from inorganic crystalline components and biopolymers. The resulting mesocrystals inspire biophysicists and material scientists alike, because of their extraordinary physical properties. Current efforts to replicate mesocrystal synthesis in vitro require understanding the principles of their self-assembly in vivo. One question, not addressed so far, is whether intracellular crystals of proteins can assemble with biopolymers into functional mesocrystal-like structures. During our electron microscopy studies into Artemia franciscana (Crustacea: Branchiopoda), we found initial evidence of such proteinaceous mesostructures. Results EM preparations with high-pressure freezing and accelerated freeze substitution revealed an extraordinary intracellular source of mesostructured inclusions in both the cyto-and nucleoplasm of the epidermal lining of ovisacs of A. franciscana. Confocal reflection microscopy not only confirmed our finding; it also revealed reflective, light dispersing activity of these flake-like structures, their positioning and orientation with respect to the ovisac inside. Both the striation of alternating electron dense and electron-lucent components and the sharp edges of the flakes indicate self-assembly of material of yet unknown origin under supposed participation of crystallization. However, selected area electron diffraction could not verify the status of crystallization. Energy dispersive X-ray analysis measured a marked increase in nitrogen within the flake-like inclusion, and the almost complete absence of elements that are typically involved in inorganic crystallization. This rise in nitrogen could possibility be related to higher package density of proteins, achieved by mesostructure assembly. Conclusions The ovisac lining of A. franciscana is endowed with numerous mesostructured inclusions that have not been previously reported. We hypothesize that their self-assembly was from proteinaceous polycrystalline units and carbohydrates. These mesostructured flakes displayed active optical properties, as an umbrella-like, reflective cover of the ovisac, which suggests a functional role in the reproduction of A. franciscana. In turn, studies into ovisac mesostructured inclusions could help to optimizing rearing Artemia as feed for fish farming. We propose Artemia ovisacs as an in vivo model system for studying mesostructure formation.
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Dorozhkin, Sergey V. "Nano-Sized and Nanocrystalline Calcium Orhophosphates in Biomedical Engineering." Journal of Biomimetics, Biomaterials and Tissue Engineering 3 (July 2009): 59–92. http://dx.doi.org/10.4028/www.scientific.net/jbbte.3.59.
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There has been much recent activity in the research area of nanoparticles and nanocrystalline materials, in many fields of science and technology. This is due to their outstanding and unique physical, mechanical, chemical and biological characteristics. Recent developments in biomineralization have demonstrated that nano-sized particles play an important role in the formation of the hard tissues of animals. It is well established that the basic inorganic building blocks of bones and teeth of mammals are nano-sized and nanocrystalline calcium orthophosphates (in the form of apatites) of a biological origin. In mammals, tens to hundreds of nanocrystals of biological apatite are found to combine into self-assembled structures under the control of bio-organic matrixes. It was also confirmed experimentally that the structure of both dental enamel and bones could be mimicked by an oriented aggregation of nano-sized calcium orthophosphates, determined by the biomolecules. The application and prospective use of nano-sized and nanocrystalline calcium orthophosphates for clinical repair of damaged bones and teeth are also known. For example, a greater viability and a better proliferation of various cells were detected on smaller crystals of calcium orthophosphates. Furthermore, studies revealed that the differentiation of various cells was promoted by nano-sized calcium orthophosphates. Thus, the nano-sized and nanocrystalline forms of calcium orthophosphates have the potential to revolutionize the field of hard tissue engineering, in areas ranging from bone repair and augmentation to controlled drug delivery devices. This paper reviews the current state of knowledge and recent developments of various nano-sized and nanocrystalline calcium orthophosphates, covering topics from the synthesis and characterization to biomedical and clinical applications. This review also provides possible directions of future research and development.
