Charge-Transfer-Induced Fluorescence Quenching of Anthracene Derivatives and Selective Detection of Picric Acid.

2,6-Divinylpyridine-appended anthracene derivatives flanked by two alkyl chains at the 9,10-position of the core have been designed, synthesized, and characterized by NMR, MALDI-TOF, FTIR, and single-crystal XRD. These anthracene derivatives are able to recognize picric acid (2,4,6-trinitrophenol, PA) selectively down to parts per billion (ppb) level in aqueous as well as nonaqueous medium. Fluorescence emission of these derivatives in solution is significantly quenched by adding trace amounts of PA, even in the presence of other competing analogues, such as 2,4-dinitrophenol (2,4-DNP), 4-nitrophenol (NP), nitrobenzene (NB), benzoic acid (BA), and phenol (PH). The high sensitivity of these derivatives toward PA is considered as a combined effect of the proton-induced intramolecular charge transfer (ICT) as well as electron transfer from the electron-rich anthracene to the electron-deficient PA. Moreover, visual detection of PA has been successfully demonstrated in the solid state by using different substrates.

Light harvesting and amplification of emission of donor perylene­acceptor perylene aggregates in aqueous medium.

With the aid of rational design, we have synthesized a pair of water-soluble donor- and acceptor-type twisted perylene bisimide units, which together form aggregates upon lowering the pH of the medium, providing bright yellow fluorescence. The light-harvesting efficiency of the co-assembled system can be tuned by controlling the ratio of donor to acceptor and 98.1 % efficiency has been achieved.

Complexation of amyloid fibrils with charged conjugated polymers.

It has been suggested that conjugated charged polymers are amyloid imaging agents and promising therapeutic candidates for neurological disorders. However, very less is known about their efficacy in modulating the amyloid aggregation pathway. Here, we studied the modulation of Parkinson's disease associated α-synuclein (AS) amyloid assembly kinetics using conjugated polyfluorene polymers (PF, cationic; PFS, anionic). We also explored the complexation of these charged polymers with the various AS aggregated species including amyloid fibrils and oligomers using multidisciplinary biophysical techniques. Our data suggests that both polymers irrespective of their different charges in the side chains increase the fibrilization kinetics of AS and also remarkably change the morphology of the resultant amyloid fibrils. Both polymers were incorporated/aligned onto the AS amyloid fibrils as evident from electron microscopy (EM) and atomic force microscopy (AFM), and the resultant complexes were structurally distinct from their pristine form of both polymers and AS supported by FTIR study. Additionally, we observed that the mechanism of interactions between the polymers with different species of AS aggregates were markedly different.

Effects of process parameters on the defects in graphene oxide-polyaniline composites investigated by positron annihilation spectroscopy.

Graphene oxide (GO)-polyaniline (PANI) composites were prepared with different relative abundance of PANI and GO by in situ polymerization of aniline in the presence of GO and ammonium persulphate at different temperatures. In the process, GO also got reduced to graphene. Positron lifetimes and coincidence Doppler broadening of the electron-positron annihilation gamma ray spectra originating from the composite samples were measured and the results are reported. The positron lifetimes indicated the presence of very large size defects in the form of vacancy clusters within the samples. Another interesting observation was the increase of relative intensity of the defect specific positron lifetime component when an increase in relative abundance of PANI led to increased reduction of GO to graphene. The reduction also shrank the volume occupied by GO and the free volume thereby released added to the overall defect concentration, resulting in a simultaneous increase of the intensity of the positron lifetime component. The variation of the positron lifetime and its intensity with the synthesis temperature suggested an optimum temperature suitable for the process. The above observations are corroborated by other experimental investigations like electron microscopy, X-ray diffraction and electrical conductivity.

Oligonucleotide tagging for copper-free click conjugation.

Copper-free click chemistry between cyclooctynes and azide is a mild, fast and selective technology for conjugation of oligonucleotides. However, technology for site-specific introduction of the requisite probes by automated protocols is scarce, while the reported cyclooctynes are large and hydrophobic. In this work, it is demonstrated that the introduction of bicyclo[6.1.0]nonyne (BCN) into synthetic oligonucleotides is feasible by standard solid-phase phosphoramidite chemistry. A range of phosphoramidite building blocks is presented for incoporation of BCN or azide, either on-support or in solution. The usefulness of the approach is demonstrated by the straightforward and high-yielding conjugation of the resulting oligonucleotides, including biotinylation, fluorescent labeling, dimerization and attachment to polymer.

