Strongly bound citrate stabilizes the apatite nanocrystals in bone.
Nanocrystals of apatitic calcium phosphate impart the organic-inorganic nanocomposite in bone with favorable mechanical properties. So far, the factors preventing crystal growth beyond the favorable thickness of ca. 3 nm have not been identified. Here we show that the apatite surfaces are studded with strongly bound citrate molecules, whose signals have been identified unambiguously by multinuclear magnetic resonance (NMR) analysis. NMR reveals that bound citrate accounts for 5.5 wt% of the organic matter in bone and covers apatite at a density of about 1 molecule per (2 nm)(2), with its three carboxylate groups at distances of 0.3 to 0.45 nm from the apatite surface. Bound citrate is highly conserved, being found in fish, avian, and mammalian bone, which indicates its critical role in interfering with crystal thickening and stabilizing the apatite nanocrystals in bone.
- Research Article
- 10.1016/0012-8252(74)90087-7
- Jun 1, 1974
- Earth-Science Reviews
Sedimentary carbonate mineralsF. Lippmann, 1973. Springer, Berlin/Heidelberg/New York, VI + 228 pp., U.S. $21.50
- Research Article
118
- 10.1016/j.powtec.2020.07.007
- Jul 6, 2020
- Powder Technology
The role of sodium alginate in the flotation separation of apatite and dolomite
- Research Article
28
- 10.1016/j.biomaterials.2011.01.015
- Feb 1, 2011
- Biomaterials
Mechanisms by which the inhibition of specific intracellular signaling pathways increase osteoblast proliferation on apatite surfaces
- Research Article
9
- 10.1039/d1bm00884f
- Jan 1, 2021
- Biomaterials Science
The adaptive response of bones to mechanical loading is essential for musculoskeletal development. Despite the importance of collagen in bone mineralization, little is known about how cyclic strain influences physicochemical responses of collagen, especially at the early stage of mineralization when the levels of strain are higher than those in mature bones. The findings in this study show that, without any cell-mediated activity, cyclic strain increases nucleation rates of calcium phosphate (CaP) nanocrystals in highly-organized collagen matrices. The cyclic strain enhances the transport of mineralization fluids with nucleation precursors into the matrix, thus forming more CaP nanocrystals and increasing the elastic modulus of the collagen matrix. The results also suggest that the multiscale spatial distribution of nanocrystals in the fibrous collagen network determines tissue-level mechanical properties more critically than the total mineral content. By linking nano- and micro-scale observations with tissue-level mechanical properties, we provide new insights into designing better biomaterials.
- Research Article
20
- 10.1016/j.apsusc.2012.07.055
- Aug 1, 2012
- Applied Surface Science
Adsorption and release of amino acids mixture onto apatitic calcium phosphates analogous to bone mineral
- Research Article
75
- 10.1002/jbm.820190307
- Mar 1, 1985
- Journal of Biomedical Materials Research
This is a review of the surface chemistry of bone mineral and its synthetic counterpart hydroxyapatite. Small-angle x-ray scattering and low-temperature nitrogen adsorption measurements show bone mineral surfaces range from 100 to 200 m2/g. The heats of adsorption of small molecules on bone and apatite surfaces show that these materials have polarizing surfaces which form strong bonds with polar and polarizable molecules. Water is hydrogen bonded to these surfaces with energies ranging from 23 Kcal/mol, for low coverage, to 11 Kcal/mol after two full layers; the latter value shows that after two monolayers the water is bonded as strongly to the solution as it is to the apatite surface. Stearic acid in cyclohexane adsorbs on bone and apatite surfaces in a closed-packed manner with the straight-chain molecules in parallel array with the end carboxyl groups hydrogen bonded to surface electronegative ions. Synthetic hydroxyapatite has long been used in chromatography because of the bonding capacity apatite surface has for certain proteins and polynucleotides. The metabolic interplay between bone mineral and the body results from the high magnitude and high reactivity of the mineral surface.
