Outstanding dielectric constant and piezoelectric coefficient in electrospun nanofiber mats of PVDF containing silver decorated multiwall carbon nanotubes: assessing through piezoresponse force microscopy

In order to enhance the piezoelectric b-phase, PVDF was electrospun from DMF solution. The enhanced b-phase was discerned by comparing the electrospun fibers against the melt mixed samples. While both the processes resulted in phase transformation of a-to electroactive b-polymorph in PVDF, the fraction of b-phase was strongly dependent on the adopted process. Two different nanoscopic particles: carboxyl functionalized multiwall carbon nanotubes (CNTs) and silver (Ag) decorated CNTs were used to further enhance the piezoelectric coefficient in the electrospun fibers. Fourier transform infrared spectroscopy (FTIR) and wide-angle X-ray diffraction (XRD) supports the development of piezoelectric b-phase in PVDF. It was concluded that electrospinning was the best technique for inducing the b-polymorph in PVDF. This was attributed to the high voltage electrostatic field that generates extensional forces on the polymer chains that aligns the dipoles in one direction. The ferroelectric and piezoelectric measurement on electrospun fibers were studied using piezo-response force microscope (PFM). The Ag-CNTs filled PVDF electrospun fibers showed the highest piezoelectric coefficient (d(33) = 54 pm V-1) in contrast to PVDF/CNT fibers (35 pm V-1) and neat PVDF (30 pm V-1). This study demonstrates that the piezoelectric coefficient can be enhanced significantly by electrospinning PVDF containing Ag decorated nanoparticles.

Synergistic effect of polymorphism, substrate conductivity and electric field stimulation towards enhancing muscle cell growth in vitro

Poly(vinylidene difluoride), a well-known candidate for artificial muscle patch applications is a semi-crystalline polymer with a host of attributes such as piezo- and pyroelectricity, polymorphism along with low dielectric constant and stiffness. The present work explores the unique interplay among the factors (conductivity, polymorphism and electrical stimulation) towards cell proliferation on poly(vinylidene difluoride) (PVDF)-based composites. In this regard, multi-walled carbon nanotubes (MWNTs) are introduced in the PVDF matrix (limited to 2%) through melt mixing to increase the conductivity of PVDF. The addition of MWNTs also led to an increase in the fraction of piezoelectric beta-phase, tensile strength and modulus. The melting and crystallization behaviour of PVDF-MWNT together with FT-IR confirms that the crystallization is found to be aided by the presence of MWNT. The conducting PVDF-MWNTs are used as substrates for the growth of C2C12 mouse myoblast cells and electrical stimulation with a range of field strengths (0-2 V cm(-1)) is intermittently delivered to the cells in culture. The cell viability results suggest that metabolically active cell numbers can statistically increase with electric stimulation up to 1 V cm(-1), only on the PVDF + 2% MWNT. Summarising, the current study highlights the importance of biophysical cues on cellular function at the cell-substrate interface. This study further opens up new avenues in designing conducting substrates, that can be utilized for enhancing cell viability and proliferation and also reconfirms the lack of toxicity of MWNTs, when added in a tailored manner.

Designer porous antibacterial membranes derived from thermally induced phase separation of PS/PVME blends decorated with an electrospun nanofiber scaffold

We report the development of porous membranes by thermally induced phase separation of a PS/PVME (polystyrene/polyvinylmethyl ether]) blend, which is a typical LCST mixture. The morphology of the membrane after etching out the PVME phase was characterized by scanning electron microscopy. To give the membrane an antibacterial surface, polystyrene (PS) and polyvinyl(methyl ether)]-alt-maleic anhydride (PVME-MAH) with silver nanoparticles (nAg) were electrospun on the membrane surface. Pure water flux was evaluated by using a cross-flow membrane setup. The microgrooved fibers changed the flux across the membrane depending on the surface properties. The antibacterial properties of the membrane were confirmed by the reduction in the colony count of E. coli. The SEM images show the disruption of the bacterial cell membrane and the antibacterial mechanism was discussed.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Targeting human telomeric G-quadruplex DNA with curcumin and its synthesized analogues under molecular crowding conditions

