Dhamodaran Arunbabu

Photonic crystal hydrogel material for the sensing of toxic mercury ions (Hg2+) in water

We report the development of a new photonic crystal hydrogel for the sensing of highly toxic mercury ion (Hg2+) in water. This new sensing material optically reports the Hg2+ concentration in watervia diffraction of visible light from polymerized crystalline colloidal array (PCCA). The PCCA consists of light diffracting crystalline colloidal array (CCA) of monodisperse, highly charged polystyrene particles, which are polymerized within the polyacrylamide hydrogel. The changes in hydrogel surroundings trigger the volume change of hydrogel, which alters the lattice spacing of CCA and hence shifts the diffraction wavelength of light. The ions responsive urease coupled PCCA (UPCCA) hydrolyzes the urea and produces the HCO3− and NH4+ ions inside the hydrogel. These ions induce the charge-screening of the polyacrylamide carboxylates by decreasing the electrostatic repulsion between carboxylates and the polyacrylamide backbone relaxes, causing the shrinkage of hydrogel. Hence the UPCCA exhibits the blue shift of the diffracted wavelength. Hg2+ being the principal inhibitor of the urease-urea hydrolysis perturbs urea hydrolysis by the UPCCA when UPCCA is exposed to Hg2+ along with urea and hence suppresses the production of ions. This intervenes the shrinkage of hydrogel and does not allow the hydrogel to shrink as it shrinks in absence of Hg2+. Therefore the PCCA net blue shift decreases in the presence of Hg2+ along with urea compared to only urea. The extent of this hydrogel volume change is a function of Hg2+ concentrations. This UPCCA photonic crystal sensor detects ultra low (1 ppb) concentration of Hg2+ in water, exhibits reversibility and displays very high selectivity towards Hg2+. The uncompetitive inhibition nature of the urease enzyme, when it is covalently attached in the polymer hydrogel backbone, is the driving force for the very high selectivity and reversibility of the UPCCA sensor.

Blends of Polybenzimidazole and Poly(vinylidene fluoride) for Use in a Fuel Cell

We report a new blend system consisting of an amorphous polymer polybenzimidazole (PBI) and a semicrystalline polymer poly(vinylidene fluoride) (PVDF). A systematic investigation of the blend pair in various compositions using Fourier transform infrared (FT-IR) spectroscopy provides direct evidence of specific hydrogen bonding interaction involving the N-H groups of PBI and the >CF(2) groups of PVDF. Blending shows a maximum 30 cm(-1) frequency shift in the N-H stretching band of PBI and also the existence of a partial double bond character in the PVDF chain. Differential scanning calorimetry (DSC) study proves the miscibility of these polymers in a wider composition range. The decrease of the T(g) with increasing PVDF in the blend and also the decrease of both the T(m) and T(c) with increasing PBI in the blend attribute the miscibility of the blend systems. The PA doping level of the blend membranes improves significantly as a result of the hydrophobic nature of the PVDF component.

Formation of core (polystyrene)–shell (polybenzimidazole) nanoparticles using sulfonated polystyrene as template

We report formation of core (polystyrene)-shell (polybenzimidazole) nanoparticles from a new blend system consisting of an amorphous polymer polybenzimidazole (PBI) and an ionomer sodium salt of sulfonated polystyrene (SPS-Na). The ionomer used for the blending is spherical in shape with sulfonate groups on the surface of the particles. An in depth investigation of the blends at various sulfonation degrees and compositions using Fourier transform infrared (FT-IR) spectroscopy provides direct evidence of specific hydrogen bonding interactions between the N-H groups of PBI and the sulfonate groups of SPS-Na. The disruption of PBI chains self association owing to the interaction between the functional groups of these polymer pairs is the driving force for the blending. Thermodynamical studies carried out by using differential scanning calorimeter (DSC) establish partially miscible phase separated blending of these polymers in a wider composition range. The two distinguishable glass transition temperatures (T(g)) which are different from the neat components and unaltered with the blends composition attribute that the domain size of heterogeneity (d(d)) of the blends is >20 nm since one of the blend component (SPS-Na particle) diameter is ∼70 nm. The diminish of PBI chains self association upon blending with SPS-Na particles and the presence of invariant T(g)s of the blends suggest the wrapping of PBI chains over the SPS-Na spherical particle surface and hence resulting a core-shell morphology. Transmission electron microscopy (TEM) study provides direct evidence of core-shell nanoparticle formation; where core is the polystyrene and shell is the PBI. The sulfonation degree affects the blends phase separations. The higher degree of sulfonation favors the disruption of PBI self association and thus forms partially miscible two phases blends with core-shell morphology.

Charged polystyrene nanoparticles: Role of ionic comonomers structures

Emulsion copolymerizations of styrene were carried out with four structurally different ionic comonomers namely acrylic acid (AAc), methacrylic acid (MAA), 2-hydroxyethyl methacrylate (HEMA), and sodium styrene sulfonate (NaSS) to study the effect of monomer structure on the copolymerization kinetics and size, morphology, charge density, and the self-assembly of the particles. The copolymerization kinetics was found to be highly dependent upon the ionic comonomer structure, and the nature of this dependence altered from homogeneous to micellar nucleation regime. The decrease in particle size (D) with increasing surfactant concentration (S) was observed in all the cases; however, the exponents of D vs. S were not similar for all the cases. In the homogeneous nucleation regime, exponents followed the order as AAc (0.446) > MAA (0.396) > NaSS (0.252) > HEMA (0.241), whereas the order was almost reversed in the micellar nucleation regime as NaSS (0.406) > HEMA (0.228) > AAc (0.206) > MAA (0.172). The hydrophobic/hydrophilic character and the steric factors were found to be the driving force for the variation in D vs. S exponents with ionic comonomer structure. The presence of charges on the particle surface contributed by the ionic comonomers triggered the self-assembly of the particles upon sedimentation and diffracted visible light obeying Braggs law.