Silica nanoparticle sols. Part 3: Monitoring the state of agglomeration at the air/water interface using the Langmuir-Blodgett technique.

Langmuir-Blodgett films were prepared at the air/water interface from dispersions of hydrophilic and partially, hydrophobically modified industrially manufactured silica nanoparticles. The hydrophilic particles featured expanded, fairly easily compressible, surface pressure (pi)-area (A) isotherms with well defined collapse pressures which appeared to be caused by the formation of loosely structured agglomerates which exhibited elastic behavior at low surface pressure and inelastic behavior at high surface pressure. Lateral electrostatic interparticle interactions seemingly played an important role in this hydrophilic system. This contrasted with the hydrophobically modified particles which were more difficult to disperse in the ethanol/chloroform spreading solvent and appeared to be in the semi-agglomerated state at low surface pressures and exhibited a more difficult to compress compacted film. Both types of particulate films were shown to be sensitive to the spreading environment and changes in pH were found to increase particle agglomeration which drastically reduced the particulate area for the hydrophilic sol but less so, in the case of the moderately hydrophobically modified sol. In general, the LB technique proved to be a useful method to monitor changes in the state of aggregation of nanosized silica particles at the air/water interface. These results also appear to give some support of our ideas, presented in earlier publications in which it was suggested that the major role of the hydrophobically modified hydrophilic particles in foaming was to produce an aggregated particulate film surrounding the air/water interface which provides a physical barrier preventing coalescence of bubbles.

Silica nanoparticle sols 1. Surface chemical characterization and evaluation of the foam generation (foamability).

Surface characterization and foaming studies were carried out with nine industrially manufactured, colloidal silica dispersions with particles sizes from 5-40 nm. All the silica sols produced transient foams with short decay times and the dynamic foam generation (foamability) was found to vary according to the sol type with the greatest foamability occurring for the hydrophobically modified sol and the deionized hydrophilic sol. However, it was found that improved foamability of all the sols could be achieved by changing the pH to within the region of the pH(pzc) which corresponds to the region of lowest hydrophilicity. An increase in pH (and build-up of negative charge) enhances the surface hydrophilicity and caused a decrease in foamability. In addition, for selected hydrophilic sols, it was shown that the foamability (a) increased with decrease in particle size (within the 6-40 nm range) and (b) increased with particle concentration (within the range of 1-15 wt%). Overall, it was concluded that the foamability was primary controlled by hydrophobicity (and hence by pH) and also by the particle concentration, the particle size and the degree of agglomeration.

Thermoresponsive poly(N-isopropylacrylamide) copolymers: contact angles and surface energies of polymer films.

Surface properties of poly(N-isopropylacrylamide) (PNIPAM) copolymer films were studied by contact angle measurements and optical and atomic force microscopy. We prepared a series of copolymers of N-isopropylacrylamide with N-tert-butylacrylamide (NtBA) in order of increasing hydrophobicity. The measurements of the advancing contact angle of water at 37 degrees C were hampered by the observation of a distinct stick/slip pattern on all polymers in the series with the exception of poly(NtBA) (PNtBA). We attributed this behavior to the film deformation by the vertical component of liquid surface tension leading to the pinning of the moving contact line. This was confirmed by the observation of a ridge formed at the pinned contact line by optical microscopy. However, meaningful contact (without the stick/slip pattern and with a time-independent advancing contact angle) angles for this thermoresponsive polymer series could be obtained with carefully selected organic liquids. We used the Li and Neumann equation of state to calculate the surface energy and contact angles of water for all polymers in the series of copolymers and van Oss, Chaudhury, and Good (vOCG) acid-base theory for PNtBA. The surface energies of the thermoresponsive polymers were in the range of 38.9 mJ/m2 (PNIPAM) to 31 mJ/m2 (PNtBA) from the equation of state approach. The surface energy of PNtBA calculated using vOCG theory was 29.0 mJ/m2. The calculated contact angle for PNIPAM (74.5 +/- 0.2 degrees ) is compared with previously reported contact angles obtained for PNIPAM-modified surfaces.

Interaction of soft condensed materials with living cells: phenotype/transcriptome correlations for the hydrophobic effect.

The assessment of biomaterial compatibility relies heavily on the analysis of macroscopic cellular responses to material interaction. However, new technologies have become available that permit a more profound understanding of the molecular basis of cell-biomaterial interaction. Here, both conventional phenotypic and contemporary transcriptomic (DNA microarray-based) analysis techniques were combined to examine the interaction of cells with a homologous series of copolymer films that subtly vary in terms of surface hydrophobicity. More specifically, we used differing combinations of N-isopropylacrylamide, which is presently used as an adaptive cell culture substrate, and the more hydrophobic, yet structurally similar, monomer N-tert-butylacrylamide. We show here that even discrete modifications with respect to the physiochemistry of soft amorphous materials can lead to significant impacts on the phenotype of interacting cells. Furthermore, we have elucidated putative links between phenotypic responses to cell-biomaterial interaction and global gene expression profile alterations. This case study indicates that high-throughput analysis of gene expression not only can greatly refine our knowledge of cell-biomaterial interaction, but also can yield novel biomarkers for potential use in biocompatibility assessment.