Diamondoid Ni(II) Coordination Polymer as an Electrocatalyst for Hydrogen and Oxygen Evolution Reactions and Overall Water Splitting.

We have successfully synthesized a new Ni(II)-based coordination polymer (CP) [Ni2(cis-1,4-chdc)2(4,4'-bpy)3(H2O)2] (1); (cis-1,4- H2chdc=cis-1,4-cyclohexanedicarboxylic acid and 4,4'-bpy=4,4'-bipyridine) employing slow diffusion method in a single pot technique. The connectivity of Ni(II) ions and bridging cis-1,4-chdc ligand gives rise to a three-dimensional (3D) framework with 2-fold interpenetrated diamondoid topology. Interestingly, the synthesized CP acts as efficient catalyst for electrocatalytic water splitting. The water oxidation activity of compound 1 exhibits Tafel slope equivalent to 361.48 mV.dec-1 for hydrogen evolution reaction (HER) and 353.53 mV.dec-1 for oxygen evolution reaction (OER) in an alkaline medium while almost similar values of Tafel slope for HER and OER equivalent to 287.33 mV.dec-1 and 289.93 mV.dec-1 respectively in acidic medium. Thus, the compound 1 has excellent efficacy in catalyzing HER and OER in acidic as well as alkaline medium, which is ascribed to its distinctive 3D architecture.

Anthracene labeled poly(pyridine methacrylamide) as a polymer-based chemosensor for detection of pyrophosphate (P2O74-) in semi-aqueous media.

To develop fluorophore-labelled pyridinium-based macromolecular architectures for fluorometric and colorimetric detection of anions, two polymers P1 and P2 are synthesized. Linear polymer P1 and cross-linked polymer P2, prepared from N-methacryloyl-3-aminopyridine monomers via free radical polymerization followed by quaternization of the pyridine ring nitrogen with anthracene as a fluorescent marker, have been successfully employed in anion sensing. P1 exhibits excellent sensing of HPPi in aqueous DMSO. In addition to the enhancement of fluorescence emission of the anthracene moiety, P1 exclusively shows excimer/exciplex emission in the presence of HPPi over other anions and exhibits selectivity to HPPi with a detection limit of about 1.63 ppm. Cross-linked P2 exhibits naked-eye detection of PPi/HPPi over other anions studied via indicator displacement assay (IDA).

Uptake and Release of Species from Carbohydrate Containing Organogels and Hydrogels.

Hydrogels are used for a variety of technical and medical applications capitalizing on their three-dimensional (3D) cross-linked polymeric structures and ability to act as a reservoir for encapsulated species (potentially encapsulating or releasing them in response to environmental stimuli). In this study, carbohydrate-based organogels were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of a ß-D-glucose pentaacetate containing methacrylate monomer (Ac-glu-HEMA) in the presence of a di-vinyl cross-linker; these organogels could be converted to hydrogels by treatment with sodium methoxide (NaOMe). These materials were studied using solid state 13C cross-polarization/magic-angle spinning (CP/MAS) NMR, Fourier transform infrared (FTIR) spectroscopy, and field emission scanning electron microscopy (FE-SEM). The swelling of the gels in both organic solvents and water were studied, as was their ability to absorb model bioactive molecules (the cationic dyes methylene blue (MB) and rhodamine B (RhB)) and absorb/release silver nitrate, demonstrating such gels have potential for environmental and biomedical applications.

Synthesis of a polymer bearing several coumarin dyes along the side chain and study of its fluorescence in pure and binary solvent mixtures as well as aqueous surfactant solutions.

A copolymer bearing several pendent dyes (coumarin derivatives) along the side chain has been synthesized, and its fluorescence parameters have been monitored in pure solvents and also as a function of composition of binary solvent mixtures. Fluorescence parameters (the maximum energy of fluorescence, quantum yield, and rate constant for the decay of the excited state) of the free fluorophore show significant dependence on the nature of the immediate environment around it. The value of a parameter measured in neat solvent for the fluorophore covalently bound to the polymer is different from that of the free fluorophore, indicating that the polymer chain influences the spectroscopic properties of the dye. Whereas the energy of maximum fluorescence of the free fluorophore shows a nonlinear correlation with the solvent composition of solvent mixtures, an almost linear correlation has been observed for the polymer. A significant variation of photophysical parameters of the dye dissolved in binary solvent mixtures, which is different from that of the free fluorophore, has been observed. Thus, the free fluorophore and the fluorophore bound to the polymer sense different environments in binary solvent mixtures. A dramatic variation of fluorescence intensity of the fluorophore bound to the polymer has been observed when sodium dodecyl sulfate (SDS) is added to an aqueous solution of the polymer. The results have been explained in terms of the existence of different species (polymer, polymer-SDS aggregates, micelles) in equilibrium in solution.

Remarkable swelling capability of amino acid based cross-linked polymer networks in organic and aqueous medium.

