S. M. Kurtz, K. L. Ong, J. Schmier, K. Zhao, F. Mowat et al., Primary and Revision Arthroplasty Surgery Caseloads in the United States from, The Journal of Arthroplasty, vol.24, pp.195-203, 1990.

B. Zhang, D. Myers, G. Wallace, M. Brandt, and P. Choong, Bioactive Coatings for Orthopaedic Implants-Recent Trends in Development of Implant Coatings, International Journal of Molecular Sciences, vol.15, pp.11878-11921, 2014.

M. Kaur and K. Singh, Review on titanium and titanium based alloys as biomaterials for orthopaedic applications, vol.102, pp.844-862, 2019.

K. Anselme and M. Bigerelle, Topography effects of pure titanium substrates on human osteoblast long-term adhesion, Acta Biomaterialia, vol.1, pp.211-222, 2005.
URL : https://hal.archives-ouvertes.fr/hal-02584384

D. D. Deligianni, N. Katsala, S. Ladas, D. Sotiropoulou, J. Amedee et al., Effect of surface roughness of the titanium alloy Ti-6Al-4V on human bone marrow cell response and on protein adsorption, Biomaterials, vol.22, p.1241, 2001.

E. Chikarakara, P. Fitzpatrick, E. Moore, T. Levingstone, L. Grehan et al., In vitro fibroblast and pre-osteoblastic cellular responses on laser surface modified Ti-6Al-4V, Biomedical Materials, vol.10, p.15007, 2014.

J. Li, I. Mutreja, S. Tredinnick, M. Jermy, G. J. Hooper et al., Hydrodynamic control of titania nanotube formation on Ti-6Al-4V alloys enhances osteogenic differentiation of human mesenchymal stromal cells, Materials Science and Engineering: C, vol.109, p.110562, 2020.

H. Qiao, G. Song, Y. Huang, H. Yang, S. Han et al., Ag co-doped hydroxyapatite/TiO 2 coating: enhancement of its antibacterial activity and osteoinductivity, RSC Advances, vol.9, pp.13348-13364, 2019.

H. Qiao, Q. Zou, C. Yuan, X. Zhang, S. Han et al., Composite coatings of lanthanum-doped fluor-hydroxyapatite and a layer of strontium titanate nanotubes: fabrication, bio-corrosion resistance, cytocompatibility and osteogenic differentiation, Ceramics International, vol.44, pp.16632-16646, 2018.

M. Kazemi, S. Ahangarani, M. Esmailian, and A. Shanaghi, Investigation on the corrosion behavior and biocompatibility of Ti-6Al-4V implant coated with HA/TiN dual layer for medical applications, Surface and Coatings Technology, vol.397, p.126044, 2020.

Q. Yao, Y. Jiang, S. Tan, X. Fu, B. Li et al., Composition and bioactivity of calcium phosphate coatings on anodic oxide nanotubes formed on pure Ti and Ti-6Al-4V alloy substrates, Materials Science and Engineering: C, vol.110, p.110687, 2020.

T. Kitsugi, T. Yamamuro, T. Nakamura, and M. Oka, Transmission electron microscopy observations at the interface of bone and four types of calcium phosphate ceramics with different calcium/phosphorus molar ratios, Biomaterials, vol.16, pp.1101-1107, 1995.

D. S. Kruijntjens, P. Kjaersgaard-andersen, P. Revald, J. S. Leonhardt, J. J. Arts et al., ten Broeke, 5-year clinical and radiographic follow-up of the uncemented Symax hip stem in an international study, Journal of Orthopaedic Surgery Research, vol.13, p.191, 2018.

T. J. Wood, M. Alzahrani, J. D. Marsh, L. E. Somerville, E. M. Vasarhelyi et al., Use of the Corail stem for revision total hip arthroplasty: evaluation of clinical outcomes and cost, canadian Journal of Surgery, vol.62, pp.78-82, 2019.

M. Stigter, J. Bezemer, K. De-groot, and P. Layrolle, Incorporation of different antibiotics into carbonated hydroxyapatite coatings on titanium implants, release and antibiotic efficacy, Journal of Controlled Release, vol.99, pp.127-137, 2004.

