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Objectives To systematically present and interpret the current literature on research and treatment perspectives for mandibular osteoradionecrosis (mORN) in the field of biomaterials. Material and methods A systematic review of the literature using the “Synthesis without meta-analysis” (SWiM) methodology was performed on PubMed, Embase and Cochrane, focusing on the implantation of synthetic biomaterials for bone reconstruction in mORN in humans and/or animal models. The primary endpoints were the composition, efficacy on mORN and tolerance of the implanted synthetic biomaterials. Results Forty-seven references were obtained and evaluated in full-text by two assessors. Ten (8 in humans and 2 in animal models) met the eligibility criteria and were included for analysis. Materials most often comprised support plates or metal mesh (5 of 10 cases) in combination with grafts or synthetic materials (phosphocalcic ceramics, glutaraldehyde). Other ceramic/polymer composites were also implanted. In half of the selected reports, active compounds (molecules, growth factors, lysates) and/or cells were associated with the reconstruction material. The number of articles referring to implantation of biomaterials for the treatment of mORN was small, and the properties of the implanted biomaterials were generally poorly described, thus limiting a thorough understanding of their role. Conclusion In preventing the morbidity associated with some reconstructive surgeries, basic research has benefitted from recent advances in tissue engineering and biomaterials to repair limited bone loss.

Multiscale and multitool advanced characterisation of pyrophosphate-stabilised amorphous calcium carbonates allowed building a cluster-based model paving the way for tunable biomaterials.

Amorphous calcium phosphate-based materials are of major interest in the field of bone substitution. Very recently, the low-temperature synthesis of a new family of amorphous calcium phosphate containing both orthophosphate and pyrophosphate ions in controlled proportions has been reported. Despite their interest, especially due to the biochemical role and the hydrolysis of pyrophosphate occurring

International audience; This work aimed at the synthesis of hydrogel-based composite core/shell nanoparticles and their subsequent surface modification with thermoresponsive copolymers. Submicron hydrogel-based nanoparticles were obtained from the layer-by-layer coating of silica nanoparticles with two natural oppositely-charged polyelectrolytes, chitosan and sodium alginate. Further modifications with a PVAm-b-PNIPAM copolymer synthetized by RAFT polymerization was achieved by the “grafting to” approach. First, the optimum feed weight ratio (fwr) was determined by a combined approach of zeta potential and T2 relaxation time measurements. Then, diblock grafting at this optimum fwr was performed and characterized by XPS. XPS analysis confirmed the presence of copolymer at the particles’ surface with the increase of C and N atomic percentage. The quantification study was carried out by spectrofluorimetry using the fluorescently labeled PVAm-b-P(NIPAM-stat-NVC) copolymer and revealed that the grafting efficiency could reach 60 %. Finally, a study of thermosensivity properties confirmed that our smart system allowed a temperature-induced destabilization of the particles suspension at 45 °C. This work has promising prospects in the field of controlled drug delivery.

α-Canaphite (CaNa2P2O7·4H2O) is a layered calcium disodium pyrophosphate tetrahydrate phase of significant geological and potential biological interest. This study overcomes the lack of a reliable protocol to synthesize pure α-canaphite by using a novel simple and reproducible approach of double decomposition in solution at room temperature. The pure α-canaphite is then characterized from the atomic to the macroscopic level using a multitool and multiscale advanced characterization strategy, providing for the first time full resolution of the α-canaphite monoclinic structure, including the hydrogen bonding network. Synchrotron X-ray diffraction and neutron diffraction are combined with multinuclear solid state NMR experimental data and computational modeling via DFT/GIPAW calculations. Among the main characteristics of the α-canaphite structure are some strong hydrogen bonds and one of the four water molecules showing a different coordination scheme. This peculiar water molecule could be the last to leave the collapsed structure on heating, leading eventually to anhydrous α-CaNa2P2O7 and could also be involved in the internal hydrolysis of pyrophosphate ions as it is the closest water molecule to the pyrophosphate ions. Relating such detailed structural data on α-canaphite to its physico-chemical properties is of major interest considering the possible roles of canaphite for biomedical applications. The vibrational spectra of α-canaphite (deuterated or not) are analyzed and Raman spectroscopy appears to be a promising tool for the identification/diagnosis of such microcrystals in vitro, in vivo or ex vivo.

