Interlayer structure and self-healing in suspensions of brush-stabilized nanoplatelets with smectic order.

We have investigated the rheology of an uncured epoxy fluid containing high aspect ratio (length/thickness ≈ 160) α-zirconium phosphate (ZrP) nanoplatelets with smectic order. The nanoplatelets were exfoliated into monocrystalline sheets with uniform thickness using a monoamine-terminated oligomer. The oligomers were densely grafted to the plate surfaces and behave as a molecular brush. Suspensions containing ∼ 2 vol.% ZrP and above show liquid crystalline order with scattering peaks characteristic of a smectic (layered) mesophase. At much higher loading, ∼ 4 vol.% ZrP, there is a sharp transition in visual appearance, steady shear rheology, and linear and non-linear viscoelasticity that is attributed to the reversible interdigitation of oligomer chains between closely spaced layers. The oligomers are proposed to serve as inter-lamellar bridges that store elastic stresses for intermediate rates of deformation, but are able to relax on longer time scales. Under steady shearing conditions, the smectic suspensions with "overlapped" microstructure show a discontinuous flow curve characteristic of shear banding that is attributed to the dynamic pull-out of oligomer chains from the overlap region. At high shear rates, the limiting viscosity of the concentrated suspensions is on the same order of magnitude as the unfilled suspending fluid. When the rate of deformation is reduced below a critical time scale, the original network strength, and corresponding microstructure, is recovered through a passive self-healing process. The unique combination of concentration-dependent yield stress, low post-yield viscosity, and self-healing is potentially useful for various applications in the liquid state, and desirable for scalable processing of nanocomposite materials for structural applications.

Phototunable Lignin Plastics to Enable Recyclability.

The accumulation of non-degradable petrochemical plastics imposes a significant threat to the environment and ecosystems. We addressed this challenge by designing a new type of phototunable plastics based on the unique lignin chemistry to enable readily end-life recycling. The advanced material design leveraged the efficient photocatalytic lignin depolymerization by ZnO nanoparticles to build lignin-polymethyl methacrylate (PMMA)-ZnO blends. We first demonstrated the highly effective phototunable lignin depolymerization in the complex polymer blend matrix and explored the molecular mechanisms. The technical barriers of mechanical property and recycling processing were then addressed by a new blend design with lignin core grafted with PMMA polymer. The new process has resulted in a new type of PMMA-g-lignin blend, which significantly improved the mechanical properties, making it comparable to PMMA alone. More importantly, the mechanical properties of the UV-treated blend decreased drastically in the new design, whereas the properties did not reduce in the non-grafted blends upon UV exposure. The results highlighted that the new blend design based on graftization maximized the impact of lignin depolymerization on blend structure and recyclability. Based on the results, we developed a process integrating UV and alkaline treatments to recycle PMMA for plastics and fractionated lignin for bioconversion or other applications in the new phototunable plastics.

Phosphate-enhanced cytotoxicity of zinc oxide nanoparticles and agglomerates.

Zinc oxide (ZnO) nanoparticles (NPs) have been found to readily react with phosphate ions to form zinc phosphate (Zn3(PO4)2) crystallites. Because phosphates are ubiquitous in physiological fluids as well as waste water streams, it is important to examine the potential effects that the formation of Zn3(PO4)2 crystallites may have on cell viability. Thus, the cytotoxic response of NIH/3T3 fibroblast cells was assessed following 24h of exposure to ZnO NPs suspended in media with and without the standard phosphate salt supplement. Both particle dosage and size have been shown to impact the cytotoxic effects of ZnO NPs, so doses ranging from 5 to 50 µg/mL were examined and agglomerate size effects were investigated by using the bioinert amphiphilic polymer polyvinylpyrrolidone (PVP) to generate water-soluble ZnO ranging from individually dispersed 4 nm NPs up to micron-sized agglomerates. Cell metabolic activity measures indicated that the presence of phosphate in the suspension media can led to significantly reduced cell viability at all agglomerate sizes and at lower ZnO dosages. In addition, a reduction in cell viability was observed when agglomerate size was decreased, but only in the phosphate-containing media. These metabolic activity results were reflected in separate measures of cell death via the lactate dehydrogenase assay. Our results suggest that, while higher doses of water-soluble ZnO NPs are cytotoxic, the presence of phosphates in the surrounding fluid can lead to significantly elevated levels of cell death at lower ZnO NP doses. Moreover, the extent of this death can potentially be modulated or offset by tuning the agglomerate size. These findings underscore the importance of understanding how nanoscale materials can interact with the components of surrounding fluids so that potential adverse effects of such interactions can be controlled.

Antimicrobial efficacy of zinc oxide quantum dots against Listeria monocytogenes, Salmonella Enteritidis, and Escherichia coli O157:H7.

Zinc oxide quantum dots (ZnO QDs) are nanoparticles of purified powdered ZnO. These were evaluated for antimicrobial activity against Listeria monocytogenes, Salmonella Enteritidis, and Escherichia coli O157:H7. The ZnO QDs were utilized as a powder, bound in a polystyrene film (ZnO-PS), or suspended in a polyvinylprolidone gel (ZnO-PVP). Bacteria cultures were inoculated into culture media or liquid egg white (LEW) and incubated at 22 degrees C. The inhibitory efficacies of ZnO QDs against 3 pathogens were concentration dependent and also related to type of application. The ZnO-PVP (3.2 mg ZnO/mL) treatment resulted in 5.3 log reduction of L. monocytogenes and 6.0 log reduction of E. coli O157:H7 in growth media after 48 h incubation, as compared to the controls. Listeria cells in the LEW control increased from 3.8 to 7.2 log CFU/mL during 8 d incubation, while the cells in the samples treated with 1.12 and 0.28 mg ZnO/mL were reduced to 1.4 and 3.0 log CFU/mL, respectively. After 8 d incubation, the cell populations of Salmonella in LEW in the presence of 1.12 and 0.28 mg ZnO/mL were reduced by 6.1 and 4.1 log CFU/mL over that of controls, respectively. ZnO powder and ZnO-PVP showed significant antimicrobial activities against all 3 pathogens in growth media and LEW. ZnO-PVP coating had less inhibitory effect than the direct addition of ZnO-PVP. No antimicrobial activities of ZnO-PS film were observed. This study suggested that the application of ZnO nanoparticles in food systems may be effective at inhibiting certain pathogens.

The effect of guest molecular architecture and host crystallinity upon the mechanism of the intercalation reaction.

The intercalation process of alpha-zirconium phosphate (alpha-ZrP) was investigated by using two alpha-ZrP samples with different levels of crystallinity and two structurally different intercalating molecules, i.e., linear hexylamine and non-planar cyclohexylamine. The results show that the intercalation energy barrier, which is affected by both host alpha-ZrP and guest intercalating molecules, has a significant effect on the intercalation process. When the intercalation energy barrier is relatively low, the interlayer distance of alpha-ZrP expands continuously with increasing amount of intercalating molecules. When the energy barrier reaches a certain level, the interlayer distance expansion becomes stepwise. The observed differences in the intercalation process correspond well with the geometric arrangement of the intercalated molecules inside the gallery of alpha-ZrP.