An In Situ Fabricated Hydrogel Polymer - Palladium Nanocomposite Electrocatalyst for the HER: Critical Role of the Polymer in Realizing High Efficiency and Stability.

Development of general and simple designs of catalytic electrodes for the hydrogen evolution reaction (HER) is critical. The present work demonstrates the multiple roles played by a hydrogel polymer in the fabrication and activity enhancement of the nanoelectrocatalyst. A nanocomposite thin film of Pd with the insulating hydrogel, poly(2-hydroxyethyl methacrylate) (PHEMA), is fabricated through a facile in situ process, the polymer itself functioning as the reducing/stabilizing agent in the formation of Pd nanoparticles. Pd-PHEMA on Ni foam enables efficient HER in alkaline medium with a low overpotential; the polymer enables the electrocatalysis by its swelling and confinement of the electrolyte. Most significantly, when the electrode is subjected to an optimized cycling protocol, the overpotential decreases steadily, reaching an impressively low value of 36 mV (@10 mA cm-2 ). A low Tafel slope (68 mV dec-1 ), high exchange current density, Faradaic efficiency and TOF (3.27 mA cm-2 , 99 %, 122.7 h-1 ), and extended stability are achieved. Detailed investigations reveal the active role of the polymer in the evolution of the nanocatalyst, itself undergoing favorable morphological changes. The study illustrates the widened scope for developing efficient and stable catalytic electrodes with hydrogel polymers and unique features that promote the generation of green hydrogen.

Hydrogel Polymer-PBA Nanocomposite Thin Film-Based Bifunctional Catalytic Electrode for Water Splitting: The Unique Role of the Polymer Matrix in Enhancing the Electrocatalytic Efficiency.

A novel approach to efficient bifunctional catalytic electrodes for water splitting is developed, based on a counterintuitive choice of an insulating hydrogel polymer (chitosan, CS)-Prussian blue analogue (PBA, KCoFe) nanocomposite thin film on nickel foam. The polymer matrix in KCoFe-CS enables the formation of framelike structures of the non-noble metal-based catalyst nanocrystals, in addition to improving their stability. An optimized cycling protocol leads to a substantial enhancement of the electrocatalytic efficiency for oxygen evolution reaction (OER) as well as hydrogen evolution reaction (HER), achieving relatively low overpotentials of 272 and 320 mV (@ 10 and 20 mA cm-2) and 146 mV (@ 10 mA cm-2), respectively, reduced Tafel slopes, and increased Faradaic efficiencies of 98 and 96%; the overpotentials estimated based on the electrochemically active surface area show similar trends. The polymer encapsulation and the cycling protocol are key to the realization of the desirable combination of enhanced efficiency and stability demonstrated up to 50 h for both OER and HER. Detailed characterizations of the postcycling catalytic electrode show that favorable morphological changes of the polymer matrix with concomitant reduction in the PBA nanocrystal size lead to the enhanced activity. The bifunctional activity of the catalytic electrode is demonstrated by the stable water splitting achieved with a 20 mA cm-2 current density at 1.55 V. The present study unravels the utility of hydrogel polymer matrices (without the use of binders like Nafion) in realizing sustainable water splitting electrocatalysts with high stability and efficiency, through the combined effect of confining the electrolyte within and favorably modifying the catalyst nanoparticles and the nanocomposite morphology.

"Sporotan" a new fluorescent stain for identifying cryptic spores of Rhodobacter johrii.

We propose a new fluorescent stain "sporotan" and staining protocol which aid in the identification of cryptic endospores which are otherwise mistaken as poly-ß-hydroxyalkanoate granules.

Zwitterionic small molecule based fluorophores for efficient and selective imaging of bacterial endospores.

