Direct Excitation Transfer in Plasmonic Metal-Chalcopyrite-Hybrids: Insights from Single Particle Line Shape Analysis.

Hybrid nanomaterials containing both noble metal and semiconductor building blocks provide an engineerable platform for realizing direct or indirect charge and energy transfer for enhanced plasmonic photoconversion and photocatalysis. In this work, silver nanoparticles (AgNPs) and chalcopyrite (CuFeS2) nanocrystals (NCs) are combined into a AgNP@CuFeS2 hybrid structure comprising NCs embedded in a self-assembled lipid coating around the AgNP core. In AgNP@CuFeS2 hybrid structures, both metallic and semiconductor NCs support quasistatic resonances. To characterize the interactions between these resonances and their effect on potential charge and energy transfer, direct interfacial excitation transfer between the AgNP core and surrounding CuFeS2 NCs is probed through single particle line shape analysis and supporting electromagnetic simulations. These studies reveal that CuFeS2 NCs localized in the evanescent field of the central AgNP induce a broadening of the metal NP line shape that peaks when an energetic match between the AgNP and CuFeS2 NC resonances maximizes direct energy transfer. Dimers of AgNPs whose resonances exhibit poor energetic overlap with the CuFeS2 NC quasistatic resonance yield much weaker line shape broadening in a control experiment, corroborating the existence of resonant energy transfer in the AgNP@CuFeS2 hybrid. Resonant coupling between the metallic and semiconductor building blocks in the investigated hybrid architecture provides a mechanism for utilizing the large optical cross-section of the central AgNP to enhance the generation of reactive charge carriers in the surrounding semiconductor NCs for potential applications in photocatalysis.

Two-color interferometric scattering (iSCAT) microscopy reveals structural dynamics in discrete plasmonic molecules.

Plasmonic molecules are discrete assemblies of noble metal nanoparticles (NPs) that are of interest as transducers in optical nanosensors. So far, NPs with diameters of ∼40 nm have been the preferred building blocks for plasmonic molecules intended as optical single molecule sensors due to difficulties associated with detecting smaller NPs through elastic scattering in conventional darkfield microscopy. Here, we apply 405 nm, 445 nm two-color interferometric scattering (iSCAT) microscopy to characterize polyethylene glycol (PEG) tethered dimers of 10 nm and 20 nm Ag NPs and their monomers. Dimers of both NP sizes can be discerned from their respective monomers through changes in the average iSCAT contrast. In the case of 20 nm Ag NPs, dimer formation induces a change in the sign of the iSCAT contrast, providing a characteristic signal for detecting binding events. 20 nm Ag NP dimers with 0.4 kDa and 3.4 kDa polyethylene glycol (PEG) spacers show iSCAT contrast distributions with significantly different averages on both wavelength channels. The iSCAT contrast measured for individual PEG-tethered 10 nm or 20 nm NP dimers as a function of time shows contrast fluctuations indicative of a rich structural dynamics in the assembled plasmonic molecules, which provides an additional metric to discern dimers from monomers and paves the path to a new class of interferometric plasmon rulers.

The Rise of Structurally Anisotropic Plasmonic Janus Gold Nanostars.

Nanostructures intrinsically possessing two different structural or functional features, often called Janus nanoparticles, are emerging as a potential material for sensing, catalysis, and biomedical applications. Herein, we report the synthesis of plasmonic gold Janus nanostars (NSs) possessing a smooth concave pentagonal morphology with sharp tips and edges on one side and, contrastingly, a crumbled morphology on the other. The methodology reported herein for their synthesis - a single-step growth reaction - is different from any other Janus nanoparticle preparation involving either template-assisted growth or a masking technique. Interestingly, the coexistence of lower- and higher-index facets was found in these Janus NSs. The general paradigm for synthesizing gold Janus NSs was investigated by understanding the kinetic control mechanism with the combinatorial effect of all the reagents responsible for the structure. The optical properties of the Janus NSs were realized by corelating their extinction spectra with the simulated data. The size-dependent surface-enhanced Raman scattering (SERS) activity of these Janus NSs was studied with 1,4-BDT as the model analyte. Finite-difference time-domain simulations for differently sized particles revealed the distribution of electromagnetic hot-spots over the particles resulting in enhancement of the SERS signal in a size-dependent manner.