Calcium is an essential component of osteogenesis and is often required for imparting significant bioactivity to synthetic bone substitutes and, in particular, silicate-based materials. However, the mechanism of calcium incorporation inside sol-gel silicates is poorly understood. In this work, we shed light on the determinant parameters for incorporation of calcium into acid-base-catalyzed sol-gel silicates at ambient temperature: increasing the pH above the isoelectric point of silicic acid and the nature of the calcium counterion in the calcium precursor are found to be the key. Based on our proposed reaction sequence, we were able to compare calcium precursors and select an ideal candidate compound for the synthesis of bioactive glasses (BG) and organic-inorganic hybrids at ambient temperature. Reproducible syntheses and gel times of SiO

International audience; Polyester-based composites with silica nanoparticles fillers are promising candidates as biomaterials due to improved mechanical and biological properties. However, nanofillers use generally leads to an inhomogeneous distribution inside the polymer matrix because of agglomeration, decreasing composites overall performances. In view of improving nanofillers dispersion, we developed a synthesis and characterization method to design poly(d,l-lactide)-grafted silica nanoparticles using “grafting to” method and to quantify the amount of grafted poly(d,l-lactide). Firstly, well-defined N-hydroxysuccinimide ester poly(d,l-lactide)s were synthesized through a new pathway. Then, amino-functionalized silica nanoparticles were grafted with those customized polyesters yielding an amide covalent bond between both reagents. Such PDLLA-grafted nanoparticles were precisely characterized and the grafting amount was quantified using a dual approach based on TGA and FTIR analysis. The synthesis and the characterization methods developed constitute a robust and reproducible way to design well-defined polymer-grafted silica nanoparticles that could be used as nanofillers in polymer matrix nanocomposites for biomedical applications.

International audience; Amorphous calcium orthophosphates (ACP) are bioactive compounds presenting high interest as bone substitute. However, the synthesis of such metastable products requires special attention as they can rapidly evolve into a crystalline phase during the elaboration process. The resulting increased stability generally leads to less bioactive reactive materials. Among the various strategies developed to obtain stable form of ACP, the use of spray drying is an effective and reproducible route. Compared to previous works, this study aims to demonstrate for the first time the feasibility of ACP elaboration by spray drying directly from a single solution of selected precursors. Moreover, structuration of the spray-dried powders was determined at different length scales, demonstrating a hierarchical organization from nanometric clusters to particles aggregates. These complementary analyses highlighted a thorough mechanism of particles formation during processing. The effect of the initial composition of the solution was observed, and it was demonstrated that there is a correlation with the purity of the final product that may be modulated. In addition, ACP powders were found to be highly reactive in aqueous medium and their fast transformation into low crystalline apatite suggests a good suitability for biomedical use.

The development of amorphous phosphate-based materials is of major interest in the field of biomaterials science, and especially for bone substitution applications. In this context, we herein report the synthesis of gel-derived hydrated amorphous calcium/sodium ortho/pyrophosphate materials at ambient temperature and in water. For the first time, such materials have been obtained in a large range of tunable orthophosphate/pyrophosphate molar ratios. Multi-scale characterization was carried out thanks to various techniques, including advanced multinuclear solid state NMR. It allowed the quantification of each ionic/molecular species leading to a general formula for these materials: [(Ca2+y Na+z H+3+x-2y-z)(PO43−)1-x(P2O74−)x](H2O)u. Beyond this formula, the analyses suggest that these amorphous solids are formed by the aggregation of colloids and that surface water and sodium could play a role in the cohesion of the whole material. Although the full comprehension of mechanisms of formation and structure is still to be investigated in detail, the straightforward synthesis of these new amorphous materials opens up many perspectives in the field of materials for bone substitution and regeneration. Statement of significance The metastability of amorphous phosphate-based materials with various chain length often improves their (bio)chemical reactivity. However, the control of the ratio of the different phosphate entities has not been yet described especially for small ions (pyrophosphate/orthophosphate) and using soft chemistry, whereas it opens the way for the tuning of enzyme- and/or pH-driven degradation and biological properties. Our study focuses on elaboration of amorphous gel-derived hydrated calcium/sodium ortho/pyrophosphate solids at 70 °C with a large range of orthophosphate/pyrophosphate ratios. Multi-scale characterization was carried out using various techniques such as advanced multinuclear SSNMR (31P, 23Na, 1H, 43Ca). Analyses suggest that these solids are formed by colloids aggregation and that the location of mobile water and sodium could play a role in the material cohesion.