In the emerging scenario of increasing antibiotic resistance and pathogen transmission channels, the grave danger posed by bacterial endospores in critical fields like food industry, health and medicine highlights the urgent need to develop efficient probes for their detection; their sturdy and impermeable multilayer coat makes desirable methods like fluorescence imaging extremely difficult. Selective imaging of the endospores in the presence of the bacteria is even more challenging. Furthermore, it is preferable to maintain the dormant state of endospores through the imaging process, if extended monitoring is required; many of the available techniques involve lethal germination or destruction of the endospores. We show that simple zwitterionic diaminodicyanoquinodimethane (DADQ) molecules with selected functionalities are efficient dyes for fluorescence imaging due to their dipolar structure that facilitates the penetration into the endospore system, and the enhanced fluorescence in their rigid/aggregated state. The facile structural tailorability allows DADQs with various appendage moieties to be synthesized; a derivative with ionic substituents (BT2), and another with optimally long alkyl chains and the resultant hydrophobic character (BHADQ) are shown to be excellent fluorescent probes for endospores. Nanomolar amounts of dyes provide effective staining; while BT2 stains bacteria and endospores, most significantly, BHADQ stains endospores selectively. To the best of our knowledge, this is the first example of selective fluorescence imaging of endospores in their dormant state. A range of spectroscopy, microscopy and calorimetry studies provide insight into the molecular level interactions that enable efficient staining and bright images. DADQ fluorophores are photostable and non-cytotoxic, hence useful in practical applications. The versatile structural tailorability of these dye molecules holds great promise for targeted imaging.

A Strongly Fluorescent Molecular Material Responsive to Physical/Chemical Stimuli and their Coupled Impact.

Molecular materials with weak but extended and pliable supramolecular interactions are versatile candidates for eliciting stimuli-sensitive optical responses. A novel diaminodicyanoquinodimethane (DADQ) molecule, 7,7-bis(2-(2-pyridyl)ethylamino)-8,8-dicyanoquinodimethane (BPEDQ), has been synthesized and structurally characterized; it exhibits enhanced fluorescence emission in the aggregated and solid states, characteristic of DADQs. The pyridine moieties in the molecule, in addition to the amino and cyano groups of the strongly dipolar fluorophore moiety, induce extensive H-bonding interactions which can impart structural integrity to the solid material; this enables reversible crystalline-amorphous transformations triggered by mechanical grinding and solvent fuming. The concomitant fluorescence color and intensity switching are prominent and reversible. Protonation-deprotonation events induced by acidic and basic vapors also produce stark fluorescence response variations; the chemical stimuli also lead to amorphization of the solid. The full cycle of chemical and physical stimuli, and the consequence of their individual and coupled impact on the fluorescence emission, are illustrated using a BPEDQ-doped polymer thin film.

Establishing the Critical Role of Oriented Aggregation in Molecular Solid State Fluorescence Enhancement.

The general occurrence of fluorescence emission quenching in molecular aggregates is circumvented in select classes of molecules. This has largely been attributed to the rigidification of the molecule and its environment, which hinders non-radiative excited state energy loss through structural relaxation; since such an effect should in principle apply to most aggregates and crystals, there must clearly be other critical factors that make the select molecules exceptional. Discovery of three crystalline structures of a new push-pull molecule in its enantiomorphic and racemic forms, exhibiting not only very high, but distinctly different solid state fluorescence enhancements, has now allowed a systematic investigation of the role of intramolecular and intermolecular excited state energy loss pathways. Crystallographic, spectroscopic and computational investigations provide a detailed appraisal of the assembly patterns in the crystals, and rigorous establishment of an inverse correlation between intermolecular energy transfer and solid state fluorescence. The study provides a clear visualization of the critical role of oriented molecular aggregation in solid state fluorescence efficiency enhancement.

Gold nanoclusters with a wide range of fluorescence characteristics generated in situ in polymer thin films: potential gas sensing application.

