Functional Nanomaterials II-05.09.2007 New hybrid inorganic-organic nanomaterials obtained in hydrothermal conditions for regenerative medicine Roxana.
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Functional Nanomaterials II-05.09.2007
New hybrid inorganic-organic nanomaterials New hybrid inorganic-organic nanomaterials obtained in hydrothermal conditions for obtained in hydrothermal conditions for
regenerative medicineregenerative medicine
Roxana M. Piticescu, National R&D Institute for Non-ferrous and Rare Metals
102 Biruintei Blvd., Pantelimon, Ilfov, Romania
IMNR
Functional Nanomaterials II-05.09.2007
IntroductionMaterials chemistry, synthesis methods for nanostructured
materials
Original resultsHybrid organic-inorganic compounds
Conclusions
Acknowledgement
Functional Nanomaterials II-05.09.2007
Materials research involves two main domains of activity [1]:
Synthesis of novel materials for improving basic knowledge, making correlations between composition, chemical bonding, structure and resulting physical properties
New routes for producing materials by the development of economically cheaper processes
The optimization of the shape of materials (nano crystallites, thin films, single crystals…) for specific applications
[1] G. Demazeau, G. Goglio, A. Largeteau, Solvothermal processes in Materials Synthesis, Mater. Res. Soc. Symp. Proc. Vol. 878E, 2005
Introduction
Functional Nanomaterials II-05.09.2007
IntroductionWhat we know from the literature data: 1.Hybrid materials synthesis routes: copolymerisation of organosilanes and metal alkoxides, encapsulation of organic components within sol-gel derived silica or metallic oxides, organic functionalisation of nanofillers, nanoclays or other compounds with lamellar structures
2. Strong chemical bonding between organic-inorganic phases enhance the mechanical properties of nanocomposites
3. Sol gel process drawbacks (large volume shrinkage due to the evaporation of large amount of solvent, small molecular hydrolysis by-products and poly-condensation reactions) limit its technological applications,
4. Fabrication ZnO nanostructured films and nanorods (diameter 90 nm, 1 micron lengths ) by CVD, PLD, electrodeposition, template methods presents some limitations to achieve a certain thickness and is incovenient for dopping when more dopants are used. ZnO-PVA was used due to well distributed ligand radicals on chain and the polymer chain limits the growth scale of ZnO core [5].
5. Fabrication of ZnO nanoparticles by thermooxidative degradation of ZnO complexes e.g.:[Zn(phen)2(H2O)2][Zn(phen)S2O3)2].4H2O [6]
[1]. Cuiming Wu &al, European Polymer Journal, 41, 1901-1908, (2005)[2]. Clement Sanchez &al, J.Mater.Chem., 15, 3559-3592 (2005)[3]. Eduardo Ruiz-Hitzky &al, J.Mater.Chem., 15, 3650-3662 (2005)[4]. Jui-Ming Yeh &al, Journal of Applied Polymer Science, 101, 1151-1159 (2006)[5].Ying He &all, J. Nanoparticles Res. 7, 307-310 (2005)[6]. A. Dumbrava&al., J. Therm. Analysis& Calorim., 79, 509-514 (2005)
Functional Nanomaterials II-05.09.2007
Methods for the preparation of nanostructured compounds
Conventional Conventional methodsmethods
Form-in-place Form-in-place processesprocesses
Gas phase synthesis Gas phase synthesis methodsmethods
Wet chemical methodsWet chemical methods(“soft chemistry”)(“soft chemistry”)
Mechanical methods
Physical vapor deposition (PVD)
Laser ablation Hydrothermal and solvothermal synthesis
Solid-state synthesis
Chemical vapor deposition (CVD)
Microwave plasma synthesis
Sol-gel method
Spray pyrolysis
Vaporization-Condensation (VC) using Solar Physical Vapor Deposition (SPVD)
Pechini method
The reactivity of the precursors play an important role in the preparation of novel materialsMild thermodynamic conditions (in terms of pressure and temperature parameters) specific to hydrothermal or solvothermal reactions are able to initiate through chemical bounding directly from solutions new nanostructures
Introduction
Functional Nanomaterials II-05.09.2007
Introduction
New Nanostructured
compounds
Previous original experimental works
Hydrothermal synthesis of nanostructured oxides, hybrids
organic-inorganic
Application in the field of Nanomedicine
Application in the field of Nanoelectronics
Application in the field of Functionally graded materials
Functional Nanomaterials II-05.09.2007
The main goal is to prepare original nanostructured compounds: hybrid organic/inorganic powders using hydrothermal method in mild conditions.