K. Zawisza, P. Sobierajska, N. Nowak, A. Kedziora, K. Korzekwa et al., Preparation and preliminary evaluation of bionanocomposites based on hydroxyapatites with antibacterial properties against anaerobic bacteria, Materials Science and Engineering: C, vol.106, p.110295, 2020.

B. Li, X. Xia, M. Guo, Y. Jiang, Y. Li et al., Biological and antibacterial properties of the micro-nanostructured hydroxyapatite/chitosan coating on titanium, Scientific Reports, vol.9, p.14052, 2019.

S. Shanmugam and B. , Antimicrobial and cytotoxicity evaluation of aliovalent substituted hydroxyapatite, Applied Surface Science, vol.303, pp.277-281, 2014.

S. Shanmugam and B. , Copper substituted hydroxyapatite and fluorapatite: Synthesis, characterization and antimicrobial properties, Ceramics International, vol.40, pp.15655-15662, 2014.

V. Stani?, S. Dimitrijevi?, J. Anti?-stankovi?, M. Mitri?, B. Joki? et al., Synthesis, characterization and antimicrobial activity of copper and zinc-doped hydroxyapatite nanopowders, Applied Surface Science, vol.256, pp.6083-6089, 2010.

S. Gomes, C. Vichery, S. Descamps, H. Martinez, A. Kaur et al., Cu-doping of calcium phosphate bioceramics: From mechanism to the control of cytotoxicity, Acta Biomaterialia, vol.65, pp.462-474, 2018.
URL : https://hal.archives-ouvertes.fr/hal-01678838

J. Forsgren, U. Brohede, M. Strømme, and H. Engqvist, Co-loading of bisphosphonates and antibiotics to a biomimetic hydroxyapatite coating, Biotechnology Letters, vol.33, pp.1265-1268, 2011.
URL : https://hal.archives-ouvertes.fr/hal-00665450

J. H. Sörensen, M. Lilja, T. C. Sörensen, M. Åstrand, P. Procter et al., Biomechanical and antibacterial properties of Tobramycin loaded hydroxyapatite coated fixation pins: Functional Ha Coatings as Local Drug Delivery Vehicles, Journal of Biomedical Materials Research Part B: Applied Biomaterials, vol.102, pp.1381-1392, 2014.

U. Brohede, J. Forsgren, S. Roos, A. Mihranyan, H. Engqvist et al., Multifunctional implant coatings providing possibilities for fast antibiotics loading with subsequent slow release, Journal of Materials Science: Materials in Medicine, vol.20, pp.1859-1867, 2009.

M. Lilja, J. H. Sörensen, U. Brohede, M. Åstrand, P. Procter et al., Drug loading and release of Tobramycin from hydroxyapatite coated fixation pins, Journal of Materials Science: Materials in Medicine, vol.24, pp.2265-2274, 2013.

S. Tang, B. Tian, Q. Ke, Z. Zhu, and Y. Guo, Gentamicin-loaded carbonated hydroxyapatite coatings with hierarchically porous structures: drug delivery properties, bactericidal properties and biocompatibility, vol.4, pp.41500-41509, 2014.

M. A. Fischbach and C. T. Walsh, Antibiotics for Emerging Pathogens, Science, vol.325, pp.1089-1093, 2009.

S. B. Levy and B. Marshall, Antibacterial resistance worldwide: causes, challenges and responses, Nature Medicine, vol.10, pp.122-129, 2004.

M. M. Cowan, Plant Products as Antimicrobial Agents, Clin Microbiol Rev, vol.12, pp.564-582, 1999.

M. Daglia, Polyphenols as antimicrobial agents, vol.23, pp.174-181, 2012.

Y. Lu, R. Joerger, and C. Wu, Study of the Chemical Composition and Antimicrobial Activities of Ethanolic Extracts from Roots of Scutellaria baicalensis Georgi, Journal of Agricultural and Food Chemistry, vol.59, pp.10934-10942, 2011.

X. Shang, X. He, X. He, M. Li, R. Zhang et al., The genus Scutellaria an ethnopharmacological and phytochemical review, Journal of Ethnopharmacology, vol.128, pp.279-313, 2010.

