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Bone grafts, commonly performed to augment bone regeneration from autologous or alleogeneic sources, carry an enormous cost, estimated at upwards of 21 billion dollars per year. Hydroxyapatite (HAP) bio-ceramic has been widely used in clinic as a bone graft substitute material due to its biocompatibility and the similarity of its structure and composition to bone mineral. However, its applications are limited due to its lack of strength and toughness. Researchers have attempted to overcome these issues by combining HAP bio-ceramics into resorbable polymers to improve their mechanical properties. However, poor bonding between the HAP and the polymer caused separation at the polymer-filler interface. To overcome this, short chains of polymers were grafted directly from the hydroxyl groups on the surface of nanocrystalline HAP. Collagens, being the most abundant proteins in the body, and having suitable properties such as biodegradability, bioabsorbability with low antigenicity, high affinity to water, and the ability to interact with cells through integrin recognition, makes them a very promising candidate for the modification of the polymer surface. In this study, a novel method of synthesizing nano-hydroxyapatite (nHAP)-g-poly(lactide-co-glycolide)-g-collagen polymer was introduced. The synthesis process was carried out in several steps. First, poly (lactide-co-glycolide) (PLGA) polymer was directly grafted onto the hydroxyl group of the surface of n-HAP particles by ring-opening polymerization, and subsequently coupled with succinic anhydride. In order to activate the co-polymer for collagen attachment, the carboxyl end group obtained from succinic anhydride was reacted with N-hydroxysuccinimide (NHS) in the presence of dicyclohexylcarbodiimide (DCC) as the cross-linking agent. Finally, the activated co-polymer was attached to calf skin collagen type I, in hydrochloric acid/phosphate buffer solution and the precipitated co-polymer with attached collagen was isolated. The synthesis was monitored by 1H NMR and FTIR spectroscopies and the products after each step were characterized by thermal analysis (TGA and DSC). These composite materials will be tested as potential scaffolds for tissue engineering applications.

We describe a novel, facile method for the alignment of multi-walled carbon nanotubes (MWNTs) in a magnetic field facilitated by the decoration of the MWNTs with monodisperse γ-Fe2O3 magnetic (maghemite) nanoparticles. The tethering of the nanoparticles was achieved by the attachment of γ-Fe2O3 nanoparticles that were synthesized using a modified sol-gel process, onto the carboxylate-activated MWNTs. Sodium dodecylbenzene sulfonate (NaDDBS) was used to prevent the formation of an iron oxide 3D network. Various characterization methods were employed to confirm the formation of homogeneously-distributed and nearly-monodispersed iron oxide nanoparticles, and show that they were indeed tethered to the walls of the MWNTs. The γ-Fe2O3 nanoparticles imparted magnetic characteristics to the MWNTs, which in turn, were oriented parallel to the direction of an externally-applied magnetic field. This facile alignment of MWNT could promote the enhancement of various properties, e.g. mechanical and electrical properties, of the resulting composites. Moreover, this facile alignment at low magnetic fields, made possible by the magnetization of the carbon nanotubes through the tethering of maghemite nanoparticles, may be applied to a variety of other useful nanofillers, such a glass fibers, clay nanoparticles and cellulose nanowhiskers.

Qualitative and quantitative studies of the oxidation of molecularly modified polycrystalline copper (Cu) thin films upon exposure to ambient air conditions for long periods (on the order of several months) are reported in this work. Thin films of Cu, prepared by thermal evaporation, were analyzed by means of x-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) to gain an understanding on the growth mechanism of oxide on bare and molecularly modified Cu surfaces. The results from all techniques points for an unstable behavior of bare Cu surfaces characterized in very fast and continuous growth of Cu oxide layers during first 60 days of exposure to overall 6 nm oxide thickness. However, Cu films prepared under the same conditions, but covered with a self-assembled organic thin film layer of 1,4-phenylene diisocyanide (PDI) molecules adsorbed from solution, showed a decrease in the thickness of the copper oxide layer on the Cu surface. Our findings imply that chemisorbed PDI monolayers can serve as protective coatings for Cu.

The synthesis of metal nanoclusters in a polymeric environment has been shown to yield nearly monodisperse particles, whose size is controlled by the strength of the polymer/metal interactions. Although the phenomenon is quite general, little is known regarding the mechanism by which the polymer controls nanocluster size. Previous studies of the kinetics of nanocluster growth in polymeric melts above the glass transition temperature (Tg) showed that the nanoparticle size is set by the critical cluster size rather than the rate of metal precursor transport. In this paper we examined the kinetics of iron-oxide (Fe2O3) nanocluster formation in two polymer melts below their Tg: polystyrene (PS) and poly(methyl methacrylate) (PMMA). We found that the rate of particle formation is nucleation-controlled for both PS and PMMA, similarly to the same process above Tg, while the growth stage is diffusion limited. Transmission electron microscopy (TEM) revealed needlelike particles morphology with larger average dimensions as the temperature is elevated towards polymer matrix Tg. The stabilizing effect of the polymer chains on the growth of the nanoparticles was dominant when the synthesis was performed in solution or in the melt, allowing the polymer to adsorb on the cluster. However, below its Tg the chains were not free to move and conform to the nanocluster surface, and hence, capping occurred when the cluster growth limitation was imposed by the geometric confines set by the voids in the polymer matrix.

