Fibrillar Network Dynamics during Oscillatory Rheology of Supramolecular Gels.

Supramolecular gels are three-dimensional network structures formed by the hierarchical self-assembly of small molecules through weak noncovalent interactions. On the basis of the various interactions contributed by specific functional groups/moieties, gels with different architectures can be constructed that are smart to the external stimuli such as pH, type of solvent, stress, temperature, etc. In the present work, we explore the oscillatory shear response of supramolecular self-assembled systems formed by the low-molecular-weight (LMW) gelator based on difunctionalized amino acid, florenylmethoxycarbonyl (Fmoc)-lysine(Fmoc), Fm-K(Fm) in aqueous buffer solution, at two different pH (6 and 7.4). Small amplitude oscillatory shear (SAOS) reported weak frequency dependence of moduli indicating a gel-like network structure. Large amplitude oscillatory shear (LAOS) indicated flow regimes dictated by yielding and subsequent network dynamics analogous to cagelike soft glassy events reported for colloidal systems. The three interval thixotropy test (3iTT) indicated recovery of moduli due to regelation contributed by the reversible interactions. A generalized network model framework is utilized to investigate the transient network characteristics of the Fm-K(Fm) gels. The "network creation" and "network loss" rates were chosen as exponential functions of scaled shear stress (= |τ12(t)G|) to effectively describe the complex response. On the basis of the insights, possible mechanisms to explain the differences/similarities in the response at different pH are speculated. It is further illustrated that the modeling strategy can be extended to supramolecular gels of different classes because of the commonality/universality of their response features under oscillatory shear.

Non-proteinogenic amino acid based supramolecular hydrogel material for enhanced cell proliferation.

Supramolecular gel material built from low-molecular-weight (LMW) gelators finds potential applications in various fields, especially in drug delivery, cell encapsulation and delivery, and tissue engineering. The majority of the LMW gelators in these applications are based on functionalized peptides/amino acids consisting of proteinogenic amino acids which are proteolytically unstable. Herein, we have developed a new LMW gelator containing non-proteinogenic amino acid namely 2,3-diaminopropionic acid (Dap), a key precursor in the synthesis of many antibiotics namely viomycin and capreomycin, by functionalizing with fluorenylmethoxycarbonyl at both amino terminals of Dap [Fm-Dap(Fm)]. Hydrogelation test at different pH indicates that Fm-Dap(Fm) can form a hydrogel in a wide range of pH (4.9 to 9.1) with minimum hydrogelation concentration depends on the pH. The mechanical strength and thermal stability of the Fm-Dap(Fm) hydrogel material are found to decrease with increasing pH (acidic > neural/physiological > basic). The thermal stability of Fm-Dap(Fm) hydrogels is pH-dependent and elicits high stability at acidic pH. Also, Fm-Dap(Fm) hydrogels exhibit strong thixotropic property where regelation (self-healing) occurs upon release of stress. Morphological analysis indicates the formation of fibrils, which are entangled to form three dimensional network structures. Several spectroscopic measurements provided evidence for the self-assembly of Fm-Dap(Fm) molecules through intermolecular aromatic π-π stacking and hydrogen bonding interactions during hydrogelation. Interestingly, Fm-Dap(Fm) not only exhibits hydrogel formation but also shows cell viability and enhanced cell proliferation at physiological pH (7.4). Further, Fm-Dap(Fm) forms a hydrogel upon co-incubation with vitamin B12 and also exhibits release of vitamin B12 over a period. The current study thus demonstrates the development of a new hydrogel material, based on LMW gelator containing the non-proteinogenic amino acid, which can elicit cell viability, enhanced cell proliferation, drug encapsulation, and drug release properties. Hence, Fm-Dap(Fm) hydrogel could be an ideal material for biomedical applications, especially in tissue engineering and drug delivery.

Influence of reduced graphene oxide on flow behaviour, glass transition temperature and secondary crystallinity of plasticized poly(vinyl chloride).

Understanding the rheological behaviour of thermoplastic nanocomposites is important to obtain a concrete knowledge of their processability. The viscoelastic properties of nanocomposites are a reflection of their morphology. The study of flow and deformation of nanocomposites provides essential information related to prevalent interactions in the system as well as contribution from the dispersion of incorporated nanofillers. In the present study, plasticized polyvinyl chloride/reduced graphene oxide nanocomposites (PPVC/RGO) were fabricated using melt mixing technique with different filler concentration. Flow behaviour of the nanocomposites was analyzed using small amplitude oscillatory shear (SAOS) measurements and it indicated an enhancement in the storage modulus (G'), loss modulus (G'') and complex viscosity (η*) with RGO content. This can be attributed to very good dispersion and reinforcing effect of RGO in PPVC matrix as supported by TEM and FTIR results. Weak gel model is used to fit the rheological parameters and is found to be in excellent agreement with the SAOS experiments. Thermal history of the prepared nanocomposites was learned using differential scanning calorimetry. A shift in glass transition temperature (T g) to higher temperature region could be seen, that manifest the effect of RGO in the amorphous portion of PPVC. An interesting property called secondary crystallinity was also found in these materials.