International audience; Calcium is an essential component of osteogenesis and is often required for imparting significant bioactivity to synthetic bone substitutes and, in particular, silicate-based materials. However, the mechanism of calcium incorporation inside sol–gel silicates is poorly understood. In this work, we shed light on the determinant parameters for incorporation of calcium into acid–base-catalyzed sol–gel silicates at ambient temperature: increasing the pH above the isoelectric point of silicic acid and the nature of the calcium counterion in the calcium precursor are found to be the key. Based on our proposed reaction sequence, we were able to compare calcium precursors and select an ideal candidate compound for the synthesis of bioactive glasses (BG) and organic–inorganic hybrids at ambient temperature. Reproducible syntheses and gel times of SiO2–CaO BG were obtained using calcium hydroxide (CH), and we demonstrate its usability in the synthesis of promising BG–polycaprolactone hybrid scaffolds. BG and hybrids prepared with CH were able to form nanocrystalline nonstoichiometric apatite in simulated body fluid. The increased reliability of low-temperature syntheses associated with the use of a stable and inexpensive alkaline-earth precursor are major steps toward the translation of calcium silicate hybrids or other alkaline-earth silicates from bench to clinic.

International audience; This paper focuses on the fabrication of three-dimensional porous PLGA-biomimetic carbonated apatite composite scaffolds by freeze-casting and using dimethyl carbonate as a solvent. Several charge/polymer ratios were tested in order to finely understand the influence of the filler rate on the scaffold porosity and mechanical and degradation properties using complementary characterization techniques (SEM, mercury porosimetry and X-ray microtomography). It was demonstrated that the apatite ratio within the composite scaffold has a strong influence in terms of architecture, material cohesion, mechanical properties and in vitro degradation properties. An optimum biomimetic apatite ratio was reached to combine good mechanical properties (higher rigidity) and material cohesion. In vitro degradation studies showed that higher apatite filler rates limited PLGA degradation and enhanced the hydrophilicity of the scaffolds which is expected to improve the biological properties of the scaffolds in addition to the bioactivity related to the presence of the apatite analogous to bone mineral.

International audience; Mesoporous Silica Nanoparticles (MSN) are used in an increasing number of applications in nanomedicine. Their synthesis and external/internal functionalization have been extensively studied as well as their biological properties. Nevertheless, the conventional drug loading processes of MSN (such as impregnation), do not enable sufficient efficiency and are difficult to consider on an industrial scale. To overcome these limitations, we implemented an innovative co-spray-drying process, using a nano spray-dryer, to load MSN with ibuprofen molecules. In this contribution, complementary techniques were used to perform a multi-scale characterization of the loaded particles. Spray-dried powders have been analysed from aggregates size and morphology to pore loading and ibuprofen conformation. This study demonstrates that ibuprofen/silica weight ratio in the initial suspension strongly affects the location (into 2 mesopores or external) and the conformation (crystallized, amorphous or liquid-like) of ibuprofen. The quantification of each phase has allowed calculating precise loading rates and demonstrate tunable pore filling.

Macroporous biomaterials have attracted much attention during the past decade because of the large range of associated applications (from drug delivery to tissue engineering). The present study focuses on the correlations between macropore size (from 400 to 1500 nm in diameter) and the early steps of biomineralization process and the reactivity in binary (SiO2-CaO) and ternary (SiO2-CaO-P2O5) bioactive glasses. Macrostructured glasses were elaborated by combining sol-gel chemistry and an inverse opal method with polystyrene beads colloidal crystals as the template. Macroporosity of these materials has been characterized thanks to thermoporosimetry. The in vitro biomineralization process was studied using particle-induced X-ray emission (PIXE) associated with Rutherford backscattering spectrometry (RBS), which are efficient methods for a highly sensitive multielemental analysis. Thanks to elemental maps of silicon, calcium, and phosphorus obtained at a micrometer scale for various interaction times, we demonstrate that the physicochemical reactions are sensitive to macropore size, even though their kinetic is not modified. This key result is an important step to build tunable biomaterials with a highly reproducible and finely controlled response for an optimized integration in living organisms.