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Oestreicher, Zachery, Carmen Valverde-Tercedor, Eric Mumper, Lumarie Pérez-Guzmán, Nadia N. Casillas-Ituarte, Concepcion Jimenez-Lopez, Dennis A. Bazylinski, Steven K. Lower, and Brian H. Lower. "Localization of Native Mms13 to the Magnetosome Chain of Magnetospirillum magneticum AMB-1 Using Immunogold Electron Microscopy, Immunofluorescence Microscopy and Biochemical Analysis." Crystals 11, no. 8 (July 28, 2021): 874. http://dx.doi.org/10.3390/cryst11080874.
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Magnetotactic bacteria (MTB) biomineralize intracellular magnetite (Fe3O4) crystals surrounded by a magnetosome membrane (MM). The MM contains membrane-specific proteins that control Fe3O4 mineralization in MTB. Previous studies have demonstrated that Mms13 is a critical protein within the MM. Mms13 can be isolated from the MM fraction of Magnetospirillum magneticum AMB-1 and a Mms13 homolog, MamC, has been shown to control the size and shape of magnetite nanocrystals synthesized in-vitro. The objective of this study was to use several independent methods to definitively determine the localization of native Mms13 in M. magneticum AMB-1. Using Mms13-immunogold labeling and transmission electron microscopy (TEM), we found that Mms13 is localized to the magnetosome chain of M. magneticum AMB-1 cells. Mms13 was detected in direct contact with magnetite crystals or within the MM. Immunofluorescence detection of Mms13 in M. magneticum AMB-1 cells by confocal laser scanning microscopy (CLSM) showed Mms13 localization along the length of the magnetosome chain. Proteins contained within the MM were resolved by SDS-PAGE for Western blot analysis and LC-MS/MS (liquid chromatography with tandem mass spectrometry) protein sequencing. Using Anti-Mms13 antibody, a protein band with a molecular mass of ~14 kDa was detected in the MM fraction only. This polypeptide was digested with trypsin, sequenced by LC-MS/MS and identified as magnetosome protein Mms13. Peptides corresponding to the protein’s putative MM domain and catalytic domain were both identified by LC-MS/MS. Our results (Immunogold TEM, Immunofluorescence CLSM, Western blot, LC-MS/MS), combined with results from previous studies, demonstrate that Mms13 and homolog proteins MamC and Mam12, are localized to the magnetosome chain in MTB belonging to the class Alphaproteobacteria. Because of their shared localization in the MM and highly conserved amino acid sequences, it is likely that MamC, Mam12, and Mms13 share similar roles in the biomineralization of Fe3O4 nanocrystals.
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Mann, Stephen, Brigid R. Heywood, Jon M. Didymus, Sundara Rajam, Vanessa J. Wade, and Justin B. A. Walker. "Biomineralization: New Routes to Crystal Engineering." MRS Proceedings 174 (1989). http://dx.doi.org/10.1557/proc-174-25.
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AbstractThis paper discusses the principal features of biomineralization in relation to the controlled crystallization of inorganic materials, and the modelling of these concepts in vitro. The biological strategies adopted in the regulation of nucleation and growth are; (a) the use of constrained reaction environments, (b) the synthesis of chemically and structurally specific organic macromolecules, and (c) the secretion of tailor-made additives of low and high molecular weight. Underlying these strategies is the concept of molecular recognition at interfaces comprising organic and inorganic surfaces. The structural, electrostatic and stereochemical aspects of these interfacial interactions in systems involving supramolecular asemblies, Langmuir monomolecular films and tailored additives will be described.
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Eco, Kenneth, and Beatriz Belonias. "Biomineralization of Calcium Oxalate Crystals in Leaves of (L.) Schott (Araceae) in Colocasia esculenta Response to Herbivory and Water Regime." Annals of Tropical Research, June 2, 2017, 54–69. http://dx.doi.org/10.32945/atr3914.2017.
