Shape-memory polyurethanes (PUs) were synthesized by 4,4 -diphenylmethane diisocyanate (MDI), 1,4-butanediol (BD), and poly(tetramethyl oxide)glycol (PTMO). The morphology of PUs was studied using DSC, DMA, and TEM. The results indicated that the PUs would show different morphology by changing the mol ratio of MDI and BD (hard segment). The specimens would show the shape-memory behavior that was fixing and recovering the deformation at different operating temperature ranges. These results demonstrated that the shape-memory behavior of the PUs would be affected by the morphology and the modulus ratio that was defined as E T g 020ЊC /E T g /20ЊC in DMA analysis. The amount of the hard-segment-rich phase would affect the ratio of recovery, that is, the low content would lead to the recovery of the deformed specimen being incomplete. The recovering rate would be influenced by the modulus ratio and the size of the dispersed phase in the micromorphology. On the other hand, the shape-memory behavior of PUs could be enhanced by the training process.

Polyurethanes (PUs) of a suitable molar ratio of monomers were found to have shape-memory behavior. In this study, four series of PUs were synthesized by 4,4-diphenylmethane diisocyanate (MDI), 1,4-butanediol (BD), and various molecular weights of poly(tetramethylene oxide)glycol (PTMO) to study the influence of the soft segment (PTMO) on the shape-memory behavior of PUs. The investigation on thermal and dynamic mechanical properties was performed using DSC and DMA; then, the morphology of the PUs was directly observed by TEM. At the range of the individual glass transition, a similar recovering behavior was found from the deformed specimen that contained the same composition but different molecular weights of PTMO. However, the phase separation between the soft and the hard segments of the PUs would influence their shape-memory behavior. On the other hand, a large number of the dispersed phase of the PUs would delay the recovery rate of the deformed specimens using a high molecular weight PTMO.

The concern about toxicity for nanosilicate platelets (NSP) derived from natural montmorillonite clay is addressed. The NSP nanoclay was isolated from polyamine-salt exfoliation of the layered silicate clay into randomized individual plates, possessing multiple ionic charges on the surface of silicate plates with an average geometric dimension of ca. 80 x 80 x 1 nm(3). The material had been previously shown to be effective for antimicrobial and tendency for adhering onto the biomaterial surface based on the direct observation by using scanning electron microscope. The material safety on genotoxic effect was investigated by using three different test systems: the Comet assay test on Chinese Hamster Ovary (CHO) cells in vitro, micronucleus (MN) assay in vivo and the Salmonella gene mutation assay on strain TA98, TA100, TA102, TA1535 and TA1537. The Comet assay showed no DNA damage after 24 h of incubation with NSP of 1000 microg/mL. The MN test indicated no significant micronucleus induction in the CHO cells at the concentrations tested. With all five strains of Salmonella typhimurium, none of mutations was found. Furthermore, cytotoxicity of the same material was assayed by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and lactate dehydrogenase (LDH) release, showing a low cytotoxicity on CHO cells below 1000 microg/mL after 12 h incubation period and a dose-dependent effect after 24 h incubation. For feeding to rats, the acute oral toxicity was shown a low lethal dose (LD(50)) or greater than 5700 mg/kg body weight for both male and female Sprague-Dawley rats. Overall, the study has demonstrated the safety of the NSP for potential uses in biomedical areas.

Silver nanoparticles (AgNPs) are known for their bactericidal abilities. The antibacterial potency is dependent on the particle size and dispersion status. In this study, we synthesized AgNP/NSP nanohybrids in two different weight ratios (1/99 and 8/92) using the fully exfoliated clay, i.e., nanosilicate platelets (NSP), as a dispersing agent and carrier for AgNPs. Due to the size of NSP, the immobilized AgNPs do not enter cells readily, which may lower the risk associated with the cellular uptake of AgNPs. The biocompatibility, immunological response, and antimicrobial activities of AgNP/NSP hybrids were evaluated. The results revealed that AgNP/NSP hybrids elicited merely mild inflammatory response and retained the outstanding antibacterial activity. The hybrids were further embedded in poly(ether)urethane (PEU) to increase the biocompatibility. At the same silver content (20 ppm), the PEU-AgNP/NSP nanocomposites were nontoxic to mouse skin fibroblasts, while simultaneously exhibiting nearly complete bacterial growth reduction (99.9%). PEU containing the same amount of free AgNPs did not display such an effect. Our results verify the better biosafety of the AgNPs/NSP hybrids and their polymer nanocomposites for further clinical use.

Nanomaterials have the characteristics associated with high surface-to-volume ratios and have been explored for their antiviral activity. Despite some success, cytotoxicity has been an issue in nanomaterial-based antiviral strategies. We previously developed a novel method to fully exfoliate montmorillonite clay to generate the most fundamental units of nanoscale silicate platelet (NSP). We further modified NSP by capping with various surfactants and found that the surfactant-modified NSP (NSQ) was less cytotoxic. In this study, we tested the antiviral potentials of a series of natural-clay-derived nanomaterials. Among the derivatives, NSP modified with anionic sodium dodecyl sulfate (NSQc), but not the pristine clay, unmodified NSP, a silver nanoparticle-NSP hybrid, NSP modified with cationic n-octadecanylamine hydrochloride salt, or NSP modified with nonionic Triton X-100, significantly suppressed the plaque-forming ability of Japanese encephalitis virus (JEV) at noncytotoxic concentrations. NSQc also blocked infection with dengue virus (DEN) and influenza A virus. Regarding the antiviral mechanism, NSQc interfered with viral binding through electrostatic interaction, since its antiviral activity can be neutralized by Polybrene, a cationic polymer. Furthermore, NSQc reduced the lethality of JEV and DEN infection in mouse challenge models. Thus, the surfactantmodified exfoliated nanoclay NSQc may be a novel nanomaterial with broad and potent antiviral activity. IMPORTANCE Nanomaterials have being investigated as antimicrobial agents, yet their antiviral potential is overshadowed by their cytotoxicity. By using a novel method, we fully exfoliated montmorillonite clay to generate the most fundamental units of nanoscale silicate platelet (NSP). Here, we show that the surfactant-modified NSP (NSQ) is less cytotoxic and that NSQc (NSP modified with sodium dodecyl sulfate) could potently block infection by dengue virus (DEN), Japanese encephalitis virus (JEV), and influenzaA virus at noncytotoxic concentrations. For the antiviral mechanism, we find that the electrostatic interaction between the negatively charged NSQc and the positively charged virus particles blocks viral binding. Furthermore, we used mouse challenge models of JEV and DEN to demonstrate the in vivo antiviral potential of NSQc. Thus, NSQc may function as a potent and safe antiviral nanohybrid against several viruses, and our success in synthesizing surfactant-modified NSP with antiviral activity may shed some light on future antiviral development.