Effect of Tricarboxylic Acids on the Formation of Hydrogels with Melem or Melamine: Morphological, Structural and Rheological Investigations.

Herein, aggregation behaviors of melem or melamine in the presence of three symmetric carboxylic acids (1,3,5-tris(4-carboxyphenyl)benzene (TPCA), 1,3,5-benzene-tri-carboxylic acid (BTA) and 1,3,5-cyclohexane-tri-carboxylic acid (CHTA)) have been performed to check the influence of acid on the formation of aggregated structures which have been investigated by optical microscopy, FESEM, FTIR, XRD and viscoelastic properties have been explored with rheological studies. Interestingly, melem, that has limited solubility in aqueous medium, forms aggregation that leads to the formation of hydrogels with TPCA. More significantly, hydrogel is formed here by matching the size selectivity. Melem forms hydrogel with only large tricarboxylic acid, whereas melamine produces hydrogel with any kind of its counterpart from small to large tricarboxylic acid derivatives. Present investigations and results provide the strategy of design of organic self-assembled materials having two component systems.

Tuning intermediate adsorption in structurally ordered substituted PdCu3 intermetallic nanoparticles for enhanced ethanol oxidation reaction.

Co and Ni-substituted structurally ordered intermetallic PdCu3 nanoparticles (NPs) synthesized at low temperature exhibit remarkable enhancement of the ethanol electrooxidation (EOR) activity with improved durability. The first-principle calculations suggest that prompted generation of OH and CH3CO radicals in close proximity and shifting of the d-band center towards the Fermi level boost the EOR efficiency.

Morphological Modulation of Conducting Polymer Nanocomposites with Nickel Cobaltite/Reduced Graphene Oxide and Their Subtle Effects on the Capacitive Behaviors.

This work reports on the urchin-like architecture-based nickel cobaltite (NiCo2O4)/reduced graphene oxide (rGO)/conducting polymer [polyaniline (PANI) or polypyrrole (PPy)] nanocomposites prepared through a hydrothermal synthesis procedure, followed by in situ polymerization techniques. Subsequently, these materials are subjected to electrochemical investigation to search for promising electrode materials for energy storage applications. Interestingly, the morphology of NiCo2O4 varies upon the addition of rGO as well as nitrogen-doped rGO (N-rGO). When it is composite with rGO, it forms an urchin-like architecture, and with N-rGO, it forms nanoparticle structures having a diameter of 90 ± 10 nm. Further, these nanostructures are intricately coated by conducting polymers (such as PANI and PPy) as evidenced from the field emission scanning electron microscopy and high-resolution transmission electron microscopy observations, and the overall shape does not alter after the modification. All composites are investigated thoroughly by Fourier transform infrared, Raman, X-ray powder diffraction, and X-ray photoelectron spectroscopies to confer the formation and presence of polymers. The NiCo2O4/rGO/PPy nanocomposites exhibit an excellent specific capacitance of 1547 ± 5 F/g at a current density of 0.5 A/g, a better energy density of 34.37 ± 0.11 W h/kg at 0.5 A/g, a notable power density of 99.98 ± 0.31 W/kg at 0.5 A/g, and retains its 94 ± 1% specific capacitance after 5000 charge-discharge cycles. The uniform coating over the urchin-like architecture by conducting polymers constructs a typical morphology, and possibly, it is the key factor behind gaining such superior electrochemical behavior owing to (a) the enhancement of surface area and (b) the combination of double-layer capacitive and pseudocapacitive properties. Furthermore, a symmetric flexible supercapacitor device made of NiCo2O4/rGO/PPy nanocomposites provides superior electrochemical behavior.

Covalently linked benzimidazole-containing reduced graphene oxide/polyaniline nanocomposites as electrode materials.

In the present manuscript, we reported the effective synthesis of 1,3-bis(2'-benzimidazolyl)-5-aminobenzene-grafted graphene oxide, followed by reduction, affording covalently linked benzimidazole-containing chemically modified reduced graphene oxide. The prepared material was further coated with polyaniline via in situ polymerization. The prepared material was successfully characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and thermo-gravimetric analysis (TGA); subsequently, it was subjected to electrochemical analysis using a three-electrode system in dilute acid solutions as electrolytes in terms of cyclic voltammetry (CV), galvanostatic charge-discharge and electrochemical impedance studies. The polyaniline-coated binary composite materials revealed maximum specific capacitance of 823 F g-1 at 0.2 A g-1 current density, whereas the value for the chemically modified reduced graphene oxide was 477 F g-1. The CV curves denoted the pseudocapacitive nature of the electrode materials. The values for the retention of specific capacitance for the electrode materials were 77.5% and 87.9% up to 5000 charge-discharge cycles.

