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.

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.

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.

Common Methodology for Cardiac and Ocular Artifact Suppression from EEG Recordings by Combining Ensemble Empirical Mode Decomposition with Regression Approach.

Electroencephalography (EEG) is a non-invasive way of recording brain activities, making it useful for diagnosing various neurological disorders. However, artifact signals associated with eye blinks or the heart spread across the scalp, contaminating EEG recordings and making EEG data analysis difficult. To solve this problem, we implement a common methodology to suppress both cardiac and ocular artifact signal, by correlating the measured contaminated EEG signals with the clean reference electro-oculography (EOG) and electrocardiography (EKG) data and subtracting the scaled EOG and EKG from the contaminated EEG recording. In the proposed methodology, the clean EOG and EKG signals are extracted by subjecting the raw reference time-series data to ensemble empirical mode decomposition to obtain the intrinsic mode functions. Then, an unsupervised technique is used to capture the artifact components. We compare the distortion introduced into the brain signal after artifact suppression using the proposed method with those obtained using conventional regression alone and with a wavelet-based approach. The results show that the proposed method outperforms the other techniques, with an additional advantage of being a common methodology for the suppression of two types of artifact.

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.

GOBF-ARMA based model predictive control for an ideal reactive distillation column.

This paper discusses the control of an ideal reactive distillation column (RDC) using model predictive control (MPC) based on a combination of deterministic generalized orthonormal basis filter (GOBF) and stochastic autoregressive moving average (ARMA) models. Reactive distillation (RD) integrates reaction and distillation in a single process resulting in process and energy integration promoting green chemistry principles. Improved selectivity of products, increased conversion, better utilization and control of reaction heat, scope for difficult separations and the avoidance of azeotropes are some of the advantages that reactive distillation offers over conventional technique of distillation column after reactor. The introduction of an in situ separation in the reaction zone leads to complex interactions between vapor-liquid equilibrium, mass transfer rates, diffusion and chemical kinetics. RD with its high order and nonlinear dynamics, and multiple steady states is a good candidate for testing and verification of new control schemes. Here a combination of GOBF-ARMA models is used to catch and represent the dynamics of the RDC. This GOBF-ARMA model is then used to design an MPC scheme for the control of product purity of RDC under different operating constraints and conditions. The performance of proposed modeling and control using GOBF-ARMA based MPC is simulated and analyzed. The proposed controller is found to perform satisfactorily for reference tracking and disturbance rejection in RDC.

Energy efficient model based algorithm for control of building HVAC systems.

Energy efficient designs are receiving increasing attention in various fields of engineering. Heating ventilation and air conditioning (HVAC) control system designs involve improved energy usage with an acceptable relaxation in thermal comfort. In this paper, real time data from a building HVAC system provided by BuildingLAB is considered. A resistor-capacitor (RC) framework for representing thermal dynamics of the building is estimated using particle swarm optimization (PSO) algorithm. With objective costs as thermal comfort (deviation of room temperature from required temperature) and energy measure (Ecm) explicit MPC design for this building model is executed based on its state space representation of the supply water temperature (input)/room temperature (output) dynamics. The controllers are subjected to servo tracking and external disturbance (ambient temperature) is provided from the real time data during closed loop control. The control strategies are ported on a PIC32mx series microcontroller platform. The building model is implemented in MATLAB and hardware in loop (HIL) testing of the strategies is executed over a USB port. Results indicate that compared to traditional proportional integral (PI) controllers, the explicit MPC's improve both energy efficiency and thermal comfort significantly.

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.

Marker-assisted introgression of a QTL region to improve rust resistance in three elite and popular varieties of peanut (Arachis hypogaea L.).

