There is currently a great interest in the preparation of nanostructured magnetic films possessing well-defined structures and controlled properties. Recent progresses in colloidal nanocrystals synthesis and processing have led to new methods for producing films and superstructures made with these materials. Hybrid films have been prepared by organizing functionalized magnetite nanoparticles in large patterns using the Langmuir Blodgett technique. Magnetite nanoparticles with an average particle diameter of 39nm have been prepared and then coated with amphiphilic molecules. The resulting decorated particles, with a hydrophobic outer layer, have proven suitable for being processed by the LB technique. The microstructure and the compacity of the nanoparticle arrays appear to depend on the nature of the organic moiety used to decorate the nanoparticles (carboxylate or phosphonate end-capped stilbene derivatives).

Materials with high specific surface areas such as pillared clays and zeolites have been studied and can be used to remediate contaminated water. Chemical functionality or compounds can be anchored or attached to the surface of a low-cost material used as a support matrix. This work studied the suitability of inexpensive natural mineral soils to decontaminate waste water from mine and metallurgic industries. Native mineral soils were also impregnated with commercial 1,3 diphenyltiourea (DFT) to improve retention of heavy metal ions. The natural mineral soils were from Hidalgo State in Mexico: white marble (calcite: CaCO3), volcanic gravels named “red and black tezontles” (anorthite matrix: CaO.Al2O3.(SiO2)2 with FexOy and PbxOy), green zeolites (mordenite: Na2CaK2. OAl2O3.10SiO2.7H2O) and kaolin (kaolinite: Al2O3(SiO2)2.H2O). They were ground and sieved. The 50 mesh fraction was studied by Raman and FTIR spectroscopy, X ray powder diffraction and scanning electronic microscopy coupled with energy dispersive X-ray spectroscopy (SEM/EDX). From these solids new hybrid materials were prepared by impregnation with DFT in ethanolic solutions. Products were characterized and compared with untreated materials. Tezontles, zeolites and kaolinite showed the best impregnation levels. In their surfaces, grown DFT crystals showed different structures. The obtained hybrid solids were tested using several metallic ion solutions: Mn(II), Ni(II), Co(II), Cd(II), Hg(II), Pb(II), Cu(II) and Zn(II). The metallic adducts were analyzed and the adsorption capacity is discussed. The materials showed high remotion percentages for all metal ions and low Hg(II), Pb(II) and Cd(II) final concentrations. They have good potential for use in remediation of contaminated water with highly toxic metal ions. The metallic adducts were characterized by FTIR and Raman spectroscopy, as well as SEM/EDX analysis. However, all of mentioned methods were not useful for detection of impregnated DFT nor adsorbed or coordinated metallic ions on the supporting materials. Only the SEM/EDX method was found to be suitable for analysis.

Functional hybrid coatings have been elaborated from a polymer matrix incorporating iron oxide nanoparticles. Stable aqueous suspensions of goethite (α-FeOOH) nanorods, obtained by controlled precipitation of Fe3+ ions, were introduced in 2-hydroxyethyl methacrylate (HEMA). The films were spin-coated on glass substrates from the solutions prior to a UV light induced free radical polymerization step. Nanoindentation tests were carried out to investigate the mechanical properties of the hybrid coatings. Swelling measurements and Fourier Transformed Infrared Spectroscopy (FTIR) were used to characterize the interface between the iron oxide nanoparticles and the PHEMA matrix. Cross-sectional scanning electron microscopy (SEM) and transmission electron microscopy (TEM) was performed to evaluate the dispersion state of the iron oxide particles through the matrix. From a mechanical point of view, iron oxide nanorods yield to a strong reinforcement effect of PHEMA (increase in modulus and hardness by a factor 2 with 5%vol goethite nanoparticles). Origins of such reinforcement are attributed to the existence of highly favourable interactions at the goethite-PHEMA interface combined with a homogeneous dispersion of the particles. The nature of these interactions and evidences of there influence on the mechanical behaviour of the nanohybrid coatings are reported.