This work reports design and synthesis of side chain amino acid based cross-linked polymeric gels, able to switch over from organogel to hydrogel by a simple deprotection reaction and showing superabsorbancy in water. Amino acid based methacrylate monomers, tert-butoxycarbonyl (Boc)-l/d-alanine methacryloyloxyethyl ester (Boc-l/d-Ala-HEMA), have been polymerized in the presence of a cross-linker via conventional free radical polymerization (FRP) and the reversible addition-fragmentation chain transfer (RAFT) technique for the synthesis of cross-linked polymer gels. The swelling behaviors of these organogels are investigated in organic solvents, and they behave as superabsorbent materials for organic solvents such as dichloromethane, acetone, tetrahydrofuran, etc. Swollen cross-linked polymer gels release the absorbed organic solvent rapidly. After Boc group deprotection from the pendant alanine moiety, the organogels transform to the hydrogels due to the formation of side chain ammonium (-NH3(+)) groups, and these hydrogels showed a significantly high swelling ratio (∼560 times than their dry volumes) in water. The morphology of organogels and hydrogels is studied by field emission scanning electron microscopy (FE-SEM). Amino acid based cross-linked gels could find applications as absorbents for oil spilled on water as well as superabsorbent hydrogels.

CdS quantum dots doped tuning of deswelling kinetics of thermoresponsive hydrogels based on poly(2-(2-methoxyethoxy)ethyl methacrylate).

Thermoresponsive poly(2-(2-methoxyethoxy)ethyl methacrylate) (PMEO2MA) based hybrid nanocomposite hydrogels (NCH) were synthesized by dispersing preformed cadmium sulfide (CdS) quantum dots (QDs) in the reaction mixture followed by polymerization via reversible addition-fragmentation chain transfer (RAFT) technique. High doping capacity and negligible QDs leakage were observed for hydrophilic QDs doped hydrogels (hpl-NCH) due to H-bonding interactions between QDs and pendant groups of hydrogel network. The hpl-NCH networks showed improved structural/orientational order and swelling ratios with increasing doping concentration compared to the organic hydrogel (OH). Opposite trends were observed for bulk-CdS (NCH-bulk) and 1-dodecanethiol capped CdS (NCH-DDT) doped hydrogels. Swelling induced linear retardance and quenching of photoluminescence (PL) intensity for hydrogels were exploited to study the deswelling kinetics respectively by Mueller matrix polarimetry and solid state fluorimetry, which were further corroborated with gravimetric analysis. For all the NCH, deswelling process significantly decreased with increasing temperature, which followed the order: 30 > 45 > 60 °C. Slower deswelling was observed for NCH-bulk and hpl-NCH compared to the OH, and also with increase in doping concentration due to the formation of skin layer. However, NCH-DDT exhibited accelerated deswelling process and the order was reversed with respect to doping concentration due to DDT mediated enhanced hydrophobic aggregation and water leakage channels created by long hydrophobic free-mobile nature of QDs surface tethered DDT molecules. The presented methodology provides tunable deswelling of PMEO2MA based hydrogels by doping with hydrophilically/hydrophobically modified CdS QDs.

Controlled synthesis of amino acid-based pH-responsive chiral polymers and self-assembly of their block copolymers.

Leucine/isoleucine side chain polymers are of interest due to their hydrophobicity and reported role in the formation of α-helical structures. The synthesis and reversible addition-fragmentation chain transfer (RAFT) polymerization of amino acid-based chiral monomers, namely Boc-L-leucine methacryloyloxyethyl ester (Boc-L-Leu-HEMA, 1a), Boc-L-leucine acryloyloxyethyl ester (Boc-L-Leu-HEA, 1b), Boc-L-isoleucine methacryloyloxyethyl ester (Boc-L-Ile-HEMA, 1c), and Boc-L-isoleucine acryloyloxyethyl ester (Boc-L-Ile-HEA, 1d), are reported. The controlled nature of the polymerization of the said chiral monomers in N, N-dimethylformamide (DMF) at 70 °C is evident from the formation of narrow polydisperse polymers, the molecular weight controlled by the monomer/chain transfer agent (CTA) molar ratio and the linear relationship between molecular weight and monomer conversion. The resulting well-defined polymers were used as macro-CTAs to prepare corresponding diblock copolymers by RAFT polymerization of methyl (meth)acrylate monomers. Deprotection of Boc groups in the homopolymers and block copolymers under acidic conditions produced cationic, pH-responsive polymers with primary amine moieties at the side chains. The optical activity of the homopolymers and block copolymers were studied using circular dichroism (CD) spectroscopy and specific rotation measurements. The self-assembling nature of the block copolymers to produce highly ordered structures was illustrated through dynamic light scattering (DLS) and atomic force microscopy (AFM) studies. The side chain amine functionality instills pH-responsive behavior, which makes these cationic polymers attractive candidates for drug delivery applications, as well as for conjugation of biomolecules.