The chapter discusses the physical–chemical properties of calcium phosphates (Ca-P), among the most used bioactive ceramics. The main calcium phosphate compounds are presented with a brief description of their synthesis methods, their characterization, using different techniques, including chemical analyzes, X-ray diffraction, Fourier transform infrared (FTIR) and Raman spectroscopies, solid-state nuclear magnetic resonance (NMR), scanning and transmission electron microscopies (SEM and TEM). Their thermochemical characteristics are given and the thermal stability and relationships between different Ca-P phases are then described. Their solubility, transformations and hydrolysis, nucleation ability, surface properties and reactivity (ion exchange, adsorption) are presented especially in the case of apatites. The biological response regarding bioactivity, biodegradation, and simulated body fluid (SBF) testing is discussed from the point of view of the Ca-P physical chemistry. Several examples of applications and processing techniques are then proposed as nanoparticles, bulk ceramics, coatings, cements, and composite materials.

The development of bioactive phosphate-based glasses is essential in biomaterials science, and especially for bone substitution applications. In this context, the preparation of amorphous calcium-phosphorus hydroxide/oxide monoliths at low temperature is a key challenge for being able to develop novel hybrid materials for these applications. We herein report for the first time the synthesis and physical chemical characterisation of a novel family of pyrophosphate-based glasses (with the formula: {[(Ca(2+))1-x(H(+)/K(+))2x]2[(P2O7(4-))1-y(PO4(3-))4y/3]} n(H2O)), which were prepared by soft chemistry using low temperatures (T70°C) and water as a solvent. The effect of the initial Ca/Pyrophosphate ratio on the structure and morphology of these pyrophosphate glasses was investigated in detail. Depending on this ratio, a glass (mixed calcium pyro- and orthophosphate) or a glass-ceramic (Ca10K4(P2O7)6·9H2O crystals embedded in the amorphous phase) was obtained. The proportion of the crystalline phase increased with an increase in the Ca/Pyrophosphate ratio in the batch solution. As expected for a glass, the formation of the glassy material was demonstrated not to be thermodynamically but rather kinetically driven, and the washing step was found to be crucial to prevent crystallisation. The stability of the amorphous phase was discussed considering the structural degrees of freedom of pyrophosphate entities, ionic strength of the initial solution and the inhibitory effect of orthophosphate ions. Overall, this new strategy of preparation of monolithic calcium-(pyro)phosphate based glasses using soft chemistry in water is highly promising in view of preparing new functional organic-inorganic hybrids for bone substitution applications.Phosphate-based glasses have gradually emerged as a potential alternative to silicate bioactive glasses in order to induce different biological mechanisms of degradation. The synthesis of such monolithic glasses at low temperature is a key step to allow new inorganic glass compositions to be reached and hybrid materials to be prepared. Although sol-gel and coacervate methods (respectively orthophosphate and metaphosphate precursors) have already been described to prepare such glasses, the use of toxic solvents and/or the final temperature treatment associated to these processes could limit the use of these materials for biomedical applications and/or the further development of hybrids. It is shown here that pyrophosphate precursors are an alternative strategy to obtain monolithic calcium (pyro)phosphate glasses under soft conditions (water solvent, 70°C).

International audience; Building mesostructured biomaterials is a challenging and exciting task that has attracted much attention because of their use as drug carriers or drug delivery systems. In the case of bioactive materials, the mesostructuration can also deeply impact their physico-chemical properties and the reactivity. In this study, we show how highly ordered mesoporosity influence the early steps of biomineralization process and the reactivity in binary (SiO2-CaO) and ternary (SiO2-CaO-P2O5) bioactive glasses. Conventional porous sol-gel glasses were synthesized using a classical route, while mesostructured glasses were elaborated using a non-ionic surfactant. Textural properties of these materials have been characterized. The in vitro biomineralization process was followed, using Particle Induced X-ray Emission (PIXE) associated to Rutherford Backscattering, Spectrometry (RBS), which are efficient methods for a highly sensitive multi-elemental analysis. Elemental maps of silicon, calcium and phosphorus were obtained at a micrometer scale and revealed for the first time a bulk reactivity for mesostructured glasses. This is a major advantage over conventional glasses, for which the first steps of biomineralization are limited to the periphery of the material. Their enhanced bioactivity combined with their possible use as drug-delivery systems make them promising candidates for bone regeneration.