Fabrication of gold nanoclusters (GNCs) with tunable fluorescence characteristics inside polymer thin films is attractive from the device application perspective. In this study, GNCs are generated in situ in poly(methyl methacrylate) films exploiting their weak reducing capability with no additional reducing agent, and by short and mild thermal annealing; the chemistry involved is probed through control experiments. The nanoclusters formed with ∼0.5 weight percent of gold are very stable and show appreciable fluorescence emission with a small Stokes shift (∼40 nm); interestingly, blending polystyrene enhances the fluorescence. The Au10 clusters formed in situ are characterized by using mass spectrometry, microscopy and computational modeling. Composite thin films fabricated with a gold content of ∼9 weight percent showed an unusually distinct absorption peak and enhanced fluorescence emission. Gradual coalescence of the nanoclusters in these films could be arrested by incorporating thiourea; the mechanistic aspects of the thiourea interaction are probed. The resulting films showed strong, stable and visible red emission, with very large Stokes shift (∼320 nm) and quantum yield (∼30%), attributable to ligand effects and nanocluster aggregation in the film. The study presents a novel and facile route to the in situ generation of GNCs in polymer thin films, exhibiting fluorescence emission with variable energy, intensity and Stokes shift. Preliminary experiments show that Au10 cluster embedded thin films can be used for the detection of POCl3, an important precursor for nerve agents.

Efficient Bioimaging with Diaminodicyanoquinodimethanes: Selective Imaging of Epidermal and Stomatal Cells and Insight into the Molecular Level Interactions.

The enhanced fluorescence emission of diaminodicyanoquinodimethanes (DADQs) in rigid and aggregated states holds great promise for bioimaging applications. This is demonstrated through their efficient application in epidermal and stomatal imaging with selective staining of cell walls and nuclei. Major advantages include the small quantities (a few nmols) of the fluorophore required, choice of DADQs soluble in water and organic solvents, and quick staining of the specimen in buffer-free state and in buffer medium. The molecular level interactions that enable staining are unraveled through isothermal calorimetry, infra-red spectroscopy and microscopy with energy dispersive X-ray spectroscopy analysis. It is proposed that DADQs with ionic or H-bonding functionalities bind to the polygalacturonic acid moieties in the epidermal layer; the former can bind also to nucleic acid polyanions. Fluorescence experiments explain the emission enhancement that enables the efficient imaging. DADQs are easy to synthesize, non-cytotoxic, and thermally, chemically and photo-stable, requiring no special storage conditions; preliminary experiments point to their potential utility in imaging different classes of cells.

Soft Chemical Fabrication of Iron-Based Thin Film Electrocatalyst for Water Oxidation under Neutral pH and Structure-Activity Tuning by Cerium Incorporation.

Design of electrocatalysts for the fundamentally important oxygen evolution reaction can be greatly aided by systematic structure-activity tuning via composition variation. We have explored the iron-cerium system as they are the most abundant transition and rare earth metals, and also due to the mutualistic impact of their size and electronic attributes that can induce critical changes in the structure and electrochemical activity. Submicrometer thick films of a series of Fe(III)-Ce(III) phosphate(oxyhydroxide) (FeCePH) are fabricated using a soft chemical strategy involving surfactant-aided assembly, spin-coating, and mild thermal annealing. FT-IR, Raman, and X-ray photoelectron spectroscopies, chemical analysis, X-ray diffraction, and electron microscopy reveal the systematic structural, electronic, and morphological variation, on tuning the iron-cerium composition. Nitrogen adsorption-desorption studies show the surface area increasing and pore size distribution shrinking with the cerium content, indicating its structure-directing role. The electrocatalysis of water oxidation by FeCePH films on FTO-coated glass is studied in neutral pH conditions. The overpotential and Tafel slope decrease with increasing cerium content, reaching minima at the optimal Fe:Ce ratio of 1:0.5; the turnover frequency shows a corresponding increase and maximum. The trends are explained on the basis of the structural changes in the films, and the coupling of Ce3+/Ce4+ with Fe3+/Fe4+ that leads to active state regeneration. This study presents a rational strategy to tune the efficiency of easily fabricated transition metal-based electrocatalyst thin films through rare earth metal incorporation; it should prove useful in the design of cost-effective catalysts for water oxidation.

Tuning the SERS Response with Ag-Au Nanoparticle-Embedded Polymer Thin Film Substrates.

