Nano-assemblies of cationic mPEG brush block copolymers with gadolinium polyoxotungstate [Gd(WO)] form stable, high relaxivity MRI contrast agents.

Polyoxometalates (POMs) incorporating paramagnetic ions, such as gadolinium, show promise as contrast agents for application in magnetic resonance imaging (MRI). Specifically, [Gd(W5O18)2]9- (denoted as GdWO) has been reported to have a higher relaxivity than commercially available contrast agents, but it's clinical utility has been limited by the intrinsic instability of POMs at physiological pH (7.4).

Encapsulation of CO2 into amorphous alpha-cyclodextrin powder at different moisture contents - Part 2: Characterization of complexed powders and determination of crystalline structure.

This study aims to characterize CO2-α-cyclodextrin (α-CD) inclusion complexes produced from amorphous α-CD powder at moisture contents (MC) close to or higher than the critical level of crystallization (e.g. 13, 15 and 17% MC on wet basis, w.

Stable non-covalent labeling of layered silicate nanoparticles for biological imaging.

Layered silicate nanoparticles (LSN) are widely used in industrial applications and consumer products. They also have potential benefits in biomedical applications such as implantable devices and for drug delivery. To study how nanomaterials interact with cells and tissues, techniques to track and quantify their movement through different biological compartments are essential.

Dispersion of hydroxyapatite nanoparticles in solution and in polycaprolactone composite scaffolds.

The dispersion behaviour of hydroxyapatite nanoparticles (HAP) and surface-modified HAP was studied in 1,4-dioxane (DO), water and poly(ε-caprolactone) (PCL) solutions and the relationship between these and the dispersion in composite PCL scaffolds prepared by thermally induced phase separation (TIPS) was examined. Investigation of the change in particle sizes by dynamic light scattering, showed that the modification of HAP by adsorption or covalent attachment of heparin via a 3-aminopropyltriethoxysilane (APTES) layer improved the dispersion stability of the particles in water/DO mixtures, while no improvement was observed in DO. The distribution of the particles within the composite scaffolds was determined using a combination of transmission electron microscopy and a calcium quantification method which was used to determine distribution of the particles in the vertical direction.

Mode of heparin attachment to nanocrystalline hydroxyapatite affects its interaction with bone morphogenetic protein-2.

Heparin has a high affinity for bone morphogenetic protein-2 (BMP-2), which is a key growth factor in bone regeneration. The aim of this study was to investigate how the rate of release of BMP-2 was affected when adsorbed to nanosized hydroxyapatite (HAP) particles functionalized with heparin by different methods. Heparin was attached to the surface of HAP, either via adsorption or covalent coupling, via a 3-aminopropyltriethoxysilane (APTES) layer.

Attachment of poly(acrylic acid) to 3-aminopropyltriethoxysilane surface-modified hydroxyapatite.

Nano-sized hydroxyapatite (HAP) is of interest in biomaterials science due to its similarity to bone mineral. In this study, HAP modification using 3-aminopropyltriethoxysilane (APTES) was carried out in toluene and the effect of reaction time and curing temperature on the surface layers formed was investigated through X-ray photoelectron spectroscopy, Fourier transform infrared (FT-IR) and solid-state nuclear magnetic resonance (NMR) spectroscopy. It is shown that the chemical composition is strongly influenced by the curing temperature; with low temperatures of 50 and 100 °C resulting in a fully condensed APTES layer, an intermediate temperature of 150 °C causing partial oxidation of the surface layer with the conversion of some amine functionality to amides while curing at a temperature of 200 °C additionally leads to thermal decomposition of the silane layer and a loss of the pendent amine groups.

Gelation kinetics and viscoelastic properties of pluronic and α-cyclodextrin-based pseudopolyrotaxane hydrogels.

The results of a systematic investigation into the gelation behavior of α-cyclodextrin (α-CD) and Pluronic (poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers) pseudopolyrotaxane (PPR) hydrogels are reported here in terms of the effects of temperature, α-CD concentration, and Pluronic type (Pluronic F68 and Pluronic F127). It was found that α-CD significantly modifies the gelation behavior of Pluronic solutions and that the PPR hydrogels are highly sensitive to changes in the α-CD concentration. In some cases, the addition of α-CD was found to be detrimental to the gelation process, leading to slower gelation kinetics and weaker gels than with Pluronic alone.

Organization of mixed dimethyldioctadecylammonium and choline modifiers on the surface of synthetic hectorite.

Understanding the nature of mixed surfactant self-assembly on the surface of organoclays is an important step toward optimizing their performance in polymer nanocomposites and for other potential applications, where selective surface interactions are crucial. In segmented thermoplastic polyurethane nanocomposite systems, dual-modified organoclays have shown significantly better performance compared to their single-modified counterparts. Until now, we had not fully characterized the physical chemistry of these dual-modified layered silicates, but had hypothesized that the enhanced composite performance arises due to some degree of nanoscale phase separation on the nanofiller surface, which enables enhanced compatibilization and more specific and inclusive interactions with the nanoscale hard and soft domains in these thermoplastic elastomers.

Control of the orientation of symmetric poly(styrene)-block-poly(D,L-lactide) block copolymers using statistical copolymers of dissimilar composition.

The interactions of block copolymers with surfaces can be controlled by coating those surfaces with appropriate statistical copolymers. Usually, a statistical copolymer comprised of monomer units identical to those of the block copolymer is used; that is, typically a poly(styrene)-stat-poly(methyl methacrylate) (PS-stat-PMMA) is used to direct the alignment of poly(styrene)-block-poly(methyl methacrylate) (PS-block-PMMA), and poly(styrene)-stat-poly(2-vinylpyridine) (PS-stat-P2VP) has been used for poly(styrene)-block-poly(2-vinylpyridine) (PS-block-P2VP). Reports of controlling the orientation of block copolymers with statistical copolymers with a dissimilar composition are limited.

