Sean A. Davis

Novel Hollow Polymer Shells by Colloid-Templated Assembly of Polyelectrolytes

Exact control of the film thickness of polyelectrolyte shells (a transmission electron microscopy image is shown) is achieved by colloid-templated consecutive adsorption of polyanions and polycations followed by decomposition of the templating core. Possible areas of application for these shells range from the pharmaceutical, food, cosmetic, and paint industries to catalysis and microcrystallization.

Growth and form of gold nanorods prepared by seed-mediated, surfactant-directed synthesis

Gold nanorods were prepared via a seed-mediated sequential growth process involving the use of citrate-stabilised seed crystals and their subsequent growth in a series of reaction solutions containing [AuCl4]−, ascorbic acid and the cationic surfactant cetyltrimethylammonuim bromide (CTAB). Electron diffraction analysis and HRTEM images of mature nanorods showed superpositions of two specific pairs of crystallographic zones, either and or and , which were consistent with a cyclic penta-twinned crystal with five {111} twin boundaries arranged radially to the [110] direction of elongation. The nanorods have an idealised 3-D prismatic morphology with ten {111} end faces and five {100} or {110} side faces, or both. TEM studies of crystals at various stages of growth indicated that the seed crystals are initially transformed by growth and aggregation into decahedral penta-twinned crystals, 4% of which become elongated when a fresh reaction solution is added, whilst the remaining twins grow isometrically. Reiteration of this procedure increases the length of the existing nanorods, induces further transformation of isometric particles to produce a second (and third) population of shorter, wider nanorods, and increases the size of the isometric crystals. The data indicate that symmetry breaking in fcc metallic structures to produce anisotropic nanoparticles is based on an intrinsic structural mechanism (twinning) that is subsequently modulated extrinsically during growth in solution by specific adsorption of AuI–surfactant complexes on the side faces/edges of the isometric penta-twinned crystals and which is responsible for the preferential growth along the common [110] axis. We propose that the coupling of multiple twinning and habit modification is a general mechanism that applies to other experimental procedures (electrochemical, inverse micellar media) currently used to prepare metallic nanoparticles with a high aspect ratio.

Stepwise polyelectrolyte assembly on particle surfaces: a novel approach to colloid design

Polyelectrolyte multilayers were deposited onto polystyrene and melamine formaldehyde latex particles by means of consecutive adsorption. Two different methods of multilayer growth were employed. First, adsorption of polyelectrolytes at a concentration exceeding saturation amounts was combined with the removal of the nonbound polyelectrolyte by means of centrifugation. Second, adsorption of polyelectrolyte was performed at a concentration just sufficient for saturation coverage. Both methods yielded continuous layer growth. The process of film formation was followed by electrophoresis, dynamic light scattering, single particle light scattering and fluorescence intensity measurements. Layer deposition onto partially crosslinked melamine resin latex particles, which were soluble at pH values of less than 1.6, resulted in the production of three-dimensional thin polyelectrolyte shells upon dissolving the core. The ultrathin shells were observed by means of scanning and transmission electron microscopy.

Nanoparticles can cause DNA damage across a cellular barrier

The increasing use of nanoparticles in medicine has raised concerns over their ability to gain access to privileged sites in the body. Here, we show that cobalt-chromium nanoparticles (29.5 +/- 6.3 nm in diameter) can damage human fibroblast cells across an intact cellular barrier without having to cross the barrier. The damage is mediated by a novel mechanism involving transmission of purine nucleotides (such as ATP) and intercellular signalling within the barrier through connexin gap junctions or hemichannels and pannexin channels. The outcome, which includes DNA damage without significant cell death, is different from that observed in cells subjected to direct exposure to nanoparticles. Our results suggest the importance of indirect effects when evaluating the safety of nanoparticles. The potential damage to tissues located behind cellular barriers needs to be considered when using nanoparticles for targeting diseased states.

Neuartige Polymerhohlkörper durch Selbstorganisation von Polyelektrolyten auf kolloidalen Templaten

Exakt steuern last sich die Schichtdicke von Polyelektrolythullen (im Bild ist eine transmissionselektronenmikroskopische Aufnahme gezeigt), indem abwechselnd Polyanionen und -kationen auf einem kolloidalen Templat abgeschieden werden und dieses dann entfernt wird. Mogliche Anwendungen dieser Hullen reichen von der Pharmazie uber die Lebensmitteltechnologie, Kosmetik und Anstrichtechnik bis hin zu Katalyse und Mikrokristallisation.

Bacterial templating of zeolite fibres with hierarchical structure

Ordered macroporous zeolite fibres are prepared from the infiltration of swollen bacterial supercellular threads with as-synthesized silicalite nanoparticles.