Development of facile routes to the fabrication of thin film substrates with tunable surface enhanced Raman scattering (SERS) efficiency and identification of the optimal conditions for maximizing the enhancement factor (EF) are significant in terms of both fundamental and application aspects of SERS. In the present work, polymer thin films with embedded bimetallic nanoparticles of Ag-Au are fabricated by a simple two-stage protocol. Ag nanoparticles are formed in the first stage, by the in situ reduction of silver nitrate by the poly(vinyl alcohol) (PVA) film through mild thermal annealing, without any additional reducing agent. In the second stage, aqueous solutions of chloroauric acid spread on the Ag-PVA thin film under ambient conditions, lead to the galvanic displacement of Ag by Au in situ inside the film, and the formation of Ag-Au particles. Evolution of the morphology of the bimetallic nanoparticles into hollow cage structures and the distribution of Au on the nanoparticles are revealed through electron microscopy and energy dispersive X-ray spectroscopy. The localized surface plasmon resonance (LSPR) extinction of the nanocomposite thin film evolves with the Ag-Au composition; theoretical simulation of the extinction spectra provides insight into the observed trends. The Ag-Au-PVA thin films are found to be efficient substrates for SERS. The EF follows the variation of the LSPR extinction vis-à-vis the excitation laser wavelength, but with an offset, and the maximum SERS effect is obtained at very low Au content; experiments with Rhodamine 6G showed EFs on the order of 10(8) and a limit of detection of 0.6 pmol. The present study describes a facile and simple fabrication of a nanocomposite thin film that can be conveniently deployed in SERS investigations, and the utility of the bimetallic system to tune and maximize the EF.

Extensively Reversible Thermal Transformations of a Bistable, Fluorescence-Switchable Molecular Solid: Entry into Functional Molecular Phase-Change Materials.

Functional phase-change materials (PCMs) are conspicuously absent among molecular materials in which the various attributes of inorganic solids have been realized. While organic PCMs are primarily limited to thermal storage systems, the amorphous-crystalline transformation of materials like Ge-Sb-Te find use in advanced applications such as information storage. Reversible amorphous-crystalline transformations in molecular solids require a subtle balance between robust supramolecular assembly and flexible structural elements. We report novel diaminodicyanoquinodimethanes that achieve this transformation by interlinked helical assemblies coupled with conformationally flexible alkoxyalkyl chains. They exhibit highly reversible thermal transformations between bistable (crystalline/amorphous) forms, along with a prominent switching of the fluorescence emission energy and intensity.

Nanoparticle assembly following Langmuir-Hinshelwood kinetics on a Langmuir film and chain networks captured in LB films.

The Langmuir-Blodgett (LB) technique is an elegant protocol for the steered assembly of metal nanoparticles, the deposition pressure serving as a convenient parameter to tune the assembly. Adsorption of nanoparticles from the subphase to the air-water interface can provide further control of the process. Citrate-stabilized gold nanoparticles in the aqueous subphase are shown to assemble into extended 2-dimensional chain networks following adsorption on a cationic amphiphile Langmuir film at the air-water interface. Kinetic investigations show that the process can be visualized as a surface-catalyzed reaction and explained in terms of the Langmuir-Hinshelwood mechanism. The LB deposition proves to be a unique route to capture the reaction product together with the amphiphile film. The deposition pressure is used to tune the density of nanoparticle chain networks in the LB film, and their optical extinction spectrum. The unusual blue shift of the extinction observed with increasing deposition pressure is attributed to the impact of the amphiphile monolayer environment. The extent of formation of the chain network is analyzed in terms of the pathways in the corresponding graph representation, and shown to scale with the deposition pressure. The current investigation highlights the use of a charged monolayer as a heterogeneous catalyst surface, provides fundamental insight into the kinetics of nanoparticle assembly at interfaces, and demonstrates the utility of the LB technique in tuning the formation of 2-dimensional nanoparticle chain networks.

In situ fabricated polymer-silver nanocomposite thin film as an inexpensive and efficient substrate for surface-enhanced Raman scattering.