The definition of biomaterial as proposed by the European Society for Biomaterials in 1986 puts forward the overall importance of the notion of contact between the biomaterial and biological medium (cell, tissue, fluid,...). The underlying concept of biocompatibility makes the interface between biomaterial and biological medium a privileged zone of interest. In this paper, we would like to give an exhaustive view of how ion beams techniques can contribute to a better understanding of such interface taking several examples dealing with bone tissue substitution. After a short presentation of ion beams techniques the paper will focus on PIXE/RBS spectroscopies and will give the basics of these coupled technique. Three examples will then be presented to illustrate the interest of these techniques to study biomaterials/biological interactions. The first example deals with metallic alloys based joint prostheses. The ionic release from the prosthesis and the wear behavior of total knee prostheses will be presented. In the last two examples, bioactive materials will be studied. The common characteristic of bioactive ceramics is the kinetic modification of their surface upon interaction which is ideally monitored by PIXE chemical mapping. The second example will review the benefit of using PIXE/RBS technique to study the effect of doping of bioactive glasses on the very first steps involved in the bioactivity mechanisms like dissolution, ionic release, and biomineralization onto the surface of the glasses. Finally, protein delivery systems based upon mesoporous hydroxyapatites will be studied. Chemical mapping allowing the quantitative determination of protein distribution inside the HAp grains will be presented for the first time.

International audience; The aim of this study is to highlight the influence of magnesium doping on the surface reactivity of binary (SiO(2)-CaO) and ternary (SiO(2)-CaO-P(2)O(5)) bioactive glasses, prepared by sol-gel chemistry, in biological conditions. These materials were produced in powder form, and their compositional and textural properties characterized. They were then soaked in biological fluids for different delays from 0 to 4 days. The surface changes were characterized using Particles Induced X-ray Emission (PIXE) associated with Rutherford Backscattering Spectroscopy (RBS), which are efficient methods for multi-elemental analysis. Elemental maps of major and trace elements were obtained at a micrometer scale and revealed the formation of a calcium phosphate-rich layer after a few days of interaction. We demonstrate that the presence of magnesium in the material has an impact on the development and the formation rate of the bone-like apatite layer.

International audience; Sodium niobium borophosphate glass, with a composition of 0.58(0.95NaPO3+0.05Na2B4O7)+0.42Nb2O5, has been doped with monovalent silver ions. Second harmonic generation (SHG) has been obtained from the poling treatment of this sample. The second order nonlinearity from the anode side was estimated from an analysis of transmitted polarized Maker-fringe patterns. Thanks to the original Maker fringe simulations, a value of 3 pm/V is obtained with the silver doped glass that unambiguously scales an enhancement of ~35% with respect to the nondoped glass susceptibility. For both glasses, the nonlinear layer is found to be sodium-depleted up to 4 µm inside the anode, in accordance with quantitative energy dispersive x-ray spectroscopy characterizations. This comparative study indicates complex space-charge-migration processes during the poling treatment. The relative enhancement of the SHG signal of the silver doped glass is correlated with the increase in its linear susceptibility.

This paper presents a series of acidoswitchable NLO-phores combining the 9-methylbenzimidazolo[2,3-b]oxazolidine core with various pi systems such as phenylethenyl, phenylethynyl, and naphthylethenyl. All the prepared derivatives are shown to display acidochromic behavior at ambient temperature. The remarkable contrast in the NLO response along the reversible transformations observed in HRS experiments is rationalized by high level theoretical calculations.