Facile Decoration of Polyaniline Fiber with Ag Nanoparticles for Recyclable SERS Substrate.

Facile synthesis of polyaniline@Ag composite has been successfully demonstrated by a simple solution-dipping method using high-aspect-ratio benzene tetracarboxylic acid-doped polyaniline (BDP) fiber as a nontoxic reducing agent as well as template cum stabilizer. In BDP@Ag composite, BDP fibers are decorated with spherical Ag nanoparticles (Ag NPs), and the population of Ag NPs on BDP fibers is controlled by changing the molar concentration of AgNO3. Importantly, Ag-NP-decorated BDP fibers (BDP@Ag composites) have been evolved as a sensitive materials for the detection of trace amounts of 4-mercaptobenzoic acid and rhodamine 6G as an analyte of surface-enhanced Raman scattering (SERS), and the detection limit is down to nanomolar concentrations with excellent recyclability. Furthermore, synthesized BDP@Ag composites are applied simultaneously as an active SERS substrate and a superior catalyst for reduction of 4-nitrothiophenol.

Graphene quantum dot-doped polyaniline nanofiber as high performance supercapacitor electrode materials.

Graphene quantum dot-doped polyaniline composites have been prepared by the chemical oxidation of aniline. Synthesized novel fibrous composites show an excellent specific capacitance value of ∼1044 F g(-1) at a current density of 1 A g(-1) as well as moderate cyclic stability with a retention of life time of 80.1% after 3000 cycles.

Vice versa donor acceptor fluorene-ferrocene alternate copolymer: a twisted ribbon for electrical switching.

Two donor-acceptor type copolymers (PFFC-1 and PFFC-2) containing ferrocene and fluorene moieties have been successfully synthesized to evaluate the redox triggered optical and electronic properties. Interestingly, PFFC-1 shows a twisted ribbon-like morphology at the liquid interface and switches to a micellar structure on oxidation.

Amphiphilic and Thermoresponsive Conjugated Block Copolymer with Its Solvent Dependent Optical and Photoluminescence Properties: Toward Sensing Applications.

Herein, we present a new class of amphiphilic, thermoresponsive rod-coil conjugated block copolymer having regioregular poly(3-hexyl thiophene) and poly(N-isopropylacrylamide). Optical and luminescence properties of theses polymers significantly depend on the self-assembled nanostructures formed in different solvent and are easily tailored by chnaging the solvent composition or external stimuli like heat. Unique optical and electronic properties of this block copolymer are believed to make it promising for applications like sensor, fluorescence thermometer, optoelectronic, and bioelectronics devices.

Self healing hydrogels composed of amyloid nano fibrils for cell culture and stem cell differentiation.

Amyloids are highly ordered protein/peptide aggregates associated with human diseases as well as various native biological functions. Given the diverse range of physiochemical properties of amyloids, we hypothesized that higher order amyloid self-assembly could be used for fabricating novel hydrogels for biomaterial applications. For proof of concept, we designed a series of peptides based on the high aggregation prone C-terminus of Aß42, which is associated with Alzheimer's disease. These Fmoc protected peptides self assemble to ß sheet rich nanofibrils, forming hydrogels that are thermoreversible, non-toxic and thixotropic. Mechanistic studies indicate that while hydrophobic, π-π interactions and hydrogen bonding drive amyloid network formation to form supramolecular gel structure, the exposed hydrophobic surface of amyloid fibrils may render thixotropicity to these gels. We have demonstrated the utility of these hydrogels in supporting cell attachment and spreading across a diverse range of cell types. Finally, by tuning the stiffness of these gels through modulation of peptide concentration and salt concentration these hydrogels could be used as scaffolds that can drive differentiation of mesenchymal stem cells. Taken together, our results indicate that small size, ease of custom synthesis, thixotropic nature makes these amyloid-based hydrogels ideally suited for biomaterial/nanotechnology applications.

Fluorene-based chemodosimeter for "turn-on" sensing of cyanide by hampering ESIPT and live cell imaging.

