Lanthanide‐Doped Nanocrystals: Strategies for Improving the Efficiency of Upconversion Emission and Their Physical Understanding

The fundamental understanding of lanthanide‐doped upconverted nanocrystals remains a frontier area of research because of potential applications in photonics and biophotonics. Recent studies have revealed that upconversion luminescence dynamics depend on host crystal structure, size of the nanocrystals, dopant concentration, and core–shell structures, which influence site symmetry and the distribution and energy migration of the dopant ions. In this review, we bring to light the influences of doping/co‐doping concentration, crystal phase, crystal size of the host, and core–shell structure on the efficiency of upconversion emission. Furthermore, the lattice strain, due to a change in the crystal phase and by the core–shell structure, strongly influences the upconversion emission intensity. Analysis suggests that the local environment of the ion plays the most significant role in modification of radiative and nonradiative relaxation mechanisms of overall upconversion emission properties. Finally, an outlook on the prospects of this research field is given.     

Influence of Size and Shape on the Photocatalytic Properties of SnO2 Nanocrystals

Tuning the functional properties of nanocrystals is an important issue in nanoscience. Here, we are able to tune the photocatalytic properties of SnO₂ nanocrystals by controlling their size and shape. A structural analysis was carried out by using X‐ray diffraction (XRD)/Rietveld and transmission electron microscopy (TEM). The results reveal that the number of oxygen‐related defects varies upon changing the size and shape of the nanocrystals, which eventually influences their photocatalytic properties. Time‐resolved spectroscopic studies of the carrier relaxation dynamics of the SnO₂ nanocrystals further confirm that the electron–hole recombination process is controlled by oxygen/defect states, which can be tuned by changing the shape and size of the materials. The degradation of dyes (90 %) in the presence of SnO₂ nanoparticles under UV light is comparable to that (88 %) in the presence of standard TiO₂ Degussa P‐25 (P25) powders. The photocatalytic activity of the nanoparticles is significantly higher than those of nanorods and nanospheres because the effective charge separation in the SnO₂ nanoparticles is controlled by defect states leading to enhanced photocatalytic properties. The size‐ and shape‐dependent photocatalytic properties of SnO₂ nanocrystals make these materials interesting candidates for photocatalytic applications.     

Imprinted ZnO nanostructure-based electrochemical sensing of calcitonin: A clinical marker for medullary thyroid carcinoma

The present work describes an exciting method for the selective and sensitive determination of calcitonin in human blood serum samples. Adopting the surface molecular imprinting technique, a calcitonin-imprinted polymer was prepared on the surface of the zinc oxide nanostructure. Firstly, a biocompatible tyrosine derivative as a monomer was grafted onto the surface of zinc oxide nanostructure followed by their polymerization on vinyl functionalized electrode surface by activator regenerated by electron transfer–atom transfer radical polymerization (ARGET–ATRP) technique. Such sensor can predict the small change in the concentration of calcitonin in the human body and it may also consider to be as cost-effective, renewable, disposable, and reliable for clinical studies having no such cross-reactivity and matrix effect from real samples. The morphologies and properties of the proposed sensor were characterized by scanning electron microscopy, cyclic voltammetry, difference pulse voltammetry and chronocoulometry. The linear working range was found to be 9.99 ng L⁻¹ to 7.919 mg L⁻¹ and the detection limit as low as 3.09 ± 0.01 ng L⁻¹ (standard deviation for three replicate measurements) (S/N = 3).     

Conjugated Polymer Nanoparticle‐Triplet Emitter Hybrids in Aqueous Dispersion: Fabrication and Fluorescence Quenching Behavior

Conjugated polymer nanoparticles based on poly[9,9‐bis(2‐ethylhexyl)fluorene] and poly[N‐(2,4,6‐trimethylphenyl)‐N,N‐diphenylamine)‐4,4′‐diyl] are fabricated using anionic surfactant sodium dodecylsulphate in water by miniemulsion technique. Average diameters of polyfluorene and polytriarylamine nanoparticles range from 70 to 100 and 100 to 140 nm, respectively. The surface of the nanoparticles is decorated with triplet emitting dye, tris(2,2′‐bipyridyl)ruthenium(II) chloride. Intriguing photophysics of aqueous dispersions of these hybrid nanoparticles is investigated. Nearly 50% quenching of fluorescence is observed in the case of dye‐coated polyfluorene nanoparticles; excitation energy transfer is found to be the dominant quenching mechanism. On the other hand, nearly complete quenching of emission is noticed in polytriarylamine nanoparticle‐dye hybrids. It is proposed that the excited state electron transfer from the electron‐rich polytriarylamine donor polymer to Ru complex leads to the complete quenching of emission of polytriarylamine nanoparticles. The current study offers promising avenues for developing aqueous solution processed‐electroluminescent devices involving a conjugated polymer nanoparticle host and Ru or Ir‐based triplet emitting dye as the guest.