Synthesis of fluorescent core–shell hydroxyapatite nanoparticles

Lanthanide-doped fluorescent hydroxyapatite/silica core–shell nanorods, 50–100 nm in length and 30 nm in width, were prepared by precipitation of calcium phosphate in the presence of Eu3+ and Y3+ ions at 60 °C, followed by hydrothermally enhanced crystallization, stabilization with poly(ethyleneimine), and reaction with tetraethyl orthosilicate. The fluorescence intensity of the Eu3+-doped hydroxyapatite nanorods was enhanced threefold by co-doping with Y3+ and doubled after hydrothermal treatment. Significantly, fluorescence quenching by water was reduced in the presence of the thin silica nanoshell to give a further doubling of the fluorescence intensity compared with lanthanide-doped hydroxyapatite nanoparticles prepared in the absence of tetraethyl orthosilicate. Our results suggest that a combination of lanthanide doping, controlled crystallization and core–shell fabrication is a promising route to the preparation of biocompatible calcium phosphate nanoparticles with enhanced fluorescence for potential use in biomedical applications.

3D Bioprinting Using a Templated Porous Bioink

3D tissue printing with adult stem cells is reported. A novel cell-containing multicomponent bioink is used in a two-step 3D printing process to engineer bone and cartilage architectures.

Macrophages detoxify the genotoxic and cytotoxic effects of surgical cobalt chrome alloy particles but not quartz particles on human cells in vitro

Particles of surgical cobalt chrome alloy are cytotoxic and genotoxic to human fibroblasts in vitro. In vivo orthopaedic patients are exposed to cobalt chrome particles as a result of wear of a joint replacement. Many of the wear debris particles that are produced are phagocytosed by macrophages that accumulate at the site of the worn implant and are disseminated to local and distant lymph nodes the liver and the spleen. In this study we have tested whether this process of phagocytosis could have altered the cytotoxic and genotoxic properties of the cobalt chrome particles. Quartz particles have been investigated as a control. Micron-sized particles of cobalt chrome alloy were internalised by either white cells of peripheral blood or by THP-1 monocytes for 1 week and 1 day, respectively. The particles were then extracted and presented at different doses to fibroblasts for 1 day. There was a reduction of the cytotoxicity and genotoxicity of the cobalt chrome particles after phagocytosis by white cells or THP-1 cells. Cobalt chrome particles that were internalised by fibroblasts also showed a reduction of their cytotoxicity but not their genotoxicity. In contrast the cytotoxicity and genotoxicity of quartz particles was increased after internalisation by THP-1 cells. The surface morphology of the cobalt chrome particles but not the quartz particles was changed after phagocytosis by THP-1 cells. This study suggests that the genotoxic and cytotoxic properties of particles that fall within the size range for phagocytosis may be highly complex in vivo and depend on the combination of material type and previous phagocytosis. These results may have relevance for particle exposure from orthopaedic implants and from environmental or industrial pollution.

The effect of pre-coating human bone marrow stromal cells with hydroxyapatite/amino acid nanoconjugates on osteogenesis.

Aqueous colloidal suspensions of positively charged, amino acid-functionalized hydroxyapatite (HAp) nanoparticles (HAp/alanine and HAp/arginine) were added to a HBMSC suspension to effect non-specific cell surface deposition due to favourable attractive electrostatic interactions. Subsequent maintenance of these hybrid precursors under in vitro basal (non-osteogenic) culture conditions for up to 21 days, either as a monolayer or as a 3D pellet culture system, resulted in significantly increased levels of markers of osteoblast differentiation in comparison with uncoated cells. In monolayer culture, osteogenic activity could be further enhanced in a dose-dependent manner by surface derivatization of the amino acid-stabilized nanoparticles with the cell surface-specific binding peptide arginine-glycine-aspartic acid (RGD). Significantly, in 3D pellet culture conditions all HAp nanoconjugates promoted osteoblast differentiation, whereas for uncoated cells even soluble osteogenic culture additives were ineffectual. We therefore tested these constructs for in vivo activity by subcutaneous implantation in immunocompromised mice. New osteoid formation was observed in samples recovered after 21 days, comparable to the extensive areas of mineralized extracellular matrix produced in vitro. Overall, these studies outline the potential of biomolecular/hydroxyapatite nanoconjugates to promote osteogenic cell differentiation in vitro and hence provide new models to examine skeletal cell differentiation and function. Moreover, the pre-coating of HBMSCs enables the formation of viable hybrid multicellular 3D constructs with demonstrable activity both in vitro and in vivo.