Template-assisted assembly of the functionalized cubic and spherical microparticles.

The patterned template-assisted assembly of the cubic microparticles driven by the competing capillary, Columbic, and van der Waals forces had been studied in comparison with the traditional spherical colloidal microparticles. We observed that the spherical and cubic microparticles assembled with different probability in the channels of the hydrophobic-hydrophilic patterned substrates due to differences in a balance of adhesive and capillary forces. In contrast to highly selective assembly of spherical microparticles, selective deposition of cubic microcrystals with channels is impeded by strong adhesive forces facilitated by large specific interfacial areas between cube facets and substrate. The modification of the patterned substrate by functionalized coatings with oppositely charged topmost layers significantly increases the probability (to 86%) of the cubic microparticles to assemble into chemically modified channels. The introduction of ultrathin LbL shells on cubic microparticles and functionalization of patterned substrates are critical for the directed colloidal assembly of anisotropic microparticles into ordered aggregates.

pH-responsive layer-by-layer nanoshells for direct regulation of cell activity.

Saccharomyces cerevisiae yeast cells encapsulated with pH-responsive synthetic nanoshells from lightly cross-linked polymethacrylic acid showed a high viability rate of around 90%, an indication of high biocompatibility of synthetic pH-responsive shells. We demonstrated that increasing pH above the isoelectric point of the polymer shell leads to a delay in growth rate; however, it does not affect the expression of enhanced green fluorescent protein. We suggest that progressive ionization and charge accumulation within the synthetic shells evoke a structural change in the outer shells which affect the membrane transport. This change facilitates the ability to manipulate growth kinetics and functionality of the cells with the surrounding environment. We observed that hollow layer-by layer nanoshells showed a remarkable degree of reversible swelling/deswelling over a narrow pH range (pH 5.0-6.0), but their assembly directly on the cell surface resulted in the suppression of large dimensional changes. We suggest that the variation in surface charges caused by deprotonation/protonation of carboxylic groups in the nanoshells controlled cell growth and cell function, which can be utilized for external chemical control of cell-based biosensors.

Direct probing of micromechanical properties of hydrogen-bonded layer-by-layer microcapsule shells with different chemical compositions.

The mechanical properties of hydrogen-bonded layer-by-layer (LbL) microcapsule shells constructed from tannic acid (TA) and poly(vinylpyrrolidone) (PVPON) components have been studied in both the dry and swollen states. In the dry state, the value of the elastic modulus was measured to be within 0.6-0.7 GPa, which is lower than the typical elastic modulus for electrostatically assembled LbL shells. Threefold swelling of the LbL shells in water results in a significant reduction of the elastic modulus to values well below 1 MPa, which is typical value seen for highly compliant gel materials. The increase of the molecular weight of the PVPON component from 55 to 1300 kDa promotes chain entanglements and causes a stiffening of the LbL shells with a more than 2-fold increase in elastic modulus value. Moreover, adding a polyethylenimine prime layer to the LbL shell affects the growth of hydrogen-bonded multilayers which consequently results in dramatically stiffer, thicker, and rougher LbL shells with the elastic modulus increasing by more than an order of magnitude, up to 4.3 MPa. An alternation of the elastic properties of very compliant hydrogen-bonded shells by variation of molecular weight is a characteristic feature of weakly bonded LbL shells. Such an ability to alter the elastic modulus in a wide range is critically important for the design of highly compliant microcapsules with tunable mechanical stability, loading ability, and permeability.

Stability of the aqueous suspensions of nanotubes in the presence of nonionic surfactant.

Stability of aqueous suspensions of multiwalled carbon nanotubes (MWNTs) and their percolation behavior are investigated. Nanotubes of aqueous suspensions show a strong tendency to aggregation and networking into electroconductive clusters. The percolation threshold of the electrical conductivity is rather low and of order phi approximately 0.01 (where phi is the volume fraction), which can be explained by the high aspect ratio of MWNTs. Strong influence of the nonionic surfactant Triton X-305 on the colloidal stability of aqueous suspensions of MWNTs is observed. Addition of surfactant exerts a stabilizing effect at surfactant concentration C(s) proportional to the weight concentration C of MWNTs, C(s) approximately C mol/dm3. The transient behavior of electrical conductivity in the aqueous suspensions is explained by fractal aggregation processes. The fractal dimension is shown to be sensitive to the surfactant concentration C(s).