Interactions of iodoperfluorobenzene compounds with gold nanoparticles.

Understanding the interactions of small molecules with gold nanoparticles is important for controlling their surface chemistry and, hence, how they can be used in specific applications. The interaction of iodoperfluorobenzene compounds with gold nanoparticles was investigated by UV-Vis difference spectroscopy, surface enhanced Raman spectroscopy (SERS) and Synchrotron X-ray photoelectron spectroscopy (XPS). Results from UV-Vis difference spectroscopy demonstrated that iodoperfluorobenzene compounds undergo charge transfer complexation with gold nanoparticles.

One-pot synthesis of block copolymers in supercritical carbon dioxide: a simple versatile route to nanostructured microparticles.

We present a one-pot synthesis for well-defined nanostructured polymeric microparticles formed from block copolymers that could easily be adapted to commercial scale. We have utilized reversible addition-fragmentation chain transfer (RAFT) polymerization to prepare block copolymers in a dispersion polymerization in supercritical carbon dioxide, an efficient process which uses no additional solvents and hence is environmentally acceptable. We demonstrate that a wide range of monomer types, including methacrylates, acrylamides, and styrenics, can be utilized leading to block copolymer materials that are amphiphilic (e.

Patterning of tailored polycarbonate based non-chemically amplified resists using extreme ultraviolet lithography.

A series of high-performance polycarbonates have been prepared with glass-transition temperatures and decomposition temperatures that are tunable by varying the repeat-unit chemical structure. Patterning of the polymers with extreme UV lithography has been achieved by taking advantage of direct photoinduced chain scission of the polymer chains, which results in a molecular-weight based solubility switch. After selective development of the irradiated regions of the polymers, feature sizes as small as 28.

Phosphorylation of alginate: synthesis, characterization, and evaluation of in vitro mineralization capacity.

Phosphorylation of alginate was achieved using a heterogeneous urea/phosphate reaction. The degree and stereoselectivity of phosphorylation as well as the effects on the physical properties of the polysaccharide were investigated by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopies, inductively coupled plasma optical-emission spectroscopy (ICP-OES), and size exclusion chromatography (SEC). Multidimensional NMR studies of the phosporylated alginate revealed that phosphorylation of the M residues occurred predominantly at the C3 (equatorial) carbon of the polysaccharide ring.

The fabrication and characterization of biodegradable HA/PHBV nanoparticle-polymer composite scaffolds.

This study reports the fabrication and characterization of nano-sized hydroxyapatite (HA)/poly(hydroxyabutyrate-co-hydroxyvalerate) (PHBV) polymer composite scaffolds with high porosity and controlled pore architectures. These scaffolds were prepared using a modified thermally induced phase-separation technique. This investigation focuses on the effect of fabrication conditions on the overall pore architecture of the scaffolds and the dispersion of HA nanocrystals within the composite scaffolds.

Understanding the roles of nanoparticle dispersion and polymer crystallinity in controlling the mechanical properties of HA/PHBV nanocomposites.

Nano-sized hydroxyapatite (HA) particles stabilized using poly(acrylic acid) (PAA) as a dispersing agent, and sonic energy to further increase dispersion, were blended with poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) using a precipitation/gelation method to produce HA/PHBV nanocomposites with up to 16% by weight of HA content. The level of HA nanoparticle dispersion was monitored in the precursor dispersions prior to composite production and in the nanocomposites by a range of techniques including visual observation, turbidity measurements and electron microscopy, and the roles of the dispersing agent and the sonic energy in controlling the dispersion of HA particles in both the precursor dispersions and the final composites as well as their effects on the compressive strength and Young's modulus were investigated. It was found that HA suspensions treated with both PAA and sonic energy possessed significantly better colloidal stability compared to untreated suspensions or suspensions treated with either PAA or sonic energy.

Protein delivery using nanoparticles based on microemulsions with different structure-types.

Poly(alkylcyanoacrylate) nanoparticles based on microemulsions with different structure-types and containing insulin as a model protein were prepared and characterised in this study. A phase diagram of the pseudoternary system isopropyl myristate, caprylocaproyl macrogolglycerides, polyglycerol oleate and water was established. All compounds used in this study were pharmaceutically acceptable and biocompatible.

Characterization and surface properties of amino-acid-modified carbonate-containing hydroxyapatite particles.

The surface properties (nature, strength, and stability of interaction of functional groups) and bulk morphologies of a series of amino-acid-functionalized carbonate-containing hydroxyapatite (CHA) particles were investigated. It was found that the amino acids were both occluded in and presented on the surface of the CHA particles. Furthermore, their presence enhanced particle colloidal stability by retardation of Ostwald ripening and in some cases increasing the magnitude of the zeta-potential.

Reduction of the in vitro pro-inflammatory response by macrophages to poly(3-hydroxybutyrate-co-3-hydroxyvalerate).

This study evaluates the pro-inflammatory response to the thermoplastic biopolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) through the analysis of cellular responses in vitro. The murine macrophage RAW264.7 cell line was cultured on solvent cast PHBV films, which was found to induce pro-inflammatory activity that required direct contact between the material and the macrophages.

Functionalized organosilica microspheres via a novel emulsion-based route.

Thiol-functionalized organosilica microspheres were synthesized via a two-step process: (1) acid-catalyzed hydrolysis and condensation of 3-mercaptopropyltrimethoxysilane (MPTMS), followed by (2) base-catalyzed condensation, which led to the rapid formation of emulsion droplets with a narrow size distribution. These droplets continued to condense to form solid microspheres. Solution (29)Si NMR and optical microscopy were applied to study the mechanism of this novel synthetic route.