     

Classes of improved estimators for parameters of a Pareto distribution

The problem of estimating parameters of a Pareto distribution is investigated under a general scale invariant loss function when the scale parameter is restricted to the interval (0, 1]. We consider the estimation of shape parameter when the scale parameter is unknown. Techniques for improving equivariant estimators developed by Stein, Brewster–Zidek and Kubokawa are applied to derive improved estimators. In particular improved classes of estimators are obtained for the entropy loss and a symmetric loss. Risk functions of various estimators are compared numerically using simulations. It is also shown that the technique of Kubokawa produces improved estimators for estimating the scale parameter when the shape parameter is known.     

Derivatization of Coumarins at the Benzenoid Ring in Aqueous Medium

Some 6‐disubstituted, 8‐disubstituted, and/6,8‐disubstituted compounds have been prepared from coumarin, 7‐methylcoumarin, and 3,4‐benzocoumarin. The Reimer–Tiemann reaction, Lederer–Manasse reaction, bromination using molecular bromine as well as 2,4,4,6‐tetrabromocyclohex‐2,5‐dien‐1‐one, Elbs reaction, and diazocoupling have been carried under controlled conditions to obtain various derivatives. Further, several reactions of aldehyde derivatives of these coumarins have been carried on to prepare important functional compounds including some heterocycles. It is noteworthy that these aldehydes behave as phenolic aldehydes under alkaline conditions to undergo the Dakin reaction. The reactions are mostly carried in aqueous media involving a dianionic intermediate and hence fulfill one important criterion of green chemistry.     

Triazole-based chromogenic and non-chromogenic receptors for halides

We designed and synthesized a series of triazole-based receptors for anion recognition. Our studies demonstrated that an amide-linked triazole unit is a promising moiety for anion recognition. We synthesized various chromogenic and non-chromogenic receptors based on this moiety. Receptor 11 binds very strongly (K = 102,750 M⁻¹) to fluoride. Receptor 18 changes color from faint yellow to orange upon binding to fluoride.     

Synthesis of cationic quantum dots via a two-step ligand exchange process

A new class of quaternary ammonium derivatives has been used to synthesize cationic CdSe/ZnS quantum dots with exceptional stability in water as well as in biological media.     

Fluorescent nanoparticles based on a microporous organic polymer network: fabrication and efficient energy transfer to surface-bound dyes

Well-defined nanoparticles composed of a tetraphenylmethane-based microporous polymer network with an average particle diameter of 30-60 nm were fabricated by a miniemulsion polymerization technique. Strong green emission was observed and efficient excitation energy transfer from nanoparticles to surface-bound dye molecules was explored.     

Unique role of ionic liquid [bmin][BF4] during curcumin-surfactant association and micellization of cationic, anionic and non-ionic surfactant solutions

Hydrophilic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroburate, modified the properties of aqueous surfactant solutions associated with curcumin. Because of potential pharmaceutical applications as an antioxidant, anti-inflammatory and anti-carcinogenic agent, curcumin has received ample attention as potential drug. The interaction of curcumin with various charged aqueous surfactant solutions showed it exists in deprotonated enol form in surfactant solutions. The nitro and hydroxyl groups of o-nitrophenol interact with the carbonyl and hydroxyl groups of the enol form of curcumin by forming ground state complex through hydrogen bonds and offered interesting information about the nature of the interactions between the aqueous surfactant solutions and curcumin depending on charge of head group of the surfactant. IL[bmin][BF4] encouraged early formation of micelle in case of cationic and anionic aqueous surfactant solutions, but slightly prolonged micelle formation in the case of neutral aqueous surfactant solution. However, for curcumin IL [bmin][BF4] favored strong association (7-fold increase) with neutral surfactant solution, marginally supported association with anionic surfactant solution and discouraged (～2-fold decrease) association with cationic surfactant solution.