B. Dinda, S. Dinda, S. Dassharma, R. Banik, A. Chakraborty et al., Therapeutic potentials of baicalin and its aglycone, baicalein against inflammatory disorders, vol.131, pp.68-80, 2017.

Y. Gao, S. A. Snyder, J. N. Smith, and Y. C. Chen, Anticancer properties of baicalein: a review, Medicinal Chemistry Research, vol.25, pp.1515-1523, 2016.

Y. Chen, T. Liu, K. Wang, C. Hou, S. Cai et al., Baicalein Inhibits Staphylococcus aureus Biofilm Formation and the Quorum Sensing System In Vitro, PLOS ONE, vol.11, 2016.

B. C. Chan, M. Ip, C. B. Lau, S. L. Lui, C. Jolivalt et al., Synergistic effects of baicalein with ciprofloxacin against NorA over-expressed methicillin-resistant Staphylococcus aureus (MRSA) and inhibition of MRSA pyruvate kinase, Journal of Ethnopharmacology, vol.137, pp.767-773, 2011.
URL : https://hal.archives-ouvertes.fr/hal-00689148

W. S. Harun, R. I. Asri, J. Alias, F. H. Zulkifli, K. Kadirgama et al., A comprehensive review of hydroxyapatite-based coatings adhesion on metallic biomaterials, Ceramics International, vol.44, pp.1250-1268, 2018.

T. Kokubo, Apatite formation on surfaces of ceramics, metals and polymers in body environment, Acta Materialia, vol.46, pp.2519-2527, 1998.

K. Achelhi, S. Masse, G. Laurent, A. Saoiabi, A. Laghzizil et al., Role of carboxylate chelating agents on the chemical, structural and textural properties of hydroxyapatite, Dalton Transactions, vol.39, p.10644, 2010.
URL : https://hal.archives-ouvertes.fr/hal-02291327

B. D. Cullity and S. R. Stock, Elements of X-Ray Diffraction, 2001.

D. G. Cory and W. M. Ritchey, Suppression of signals from the probe in bloch decay spectra, Journal of Magnetic Resonance, vol.80, issue.88, pp.90064-90073, 1969.

E. L. Hahn, Spin Echoes, Phys. Rev, vol.80, pp.580-594, 1950.

C. Jäger, T. Welzel, W. Meyer-zaika, and M. Epple, A solid-state NMR investigation of the structure of nanocrystalline hydroxyapatite, Magnetic Resonance in Chemistry, vol.44, pp.573-580, 2006.

D. Marion, M. Ikura, R. Tschudin, and A. Bax, Rapid recording of 2D NMR spectra without phase cycling. Application to the study of hydrogen exchange in proteins, Journal of Magnetic Resonance, vol.85, pp.393-399, 1969.

B. M. Fung, A. K. Khitrin, and K. Ermolaev, An Improved Broadband Decoupling Sequence for Liquid Crystals and Solids, Journal of Magnetic Resonance, vol.142, pp.97-101, 2000.

M. S. Blois, Antioxidant determination by the use of a stable free radical, Nature, vol.181, pp.1199-1200, 1958.

M. I. Alvarez-echazú, C. E. Olivetti, C. Anesini, C. J. Perez, G. S. Alvarez et al., Development and evaluation of thymol-chitosan hydrogels with antimicrobial-antioxidant activity for oral local delivery, Materials Science and Engineering: C, vol.81, pp.588-596, 2017.

F. Pourpoint, C. Gervais, L. Bonhomme-coury, T. Azaïs, C. Coelho et al., Calcium Phosphates and Hydroxyapatite: Solid-State NMR Experiments and First-Principles Calculations, Appl Magn Reson, vol.32, pp.435-457, 2007.
URL : https://hal.archives-ouvertes.fr/hal-00343640

K. Beshah, C. Rey, M. J. Glimcher, M. Schimizu, and R. G. Griffin, Solid state carbon-13 and proton NMR studies of carbonate-containing calcium phosphates and enamel, Journal of Solid State Chemistry, vol.84, pp.71-81, 1990.

D. K. Pattanayak, S. Yamaguchi, T. Matsushita, T. Nakamura, and T. Kokubo, Apatite-forming ability of titanium in terms of pH of the exposed solution, Journal of The Royal Society Interface, vol.9, pp.2145-2155, 2012.