The formation of telomeric G-quadruplexes has been shown to inhibit telomerase activity. Indeed, a number of small molecules capable of p-stacking with G-tetrads have shown the ability to inhibit telomerase activity through the stabilization of G-quadruplexes. Curcumin displays a wide spectrum of medicinal properties ranging from anti-bacterial, anti-viral, anti-protozoal, anti-fungal and anti-inflammatory to anti-cancer activity. We have investigated the interactions of curcumin and its structural analogues with the human telomeric sequence AG(3)(T(2)AG(3))(3) under molecular crowding conditions. Experimental studies indicated the existence of a AG(3)(T(2)AG(3))(3)/curcumin complex with binding affinity of 0.72 x 10(6) M-1 under molecular crowding conditions. The results from UV-visible absorption spectroscopy, a fluorescent TO displacement assay, circular dichroism and molecular docking studies, imply that curcumin and their analogues interact with G-quadruplex DNA via groove binding. While other analogs of curcumin studied here bind to G-quadruplexes in a qualitatively similar manner their affinities are relatively lower in comparison to curcumin. The Knoevenagel condensate, a methoxy-benzylidene derivative of curcumin, also exhibited significant binding to G-quadruplex DNA, although with two times decreased affinity. Our study establishes the potential of curcumin as a promising natural product for G-quadruplex specific ligands.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Targeting human telomeric G-quadruplex DNA with curcumin and its synthesized analogues under molecular crowding conditions

The formation of telomeric G-quadruplexes has been shown to inhibit telomerase activity. Indeed, a number of small molecules capable of p-stacking with G-tetrads have shown the ability to inhibit telomerase activity through the stabilization of G-quadruplexes. Curcumin displays a wide spectrum of medicinal properties ranging from anti-bacterial, anti-viral, anti-protozoal, anti-fungal and anti-inflammatory to anti-cancer activity. We have investigated the interactions of curcumin and its structural analogues with the human telomeric sequence AG(3)(T(2)AG(3))(3) under molecular crowding conditions. Experimental studies indicated the existence of a AG(3)(T(2)AG(3))(3)/curcumin complex with binding affinity of 0.72 x 10(6) M-1 under molecular crowding conditions. The results from UV-visible absorption spectroscopy, a fluorescent TO displacement assay, circular dichroism and molecular docking studies, imply that curcumin and their analogues interact with G-quadruplex DNA via groove binding. While other analogs of curcumin studied here bind to G-quadruplexes in a qualitatively similar manner their affinities are relatively lower in comparison to curcumin. The Knoevenagel condensate, a methoxy-benzylidene derivative of curcumin, also exhibited significant binding to G-quadruplex DNA, although with two times decreased affinity. Our study establishes the potential of curcumin as a promising natural product for G-quadruplex specific ligands.

Chitosan Immobilized Porous Polyolefin As Sustainable and Efficient Antibacterial Membranes

Polyolefinic membranes have attracted a great deal of interest owing to their ease of processing and chemical inertness. In this study, porous polyolefin membranes were derived by selectively etching PEO from PE/PEO (polyethylene/poly(ethylene oxide)) blends. The hydrophobic polyolefin (low density polyethylene) was treated with UV-ozone followed by dip coating in chitosan acetate solution to obtain a hydrophilic-antibacterial surface. The chitosan immobilized PE membranes were further characterized by Fourier transform infrared spectroscope (FTIR) and X-ray photoelectron spectroscope (XPS). It was found that surface grafting of chitosan onto PE membranes enhanced the surface roughness and the concentration of nitrogen (or amine) scaled with increasing concentration of chitosan (0.25 to 2% wt/vol), as inferred from Kjeldahl nitrogen analysis. The pure water flux was almost similar for chitosan immobilized PE membranes as compared to membranes without chitosan. The bacterial population, substantially reduced for membranes with higher concentration of chitosan. For instance, 90 and 94% reduction in Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) colony forming unit respectively was observed with 2% wt/vol of chitosan. This study opens new avenues in designing polyolefinic based antibacterial membranes for water purification.