The present work concerns the study of an amorphous hydrated calcium and sodium mixed ortho- and pyrophosphate materials which present an interest for biomaterial application in the case of bone regeneration due to the presence of orthophosphate ions (elementary brick of biological apatite formation) and pyrophosphate ions (hydrolysis phenomenon at low pH or by enzymatic activities in bone tissue). These materials are synthesis using soft chemistry protocol including a solution-gel transition and then to a solid state. The objective of this thesis is to study the effect of different synthesis parameters in order to determine the formation mechanism of the original materials and to describe their structure. In fact, we studied the effect of relative composition of initial solution on phosphate precursor (various ranges of molar ratios of ortho- and pyrophosphates) and the drying temperature effect during the last step of the synthesis protocol on the composition of the composition and the structure of the final material by using several complementary characterizations and at various scales (XRD, SEM, TEM, Raman spectroscopy, GTA/DTA, solid-state NMR and chemical analysis). Firstly, we showed that it is possible to control the composition of the final material using the composition of the initial phosphate precursor solution. The extreme compositions (100% pyro- and 100% ortho-) lead to a more or less crystallized phase such as a-canaphite and nanocrystalline apatite, respectively. On the other hand, all materials synthesised with an intermediate composition of phosphate precursor solution (mixed ortho- and pyro-) are amorphous and their compositions were used to propose a general chemical formula for theses amorphous hydrated calcium and sodium mixed ortho- and pyrophosphate materials. It has been possible to clarify certain hypotheses, such as the inhibitory effect of the pyrophosphate ions on the calcium orthophosphate crystallization (and vice-versa), which control the final structure of the material (amorphous or crystalline) and this control can be extended to a large range of composition. The solid-state NMR and the TEM highlight the colloidal formation of the materials and it can be relevant to compare them with Posner cluster model. In a second part, we showed that the drying temperature is a key parameter to control the hydration state of these materials but we can also use this parameter to understanding the internal hydrolysis reaction of the pyrophosphate ions into orthophosphate ions in the final material.[...]; Ce mémoire porte sur l'étude de nouveaux matériaux amorphes mixtes orthophosphate et pyrophosphate de calcium et de sodium qui présentent un intérêt pour des applications en tant que biomatériaux de régénération osseuse du fait de la présence des ions ortho- (briques élémentaires pour la formation d'apatite biologique) et d'ions pyrophosphate (hydrolysables en orthophosphates à pH acide ou par action d'enzymes présentes dans le tissu osseux). Ces matériaux sont élaborés par chimie douce incluant le passage d'une solution à un gel puis à un solide. L'objectif de cette thèse est d'étudier l'effet de différents paramètres de synthèse en vue de déterminer les mécanismes de formation de ces matériaux originaux et de décrire leur structure. En particulier, nous avons étudié l'effet de la composition relative de la solution initiale en précurseurs phosphates (différents ratios molaires en ions ortho- et pyrophosphates) et de la température de séchage lors de la dernière étape du protocole d'élaboration sur la composition et la structure du matériau final en mettant en œuvre différentes techniques de caractérisation complémentaires et à différentes échelles (DRX, MEB, MET, spectroscopie Raman, ATG/ATD, RMN du solide, analyses chimiques). Dans un premier temps, nous montrons qu'il est possible de contrôler la composition du matériau final à partir de celle de la composition de la solution initiale de précurseurs phosphates. Les compositions extrêmes étudiées (100% pyro- et 100% ortho-) conduisent à une phase plus ou moins bien cristallisée : la canaphite a et l'apatite nanocristalline, respectivement. En revanche, tous les matériaux élaborés à partir d'une solution de composition intermédiaire (mixte ortho- et pyro-) sont amorphes et leur composition a été déterminée ce qui a permis de proposer une formule chimique générale pour ces matériaux amorphes mixtes ortho et pyrophosphates de calcium et sodium hydratés. Il a été possible de préciser certaines hypothèses, comme l'effet inhibiteur de l'ion pyrophosphate sur la cristallisation de l'orthophosphate de calcium (et vice-versa), qui contrôle la structure du matériau final (amorphe ou cristallin) et ce pour une grande gamme de compositions de matériaux. La caractérisation fine par RMN du solide et par MET ont permis de mettre en évidence une formation de type colloïdale de ces types de matériaux et pouvant s'appuyer sur le modèle de cluster de type Posner. Dans un second temps, nous montrons que la température de séchage, est un paramètre contrôlant l'état d'hydratation de ces matériaux mais aussi la réaction d'hydrolyse interne des ions pyrophosphate en ions orthophosphate au sein du matériau ainsi que la réaction inverse de condensation des ions ortho- en ions pyrophosphate vers 400°C.[...]