A new salicylaldehyde appended fluorene-based chemodosimeter (FSal) has been designed by taking consideration of the special nucleophilicity of cyanide ion. FSal shows selective affinity towards CN- over other anions (namely F-, Br-, NO3 -, ClO4 -, N3 -, H2PO4 -, AcO-, I-, Cl-, and NO2 -) through turn-on fluorescence with a minimum detection limit of 0.06 ppm. The turn-on fluorescence of the FSal-CN complex resulting from hampering ESIPT is also supported by DFT and TDDFT calculations. Biological compatibility and live cell imaging of this unique probe have also been explored.

Aggregation induced chirality in a self assembled perylene based hydrogel: application of the intracellular pH measurement.

With the aim of controlling helicity of self-assembled fibers, a pair of water soluble perylene derivatives has been designed and synthesized. Intermolecular hydrogen bonding interactions and π-π stacking, combined with the effect of molecular chirality, have been found to guide the aggregation that eventually led to gelation in water upon decreasing pH. This work has demonstrated a new paradigm of simple and non-toxic perylene derivatives for biological applications.

Layered double hydroxide induced advancement in joint prosthesis using bone cement: the effect of metal substitution.

Poly(methyl methacrylate) based bone cement and its nanocomposites with layered double hydroxide (LDH) have been developed with greater mechanical strength and biocompatibility as a grouting material for total joint arthroplasty. Bivalent magnesium has been replaced with trivalent aluminium with various mole ratios, keeping the layered pattern of the LDH intact, to cater for the effect of varying substitution on the property enhancement of the nanocomposites. The intercalation of polymer inside the LDH layers makes them disordered and mechanically stiffer and tougher by more than 100%. The thermal stability of bone cement has increased by more than 30 °C in the presence of 1 wt% of nanoLDH, homogenously distributed in the bone cement matrix by creating an inorganic thermal barrier out of the LDH dispersion. The improvement in the properties of the nanocomposites has been explained in terms of the strong interaction between nanoLDH and polymer. The superior bioactivity and biocompatibility of the nanocomposites, as compared to pure bone cement, has been established through hemolysis assay, cell adhesion, MTT assay and cell proliferation using fluorescence imaging. The developed nanocomposites have been used as a grouting material and significant improvements have been achieved in fatigue behaviour with gradual increment of Al substitution in the Mg : Al mole ratio in nanoLDH, demonstrating the real use of the material in the biomedical area. In vivo experiments on rabbits clearly revealed the superior efficacy of bone cement nanocomposites, over pure bone cement and a blank.

Graphene oxide/polyaniline nanostructures: transformation of 2D sheet to 1D nanotube and in situ reduction.

The formation of unique polyaniline nanotubes has been reported in presence of graphene oxide (GO) which plays crucial dual role as dopant and soft template, simultaneously. GO in nanotubes is in situ reduced to reduced GO with restoration of electrical conductivities and enhanced thermal stabilities.

Immobilization of poly(fluorene) within clay nanocomposite: an easy way to control keto defect.

Blue light emitting cationic polyfluorene polymer(PF)/montmorillonite (MMT) nanocomposites were prepared by solution intercalation and exfoliation method to evaluate the effect of MMT on the nanocomposite structures, properties and morphologies. The properties of PF-MMT composites, containing 1-50 mass% MMT, were characterized unambiguously with the help of multiple analytical techniques, with focus on the keto defect and photostability of PF in the nanocomposites. XRD and HRTEM studies reveal both exfoliation of MMT galleries at lower content of MMT in composites and intercalation of PF chains into the MMT galleries at higher MMT content. The nanocomposites show higher thermal stability than pristine PF as anchorage of nanoclay in PF matrix occur through the electrostatic interaction between nanoclay and polymer. The decrease in Si-O-Si stretching frequency during exfoliation is much higher than in intercalation, as Si-O-Si experience lesser hindrance to vibrate in exfoliated MMT galleries. The gradual redshift of π-π(*) transition peak of PF with increasing MMT content in composites confirms the uncoiling of PF in clay galleries. The photoluminescence characteristics reveal interruption of interchain interaction in this intercalated and exfoliated organic/inorganic hybrid system, which reduces the low-energy emission that results from keto defect. Due to very high aspect ratio of MMT, it can act as an efficient exciton blocking layer and a barrier to oxygen diffusion, which may lead to a device with high color purity and enhanced photostability. Again current-voltage characteristics of nanocomposite films confirm the retention of LED properties after nanocomposite formation.

An all-organic steroid-D-π-A modular design drives ferroelectricity in supramolecular solids and nano-architectures at RT.

Confluence of a modular design approach and self-assembly with a 'steroid-D-π-A' module generates spontaneous polarization in solids and for the first time in nano-architectures constituted from organogels, at room temperature (RT).