High refractive index materials are attractive for many photonic elements. For example, 3D photonic bandgap (PBG) materials have been proposed as the basis of many devices. In order to create complete 3D PBGs, materials enabling high refractive index contrast are needed. We here report on novel high refractive index hybrid polymers. They were synthesized by hydrolysis/polycondensation reactions of organo-alkoxysilanes and Ti alkoxide precursors, resulting in organically modified inorganic-oxidic pre-polymer resins. These can be organically cross-linked by one- or two-photon polymerization (2PP). The latter method enables the writing of arbitrary 3D structures. The introduction of Ti into the inorganic-oxidic network accounts for an increase in the material's refractive index, which could be varied between 1.62 and 1.8. Optical properties such as refractive index and absorption losses were determined on an exemplary material system in the lower refractive index range. The influence of the processing parameters on the degree of organic polymerization, and the refractive index of these novel high index materials was investigated in particular. 3D photonic crystal structures were written for the first time in a high-refractive index hybrid polymer.

The multifunctionality of hybrid organic-inorganic materials has been clearly demonstrated in recent years. Their application in solar- related devices is a growing research area with important technological implications. Our interest is centered on the interplay between the light-harvesting and hole-conducting properties of conjugated polymers and the wide band gap values observed from different inorganic semiconductor oxides. The materials applied in this work are the combination of semiconductor oxides like TiO2, ZnO, Nb2O5, CeO2 and TiO2-CeO2, and different conjugated polymers like poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) or poly(3,4-ethylenedioxythiophene) (PEDOT). Semiconductor oxides have been applied in different configurations like dense thin films, nanostructured electrodes or as nanoparticles. The conjugated polymers have been chosen depending on their light-harvesting properties (e.g. MEH-PPV) or due to their good electrical conductivity and hole conducting properties (e.g. PEDOT). We have characterized our devices in terms of Voc, Jsc, IV-curves, effect of different atmospheres and device lifetime under simulated sunlight irradiation. Tuning the different device parameters such as type of oxide applied, active layer thickness, starting materials concentration, effect of different atmospheres, effect of UV irradiation, etc., permit the fabrication of devices with well-defined properties. A brief discussion and comparison of hybrid solar cells (HSC) with solid-state Dye Sensitized Solar Cells (ss-DSC) applying nanocomposite materials based on TiO2 and PEDOT, as the electron and hole conducting materials respectively, is also included.

Polystannanes, i.e. organometallic polymers of the chemical formula (SnR2)n, are relatively little explored, although they belong to the rare examples of polymers which are characterized by a backbone of metal atoms which are linked by covalent bonds. We developed a new synthetic route which yields pure linear poly(dibutylstannane) [Sn(Bu)2]n by polymerization of dibutylstannane (dibutyltin dihydride) with the catalyst [RhCl(PPh3)3]. Here, we report that the conversion and the reaction rate of dibutylstannane depends crucially on the temperature and [RhCl(PPh3)3] is also suited for the polymerization of dioctylstannane and didodecylstannane. The polymers thus obtained were characterized by 1H, 13C and 119Sn NMR spectroscopy: Orientation of all polystannanes was achieved by tensile drawing. The orientation was examined by UV-vis spectroscopy with polarized light and X-ray diffraction. Remarkably, the orientation of the backbone depended on the length of the alkyl groups.

A new route to synthesize hybrid silica-based network with bridging organic units via molecular recognition is described. The hydrolysis of two monosilylated complementary base pairs, one bearing an adenine fragment and the other a thymine fragment leads to the formation of a powdered sample that has been characterized by Scanning Electron Microscopy (SEM), Powder X-ray Diffraction (PXRD) FTIR and solid state NMR (1H, 13C and 29Si). This last technique proved to be extremely powerful to directly demonstrate the occurrence of heteroassembly of the nucleobase-based silylated fragments, through the use of two-dimensional 1H double-quanta MAS-NMR that could probe spatial proximities between the thymine NH groups and the adenine NH2 groups.