Systematic Thiol Decoration in a Redox-Active UiO-66-(SH)2 Metal-Organic Framework: A Case Study under Oxidative and Reductive Conditions.

The practical applicability of thiolated metal-organic frameworks (MOFs) remains challenging due to their low crystallinity and transient stability. Herein, we present a one-pot solvothermal synthesis process using varying ratios of 2,5-dimercaptoterephthalic acid (DMBD) and 1,4-benzene dicarboxylic acid (100/0, 75/25, 50/50, 25/75, and 0/100) to prepare stable mixed-linker UiO-66-(SH)2 MOFs (ML-U66SX). For each variant, the effects of different linker ratios on the crystallinity, defectiveness, porosity, and particle size have been discussed in detail. In addition, the impact of modulator concentration on these features has also been described. The stability of ML-U66SX MOFs was investigated under reductive and oxidative chemical conditions. The mixed-linker MOFs were used as sacrificial catalyst supports to highlight the interplay of template stability on the rate of the gold-catalyzed 4-nitrophenol hydrogenation reaction. The release of catalytically active gold nanoclusters originating from the framework collapse decreased with the controlled DMBD proportion, resulting in a 59% drop in the normalized rate constants (9.11-3.73 s-1 mg-1). In addition, post-synthetic oxidation (PSO) was used to further probe the stability of the mixed-linker thiol MOFs under harsh oxidative conditions. Following oxidation, the UiO-66-(SH)2 MOF underwent immediate structural breakdown, unlike other mixed-linker variants. Along with crystallinity, the microporous surface area of the post-synthetically oxidized UiO-66-(SH)2 MOF could be increased from 0 to 739 m2 g-1. Thus, the present study delineates a mixed-linker strategy to stabilize the UiO-66-(SH)2 MOF under harsh chemical conditions through meticulous thiol decoration.

Montmorillonite stabilized chitosan-co-mucin hydrogel for tissue engineering applications.

The role of polymers has played a crucial role in developing templates that can promote regeneration as tissue-engineered matrices. The present study aims to develop functional matrices involving the protein mucin. The mucin used in this study is characterised using MALDI-TOF TOF and CD spectroscopy prior to conjugation. Thereupon, a hybrid scaffold comprising of a polysaccharide, chitosan, chemically conjugated to a protein, mucin, and encapsulated with montmorillonite is developed. Grafting of hydroxyethyl methacrylate (HEMA) is done to overcome the issue of mechanical weakness that mucin hydrogels usually undergo. It was observed that the presence of montmorillonite led to the stability of the hydrogels. The conjugations with varied ratios of the polysaccharide and protein were characterized using spectroscopic techniques. The prepared gels showed appreciable material properties in terms of water uptake and porosity. Hydrogels with different ratios of the polysaccharide and protein were evaluated for their biocompatibility. The biological evaluation of the hydrogels was performed with MC3T3E1 and C2C12 cell lines indicating their potential for wider tissue engineering applications.

Synthesis, characterization and applications of polyacrylamide grafted fenugreek gum (FG-g-PAM) as flocculant: Microwave vs thermal synthesis approach.

Fenugreek gum is modified using two different techniques: microwave-assisted and thermal synthesis technique of graft copolymerization. The synthesis was done by varying the concentration of acrylamide monomer and CAN initiator to get the best-grafted product. The physicochemical characteristics were determined by elemental analysis, FTIR spectroscopy, SEM, XRD, DSC, TGA, number-average molecular weight and intrinsic viscosity. All the grafted materials were tested by flocculation of different synthetic suspension media as well as river water. The process of deflocculation and refloccculation was also carried out and it was observed that refloccculation process has a good potential as the flocculation efficacy increased to a considerable extent. The flocculation efficacy increased from 92.05% to 94.32% upto a maximum of 95.98% in refloccculation process. The flocculation efficacy was found out to be 95.98%, 40.52% and 68.94% respectively kaolin, coal fine and iron ore suspensions. Flocculation was done in kaolin suspension of pH 2, 4, 7 and 10 and at different temperature range of 100, 250, 400 and 550C. It is expected that this material can be used as a highly efficient flocculant in future.