Facile Synthesis and Fabrication of NIPAM-Based Cryogels for Environmental Remediation.

Herein, polymeric cryogels containing poly(N-isopropylacrylamide) were synthesized by cryo-polymerization at subzero temperature. The synthesized cryogels were loaded with silver and palladium nanoparticles by the chemical reduction method at room temperature using the reducing agent NaBH4. Moreover, for comparison with cryogels, pure poly(N-isopropylacrylamide) hydrogel and its silver hybrid were also prepared by the conventional method at room temperature. The chemical structure and functional group analysis of the pure cryogels was confirmed by Fourier transform infrared spectroscopy. The synthesis of hybrid cryogels was confirmed by the X-ray diffraction technique and energy dispersive X-ray. The pore size and surface morphology of the pure cryogels, their respective hybrid cryogels and of conventional hydrogels were studied by using the scanning electron microscopy technique. The hybrid cryogels were successfully used as a catalyst for the degradation of methyl orange dye. The degradation performance of the hybrid cryogels was much better than its counterpart hybrid hydrogel for methyl orange dye. The effect of temperature and amount of catalyst on catalytic performance was studied by UV-visible spectroscopy. The reduction follows pseudo-first-order reaction kinetics. In addition, the antibacterial activities of these cryogels were evaluated against Gram-positive bacteria (Staphylococcus aureus, ATCC: 2593) and Gram-negative bacteria (Escherichia coli, ATCC: 25922). Both hybrid cryogels have shown much better antibacterial activity for these two strains of bacteria compared to pure cryogels. The results indicate that these cryogels are potential candidates for water purification systems as well as biomedical applications.

Preparation of stimuli responsive microgel with silver nanoparticles for biosensing and catalytic reduction of water pollutants.

Herein, we report poly(N-isopropylacrylamide/2-acrylamido-2-methylpropane sulfonic acid) microgel fabricated with silver nanoparticles. The identification of copolymerization and functional groups in the bare microgel and those fabricated with silver nanoparticles was examined by Fourier transform infrared spectroscopy. The pH and temperature sensitivity of microgels was studied using dynamic light scattering. Thermogravimetric analysis was carried out to study the thermal stability. X-Ray diffraction patterns indicated the amorphous nature of bare microgel and crystalline nature of those containing silver nanoparticles. A bathochromic shift was found in the surface plasmon resonance of silver nanoparticles present in microgel with increase in pH of the medium. Moreover, the microgel containing silver nanoparticles served as an effective catalyst for reducing the toxic nitroaromatic pollutants and carcinogenic dyes. The microgel containing silver nanoparticles also showed good capability to serve as biosensor for the detection of hydrogen peroxide.

Tailoring the bandgap of Mn3O4 for visible light driven photocatalysis.

The photocatalytic activity of pure Mn3O4 and silver (Ag) modified Mn3O4 nanoparticles have been investigated. The nanoparticles were prepared by using co-precipitation technique. The structural analysis showed that the Ag modified Mn3O4 was successfully synthesized. For instance, a slight shift to lower angle of XRD pattern was observed after Ag doping. Morphological analysis revealed that the particles have an average size of 274 nm, 287 nm and 321 nm for pure, 1% and 3% Ag modified Mn3O4 respectively. The UV-Visible analysis indicated that the bandgap of Mn3O4 decreased with increased Ag content and the band gap is 1.4 eV with the 3% of Ag content. The spectra obtained from DRS were also evaluated through inverse logarithmic derivative method (ILD) to counter check the bandgap values. 3% Ag-modified photocatalysts exhibited the enhanced decolorization efficiency compared to pure Mn3O4 nanoparticles. The pseudo first order kinetic model is used to explain the photocatalytic kinetics of the photocatalyst. The rate constant values are 0.01/min, 0.017/min and 0.024/min for pure Mn3O4, 1% Ag and 3% Ag modified Mn3O4 nanoparticles, respectively.

Study of electric conduction mechanisms in bismuth silicate nanofibers.

This work represents the nature of conduction mechanism in bismuth silicate (BiSiO) nanofibers as a function of temperature and frequency. Scanning electron micrographs and X-rays diffraction patterns exhibited the formation of cubic phases of Bi4(SiO4)3 and Bi12SiO20 nanofibers respectively with an average diameter of ~200 nm. Temperature dependent (300 K-400 K) electrical characterization of fibers was carried out in frequency range of ~20 Hz-2 MHz. The complex impedance analysis showed contribution from bulk and intergranular parts of nanofibers in conduction. Moreover, analysis of the Cole-Cole plot confirmed the space charge dependent behavior of BiSiO nanofibers. Two types of relaxation phenomena were observed through Modulus analysis. In ac conductivity curve, step like feature of plateau and dispersive regions were described by Maxwell-Wagner effect while the dc part obeyed the Arrhenius law. However, frequency dependent ac conductivity revealed the presence of conduction mechanism in diverse regions that was ascribed to large polaron tunneling model. Detailed analysis of complex Impedance and ac conductivity measurement showed negative temperature coefficient of resistance for the BiSiO nanofibers. Current-voltage (IV) characteristics represented ohmic conduction; followed by space charge limited current conduction at intermediate voltages. Results from both ac and dc measurements were in good agreement with each other.

Correlating the effect of co-monomer content with responsiveness and interfacial activity of soft particles with stability of corresponding smart emulsions.

HYPOTHESIS: This study presents the synthesis and characterization of Poly(N-isopropylacrylamide)-co-methacrylic acid (PNIPAM-co-MAA) based multi-responsive soft microgel particles employed as "smart emulsifiers" for controlled stabilization and breakage of the decane-in-water Pickering emulsions. These soft microgel particles can act as reversible stabilizers, i.e. they can either stay at the oil-water interface by supporting emulsion formation or preventing aggregates; while triggering demulsification can be controlled by varying the temperature, pH or ionic strength of the microgel system. EXPERIMENTS: Dynamic light scattering was applied to observe the variation in hydrodynamic radius of the particles as a function of temperature and pH of the multi-responsive microgel system. Microgel composition was varied in terms of MAA-content and influence of this variation on their thermo-sensitivity and pH responsiveness as well as on the stability of corresponding emulsions was evaluated. FINDINGS: The microgel particles with highest MAA content showed a significant impact on multi-responsive behaviour. Thermal sensitivity is pH dependent under acidic conditions but this dependence is gradually reduced as the pH increases above 7.5. On the other hand, pH-responsiveness is enhanced with the rise in temperature and stable emulsions were formed under highly alkaline conditions even the temperature was far above the volume phase transition temperature (VPTT). Understanding the correlation of stimuli responsiveness at interface with the emulsion stability would help to fabricate and design novel smart Pickering emulsions with better control over desired properties.