Reactive metallic fragments that are formed by the decomposition of organometallic complexes, undergo a nucleation and growth process that gives rise to the formation of nanocrystals. In the absence of stabilizing molecules, the aggregation process is restricted mainly due to the decreasing mobility of the particles and their declining diffusional rates as a function of their increasing size. On the other hand, in the presence of a polymer in the reaction medium, the growing metallic particles are stabilized by the surface adsorption of the polymer chains, thus lowering their surface energy and creating a barrier to further aggregation. Studies of the nucleation and aggregation kinetics of metallic particles formed from the decomposition of organometallic precursors have been used to shed light on the mechanism of their formation. In these studies, the rate of decomposition of the precursor organometallic complexes used has been considered to represent the overall rate of the process. Moreover, it has been implicitly assumed that the formation kinetics of the metal nanoclusters directly coincides with the decomposition kinetics of their precursors. In this study, we attempt to decouple the kinetic characteristics of the various steps that comprise the overall nucleation and aggregation process cobalt oxide nanoclusters. A combination of infrared and x-ray photoelectron spectroscopies, and particle size determination by dynamic light scattering, are used to identify the individual contribution of each step to the overall mechanism of metal nanocluster formation.

This study is concerned with the development of a modified sol-gel synthesis of Fe2O3 xerogels that would allow the design and control of the interfacial area between the oxidant iron oxide matrix and the metal reducing agent, thus optimizing the energetic yield of these highly energetic reactions. The modification consisted in the addition of a new class of di-functional template molecules, such as diamines or di-acids, as gelation agents. pH profile measurements indicated that the mechanism of reaction of propylene oxide and of succinic acid as the gelation agents was fundamentally different. Propylene oxide acts as a proton scavenger, reducing the hydrated iron species to Fe2O3, thus reducing the concentration of protons in the reaction mixture leading to an increase in pH. When succinic acid is used as the gelation agent, a decrease in pH versus time during the reaction indicates the formation of carboxylate ions, thus creating reactive molecules that are capable of stabilizing the Fe2O3 clusters during the growth process. Infrared spectra of the products in both reactions support presence of carboxylate groups in the Fe2O3 xerogels. X-ray diffraction analyses revealed low levels of crystallinity in both products, and the presence of different phases of Fe2O3.

The selective interaction of metal clusters with various polymers constitutes the basis for the self-assembly approach to the synthesis of organic-inorganic hybrid materials, that leads to the control of particle size, geometry and dispersion gradient. Metal particles were synthesized by the thermal decomposition of an organometallic precursor, in this case, iron pentacarbonyl, in the presence of a polymer matrix. Under the conditions utilized for these reactions, the aggregation of the metallic clusters competed with the interactions between the growing metal fragments and the polymer matrix. The dominance of one reaction route as compared to the other, ultimately determined the equilibrium particle shape, size and distribution for each metal-polymer system. In this work, we attempted to analyze the formation of iron oxide nanoclusters in several structurally-distinct polymers, and developed a general mechanistic view to explain the characteristics of the polymer-metal oxide hybrid materials that were obtained.

In this paper we are proposing the synthesis of iron and cobalt nanoalloys via the codecomposition of iron and cobalt carbonyl precursors in the presence of polystyrene as the surface stabilizing agent. In order to form iron-cobalt nanoalloys with no preferential aggregation of metal atoms resulting in phase segregation, the decomposition kinetics of the iron pentacarbonyl and dicobalt octacarbonyl precursors had to be firmly established. The kinetics of cobalt cluster formation has been thoroughly investigated, but data for iron pentacarbonyl decomposition is relatively scarce. To fully understand the formation of the iron nanoclusters, a kinetic study was performed by varying carbonyl concentrations and reaction media in order to establish reaction order and rate constants. Our results suggest this decomposition to be a higher order process (not first order as previously assumed), with a complicated intermediate mechanism, which has been postulated and experimentally verified. By using this kinetic data, we will be able to predict the necessary conditions for the creation of new in-situ iron-cobalt nanoalloys using carbonyl precursors.

This paper describes the formation of cobalt and iron metal nanoclusters in various polymeric domains. The size of the particles, their size distribution and their geometry is controlled by the extent of the interfacial interactions between the polymeric phase and the growing metal fragments. Iron oxide particles are shown to exhibit various geometries as a function of the polymer medium and the temperature at which they are formed. The selective phase separation and particle confinement of cobalt clusters in the presence of PS25300-b-PMMA25900 block co-polymer was achieved due to the different reactivities of the functional groups in the blocks towards the metal fragments. Transmission electron micrographs showed that cobalt clusters aggregated primarily in the poly(methyl methacrylate) block, while no cobalt nanoclusters were observed in the polystyrene block, thus creating a patterned distribution that coincided with the morphology of the block copolymer.