R. Legros, N. Balmain, and G. Bonel, Age-related changes in mineral of rat and bovine cortical bone, Calcif Tissue Int, vol.41, pp.137-144, 1987.

I. A. Karampas and C. G. Kontoyannis, Characterization of calcium phosphates mixtures, Vibrational Spectroscopy, vol.64, pp.126-133, 2013.

G. Penel, C. Delfosse, M. Descamps, and G. Leroy, Composition of bone and apatitic biomaterials as revealed by intravital Raman microspectroscopy, Bone, vol.36, pp.893-901, 2005.

M. Kazanci, P. Fratzl, K. Klaushofer, and E. P. Paschalis, Complementary Information on In Vitro Conversion of Amorphous (Precursor) Calcium Phosphate to Hydroxyapatite from Raman Microspectroscopy and Wide-Angle X-Ray Scattering, Calcif Tissue Int, vol.79, pp.354-359, 2006.

M. M. Kerssens, P. Matousek, K. Rogers, and N. Stone, Towards a safe non-invasive method for evaluating the carbonate substitution levels of hydroxyapatite (HAP) in micro-calcifications found in breast tissue, Analyst, vol.135, p.3156, 2010.

M. Ben-osman, J. M. Krafft, Y. Millot, F. Averseng, T. Yoshioka et al., Molecular Understanding of the Bulk Composition of Crystalline Nonstoichiometric Hydroxyapatites: Application to the Rationalization of Structure-Reactivity Relationships, European Journal of Inorganic Chemistry, pp.2709-2720, 2016.
URL : https://hal.archives-ouvertes.fr/hal-01378491

S. Diallo-garcia, D. Laurencin, J. Krafft, S. Casale, M. E. Smith et al., Influence of Magnesium Substitution on the Basic Properties of Hydroxyapatites, The Journal of Physical Chemistry C, vol.115, pp.24317-24327, 2011.
URL : https://hal.archives-ouvertes.fr/hal-00653862

W. J. Landis and J. R. Martin, X-ray photoelectron spectroscopy applied to gold-decorated mineral standards of biological interest, Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, vol.2, pp.1108-1111, 1984.

D. J. Miller, M. C. Biesinger, and N. S. Mcintyre, Interactions of CO2 and CO at fractional atmosphere pressures with iron and iron oxide surfaces: one possible mechanism for surface contamination?, Surface and Interface Analysis, vol.33, pp.299-305, 2002.

A. Shchukarev and D. Korolkov, XPS Study of group IA carbonates, Central European Science Journals, vol.2, pp.347-362, 2004.

T. R. Machado, J. C. Sczancoski, H. Beltrán-mir, I. C. Nogueira, M. S. Li et al., A novel approach to obtain highly intense self-activated photoluminescence emissions in hydroxyapatite nanoparticles, Journal of Solid State Chemistry, vol.249, pp.64-69, 2017.

K. T. Arul, E. Kolanthai, E. Manikandan, G. M. Bhalerao, V. S. Chandra et al., Green synthesis of magnesium ion incorporated nanocrystalline hydroxyapatite and their mechanical, dielectric and photoluminescence properties, Materials Research Bulletin, vol.67, pp.55-62, 2015.

C. Zhang, J. Yang, Z. Quan, P. Yang, C. Li et al., Hydroxyapatite Nano-and Microcrystals with Multiform Morphologies: Controllable Synthesis and Luminescence Properties, vol.9, pp.2725-2733, 2009.

K. Farbod, M. R. Nejadnik, J. A. Jansen, and S. C. Leeuwenburgh, Interactions Between Inorganic and Organic Phases in Bone Tissue as a Source of Inspiration for Design of Novel Nanocomposites, Tissue Engineering Part B: Reviews, vol.20, pp.173-188, 2014.

H. Bouyarmane, S. E. Asri, A. Rami, C. Roux, M. A. Mahly et al., Pyridine and phenol removal using natural and synthetic apatites as low cost sorbents: Influence of porosity and surface interactions, Journal of Hazardous Materials, vol.181, pp.736-741, 2010.
URL : https://hal.archives-ouvertes.fr/hal-00504830

M. Harja and G. Ciobanu, Studies on adsorption of oxytetracycline from aqueous solutions onto hydroxyapatite, Science of The Total Environment, pp.36-43, 2018.