- Single Book
557
- 10.1201/9780203751367
- Dec 14, 2017
Biological and Synthetic Apatites (R.Z. LeGeros). Calcium Phosphate Apatites in Nature (D.K. Smith). Hydrothermal Processing of Hydroxyapatite: Past, Present, and Future (M. Yoshimura and H. Suda). Formation and Dissolution Mechanisms of Calcium Phosphates in Aqueous Systems (G.H. Nancollas and J. Zhang). Pathological Crystallization of Calcium Oxalate and Calcium Phosphate (S.R. Khan and R.L. Hackett). Characterization of Mineral Phases in Cardiovascular Calcification (B.B. Tomazic). Chemistry and Structure of Calcium-Containing Coatings and Modified Surfaces for Titanium Alloy Orthopedic Prostheses (M. Spector, J.G. Hanlon, G.H. Nancollas). Formation of Hydroxyapatite in Cement Systems (L.C. Chow, S. Takagi, and K. Ishikawa). Octacalcium Phosphate Carboxylates. 5. Incorporation of Excess Succinate and Ammonium Ions in the Octacalcium Phosphate Succinate Structure (M. Markovic, B.O. Fowler, W.E. Brown). The Effect of Ethanol on the Solubility of Hydroxyapatite in the System Ca(OH)2-H3PO4-H2O at 25 and 33 C (M.S. Tung, C. Lin, T.H. Chow, and P. Sung). Constant-Composition Study of the Precipitation Behaviour of Calcium Phosphate in the Presence of Non-Collagenous Bio-Chemicals (A.T.-C. Wong and J.T. Czernuszka). Dual Constant Composition Kinetics Studies of Ceramic Hydroxyapatite and Hydroxyapatite Plasma Coated Implants (E.P. Paschalis, B.E. Tucker, S. Mukhopadhyay, K. Wikiel, N.B. Beals, J.A. Bearcroft, M. Spector, G.H. Nancollas). Comparative Utility of Mineralized Collagen as an Osteoinductive Material (S. Gunasekaran, I.C. Bathurst, B. Constantz, J. Quiaoit, J. Ross, P.J. Barr, and D. Gospodarowicz). Maturation of Poorly Crystalline Synthetic and Biological Apatites (C. Rey, H-M. Kim, M.J. Glimcher). Prediction of Precipitation and Transformation Behaviour of Calcium Phosphate in Aqueous Media (A.T.-C. Wong and J.T. Czernuszka). The Role of Interfacial Chemistry in Surface Nucleation and Growth of Calcium Oxalate Monohydrate (L. Song, A.A. Campbell, and B.C. Bunker). Effect of Particle Size of Metastable Calcium Phosphates on Crushing Strength of Self-Setting Bioactive Calcium Phosphate Cement (M. Otsuka, Y. Matsuda, Y. Suwa, J.L. Fox, and W.I. Higuchi). An Hydraulic Cement for Biological Uses (E. Mejdoubi, J.L. Lacout, P. Michaud, and P. Rodriguez). Synthesis of Dahllite: The Mineral Phase of Bone (I.C. Ison, M.T. Fulmer, B.M. Barr, and B.R. Constantz). Deposition of Hydroxyapatite Coatings by Laser Ablation (G. Sardin, M. Varela, J.L. Morenza). Grafting of Phosphorylated Molecules on Apatite Surface (A. Lebugle, M. Subirade, and V. Delpech). Influence of the Crystallinity of Plasma Sprayed HA-Coatings on Their Osseointegration (P. Frayssinet, P. Conte, F. Tourenne, and N. Rouquet). In Situ TEM Observation of Radiation Induced Amorphization of Crystals with Apatite Structure (L.M. Wang, M. Cameron, W.J. Weber, K.D. Crowley, and R.C. Ewing). Carbonate-Containing Europium Apatite (J.L. Lacout and A. Taitai). Apatite Channels and Zeolite-Like