The stabilization of hybrid organic/inorganic materials is favored by low temperature and high pressure values.
Pressure can be the autogenous pressure (the vapor pressure of components in solution) or a higher pressure due to the barbotage of an inert gas before heating.
Some examples of hybrid organic/inorganic nanostructured compounds are presented :
Hydroxyapatite/collagen nanocomposites
Hybrid nanostructures based on hydroxyapatite/maleic acid copolymers
Hybrid nanostructures based on hydroxyapatite/layered silicate
Hybrid nanostructures based on ZnO/maleic acid copolymers
Functional Nanomaterials II-05.09.2007
S (STRENGTH) - O (OPORTUNITIES)
The ability to create crystalline phases which are not stable at the melting point
Materials which have a high vapor pressure near their melting points can be grown by a high pressure method
Suitable for the growth of large good-quality crystals while maintaining good control over their composition
Rapid nanoparticles production, morphology control with a little change of temperature or pressure, control of oxidation state by introducing oxygen or hydrogen gas
By introducing organic substances including biomolecules in a reaction atmosphere of supercriticalhydrothermal / solvothermal synthesis, nanoparticles whose surface is modified with organicmaterials can be synthesized. In supercritical state, water and organic materials form ahomogeneous phase, which provides an excellent reaction atmosphere for the organic modification of nanoparticles
Modification with bio-materials including amino acids is also possible. By changing organic modifiers, particle morphology and crystal structure can be changed. This organic surface modification provides a various unique characteristics for the nanoparticles; possibility to form strength chemical bonding under high pressures conditions between organic-inorganic phases
Dispersion of nanoparticles in aqueous solutions, organic solvents or in liquid polymers can becontrolled by selecting hydrophilic or hydrophobic modifiers
W (WEAKS) – T (THREATS)
Lack of thermodynamic and kinetic data
Very fine powders require high special compacting procedures
SWOT analysis of hydrothermal synthesis
Functional Nanomaterials II-05.09.2007
Inorganic salt solution Mineralising agent
Hydrothermal synthesis
Washing/Filtering
Wet powders
Mother liquor/Washing waters
Chemical analysis
Nanocrystalline powders
Solution of doping element
Polymer
UV-VIS, ICP,AAS
XRD, DSC,FT-IR, HRTEM
Structural characterisation
Hydrothermal synthesis of nanostructured compounds
Functional Nanomaterials II-05.09.2007
Hydroxyapatite/collagen Hydroxyapatite/collagen nanocompositesnanocomposites
FT-IR analysis of HAp/COL nanocomposites shows the specific bands of hydroxyapatite as well as the presence of collagen with its characteristic functional groups [2].
[2] L.M. Popescu, A. Meghea, R.M. Piticescu, E.Vasile, High pressure synthesis procedure to obtained nanostructured composites for regenerative medicine, submitted to Journal of Optoelectronics and Advanced Materials.
Original results
Functional Nanomaterials II-05.09.2007
Hydroxyapatite/collagen Hydroxyapatite/collagen nanocompositesnanocomposites
Hydroxyapatite-collagen hybrid powder consists of particles with spherical or polyhedral shape, grouped in small chains and measuring nearly 4-7 nm in diameter [2].
Nanocrystalline HAp
TEM image of one
representative sample (scale 100
nm)
Original results
[2] L.M. Popescu, A. Meghea, R.M. Piticescu, E.Vasile, High pressure synthesis procedure to obtained nanostructured composites for regenerative medicine, submitted to Journal of Optoelectronics and Advanced Materials.