L. C. Bell, A. M. Posner, and J. P. Quirk, The point of zero charge of hydroxyapatite and fluorapatite in aqueous solutions, Journal of Colloid and Interface Science, vol.42, pp.90288-90297, 1973.

W. M. Chirdon, W. J. O'brien, and R. E. Robertson, Adsorption of catechol and comparative solutes on hydroxyapatite, Journal of Biomedical Materials Research Part B: Applied Biomaterials, vol.66, pp.532-538, 2003.

O. W. Duckworth and S. T. Martin, Surface complexation and dissolution of hematite by C1-C6 dicarboxylic acids at pH = 5.0, Geochimica et Cosmochimica Acta, vol.65, pp.4289-4301, 2001.

H. Gulley-stahl, P. A. Hogan, W. L. Schmidt, S. J. Wall, A. Buhrlage et al., Surface Complexation of Catechol to Metal Oxides: An ATR-FTIR, Adsorption, and Dissolution Study, Environmental Science & Technology, vol.44, pp.4116-4121, 2010.

M. Patra, R. Mukherjee, M. Banik, D. Dutta, N. A. Begum et al., Calcium phosphatequercetin nanocomposite (CPQN): A multi-functional nanoparticle having pH indicating, highly fluorescent and anti-oxidant properties, Colloids and Surfaces B: Biointerfaces, vol.154, pp.63-73, 2017.

G. Venkatasubbu, S. Ramasamy, V. Ramakrishnan, and J. Kumar, Nanocrystalline hydroxyapatite and zinc-doped hydroxyapatite as carrier material for controlled delivery of ciprofloxacin, pp.173-186, 2011.

J. Jiang, Y. Li, T. Fang, J. Zhou, X. Li et al., Vancomycin-loaded nano-hydroxyapatite pellets to treat MRSA-induced chronic osteomyelitis with bone defect in rabbits, Inflamm. Res, vol.61, pp.207-215, 2012.

L. Ploux, M. Mateescu, L. Guichaoua, J. Valentin, J. Böhmler et al., New colloidal fabrication of bioceramics with controlled porosity for delivery of antibiotics, J Mater Sci, vol.51, pp.8861-8879, 2016.
URL : https://hal.archives-ouvertes.fr/hal-01877735

O. Geuli, N. Metoki, T. Zada, M. Reches, N. Eliaz et al., Synthesis, coating, and drugrelease of hydroxyapatite nanoparticles loaded with antibiotics, J. Mater. Chem. B, vol.5, pp.7819-7830, 2017.

M. Rivas, L. J. Valle, A. M. Rodríguez-rivero, P. Turon, J. Puiggalí et al., Loading of Antibiotic into Biocoated Hydroxyapatite Nanoparticles: Smart Antitumor Platforms with Regulated Release, ACS Biomaterials Science & Engineering, vol.4, pp.3234-3245, 2018.

E. Palierse, Conceptualization, Investigation, Formal analysis, Visualization, Validation, Writing -Original Draft Christophe Hélary: Methodology, Validation, Writing -Review & Editing Jean-Marc Krafft: Methodology, Investigation, Validation, Writing -Review & Editing Isabelle Génois: Investigation, Writing -Review & Editing Sylvie Masse: Methodology, Investigation, Writing -Review & Editing Guillaume Laurent: Methodology, Investigation, Visualization, Formal analysis, Writing -Review & Editing Maria I. Alvarez Echazu: Investigation, Writing -Review & Editing Mohamed Selmane: Investigation, Writing -Review & Editing Sandra Casale: Investigation, Writing -Review & Editing Antoine Miche: Investigation, Writing -Review & Editing Ben C.L. Chan: Resources, Writing -Review & Editing Clara B.S. Lau: Resources, Writing -Review & Editing Margaret Ip : Resources, Writing -Review & Editing Martin F. Desimone : Methodology, Validation, Writing -Review & Editing Thibaud Coradin : Funding acquisition