Wendelin J. Stark

Nanoparticles in Biological Systems

Understanding the behavior of nanoparticles in biological systems opens up new directions for medical treatments and is essential for the development of safe nanotechnology. This Review discusses molecules and nanoparticles when in contact with cells or whole organisms, with a focus on inorganic materials. The interaction of particles with biology unravels a series of new mechanisms not found for molecules: altered biodistribution, chemically reactive interfaces, and the combination of solid-state properties and mobility. Externally guided movement of medicaments by using functional nanomagnets brings mechanics into drug design. In subsequent sections, the role of inertness and bioaccumulation is discussed in regard to the long-term safety of nanoparticles.

Nanoparticles as Semi‐Heterogeneous Catalyst Supports

Nanoparticles can serve as semi-heterogeneous supports since they readily disperse in common solvents and combine high surface area with excellent accessibility. Reversible agglomeration through solvent changes and magnetic separation provide technically attractive alternatives to classical catalyst filtration. This account places emphasis on recent developments in this emerging area.

Flame-made Ceria Nanoparticles

Flame spray pyrolysis (FSP) has been used to synthesize high-surface-area ceria from cerium acetate in acetic acid solution. With the addition of an iso-octane/2-butanol mixture to that solution, homogeneous CeO 2 nanoparticles were obtained. The specific surface area of the powders ranged from 240 to 101 m 2 /g by controlling the oxygen dispersion and liquid precursor flow rates through the flame. Furthermore, for production rates from 2 to 10 g/h a constant average primary particle size could be obtained at selected process parameters. The ceria showed high crystallinity and primary particles with a stepped surface. The powder exhibited good thermal stability and conserved up to 40% of its initial specific surface area when calcinated for 2 h at 900 °C. This shows the potential of FSP made ceria for high-temperature applications as in three-way catalysts or fuel cells.

Comparison of nanoscale and microscale bioactive glass on the properties of P(3HB)/Bioglass composites.

This study compares the effects of introducing micro (m-BG) and nanoscale (n-BG) bioactive glass particles on the various properties (thermal, mechanical and microstructural) of poly(3hydroxybutyrate) (P(3HB))/bioactive glass composite systems. P(3HB)/bioactive glass composite films with three different concentrations of m-BG and n-BG (10, 20 and 30 wt%, respectively) were prepared by a solvent casting technique. The addition of n-BG particles had a significant stiffening effect on the composites, modulus when compared with m-BG. However, there were no significant differences in the thermal properties of the composites due to the addition of n-BG and m-BG particles. The systematic addition of n-BG particles induced a nanostructured topography on the surface of the composites, which was not visible by SEM in m-BG composites. This surface effect induced by n-BG particles considerably improved the total protein adsorption on the n-BG composites compared to the unfilled polymer and the m-BG composites. A short term in vitro degradation (30 days) study in simulated body fluid (SBF) showed a high level of bioactivity as well as higher water absorption for the P(3HB)/n-BG composites. Furthermore, a cell proliferation study using MG-63 cells demonstrated the good biocompatibility of both types of P(3HB)/bioactive glass composite systems. The results of this investigation confirm that the addition of nanosized bioactive glass particles had a more significant effect on the mechanical and structural properties of a composite system in comparison with microparticles, as well as enhancing protein adsorption, two desirable effects for the application of the composites in tissue engineering.

Nanoparticle cytotoxicity depends on intracellular solubility: comparison of stabilized copper metal and degradable copper oxide nanoparticles

Metal nanoparticles have distinctly different chemical and physical properties than currently investigated oxides. Since pure metallic nanoparticles are igniting at air, carbon stabilized copper nanoparticles were used as representative material for this class. Using copper as a representative example, we compare the cytotoxicity of copper metal nanoparticles stabilized by a carbon layer to copper oxide nanoparticles using two different cell lines. Keeping the copper exposure dose constant, the two forms of copper showed a distinctly different response. Whilst copper oxide had already been reported to be highly cytotoxic, carbon-coated copper nanoparticles were much less cytotoxic and more tolerated. Measuring the two materials intra- and extracellular solubility in model buffers explained this difference on the basis of altered copper release when supplying copper metal or the corresponding oxide particles to the cells. Control experiments using pure carbon nanoparticles were used to exclude significant surface effects. Reference experiments with ionic copper solutions confirmed a similar response of cultures if exposed to copper oxide nanoparticles or ionic copper. These observations are in line with a Trojan horse-type mechanism and illustrate the dominating influence of physico-chemical parameters on the cytotoxicity of a given metal.