Functional Nanomaterials II-05.09.2007
4500 4000 3500 3000 2500 2000 1500 1000 500
0
10
20
30
40
1992
3571
1411
3434
3631
894
1035
1641
3451
T [
%]
Wavenumber [cm-1]
BVCUAP-purified montmorillonite HBP 4
3635
3224
Roxana Piticescu&al., J. Liquid&Molecular Crystals 2007(In press)
Hybrid nanostructures based on Hybrid nanostructures based on hydroxyapatite/layered silicatehydroxyapatite/layered silicate
Original results
Functional Nanomaterials II-05.09.2007
Bright field transmission micrograph of sample HBP2
HRTEM micrograph of sample HBP2
Roxana Piticescu&al., J. Liquid&Molecular Crystals 2007(In press)
Original results
Hybrid nanostructures based on Hybrid nanostructures based on hydroxyapatite/layered silicatehydroxyapatite/layered silicate
Functional Nanomaterials II-05.09.2007
Original results
Some preliminary biocompatibility testsSome preliminary biocompatibility tests
SA
SA
SA
SNA
SNA
SA
TiNb/P1HA6S1 TiNb/P1HA6S1
SA
TiNb/P1HA6S2 TiNb/P1HA6S2
SA
SNASNA
SA
TiNb/P1HA6S3
TiNb/P1HA6S3
SA
Citotoxicity tests for TiAlNb alloys coated by spin coating procedure with Phosphorilated polissacharide-Hap nanostructured hybrids
Biocompatibility evaluation of a novel hydroxyapatite-polymer coating for medical implants ( in vitro tests)G.Negroiu, L. Zdrentu R.M. Piticescu ,G. C. Chitanu , I.N. MihailescuAccepted for publication in J.Materials Science: Materials in Medicine
Functional Nanomaterials II-05.09.2007
Original results
Hybrid nanostructures based on Hybrid nanostructures based on ZnO/maleic acid copolymerZnO/maleic acid copolymer
Zn(OH)2 - Zinc Hydroxide - 01-074-0094 (I)
ZnO - Zinc Oxide - 01-089-1397 (*)
File: ZnO - AM222.raw
Inte
nsity
(cps
)
0
100
200
300
400
500
2Theta (deg)
20 30 40 50 60 70
Functional Nanomaterials II-05.09.2007
Ca10(PO4)6 (OH)2A possible explanation of interactions between natural silicate and HAP
dTRT
Hpd
2ln
Vg > > Vl
Formation of nanocrystalline solid species is favored underhydrothermal conditions
New types of binary systems
Original results
Functional Nanomaterials II-05.09.2007
Conclusions
New binary systems based on hydroxyl apatite- purified montmorillonite - were synthesized in situ in hydrothermal conditions at high pressures and low temperatures. The process enables the formation of complex nanostructured materials with controlled phase composition.
The possibility to form chemical bonding between phases was revealed by different methods: XRD, FT-IR
Microstructure and morphology investigation by HRTEM shows the presence of both hydroxyl apatite with rod-like shapes of lengths up to 100 nm and montmorillonite forming a complex nanostructured material.
Further works are in course to detail the mechanisms of formation of the new binary systems.
Further works are in course to analyse and characterise some binary systems synthesised in hydrothermal conditions at very high pressures (3000, 4000, and 7000 bars respectively) at Université de BORDEAUX 1-Centre de Ressources Hautes Pressions (experiments performed in the frame of COST D30 action).
Functional Nanomaterials II-05.09.2007
Conclusions
Performed multidisciplinary works try to answer to the ETP Nanomedicine questions:-What are the best materials to be used in regenerative medicine;-What are the appropriate cellular lines ;-Do we need new materials/new technologies;- What is the level of the research in the field of regenerative medicine: basic research and applicative research.
Functional Nanomaterials II-05.09.2007
Aknowledgement
This paper is a result of experimental works performed in the frame of Research for Excellence contracts 46-ReteBdent, 69-SINAPS and 16-TECOREMED financed by Romanian Agency for Scientific Research and COST D30 – High pressure Tuning of Materials.
The authors thank:
Prof. Gerard Demazeau - Univ.Bordeaux for fruitfull disscusionsDr.Maria Giurginca - CNC-UPB for performing FT-IR spectra of composites, Dr. Zina Vuluga – ICECHIM for providing natural purified montmorillonite Dr. Gabrielle Chitanu – ICMPP for providing synthetic polymers.Dr. Gabriela Negroiu – Biochemistry Institute, Bucharest, Romanian Academy-for in vitro tests.
Functional Nanomaterials II-05.09.2007
Thank you for your attention !
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