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Calcium oxalate crystals are common constituents of plant tissues and are believed to play a role in protection against herbivory, calcium regulation and even heavy metal sequestration. In this study, calcium oxalate crystals in leaves of Colocasia esculenta were studied in order to elucidate the biomineralization process of these inorganic components in response to herbivory and different water regimes. Different crystal types occurring in the leaves of C. esculenta were identified, described and quantified in terms of density and distribution. Two general types of calcium oxalate crystals were found, namely: the raphides and druses. The raphides were of two types, the defensive and non- defensive, and both occurred as bundles of elongated crystals enclosed in specialized cells called idioblasts. Druses were spherical conglomerate crystals extensively distributed throughout the leaf. Although degree of herbivory did not significantly affect overall density of calcium oxalate crystals, there was a highly significant interaction effect between herbivory and crystal type. With increasing degree of herbivory from 10% to 30%, the density of druses and non-defensive raphides decreased significantly but that of the defensive type increased. Water availability had a highly significant effect on overall crystal density. Interaction effect between water regime and crystal type was also highly significant. Density of druses significantly increased under waterlogged than non-waterlogged conditions while those of the defensive and non-defensive raphides were unaffected.
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Mikami, Takahiro, Shunichi Matsumura, Rino Ichikawa, Riki Kato, Junya Uchida, Tatsuya Nishimura, and Takashi Kato. "Bioinspired macromolecular templates for crystallographic orientation control of ZnO thin films through zinc hydroxide carbonate." Polymer Journal, June 10, 2022. http://dx.doi.org/10.1038/s41428-022-00661-9.
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AbstractThe biomineralization-inspired preparation of inorganic hybrid materials has attracted attention. Here, we report a new approach to the orientation control of zinc oxide (ZnO) thin-film crystals through the preparation of zinc hydroxide carbonate (ZHC) by the macromolecular templates of poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(vinyl alcohol) (PVA). Using 100-nm-thick PHEMA templates, ZHC thin films with the c-axis oriented parallel to the substrate were obtained, while ZHC thin films prepared by 100-nm-thick PVA templates showed perpendicular orientation. After the thermal treatment of ZHC, the crystal orientations of the ZnO thin films were maintained. The effects of the thickness and annealing time for the polymer templates on the morphologies of the ZnO thin films were examined.
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Hong, Min-Ho, Jung Heon Lee, Hyun Suk Jung, Heungsoo Shin, and Hyunjung Shin. "Biomineralization of bone tissue: calcium phosphate-based inorganics in collagen fibrillar organic matrices." Biomaterials Research 26, no. 1 (September 6, 2022). http://dx.doi.org/10.1186/s40824-022-00288-0.
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Abstract Background Bone regeneration research is currently ongoing in the scientific community. Materials approved for clinical use, and applied to patients, have been developed and produced. However, rather than directly affecting bone regeneration, these materials support bone induction, which regenerates bone. Therefore, the research community is still researching bone tissue regeneration. In the papers published so far, it is hard to find an improvement in the theory of bone regeneration. This review discusses the relationship between the existing theories on hard tissue growth and regeneration and the biomaterials developed so far for this purpose and future research directions. Mainbody Highly complex nucleation and crystallization in hard tissue involves the coordinated action of ions and/or molecules that can produce different organic and inorganic composite biomaterials. In addition, the healing of bone defects is also affected by the dynamic conditions of ions and nutrients in the bone regeneration process. Inorganics in the human body, especially calcium- and/or phosphorus-based materials, play an important role in hard tissues. Inorganic crystal growth is important for treating or remodeling the bone matrix. Biomaterials used in bone tissue regeneration require expertise in various fields of the scientific community. Chemical knowledge is indispensable for interpreting the relationship between biological factors and their formation. In addition, sources of energy for the nucleation and crystallization processes of such chemical bonds and minerals that make up the bone tissue must be considered. However, the exact mechanism for this process has not yet been elucidated. Therefore, a convergence of broader scientific fields such as chemistry, materials, and biology is urgently needed to induce a distinct bone tissue regeneration mechanism. Conclusion This review provides an overview of calcium- and/or phosphorus-based inorganic properties and processes combined with organics that can be regarded as matrices of these minerals, namely collagen molecules and collagen fibrils. Furthermore, we discuss how this strategy can be applied to future bone tissue regenerative medicine in combination with other academic perspectives.