Lysozyme and chitosan were evaluated as cationic polymers for the design of silica-coated alginate capsules. No direct relationship was found between the strength of the bio-organic poly-electrolyte membrane and the stability of capsules after the silica coating, which depends mainly on the nature of poly-cation/silicate interactions.

Luminescent silica films were prepared by sol-gel synthesis under acidic conditions in the presence of fluoride ions. Luminescence was observed for both the pure inorganic film or film of a silica-based inorganic-organic hybrid material. Powders prepared from the same precursor mixtures were only fluorescent after calcination.

As part of our ongoing exploration into the field of hybrid organic/inorganic particles as HPLC packing materials, we have recently evaluated the use of porous particles synthesized from the co-condensation of ethylene-bridged alkoxysilanes with tetraethoxysilane [1,2]. By employing 4-100 mol% of hybrid organic/inorganic groups (i.e., O1.5SiCH2CH2SiO1.5) to 96-0 mol% inorganic groups (i.e., SiO2), novel hybrid particles have been prepared and shown to be excellent materials for the preparation of efficient and chemically resilient reversed-phase packing materials.

The description of three titanium oxo-clusters and their use as inorganic components of hybrid organic-inorganic materials are reported. The first approach consists to add titanium oxo-clusters, [Ti6O4(C6H5COO)8(OPrn)8], in an ORMOCER⊗ based hybrid medium. Nano-sized titanium oxo-clusters combined with the chemical nature of the components, allow the tuning of the optical properties, especially the refractive index. The second approach consists to associate functionalized titanium oxo-clusters to elaborate hybrid materials with perfectly defined inorganic domains. The more relevant example of titanium oxo-cluster to build hybrid networks from nano-building blocks is the oxo-cluster [Ti16O16(OEt)32]. Indeed, the nature and the number of functional groups at the surface of these metallic oxo-clusters can be tuned in order to generate cross-linking agents of organic polymers. The studies of the structure-property relationships of the resulting nanocomposites have been investigated. Finally the structure of a purely carboxylate oxo-clusters is briefly described. This new family of stable oxo-clusters opens the way for the production of original hybrid compounds.

By inducing phase separation parallel to the sol-gel transition of alkoxy-derived silica systems, gels having both macroporous and mesoporous structures can be obtained. Using poly(acrylamide) (PAAm) as a phase-separation inducer, macro/mesoporous silica gels were synthesized. After solvent exchange by water, the size distribution of mesopores of wet gels was evaluated by thermoporometry using a differential scanning calorimetry (DSC). Alternatively, gels were evaporation-dried after solvent exchange by ethanol or water/ethanol, followed by heat-treatment to completely remove volatile and organic components. Characterization of the dried or heat-treated samples was carried out using a scanning electron microscope (SEM) and by nitrogen adsorption measurements. Experimental results showed that the interaction between PAAm and silica is not so strong as the case of polymers having poly(oxyethylene) chains. The contribution of the secondary phase separation within the crosslinking silica-rich phase was suggested to be responsible for the mesopore formation in the PAAm-silica system.

A novel chemical route in thin film formation that includes the use of inorganic and organic peroxides and metal organic complexes soluble in supercritical carbon dioxide has been investigated for the deposition of alumina, titania and zirconia thin films at low temperatures (<150°C). The metal organic precursors used include: Al(acac)3, OTi(tmhd)2, and Zr(acac)4. Tert-butyl peroxide, and a 30% aqueous solution of hydrogen peroxide were used as oxidants. Depositions were carried out in a 25 ml hot wall reactor at pressures ranging from 2100 to 3900 psi at 80-140°C. The deposited thin films were investigated by using X-ray photoelectron spectroscopy (XPS) and transmission Fourier transform infrared spectroscopy (FTIR). XPS and FTIR results indicate the formation of metal oxides thin films with some bonded carbon. The deposition temperatures achieved in this process are substantially lower than those used in conventional vacuum deposition techniques making feasible the deposition on temperature sensitive substrates and organic materials required for the development of hybrid organic/inorganic devices. Processing at low temperatures in supercritical carbon dioxide may provide the basis for the development of an alternative, environmentally friendly, thin film deposition technique for the processing of nanostructures.

