Photophysical Properties of Linear, Net-structured and Branched Polybenzimidazoles.

Polybenzimidazoles with three different network structures are synthesized by condensation polymerization between the conventional monomer 3,3'-Diaminobenzidine and three different acid monomers. The synthesised polymer networks are characterized using several characterization techniques such as FT-IR, powder XRD, HR-SEM and TG-DTA analyses. The polybenzimidazoles are amorphous in nature with excellent thermal stability up to 450 ºC. The photophysical properties of polybenzimidazoles are studied using UV-visible absorption and Emission spectral techniques. Further, the excited state photoluminescence decay time measurement shows a functional group dependant decay behaviour. All the three polymers display narrow optical band gap energy and could be applied as a material for solar energy conversion and semiconductors.

Synthesis and Photoluminescence Properties of MoS2/Graphene Heterostructure by Liquid-Phase Exfoliation.

Here, we report the synthesis of MoS2/graphene heterostructure in single-stage, liquid-phase exfoliation using a 7:3 isopropyl alcohol/water mixture. Further, the synthesized heterostructure was characterized using UV-visible and micro-Raman spectroscopies, transmission electron microscopy (TEM), and dynamic light scattering (DLS) analysis. UV-visible and micro-Raman analyses confirmed that the synthesized heterostructure had mostly few-layered (two-to-four sheets) MoS2. The photophysical properties of the heterostructure were analyzed using steady-state and time-resolved luminescence techniques. Enhanced photoluminescence was observed in the case of the heterostructure probably due to an increase in the defect sites or reduction in the rate of nonradiative decay upon formation of the sandwiched heterostructure. Applications of this heterostructure for fluorescence live-cell imaging were carried out, and the heterostructure demonstrated a better luminescence contrast compared to its individual counterpart MoS2 in phosphate-buffered saline (PBS).

Bi2WO6 and FeWO4 Nanocatalysts for the Electrochemical Water Oxidation Process.

Polyvinylpyrrolidone (PVP)-assisted nanocatalyst preparation was succeeded by employing a controlled solvothermal route to produce efficient electrodes for electrochemical water-splitting applications. Bi2WO6 and FeWO4 nanocatalysts have been confirmed through the strong signature of (113) and (111) crystal planes, respectively. The binding natures of Bi-W-O and Fe-W-O have been thoroughly discussed by employing X-ray photoelectron spectroscopy which confirmed the formation of Bi2WO6 and FeWO4. The freestanding nanoplate array morphology of Bi2WO6 and the fine nanosphere particle morphology of FeWO4 nanocatalysts were revealed by scanning electron microscopy images. With these confirmations, the fabrication of durable, long-term electrodes for electrochemical water splitting has been subjected to efficient oxidation of water, confirmed by obtaining 2.79 and 1.96 mA/g for 0.5 g PVP-assisted Bi2WO6 and FeWO4 nanocatalysts, respectively. The water oxidation mechanism of both nanocatalysts has been revealed with the support of 24 h stability test over continuous water oxidation and faster charge transfer achieved by the smaller Tafel slope values of 75 and 78 mV/dec, respectively. Generally, these nanocatalysts are utilized for photocatalytic applications. The present study revealed the PVP-assisted synthesis to produce electrocatalytically active nanocatalysts and their electrochemical water-splitting mechanism which will offer a pathway for research interests with regard to the production of multifunctional nanocatalysts for both electro- and photocatalytic applications in the near future.

FRET-based Solid-state Luminescent Glyphosate Sensor Using Calixarene-grafted Ruthenium(II)bipyridine Doped Silica Nanoparticles.

Calixarene-functionalized luminescent nanoparticles were successfully fabricated for the FRET-based selective and sensitive detection of the organophosphorus pesticide glyphosate (GP). p-Tert-butylcalix[4]arene was grafted on the surface of [Ru(bpy)3 ]2+ incorporated SiNps to produce self-assembled nanosensors (RSC). FRET was switched on in the presence of GP by means of energy transfer due to binding with p-tert-butylcalix[4]arene grafted on the surface of the RSC. The FRET efficiency of the GP-RSC system was increased gradually with the addition of GP. The FRET efficiency was evaluated as 87.69 % and a high binding affinity was established by the binding constant value, 1.16×107  M-1 , using a Langmuir binding isotherm plot. The estimated limit of detection (LOD) was 7.91×10-7  M, which was lower than the Environmental Protection Agency (EPA) recommendation. The probe also effectively responds to real sample analysis. The sensitivity and selectivity was realized due to the efficient FRET towards the fluorescence properties of the [Ru(bpy)3 ]2+ complex.