KEY MESSAGE: Successful introgression of a major QTL for rust resistance, through marker-assisted backcrossing, in three popular Indian peanut cultivars generated several promising introgression lines with enhanced rust resistance and higher yield. Leaf rust, caused by Puccinia arachidis Speg, is one of the major devastating diseases in peanut (Arachis hypogaea L.). One QTL region on linkage group AhXV explaining upto 82.62 % phenotypic variation for rust resistance was validated and introgressed from cultivar 'GPBD 4' into three rust susceptible varieties ('ICGV 91114', 'JL 24' and 'TAG 24') through marker-assisted backcrossing (MABC). The MABC approach employed a total of four markers including one dominant (IPAHM103) and three co-dominant (GM2079, GM1536, GM2301) markers present in the QTL region. After 2-3 backcrosses and selfing, 200 introgression lines (ILs) were developed from all the three crosses. Field evaluation identified 81 ILs with improved rust resistance. Those ILs had significantly increased pod yields (56-96 %) in infested environments compared to the susceptible parents. Screening of selected 43 promising ILs with 13 markers present on linkage group AhXV showed introgression of the target QTL region from the resistant parent in 11 ILs. Multi-location field evaluation of these ILs should lead to the release of improved varieties. The linked markers may be used in improving rust resistance in peanut breeding programmes.

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.

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.

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.

Identification of several small main-effect QTLs and a large number of epistatic QTLs for drought tolerance related traits in groundnut (Arachis hypogaea L.).

Cultivated groundnut or peanut (Arachis hypogaea L.), an allotetraploid (2n = 4x = 40), is a self pollinated and widely grown crop in the semi-arid regions of the world. Improvement of drought tolerance is an important area of research for groundnut breeding programmes. Therefore, for the identification of candidate QTLs for drought tolerance, a comprehensive and refined genetic map containing 191 SSR loci based on a single mapping population (TAG 24 x ICGV 86031), segregating for drought and surrogate traits was developed. Genotyping data and phenotyping data collected for more than ten drought related traits in 2-3 seasons were analyzed in detail for identification of main effect QTLs (M-QTLs) and epistatic QTLs (E-QTLs) using QTL Cartographer, QTLNetwork and Genotype Matrix Mapping (GMM) programmes. A total of 105 M-QTLs with 3.48-33.36% phenotypic variation explained (PVE) were identified using QTL Cartographer, while only 65 M-QTLs with 1.3-15.01% PVE were identified using QTLNetwork. A total of 53 M-QTLs were such which were identified using both programmes. On the other hand, GMM identified 186 (8.54-44.72% PVE) and 63 (7.11-21.13% PVE), three and two loci interactions, whereas only 8 E-QTL interactions with 1.7-8.34% PVE were identified through QTLNetwork. Interestingly a number of co-localized QTLs controlling 2-9 traits were also identified. The identification of few major, many minor M-QTLs and QTL × QTL interactions during the present study confirmed the complex and quantitative nature of drought tolerance in groundnut. This study suggests deployment of modern approaches like marker-assisted recurrent selection or genomic selection instead of marker-assisted backcrossing approach for breeding for drought tolerance in groundnut.

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.

Influence of Nickel molybdate nanocatalyst for enhancing biohydrogen production in microbial electrolysis cell utilizing sugar industrial effluent.

Biohydrogen production in Microbial Electrolysis Cell (MEC) had inspired the researchers to overcome the challenges associated towards sustainability. Despite microbial community and various substrates, economical cathode catalyst development is most significant factor for enhancing hydrogen production in the MEC. Hence, in this study, the performance of MEC was investigated with a sugar industry effluent (COD 4200 ± 20 mg/L) with graphite anode and modified Nickel foam (NF) cathode. Nickel molybdate (NiMoO4) coated NF achieved a higher hydrogen production rate 0.12 ± 0.01 L.L-1D-1 as compared to control under favorable conditions. Electrochemical characterizations demonstrated that the improved catalytic activity of novel nanocatalyst with lower impedance favoring faster hydrogen evolution kinetics. The MEC with the novel catalyst performed with 58.2% coloumbic efficiency, 20.36% cathodic hydrogen recovery, 11.96% overall hydrogen recovery and 54.38% COD removal efficiency for a 250 mL substrate during 5 days' batch cycle. Hence, the potentiality of modified cathode was established with the real time industrial effluent highlighting the waste to wealth bio-electrochemical technology.

Simultaneous bioelectricity generation and water desalination using Oscillatoria sp. as biocatalyst in photosynthetic microbial desalination cell.