The present work concerns the study of an amorphous hydrated calcium and sodium mixed ortho- and pyrophosphate materials which present an interest for biomaterial application in the case of bone regeneration due to the presence of orthophosphate ions (elementary brick of biological apatite formation) and pyrophosphate ions (hydrolysis phenomenon at low pH or by enzymatic activities in bone tissue). These materials are synthesis using soft chemistry protocol including a solution-gel transition and then to a solid state. The objective of this thesis is to study the effect of different synthesis parameters in order to determine the formation mechanism of the original materials and to describe their structure. In fact, we studied the effect of relative composition of initial solution on phosphate precursor (various ranges of molar ratios of ortho- and pyrophosphates) and the drying temperature effect during the last step of the synthesis protocol on the composition of the composition and the structure of the final material by using several complementary characterizations and at various scales (XRD, SEM, TEM, Raman spectroscopy, GTA/DTA, solid-state NMR and chemical analysis). Firstly, we showed that it is possible to control the composition of the final material using the composition of the initial phosphate precursor solution. The extreme compositions (100% pyro- and 100% ortho-) lead to a more or less crystallized phase such as a-canaphite and nanocrystalline apatite, respectively. On the other hand, all materials synthesised with an intermediate composition of phosphate precursor solution (mixed ortho- and pyro-) are amorphous and their compositions were used to propose a general chemical formula for theses amorphous hydrated calcium and sodium mixed ortho- and pyrophosphate materials. It has been possible to clarify certain hypotheses, such as the inhibitory effect of the pyrophosphate ions on the calcium orthophosphate crystallization (and vice-versa), which control the final structure of the material (amorphous or crystalline) and this control can be extended to a large range of composition. The solid-state NMR and the TEM highlight the colloidal formation of the materials and it can be relevant to compare them with Posner cluster model. In a second part, we showed that the drying temperature is a key parameter to control the hydration state of these materials but we can also use this parameter to understanding the internal hydrolysis reaction of the pyrophosphate ions into orthophosphate ions in the final material.[...], Ce mémoire porte sur l'étude de nouveaux matériaux amorphes mixtes orthophosphate et pyrophosphate de calcium et de sodium qui présentent un intérêt pour des applications en tant que biomatériaux de régénération osseuse du fait de la présence des ions ortho- (briques élémentaires pour la formation d'apatite biologique) et d'ions pyrophosphate (hydrolysables en orthophosphates à pH acide ou par action d'enzymes présentes dans le tissu osseux). Ces matériaux sont élaborés par chimie douce incluant le passage d'une solution à un gel puis à un solide. L'objectif de cette thèse est d'étudier l'effet de différents paramètres de synthèse en vue de déterminer les mécanismes de formation de ces matériaux originaux et de décrire leur structure. En particulier, nous avons étudié l'effet de la composition relative de la solution initiale en précurseurs phosphates (différents ratios molaires en ions ortho- et pyrophosphates) et de la température de séchage lors de la dernière étape du protocole d'élaboration sur la composition et la structure du matériau final en mettant en œuvre différentes techniques de caractérisation complémentaires et à différentes échelles (DRX, MEB, MET, spectroscopie Raman, ATG/ATD, RMN du solide, analyses chimiques). Dans un premier temps, nous montrons qu'il est possible de contrôler la composition du matériau final à partir de celle de la composition de la solution initiale de précurseurs phosphates. Les compositions extrêmes étudiées (100% pyro- et 100% ortho-) conduisent à une phase plus ou moins bien cristallisée : la canaphite a et l'apatite nanocristalline, respectivement. En revanche, tous les matériaux élaborés à partir d'une solution de composition intermédiaire (mixte ortho- et pyro-) sont amorphes et leur composition a été déterminée ce qui a permis de proposer une formule chimique générale pour ces matériaux amorphes mixtes ortho et pyrophosphates de calcium et sodium hydratés. Il a été possible de préciser certaines hypothèses, comme l'effet inhibiteur de l'ion pyrophosphate sur la cristallisation de l'orthophosphate de calcium (et vice-versa), qui contrôle la structure du matériau final (amorphe ou cristallin) et ce pour une grande gamme de compositions de matériaux. La caractérisation fine par RMN du solide et par MET ont permis de mettre en évidence une formation de type colloïdale de ces types de matériaux et pouvant s'appuyer sur le modèle de cluster de type Posner. Dans un second temps, nous montrons que la température de séchage, est un paramètre contrôlant l'état d'hydratation de ces matériaux mais aussi la réaction d'hydrolyse interne des ions pyrophosphate en ions orthophosphate au sein du matériau ainsi que la réaction inverse de condensation des ions ortho- en ions pyrophosphate vers 400°C.[...]