The utility of polymer-metal nanocomposite thin films with in situ generated silver nanoparticles as substrates for surface-enhanced Raman scattering (SERS) is demonstrated. Thin films of poly(vinyl alcohol) and poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) containing Ag nanoparticles generated in situ through thermal annealing and photoirradiation, respectively (Ag-PVA and Ag-PVVV), are investigated as potential SERS substrates using 4-aminothiophenol and rhodamine 6G as probe molecules. The fabrication protocols are extremely simple and the materials inexpensive. The Ag-PVA substrate is found to produce Raman spectral enhancement factors of ~10(6), whereas Ag-PVVV, a novel nanocomposite thin film developed in the present study, provides enhancement factors of ~10(7). A unique advantage of these nanocomposite films is demonstrated by fabricating them by the in situ process as a thin coating inside glass capillaries and using these disposable SERS substrates for the sensitive detection of the probe molecules. The thin film substrates prepared on glass plates and capillaries facilitate convenient sample preparation for recording the Raman spectra and provide strongly enhanced spectra with high reproducibility, allowing picomols of the analytes to be detected. These aspects combined with the ease of fabrication and low cost of these in situ fabricated nanocomposite thin films make them highly attractive SERS substrates.

Mechanical control of molecular aggregation and fluorescence switching/enhancement in an ultrathin film.

Optical responses of molecular aggregates and assemblies are often different from that of the individual molecules. Self-assembly approaches provide little physical control on the extent of aggregation. Mechanical compression of amphiphilic molecules (with chromophore/fluorophore head groups) at the air-water interface, followed by transfer as Langmuir-Blodgett (LB) films, should prove to be an elegant route to molecular assemblies with systematically tunable aggregation and optical responses. This concept is demonstrated using monolayer LB films of a diaminodicyanoquinodimethane (DADQ)-based amphiphile fabricated at different surface pressures. Films deposited above a threshold pressure exhibit a strong blue-shift in the absorption and fluorescence relative to those deposited below; computational investigations suggest that this is due to the formation of 2-dimensional close-packed assemblies. Significantly, the blue emission of the films deposited above the threshold pressure increases with compaction, demonstrating aggregation-induced fluorescence enhancement in ultrathin films, a phenomenon well-established in crystals and nanocrystals of selected classes of molecules including the DADQs. The sharp contrast with aggregation-induced fluorescence quenching observed with most dye molecules is illustrated by a parallel investigation of LB films of a hemicyanine-based amphiphile. The present study illustrates the efficacy of simple mechanical compression and the LB technique in fabricating ultrathin films with tailored supramolecular assembly and optical responses.

Optical materials based on molecular nanoparticles.

A major part of contemporary nanomaterials research is focused on metal and semiconductor nanoparticles, constituted of extended lattices of atoms or ions. Molecular nanoparticles assembled from small molecules through non-covalent interactions are relatively less explored but equally fascinating materials. Their unique and versatile characteristics have attracted considerable attention in recent years, establishing their identity and status as a novel class of nanomaterials. Optical characteristics of molecular nanoparticles capture the essence of their nanoscale features and form the basis of a variety of applications. This review describes the advances made in the field of fabrication of molecular nanoparticles, the wide spectrum of their optical and nonlinear optical characteristics and explorations of the potential applications that exploit their unique optical attributes.

A universal sensor for mercury (Hg, Hg(I), Hg(II)) based on silver nanoparticle-embedded polymer thin film.

Detection of mercury at concentration levels down to parts-per-billion is a problem of fundamental and practical interest due to the high toxicity of the metal and its role in environmental pollution. The extensive research in this area has been focused primarily on specific sensing of mercuric (Hg(2+)) ion. As mercury exists in the oxidation states, +2, +1 and 0 all of which are highly toxic, a universal sensor covering all the three while ensuring high sensitivity, selectivity, and linearity of response, and facilitating in situ as well as ex situ deployment, would be very valuable. Silver nanoparticle-embedded poly(vinyl alcohol) (Ag-PVA) thin film fabricated through a facile protocol is shown to be a fast, efficient and selective sensor for Hg(2+), Hg(2)(2+) and Hg in aqueous medium with a detection limit of 1 ppb. The sensor response is linear in the 10 ppb to 1 ppm concentration regime. A unique characteristic of the thin film based sensor is the blue shift occurring concomitantly with the decrease in the surface plasmon resonance absorption upon interaction with mercury, making the sensing highly selective. Unlike the majority of known sensors that work only in situ, the thin film sensor can be used ex situ as well. Examination of the thin film using microscopy and spectroscopy through the sensing process provides detailed insight into the sensing event.

