Solvent triggered irreversible shape morphism of biopolymer films.

We report the controlled reversible and irreversible folding behavior of a biopolymer film simply by tuning the solvent characteristics. Generally, solvent triggered folding of soft membranes or film is achieved by unfolding. Here, we show that this unfolding behavior can be suppressed/delayed or even completely eliminated by altering the intrinsic nature of the solvent. A reversible folding of biopolymer film is observed in response to water, whereas, an irreversible folding is observed in the presence of an aromatic alcohol (AA) solution of different molar concentrations. The folding and unfolding behavior originates from the coupled deformation-diffusion phenomena. Our study indicates that the presence of an AA influences the relaxation behavior of polymer chains, which in turn affects the release of stored strain energy during folding. Controlling the reversibility as well as the actuation time of the biopolymer film by tuning the solvent is explained in detail at the bulk scale by applying appropriate experimental techniques. The underlying mechanism for the observed phenomena is complemented by performing a simulation study for a single polymer chain at the molecular length scale. Due to the solvent-triggered hygromorphic response, biopolymer films exhibit huge potential as sensors, soft robots, drug delivery agents, morphing medical devices and in biomedical applications. We provide experimental evidence for the weight lifting capacity of permanently folded membranes, amounting to ∼200 times their own weight.

Enhancement in Elastic Bending Rigidity of Polymer Loaded Reverse Microemulsions.

Elastic bending rigidity of the surfactant shell is a crucial parameter which determines the phase behavior and stability of microemulsion droplets. For water-in-oil reverse microemulsions stabilized by AOT (sodium 1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate) surfactant, the elastic bending rigidity is close to thermal energy at room temperature (kBT) and can be modified by the presence of hydrophilic polymers. Here, we explore the influence of two polymers polyethylene glycol (PEG) and polyvinylpyrrolidone (PVP), both having nearly same size (radius of gyration, Rg) but different dipole moment, on elastic bending rigidity of water-AOT-n-decane reverse microemulsions via estimating the percolation temperatures (TP) and droplet radii using dielectric relaxation spectroscopy (DRS) and small-angle neutron scattering (SANS) techniques. Notably, an increase in TP is observed on introducing PEG and PVP polymers and is attributed to the adsorption of polymer chains onto the surfactant monolayer. The stability of the droplet phase of microemulsion after the incorporation of PEG and PVP polymers is confirmed by contrast matching SANS experiments. An enhancement in elastic bending rigidity of AOT surfactant shell amounting to ∼46% is observed upon incorporation of PVP into the droplet core, whereas for PEG addition, a smaller increase of about 17% is recorded. We conjecture that the considerable increase in elastic bending rigidity of the surfactant monolayer upon introducing PVP is because of the strong ion-dipole interaction between anionic AOT and dipoles present along the PVP polymer chains. Scaling exponents extracted from the temperature dependent electrical conductivity measurements and the frequency dependent scaling of conductivity at percolation indicate the dynamic nature of percolation for both pure and polymer loaded reverse microemulsions. The decrease in activation energy of percolation upon incorporating PEG and PVP polymer molecules also reflects the increased stability of microemulsion droplets against thermal fluctuations.

Inferences on hydrogen bond networks in water from isopermitive frequency investigations.

Intermolecular hydrogen bonds play a crucial role in determining the unique characteristics of liquid water. We present low-frequency (1 Hz-40 MHz) dielectric spectroscopic investigations on water in the presence and absence of added solutes at different temperatures from 10 °C to 60 °C. The intersection points of temperature dependent permittivity contours at the vicinity of isopermitive frequency (IPF) in water are recorded and its properties are presumed to be related to the extent of hydrogen bond networks in water. IPF is defined as the frequency at which the relative permittivity of water is almost independent of temperature. The set of intersection points of temperature dependent permittivity contours at the vicinity of IPF are characterized by the mean [Formula: see text] and root-mean-square deviation/standard deviation [Formula: see text] associated with IPF. The tunability of M IPF by the addition of NaCl and MgCl2 salt emphasizes the strong correlation between the concentration of ions in water and the M IPF. The [Formula: see text] is surmised to be related to the orientational correlations of water dipoles as well as to the intermolecular hydrogen bond networks in water. Further, alterations in [Formula: see text] is observed with the addition of kosmotropic and chaotropic solutes into water and are thought to arise due to the restructuring of hydrogen bond networks in water in presence of added solutes. Notably, the solute induced reconfiguration of hydrogen bond networks in water or often-discussed structure making/breaking effects of the added solutes in water can be inferred, albeit qualitatively, by examining the M IPF and [Formula: see text]. Further, the Gaussian deconvoluted OH-stretching modes present in the Raman spectra of water and aqueous solutions of IPA and DMF strongly endorses the structural rearrangements occurring in water in presence of kosmotropes and chaotropes and are in line with the results derived from the root-mean-square deviation in IPF.