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"Crystal growth and the role of the organic network in eggshell biomineralization." Proceedings of the Royal Society of London. Series B. Biological Sciences 227, no. 1248 (April 22, 1986): 303–24. http://dx.doi.org/10.1098/rspb.1986.0025.
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A model based on geometrical crystal growth considerations is proposed for the deposition of the crocodilian, testudinian and avian eggshells. Ir each shell column, crystal deposition is initiated at a single location, from which growth fans out at all angles to the shell normal. In both co1citic and aragonitic shells, growth is in the [001] direction, resulting in an increase in the degree of (001) preferred orientation with distance from nucleation. Where there is unhindered crystal growth, the shells show a crystalline fracture morphology, and the degree of texture that develops is a simple function of the column radius. This type of growth makes up the whole of the testudinian shell, the inner 0.3-0.4 (30-40 %) of the thick ratite shells and the cone layer of the other avian shells. At the start of the palisade layer of the avian shell, the onset of deposition of the organic component coincides with a hindrance to texture development, which thereafter proceeds at a lower rate. A further hindrance occurs about halfway through the shell, probably caused by a change in the physical characteristics of the organic network. The degree of texture that develops in the avian shell is a function of the column radius and the degree of physical hindrance presented by the organic network. The palisade layer of the avian shell has a composite fracture morphology resulting from the intermingling of the network with the inorganic phase.The organic component does not appear to control crystal growth, as previously believed, but instead acts as a reinforcing fibrous network.
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Arias, Jose L., Maria S. Fernandez, Vincent J. Laraia, Jaroslaw Janicki, Arthur H. Heuer, and Arnold I. Caplan. "The Avian Eggshell as a Model of Biomineralization." MRS Proceedings 218 (1990). http://dx.doi.org/10.1557/proc-218-193.
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AbstractThe avian eggshell is one of the most rapidly mineralizing biological systems known. By understandi'ng the key components and steps in this process, we hope to provide relevant information for fabrication of ceramic composites. The calcification of the eggshell occurs in three main steps: 1) fabrication of an organic matrix, 2) nucleation of an inorganic phase on the organic matrix, and 3) space-filling growth of the calcite phase. The different layers of an eggshell can be separately isolated and studied. Three approaches have been used in our study of the eggshell: 1) characterization of the organization and chemical composition of the shell, 2) selective removal or blocking of particular components to improve the remineralization of demineralized shells, and 3) addition of new components to produce composite ceramics of different kinds. In this preliminary communication, the organization of the shell matrix and membranes and their association with the crystal phase, the immunohistochemical occurrence and distribution of types I and X collagen, and of different proteoglycans are reviewed. Also the preliminary findings of the remineralization of the intact or modified eggshell are presented. These experiments allow us to identify the essential steps in forming a natural composite ceramic.
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Li, Zhimin, and Tianxiao Li. "New Insights Into Microbial Induced Calcium Carbonate Precipitation Using Saccharomyces cerevisiae." Frontiers in Microbiology 13 (April 29, 2022). http://dx.doi.org/10.3389/fmicb.2022.904095.
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Saccharomyces cerevisiae plays an important role in the mineralization of many metal ions, but it is unclear whether this fungus is involved in the mineralization of calcium carbonate. In this study, S. cerevisiae was cultured under various conditions to explore its ability to perform microbially induced calcium carbonate precipitation (MICP). Organic acids, yeast extract, and low-carbon conditions were the factors influencing the biomineralization of calcium carbonate caused by S. cerevisiae, and biomolecules secreted by the fungus under different conditions could change the morphology, size, and crystal form of the biosynthesized mineral. In addition, transcriptome analysis showed that the oxidation of organic acids enhanced the respiration process of yeast. This implied that S. cerevisiae played a role in the formation of calcium carbonate through the mechanism of creating an alkaline environment by the respiratory metabolism of organic acids, which could provide sufficient dissolved inorganic carbon for calcium carbonate formation. These results provide new insights into the role of S. cerevisiae in biomineralization and extend the potential applications of this fungus in the future.