Selective and sensitive fluorescent sensor for Pd2+ using coumarin 460 for real-time and biological applications.

The efficient fluorescent property of coumarin 460 (C460) is utilized to sense the Pd2+ selectively and sensitively. Fabrication of a sensor strip using commercial adhesive tape is achieved and the detection of Pd2+ is attempted using a handy UV torch. The naked eye detection in solution state using UV chamber is also attempted. The calculated high binding constant values support the strong stable complex formation of Pd2+ with C460. The detection limit up to 2.5 × 10-7 M is achieved using fluorescence spectrometer, which is considerably low from the WHO's recommendation. The response of coumarin 460 with various cations also studied. The quenching is further studied by the lifetime measurements. The binding mechanism is clearly explained by the 1H NMR titration. The sensing mechanism is established as ICT. C460 strip's Pd2+ quenching detection is further confirmed by solid-state PL study. The in-vitro response of Pd2+ in a living cell is also studied using fluorescent imaging studies by means of HeLa cell lines and this probe is very compatible with biological environments. It could be applicable to sense trace amounts of a Pd2+ ion from various industries. Compared with previous reports, this one is very cheap, sensitive, selective and suitable for biological systems.

Spectral, Electrochemical and Computational Investigations of Binding of n-(4-Hydroxyphenyl)-imidazole with p-Sulfonatocalix[4]arene.

The interaction of n-(4-hydroxyphenyl)-imidazole with p-sulfonatocalix[4]arene is studied using fluorescence technique. The quenching of fluorescence intensity explains the efficiency of binding via binding constant and quenching constant. The excited state lifetime of n-(4-hydroxyphenyl)-imidazole is decreased upon interaction with p-sulfonatocalix[4]arene. The cyclic voltametric studies emphasized the interaction of n-(4-hydroxyphenyl)-imidazole with p-sulfonatocalix[4]arene. Quantum chemical calculations are carried out to study the interactions as well as charge transfer between the host and the guest upon complexation. The simulations revealed that the n-(4-hydroxyphenyl)-imidazole interacts with p-sulfonatocalix[4]arene with horizontal orientation with in the p-sulfonatocalix[4]arene cavity.

Electron Transfer Studies of Ruthenium(II) Complexes with Biologically Important Phenolic Acids and Tyrosine.

The ruthenium(II) complexes having 2,2'-bipyridine and phenanthroline derivatives are synthesized and characterized. The photophysical properties of these complexes at pH 12.5 are studied. The electron transfer reaction of biologically important phenolic acids and tyrosine are studied using absorption, emission and transient absorption spectral techniques. Semiclassical theory is applied to calculate the rate of electron transfer between ruthenium(II) complexes and biologically important phenolic acids.

Sensing and inhibition of amyloid-ß based on the simple luminescent aptamer-ruthenium complex system.

Aggregation of amyloid-ß (Aß) peptide has been known to be pathologically associated with Alzheimer and dementia diseases. Amyloid-ß fibrils serve as an important target for the drugs development and diagnosis of neurodegenerative diseases. Herein, we report a new [Ru(dmbpy)(dcbpy)dppz)] complex (dmbpy; 4,4'-dimethyl-2,2'-bipyridine, dcbpy; 4,4'-dicorboxy-2,2'-bipyridine, dppz; dipyridophenazine) intercalated aptamer based recognition of amyloid-ß. Interestingly, aforementioned Ru(II) complex shows weak luminescence intensity in the aqueous medium but it shows strong luminescence intensity in the presence of RNA aptamer. Upon addition of amyloid-ß monomers, the luminescence intensity of Ru(II) complex is reduced due to the strong interaction of aptamer with amyloid-ß monomer/small oligomers. Furthermore, present study implies that our system has ability to inhibit the formation of amyloid-ß fibrils, which is confirmed from the AFM morphological structures in the absence and presence of aptamer. This work may contribute the rapid diagnosis and inhibition of amyloid-ß aggregation in the clinical applications.

A selective, long-lived deep-red emissive ruthenium(II) polypyridine complexes for the detection of BSA.

A selective, label free luminescence sensor for bovine serum albumin (BSA) is investigated using ruthenium(II) complexes over the other proteins. Interaction between BSA and ruthenium(II) complexes has been studied using absorption, emission, excited state lifetime and circular dichroism (CD) spectral techniques. The luminescence intensity of ruthenium(II) complexes (I and II), has enhanced at 602 and 613 nm with a large hypsochromic shift of 18 and 5 nm respectively upon addition of BSA. The mode of binding of ruthenium(II) complexes with BSA has analyzed using computational docking studies.