Properties (C. Rey). Preparation of Calcium Phosphates Powders by Water Extraction Variant of Sol-Gel Process (A. Deptula, T. Olczak, W. Lada, A. Borello, C. Alvani, L. Lorenzini, and A. DiBartolomeo). Thermal Stability of Synthetic Hydroxyapatite (Y. Fang, D.K. Agrawal, D.M. Roy). Human Bone Marrow Cell Culture-Analysis of Cell Behaviour at Biocompatibility Testing of Ceramics (A. Wilke, S.V. Hirschheydt, and J. Orth). Mineral-Organic Interfacial Bonding: Effect of Strain Rate on the Mechanical Properties of Bone (W.R. Walsh, H.D. Kim, D.P. Labrador, N. Guzelsu). Structural Analysis of the Human Tooth Enamel by Transmission Electron Microscopy (J. Reyes-Gasga and C.M. Alcantara-Rodriguez). The in Vitro Growth Potential of Human Bone Derived Cells on Polytetrafluoroethylene Grafts (M.L. Olmedo, A.-P.C. Weiss, W.E. Walsh, L. Zou, M.G. Ehrlich). Ultrasonic Properties of Cortical Bone Following in-Vitro Fluoride Ion Treatment (W.R. Walsh, D.P. Labrador, H.D. Kim, and N. Guzelsu). XPS Study of Apatites and Related Calcium Phosphates (A. Lebugle and B. Sallek). Calcium Phosphate Deposition in Rat Kidneys (S.R. Kahn, J.H. Adair, A.A. Morrone, G.P. Latorre). Isolation of Calcium-Phosphate Crystals of Mature Bovine Bone by Reaction with Hydrazine at Low Temperature (H-M. Kim, C. Rey, and M.J. Glimcher). Author Index.
- Research Article
45
- 10.1002/oa.1390020110
- Mar 1, 1992
- International Journal of Osteoarchaeology
It is commonly assumed that, at least when considering similar sized animals, the bones from all taxa stand an equal chance of preservation. This paper summarizes one aspect of a larger study undertaken in order to assess whether this assumption is true, based on the results of experiments and observations into the effects of a range of pre‐depositional processes. The rates of bone destruction by sedimentary abrasion and by trampling are determined for small mammal, fish and frog bones. Patterns of bone loss and fragmentation are examined both between species and within the skeleton, for fresh and boiled bone. It is shown that there is considerable interspecies variation in the ability of bones to withstand these physical forces. Frog bone proved particularly resistant, while within the fish, bone from the Gadidae was less resilient than might be expected, given its predominance in British Medieval archaeological sites and coastal sites of all periods. Within the skeleton, bone shape appears to be a very important determinant of relative survival. Boiling dramatically reduces bone's resistence to destruction. The physical properties of fresh, boiled and burnt bone are compared mechanically, and the dramatic loss of strength induced by heating is demonstrated. The often voiced assumption that fish bone is more prone to destruction than mammal bone is shown to have some validity. The results add more evidence to support the view that comparison of species abundance by fragment counts may not always be appropriate, and that interpretation of skeletal element frequencies should be approached with caution.
