Christoph O. Blattmann

Real-Time Nanoparticle-Cell Interactions in Physiological Media by Atomic Force Microscopy.

Particle–cell interactions in physiological media are important in determining the fate and transport of nanoparticles and biological responses to them. In this work, these interactions are assessed in real time using a novel atomic force microscopy (AFM) based platform. Industry-relevant CeO2 and Fe2O3 engineered nanoparticles (ENPs) of two primary particle sizes were synthesized by the flame spray pyrolysis (FSP) based Harvard Versatile Engineering Nanomaterials Generation System (Harvard VENGES) and used in this study. The ENPs were attached on AFM tips, and the atomic force between the tip and lung epithelia cells (A549), adhered on a substrate, was measured in biological media, with and without the presence of serum proteins. Two metrics were used to assess the nanoparticle cell: the detachment force required to separate the ENP from the cell and the number of bonds formed between the cell and the ENPs. The results indicate that these atomic level ENP–cell interaction forces strongly depend on the physiological media. The presence of serum proteins reduced both the detachment force and the number of bonds by approximately 50% indicating the important role of the protein corona on the particle cell interactions. Additionally, it was shown that particle to cell interactions were size and material dependent.

Nanoparticle-nanoparticle interactions in biological media by atomic force microscopy.

Particle-particle interactions in physiological media are important determinants for nanoparticle fate and transport. Herein, such interactions are assessed by a novel atomic force microscopy (AFM)-based platform. Industry-relevant CeO2, Fe2O3, and SiO2 nanoparticles of various diameters were made by the flame spray pyrolysis (FSP)-based Harvard Versatile Engineering Nanomaterials Generation System (Harvard VENGES). The nanoparticles were fully characterized structurally and morphologically, and their properties in water and biological media were also assessed. The nanoparticles were attached on AFM tips and deposited on Si substrates to measure particle-particle interactions. The corresponding force was measured in air, water, and biological media that are widely used in toxicological studies. The presented AFM-based approach can be used to assess the agglomeration potential of nanoparticles in physiological fluids. The agglomeration potential of CeO2 nanoparticles in water and RPMI 1640 (Roswell Park Memorial Institute formulation 1640) was inversely proportional to their primary particle (PP) diameter, but for Fe2O3 nanoparticles, that potential is independent of PP diameter in these media. Moreover, in RPMI+10% Fetal Bovine Serum (FBS), the corona thickness and dispersibility of the CeO2 are independent of PP diameter, while for Fe2O3, the corona thickness and dispersibility were inversely proportional to PP diameter. The present method can be combined with dynamic light scattering (DLS), proteomics, and computer simulations to understand the nanobio interactions, with emphasis on the agglomeration potential of nanoparticles and their transport in physiological media.

In Situ Monitoring of the Deposition of Flame-Made Chemoresistive Gas-Sensing Films

Flame-deposited semiconducting nanomaterials on microelectronic circuitry exhibit exceptional performance as chemoresistive gas sensors. Current manufacturing technology, however, does not monitor in situ the formation of such nanostructured films, even though this can facilitate the controlled and economic synthesis of these sensors. Here, the resistance of such growing films is measured in situ during fabrication to monitor the creation of a semiconducting nanoparticle network for gas sensors. Upon formation of that network, the film resistance drops drastically to an asymptotic value that depends largely on the film structure or morphology rather than on its thickness and size of nanoparticle building blocks. Precursor solutions of various concentrations enable the flame deposition of Sb-doped SnO2 sensing films of different morphologies, each of which exhibit a characteristic in situ resistance pattern. Low precursor concentrations (1 mM) lead to thin (ca. 0.16 μm) films with slender columnar structures of increasing diameter (up to 25 nm) after prolonged deposition (up to 6 min) and show an oscillating in situ resistance during their fabrication. On the other extreme, high precursor concentrations (100 mM) lead to thick (up to 80 μm) dendritic and porous films consisting of nanoparticles with relatively small primary particle diameter (around 7 nm) that remain invariant of deposition duration, which is in agreement with the stable in situ resistance. Such dendritic films exhibit a sensor recovery time that is an order of magnitude longer than that of those made at lower concentrations. The above understanding enables the rapid and economic flame synthesis of thin gas sensors consisting of minimal semiconducting nanomaterial mass possessing a tuned baseline resistance and exhibiting excellent response to ethanol vapor.

Single-Step Fabrication of Polymer Nanocomposite Films

Polymer nanocomposites are employed in (micro)electronic, biomedical, structural and optical applications. Their fabrication is challenging due to nanoparticle (filler) agglomeration and settling, increased viscosity of blended solutions and multiple tedious processing steps, just to name a few. Often this leads to an upper limit for filler content, requirements for filler–polymer interfacial chemistry and expensive manufacturing. As a result, novel but simple processes for nanocomposite manufacture that overcome such hurdles are needed. Here, a truly single-step procedure for synthesis of polymer nanocomposite films, structures and patterns at high loadings of nanoparticles (for example, >24 vol %) for a variety of compositions is presented. It is highly versatile with respect to rapid preparation of films possessing multiple layers and filler content gradients even on untreated challenging substrates (paper, glass, polymers). Such composites containing homogeneously dispersed nanoparticles even at high loadings can improve the mechanical strength of hydrogels, load-bearing ability of fragile microstructures, gas permeability in thin barriers, performance of dielectrics and device integration in stretchable electronics.