Enhanced optical and nonlinear optical responses in a polyelectrolyte templated Langmuir-Blodgett film.

Optical and nonlinear optical properties like fluorescence and second harmonic generation (SHG) of molecular materials can be strongly influenced by the mode of assembly of the molecules. The Langmuir-Blodgett (LB) technique is an elegant route to the controlled assembly of molecules in ultrathin films, and complexation of ionic amphiphiles in the Langmuir film by polyions introduced in the aqueous subphase provides a simple and efficient access to further control, stabilization, and optimization. The monolayer LB film of the hemicyanine-based amphiphile, N-n-octadecyl-4-[2-(4-(N,N-ethyloctadecylamino)phenyl)ethenyl]pyridinium possessing a "tail-head-tail" structure, shows fluorescence as well as SHG response. The concomitant enhancement of both of these linear and nonlinear optical attributes is achieved through templating with the polyanion of carboxymethylcellulose. Brewster angle and atomic force microscopy reveal the influence of polyelectrolyte templating on the morphology of the Langmuir and LB films. Polarized absorption and fluorescence spectroscopy provide insight into the impact of complexation with the polyelectrolyte on the orientation and deaggregation of the hemicyanine headgroup leading to fluorescence and SHG enhancement in the LB film.

A highly efficient and extensively reusable "dip catalyst" based on a silver-nanoparticle-embedded polymer thin film.

Achieving a harmonious combination of the efficiency of homogeneous catalysts with the reusability of heterogeneous catalysts is a fundamental and challenging problem. Metal nanoparticles in a suitable matrix offer a potential solution. However an ideal design is yet to be realized, because the critical requirements of facile access to the catalyst, its durability, and ease of retrieval and reuse are difficult to reconcile. We report herein a multilayer free-standing thin-film catalyst based on silver nanoparticles, generated in situ inside poly(vinyl alcohol) by using a facile protocol, which shows excellent efficiency and extensive reusability in the prototypical reaction, the reduction of 4-nitrophenol by sodium borohydride. The "dip catalyst" film, which can start/stop the reaction instantaneously by mere insertion/removal, is used 30 times leading to a total turnover number (TON) of ≈3390, which is unprecedented for this reaction. The efficiency of the catalyst is reduced only marginally at the end of these runs, promising further extended usage. The unique advantage of convenient catalyst monitoring is illustrated by the periodic spectroscopic and microscopic examinations of the thin film, which revealed the basis of its durability. The demonstrated potential of metal-nanoparticle-embedded polymer thin films, coupled with their versatility and ease of fabrication, promises extensive applications in chemical catalysis.

Polyelectrolyte-assisted formation of molecular nanoparticles exhibiting strongly enhanced fluorescence.

A polyelectrolyte-assisted reprecipitation method is developed to fabricate nanoparticles of highly soluble molecules. The approach is demonstrated by using a zwitterionic diaminodicyanoquinodimethane molecule bearing remote ammonium functionalities with high solubility in water as well as organic solvents. Nanoparticles are prepared by injecting aqueous solutions of this compound containing an optimum concentration of sodium poly(styrenesulfonate) into methanol. The strong fluorescence exhibited by the compound in the aggregated state is reflected in the enhanced fluorescence of the polyelectrolyte complex in water. The nanoparticles formed in the colloidal state manifest even stronger fluorescence, which leads to an overall enhancement by about 90 times relative to aqueous solutions of the pure compound. The conditions for achieving the emission enhancement are optimized and a model for the molecular-level interactions and aggregation effects is developed through a range of spectroscopy, microscopy, and calorimetry investigations and control experiments.