Mineralized biological concretions have attracted increasing interest because of their outstanding properties. The mineralized concretion of terrestrial isopods is an excellent model for acellular natural composite material. Before the molt terrestrial isopods resorb calcium from the posterior cuticle and store it in concretion within the cranial (head) and caudal (tail) ventral segments. This paper present for the first time an analysis of ultrastructural changes occurring in the caudal ventral segmental (CaVS) concretion of a terrestrial isopod Porcellius chilensis during their formation and degradation. The CaVS concretion of the woodlice Porcellius chilensis was analyzed with respect to their content of inorganic material. It was found that the concretion consists of amorphous calcium carbonate (ACC), and amorphous calcium phosphate (ACP), besides small amounts of water and an organic matrix. The CaVS concretion consists of structurally distinct stratum due to inhomogeneous solubility of ACC within the organic matrix that consists of calcareous knob with reticules elements. The organic matrix plays a role in the structural organization of the concretion and in the stabilization of ACC, which is unstable in vitro. We present an analysis of the distribution of minerals, elements, and organic matrix with in the CaVS concretion by using SEM, XRD, IR and EDS. The decalcification experiments exactly imitated the natural demineralization of the CaVS concretion of the Porcellius chilensis and it is thought that an inhomogeneous solubility of ACC and ACP within the CaVS concretion probably caused by variations in the stabilizing properties of matrix components.

In various crosslinking systems containing metal oxides, organo-siloxane polymers and pure hydrocarbons, monolithic materials with hierarchical well-defined macropores and controlled mesopores have been synthesized. Synthetic progress in alkoxy-derived macroporous silica lead to the preparation of long-range ordered mesoporous skeletons in well-defined macroporous framework. Alkylene-bridged silicon alkoxides can also be prepared into similarly hierarchical porous structures with broadened variations in framework morphology. Macro-mesoporous alkoxy-derived pure titania and zirconia have been prepared using hydrochloric acid – mediated processes. Compared with those prepared from colloidal dispersions, alkoxy-derived macroporous titania exhibited much higher mechanical strength. Titania monolith is a promising candidate as a separation medium to discriminate phosphorylated compounds in a liquid chromatography mode. Pure alumina macroporous monolith has been first synthesized from aluminum salt using propylene glycol as a proton scavenger to thrust the solution pH from acidic into neutral conditions. Alumina-based complex oxides such as garnets and spinels can also be prepared in pure phases. Polymerization and phase separation in organic crosslinker system was also controlled to obtain well-defined co-continuous macro-frameworks instead of those composed of aggregated particles. These examples demonstrate the versatility of using phase-separation in gelling systems to obtain well-defined macroporous structures.

Fluorescent metal nanoclusters, which consist of collections of small numbers of noble metal atoms, are of great interest in photochemistry and photophysics due to their strong size-dependent emission. Historically their generation was confined to gaseous and solid phases; however, recently a unique organic/inorganic hybrid materials approach was developed that utilizes dendrimers as templates to protect nanoclusters from solution based fluorescence quenching. These hybrid dendrimer/gold nanoclusters are water-soluble and highly fluorescent. Yet there are several intrinsic deficiencies in their synthetic method: first, NaBH4, a toxic chemical, was used as reducing agent in the reaction; and second, the reaction yield was low due to the concurrent formation of large, non-emissive, gold particles. Here we report a particle-free method to produce dendrimer-encapsulated gold nanoclusters in high-yield. Proof of concept is demonstrated using OH-terminated poly(amidoamine) dendrimer and Au(PX3)3Cl (X = Ph, Me), but the approach can also be extended to the combination of other dendrimers and organic noble metal salts. Our approach yields fluorescent clusters with homogeneous size distribution. These clusters can be transferred to aqueous solution and used directly for biological applications.