A strategy to achieve enhanced electromagnetic interference shielding at ultra-low concentration of multiwall carbon nanotubes in P alpha MSAN/PMMA blends in the presence of a random copolymer PS-r-PMMA

A unique strategy was adopted to achieve an ultra-low electrical percolation threshold of multiwall carbon nanotubes (MWNTs) (0.25 wt%) in a classical partially miscible blend of poly-alpha-methylstyrene-co-acrylonitrile and poly(methyl methacrylate) (P alpha MSAN/PMMA), with a lower critical solution temperature. The polymer blend nanocomposite was prepared by standard melt-mixing followed by annealing above the phase separation temperature. In a two-step mixing protocol, MWNTs were initially melt-mixed with a random PS-r-PMMA copolymer and subsequently diluted with 85/15 P alpha MSAN/PMMA blends in the next mixing step. Mediated by the PS-r-PMMA, the MWNTs were mostly localized at the interface and bridged the PMMA droplets. This strategy led to enhanced electromagnetic interference (EMI) shielding effectiveness at 0.25 wt% MWNTs through multiple scattering from MWNT-covered droplets, as compared to the blends without the copolymer, which were transparent to electromagnetic radiation.

Tailored electrical conductivity, electromagnetic shielding and thermal transport in polymeric blends with graphene sheets decorated with nickel nanoparticles

Electromagnetic interference shielding (EMI) materials were designed using PC (polycarbonate)/SAN poly(styrene-co-acrylonitrile)] blends containing few-layered graphene nanosheets decorated with nickel nanoparticles (G-Ni). The graphene nanosheets were decorated with nickel nanoparticles via the uniform nucleation of the metal salt precursor on graphene sheets as the substrate. In order to localize the nanoparticles in the PC phase of the PC/SAN blends, a two-step mixing protocol was adopted. In the first step, graphene sheets were mixed with PC in solution and casted into a film, followed by dilution of these PC master batch films with SAN in the subsequent melt extrusion step. The dynamic mechanical properties, ac electrical conductivity, EMI shielding effectiveness and thermal conductivity of the composites were evaluated. The G-Ni nanoparticles significantly improved the electrical and thermal conductivity in the blends. In addition, a total shielding effectiveness (SET) of -29.4 dB at 18 GHz was achieved with G-Ni nanoparticles. Moreover, the blends with G-Ni exhibited an impressive 276% higher thermal conductivity and 29.2% higher elastic modulus with respect to the neat blends.

Conversion of plastic waste into CNTs using Ni/Mo/MgO catalystAn optimization approach by mixture experiment

A combustion technique is used to study the synthesis of carbon nano tubes from waste plastic as a precursor and Ni/Mo/MgO as a catalyst. The catalytic activity of three components Ni, Mo, MgO is measured in terms of amount of carbon product obtained. Different proportions of metal ions are optimized using mixture experiment in Design expert software. D-optimal design technique is adopted due to nonsimplex region and presence of constraints in the mixture experiment. The activity of the components is observed to be interdependent and the component Ni is found to be more effective. The catalyst containing Ni0.8Mo0.1MgO0.1 yields more carbon product. The structure of catalyst and CNTs are studied by using SEM, XRD, and Raman spectroscopy. SEM analysis shows the formation of longer CNTs with average diameter of 40-50 nm.

Unimpeded permeation of water through biocidal graphene oxide sheets anchored on to 3D porous polyolefinic membranes

3D porous membranes were developed by etching one of the phases (here PEO, polyethylene oxide) from melt-mixed PE/PEO binary blends. Herein, we have systematically discussed the development of these membranes using X-ray micro-computed tomography. The 3D tomograms of the extruded strands and hot-pressed samples revealed a clear picture as to how the morphology develops and coarsens over a function of time during post-processing operations like compression molding. The coarsening of PE/PEO blends was traced using X-ray micro-computed tomography and scanning electron microscopy (SEM) of annealed blends at different times. It is now understood from X-ray micro-computed tomography that by the addition of a compatibilizer (here lightly maleated PE), a stable morphology can be visualized in 3D. In order to anchor biocidal graphene oxide sheets onto these 3D porous membranes, the PE membranes were chemically modified with acid/ethylene diamine treatment to anchor the GO sheets which were further confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and surface Raman mapping. The transport properties through the membrane clearly reveal unimpeded permeation of water which suggests that anchoring GO on to the membranes does not clog the pores. Antibacterial studies through the direct contact of bacteria with GO anchored PE membranes resulted in 99% of bacterial inactivation. The possible bacterial inactivation through physical disruption of the bacterial cell wall and/or reactive oxygen species (ROS) is discussed herein. Thus this study opens new avenues in designing polyolefin based antibacterial 3D porous membranes for water purification.