Aerosol flame reactors for manufacture of nanoparticles

Modern flame aerosol synthesis of nanoparticles is a rapidly changing terrain: While producing mainly simple oxide commodities such as silica or titania in the last few decades, a deeper understanding of the process allows now the production of more sophisticated products with high functionality. Advances in process simulation and diagnostics of early particle formation and growth contributed to this development. This is illustrated in the synthesis of heterogeneous catalysts, where dry flame technology can be used to produce highly active nanoparticles. That way, inorganic submicron particles with closely controlled morphology and composition are produced, giving rise to a series of new products or processes that have been dominated by wet chemistry for years.

Crosslinking Metal Nanoparticles into the Polymer Backbone of Hydrogels Enables Preparation of Soft, Magnetic Field‐Driven Actuators with Muscle‐Like Flexibility

The combination of force and flexibility is at the core of biomechanics and enables virtually all body movements in living organisms. In sharp contrast, presently used machines are based on rigid, linear (cylinders) or circular (rotator in an electrical engine) geometries. As a potential bioinspired alternative, magnetic elastomers can be realized through dispersion of micro- or nanoparticles in polymer matrices and have attracted significant interest as soft actuators in artificial organs, implants, and devices for controlled drug delivery. At present, magnetic particle loss and limited actuator strength have restricted the use of such materials to niche applications. We describe the direct incorporation of metal nanoparticles into the backbone of a hydrogel and application as an ultra-flexible, yet strong magnetic actuator. Covalent bonding of the particles prevents metal loss or leaching. Since metals have a far higher saturation magnetization and higher density than oxides, the resulting increased force/volume ratio afforded significantly stronger magnetic actuators with high mechanical stability, elasticity, and shape memory effect.

No evidence for cerium dioxide nanoparticle translocation in maize plants

The rapidly increasing production of engineered nanoparticles has raised questions regarding their environmental impact and their mobility to overcome biological important barriers. Nanoparticles were found to cross different mammalian barriers, which is summarized under the term translocation. The present work investigates the uptake and translocation of cerium dioxide nanoparticles into maize plants as one of the major agricultural crops. Nanoparticles were exposed either as aerosol or as suspension. Our study demonstrates that 50 μg of cerium/g of leaves was either adsorbed or incorporated into maize leaves. This amount could not be removed by a washing step and did not depend on closed or open stomata investigated under dark and light exposure conditions. However, no translocation into newly grown leaves was found when cultivating the maize plants after airborne particle exposure. The use of inductively coupled mass spectrometer allowed detection limits of less than 1 ng of cerium/g of leaf. Exposure of plants to well-characterized nanoparticle suspensions in the irrigation water resulted also in no detectable translocation. These findings may indicate that the biological barriers of plants are more resistant against nanoparticle translocation than mammalian barriers.

Antimicrobial Effect of Nanometric Bioactive Glass 45S5

Most recent advances in nanomaterials fabrication have given access to complex materials such as SiO2-Na2O-CaO-P2O5 bioactive glasses in the form of amorphous nanoparticles of 20- to 60-nm size. The clinically interesting antimicrobial properties of commercially available, micron-sized bioactive glass 45S5 have been attributed to the continuous liberation of alkaline species during application. Here, we tested the hypothesis that, based on its more than ten-fold higher specific surface area, nanometric bioactive glass releases more alkaline species, and consequently displays a stronger antimicrobial effect, than the currently applied micron-sized material. Ionic dissolution profiles were monitored in simulated body fluid. Antimicrobial efficacy was assessed against clinical isolates of enterococci from persisting root canal infections. The shift from micron- to nano-sized treatment materials afforded a ten-fold increase in silica release and solution pH elevation by more than three units. Furthermore, the killing efficacy was substantially higher with the new material against all tested strains.

Rapid synthesis of stable ZnO quantum dots

Zinc oxide nanocrystallites down to 1.5 nm in diameter were made by spray combustion of Zn/Si precursors. These crystallites exhibit a quantum size effect: blueshift of light absorption with decreasing crystallite size. X-ray diffraction, high-resolution transmission electron microscopy, and nitrogen adsorption showed that the addition of controlled amounts of silica prevented the growth and stabilized the ZnO crystals. The blue shift of the ultraviolet-vis absorption edge with decreasing ZnO crystal size closely followed a correlation between optical band gap and crystallite size from the literature. The band-gap energy of these ZnO quantum dots increased with silica content in the spray and particles consistently. The as-prepared quantum dots were stable and did not require any post processing.