- Research Article
7
- 10.1016/j.jasrep.2018.08.049
- Sep 28, 2018
- Journal of Archaeological Science: Reports
Using bone fragmentation records to investigate coastal human ecodynamics: A case study from Čḯxwicən (Washington State, USA)
- Research Article
- 10.1016/j.asej.2026.104068
- Mar 1, 2026
- Ain Shams Engineering Journal
In this study, waste products such as fish bones (H) known as biocompatible natural apatite sources were performed to develop sustainable, recycled and environmentally friendly materials. The study investigated the polymerization of 1-vinylimidazole (VIM) monomer on direct and silane-assisted waste fish bone particle surfaces. In the first method (HP 5 ), direct polymerization of VIM was performed on the fish bone particles. In the second method (HS 3 P 5 ), the apatite surface was firstly silanized with 3-(Methacryloyloxy)propyl-trimethoxy silane (MPS) and then polymerized with VIM. Elemental analysis results showed that the number of monomers bound to the surface was calculated as 302 µmol/g for HP5 and 714 µmol/g for HS3P5, using nitrogen as the indicator element for VIM. Zeta potential shifted from −20.40 to −35.91 mV and conductivity from 3.03 × 10 −2 to 7.67 × 10 −2 S/cm. This study proposes an eco-friendly and sustainable material design by reusing biological waste and employing non-toxic, biocompatible polymers.
- Research Article
38
- 10.1016/j.ces.2022.117463
- Jan 25, 2022
- Chemical Engineering Science
Selective flotation separation of apatite from calcite using hydrolytic polymaleic anhydride as an eco-friendly and efficient depressant
- Research Article
147
- 10.1016/j.mineng.2015.04.020
- May 16, 2015
- Minerals Engineering
A mixed collector system for phosphate flotation
- Research Article
6
- 10.3390/min15080822
- Aug 1, 2025
- Minerals
Maximizing the efficient utilization of critical apatite resources through flotation necessitates the exploration of effective and innovative collectors. This study investigates the potential of a fatty acid mixture (FAM) synthesized from saturated palmitic and stearic acids, monounsaturated oleic and palmitoleic acids, and polyunsaturated linoleic acid. The saponified collector FAM and the depressant sodium alginate (NaAl) achieved a direct flotation of apatite from calcite and quartz (97% apatite, 10% calcite, and 7% quartz). The flotation performance with the tested combination exhibited a highly effective enrichment of apatite, mainly from calcite, which aligns with the surface chemistry assessments. Adsorption tests and zeta potential measurements confirmed the micro-flotation results. They provided compelling evidence of a chemisorption interaction between Ca2+ sites on calcite and the carboxyl and hydroxyl groups of NaAl. FTIR analyses suggested a reaction between the apatite surface and the carboxyl groups of saturated and unsaturated acid groups in FAM, even those conditioned with NaAl before, facilitating the complex formation. Remarkably, the synergistic effect of the functional groups demonstrates dual functionality, serving as both a hydrophilic entity for calcite and a hydrophobic entity for apatite flotation. The universal mechanism unveils substantial potential for the extensive application of FAM within apatite flotation.
- Book Chapter
- 10.1017/cbo9780511489570.013
- Dec 14, 2006
The people of the ancient Mediterranean world, or at least those who wrote books, had a somewhat ambiguous view of seafood. It was at the same time a dubious foodstuff, and one that had connotations of great luxury, especially in the Roman milieu. There are ongoing debates as to what contribution to the diet fish actually made. In Britain we do not have the wealth of literary sources, but we do have an increasing number of fish bone assemblages, and patterns of consumption are starting to emerge. For fish bones, sampling and flotation are essential. They can be recovered by hand excavation, but the result will be governed by the competence and knowledge of the excavator, and the size of the bone. I well recall in the mid-1970s, when working as a finds supervisor for a big urban excavation, the sudden appearance of cod and ling vertebrae on the finds trays amongst all the normal potsherds and mammal bone. This took place the day after everyone working on the site had listened to a lecture by a highly enthusiastic fish bone specialist. As fish bones go, these are large; but they had rarely appeared in the preceding weeks. It was a classic example of the phenomenon that what goes on the finds tray is what the excavator recognises. Not all digging teams can have the opportunity of being similarly enthused and, even if they are, they would still miss the smaller species.
- Research Article
282
- 10.1016/j.jas.2011.07.022
- Jul 30, 2011
- Journal of Archaeological Science
Fish bone chemistry and ultrastructure: implications for taphonomy and stable isotope analysis