Sol-gel routes to metal oxide nanoparticles in organic solvents under exclusion of water represent a valuable alternative to aqueous methods. In comparison to the complex aqueous chemistry, nonaqueous processes offer the possibility to better understand and to control the reaction pathways on a molecular level, enabling the synthesis of nanomaterials with high crystallinity and well-defined and uniform particle morphologies. The manifold role of the organic species in providing the oxygen for the oxide formation and in controlling the crystal growth and the assembly properties makes it possible to tailor the morphological, structural and compositional characteristics of the final inorganic products.

In addition to metal oxides with nearly spherical crystallite sizes in the range of just a few nanometers, also more complex morphologies such as nanowire bundles, nanorods or lamellar organic-inorganic hybrids of varying hierarchical complexity can be achieved in one step and without the use of any surfactants. The spherical nanocrystallites are on the one hand versatile building blocks for the fabrication of fully crystalline and ordered mesoporous materials and on the other hand suitable precursors for the synthesis of metal nitride nanoparticles.

This proceeding provides an overview of the various oxidic nanoparticles synthesized via the nonaqueous and surfactant-free sol-gel approach, summarizes the most frequently found formation mechanisms, and offers some insight into the crystallization pathway of nanoparticles. Furthermore, the use of metal oxide nanoparticles as nanobuilding blocks for the preparation of nano- and mesostructures as well as their transformation into metal nitride nanocrystals will be discussed.

The elaboration of organosilica based hybrid monoliths exhibiting a hierarchically structured bimodal porous structure with tunable functionality have been processed via High Internal Polymeric Emulsion (HIPE) process for the first time. Through one pot synthesis, many organic functionalities that can act as network modifiers (Methyl, Dinitrophenylamino, Benzyl, Mercaptopropyl) or co-network formers (Pyrrol) have been anchored to the amorphous silica porous network. The resulting materials have been thoroughly characterized via a large set of techniques SEM, TEM, SAXS, mercury porosimmetry, nitrogen adsorption isotherms, FTIR, 29Si MAS NMR. These sol-gel derived hierarchical open cell functional hybrid monoliths exhibit macroscopic void spaces ranging from 5 up to 30 [.proportional]m and their accessible micro-mesoporosity, reveal hexagonal organisation for the dinitrophenylamino, benzyl, and pyrrol based hybrids. The average condensation degree for these hybrid networks ranges between 86 and 90% yielding shaped monoliths with both good integrity and sufficient mechanical properties to be usable as functional catalytic or chromatographic supports.

Despite the huge amount of experimental investigations dedicated to the grafting of organoalkoxysilanes on silica, the characterization of covalent linkages remains a difficult task from a spectroscopic point of view. In most cases, the formation of a covalent link is taken for granted and not discussed. 29Si NMR, IR or UV spectroscopies are commonly used to study the modification of silica surface. Herein we report an unambiguous method to evidence the formation of covalent links. It is based on NMR spectroscopy analysis coupled with a rigorous synthetic grafting protocol.

In the present work, sol-gel method was used to incorporate in a ceramic material a non steroidal anti-inflammatory drug (piroxicam) as model drug. The incorporation of the drug in the SiO2 network was carried out at different sol-gel synthesis parameters, such as pH (3 and 5) and the alkoxide/water ratio (1:6 and 1:8). The biomaterial obtained was analyzed by thermal analysis TGA-DTA, infrared spectroscopy (FTIR), Scanning Electronic Microscopy (SEM) and X-ray diffraction (XRD); specific surface area and porosity were analyzed from nitrogen adsorption isotherm. Better drug incorporation into the material was achieved at the synthesis conditions of pH 5 and 1:6 alkoxide/water molar ratio.