Globally, the scarcity of drinking water has triggered the researchers towards the development of desalination techniques to turn up saline water into potable. Microbial Desalination Cell (MDC) is a novel green technology that shows potential approach for desalination along with electricity generation and wastewater treatment. However, the expensive catholyte/catalyst in the cathode side has limited the MDC for real time application. Hence, the main objective of this work was to investigate the electricity generation during dairy wastewater treatment and desalination efficiency using biocathode (Oscillatoria sp.) in the MDC. The results showed that the maximum open circuit voltage of 652 ± 10 mV, COD removal efficiency of 80.2 ± 0.5% and desalination efficiency of 65.8 ± 0.5%, were achieved respectively. The effect of saline water concentration was investigated and the performance of MDC was compared with real (sea) water. This study demonstrated that Oscillatoria sp. could be used as a potential biocatalyst in the cathode chamber for enhancing salinity removal along with electricity generation and wastewater treatment in the MDC.

Alleviation of Salinity Stress in Peanut by Application of Endophytic Bacteria.

The development of salinity affects 7% of the world's land surface, acting as a major constraint to crop productivity. This study attempted to use the co-evolving endophytes of peanut to alleviate salinity stress and enhance the yield of peanut. Diverse and different tissue colonizing endophytes were isolated from peanut and screened in vitro by seed germination bioassay imposing gradients of salinity, with two cultivars TG37A (susceptible) and GG2 (moderately resistant), in potted conditions using saline irrigation water. Finally, nine endophytes capable of producing IAA and ACC-deaminase, promoting root growth and yield in potted conditions were selected for further evaluation in field conditions. They were evaluated with saline water (1.5-2.0 dS/m) in saline soil with susceptible cultivar TG37A. Simultaneously, three endophytes (Bacillus firmus J22N; Bacillus tequilensis SEN15N; and Bacillus sp. REN51N) were evaluated with two cultivars, GG2 and TG37A, during rainy and post-rainy seasons with elevated salinity. The application of endophytes like Bacillus firmus J22N and Bacillus sp. REN51N enhanced the pod and haulm yield of peanuts by 14-19% across cultivars, salinity, and seasons. In addition, there was significant modulation in parameters like relative water content; production of enzymes like superoxide dismutase (SOD), glutathione reductase (GR), catalase (CAT), ascorbate peroxidase (APX), lipid peroxidase (POD), and H2O2 content in leaf; and uptake of potassium. The activities of the enzymes involved in scavenging reactive oxygen species (ROS) increased with salinity, and further increased with endophytes like Bacillus firmus J22N, Bacillus tequilensis SEN15N, and Bacillus sp. REN51N. There was an enhanced accumulation of proline, reduced level of phenol and H2O2, and enhanced uptake of potassium with the inoculation of endophytes. This improved scavenging capacity of plants by endophytic modulation of ROS scavengers, uptake of K, production of ACC deaminase and IAA, root and biomass growth, modulation in relative water content, and enhanced accumulation of osmoprotectant might be the reasons of alleviation of salinity stress. Endophytes could have alleviated salinity stress in peanuts, indicating the mechanisms and potential of peanuts at the field level. These endophytes could be applied to bring agricultural sustainability to salinity-affected areas in the future. Furthermore, few genera viz. Kocuria, Brevundimonas, Agrococcus, Dietzia, and Kytococcus were observed in peanut tissue for the first time.

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.

Assembly of gold nanoparticles on a molecular ultrathin film: tuning the surface plasmon resonance.

A number of methodologies for immobilizing metal nanoparticles in 2-dimensional aggregate structures on various substrates, some with concomitant tuning of the surface plasmon resonance (SPR), have been reported. Many of them involve special functionalization of the nanoparticles, multiple fabrication steps or lengthy procedures. The present study demonstrates that monolayer Langmuir-Blodgett (LB) film of a hemicyanine-based amphiphile with cationic headgroup is an easily fabricated platform for harnessing citrate-stabilized gold nanoparticles. It is shown that a single immersion step can be used to immobilize the nanoparticles uniformly on large area films and that systematic variation of the immersion time from 10 min to 6 h leads to controlled assembly of the particles and tuning of the SPR band over approximately 100 nm. A model for the structural reorganization in the LB film that facilitates the assembly of nanoparticles is presented and the advantages of the current methodology over earlier protocols are pointed out. The versatility of LB films in terms of the molecular level control of fabrication it enables and the variety of film structures that can be realized, point to the wide scope for future explorations, expanding upon the present observations.