The mechanism of aromatic nucleophilic substitution reaction between ethanolamine and fluoro‐nitrobenzenes: an investigation by kinetic measurements and DFT calculations

We have studied the kinetics and elucidated the mechanism by DFT calculation of the reaction between ethanolamine (EOA) and 1‐fluoro‐2,4‐dinitrobenzene (DNFB) in acetonitrile and toluene. To determine the contribution of the nitro group, the activation energy of the reaction between ethanolamine and 1‐fluoro‐2‐nitrobenzene (MNFB) vs. DNFB was determined in acetonitrile and calculated by DFT method. Kinetic measurements reveal that the reaction is faster in acetonitrile than in toluene. The reaction follows overall second‐order kinetics: first order with respect to both EOA and DNFB which is similar to the results reported for reaction between other primary amines and 1‐substituted‐2,4‐dinitrobenzenes. The calculations by using DFT methods reveal that the mechanism of the reaction involves the formation and decomposition of a Meisenheimer complex (MC). DFT calculations also reveal that the activation energy of the reaction is highest in vacuum and decreases with increasing polarity of the solvent reaching a minimum in acetonitrile. In addition, activation energies obtained by both DFT calculations and experiments show that the reactivity of MNFB is less than that of DNFB showing the effect of the 4‐nitro group. Copyright © 2010 John Wiley & Sons, Ltd.     

pH-sensitive response of a highly photoluminescent MoS2 nanohybrid material and its application in the nonenzymatic detection of H2O2

Analytical and Bioanalytical Chemistry - The mechanism behind the variation in the photoluminescence (PL) of a MoS2 nanohybrid material with pH was investigated. Highly fluorescent MoS2 quantum...     

Upconversion of Reductants

The many applications of photon upconversion—conversion of low‐energy photons into high‐energy photons—raises the question of the possibility of “electron upconversion”. In this Review, we illustrate how the reduction potential can be increased by using the free energy of exergonic chemical reactions. Electron (reductant) upconversion can produce up to 20–25 kcal mol^?1 of additional redox potential, thus creating powerful reductants under mild conditions. We will present the two common types of electron‐upconverting systems—dissociative (based on unimolecular fragmentations) and associative (based on the bimolecular formation of three‐electron bonds). The possible utility of reductant upconversion encompasses redox chain reactions in electrocatalytic processes, photoredox cascades, design of peroxide‐based medicines, firefly luminescence, and reductive repair of DNA photodamage.     

An efficient method to prepare sulfoxonium ylides and their reactivity studies using copper powder and Sc(III) as catalysts: Molecular and electronic structure analysis

Sulfoxonium ylides are the viable alternatives for diazo compounds as carbene precursors. Unlike diazo compounds, these are bench-stable and crystalline solids. However, the existing methods for the synthesis of sulfoxonium ylides have disadvantages related to the yields, substrate scope, and usage of expensive catalysts. Therefore, it is necessary to develop efficient and competitive protocols for the preparation of sulfoxonium ylides. In this study, we developed an economically affordable protocol for the synthesis of sulfoxonium ylides from diazo compounds using copper powder as a catalyst. This protocol leads to the efficient multigram-scale synthesis of a wide range of sulfoxonium ylides in good yields. Further, we demonstrated scandium triflate–catalyzed carbene insertion into the N−H bond from sulfoxonium ylide. A variety of anilines and sulfoxonium ylides with various functional groups reacted well and produced the corresponding α-amino esters in good yields. All the synthesized compounds were characterized using various standard spectroscopic and analytical techniques. We also used computational methods to understand the electronic structure of all the sulfoxonium ylides using geometry optimization, frequency calculation, molecular orbital and natural bond orbital analysis, and energy decomposition analysis. Our computational results revealed that the interaction between carbene and dimethyl sulfoxide is covalent in nature and stable enough to handle in the absence of any catalyst.     

Reactions of Organic Ions at Ambient Surfaces in a Solvent-Free Environment

Solvent-free ion/surface chemistry is studied at atmospheric pressure, specifically pyrylium cations, are reacted at ambient surfaces with organic amines to generate pyridinium ions. The dry reagent ions were generated by electrospraying a solution of the organic salt and passing the resulting electrosprayed droplets pneumatically through a heated metal drying tube. The dry ions were then passed through an electric field in air to separate the cations from anions and direct the cations onto a gold substrate coated with an amine. This nontraditional way of manipulating polyatomic ions has provided new chemical insights, for example, the surface reaction involving dry isolated 2,4,6-triphenylpyrylium cations and condensed solid-phase ethanolamine was found to produce the expected N-substituted pyridinium product ion via a pseudobase intermediate in a regiospecific fashion. In solution however, ethanolamine was observed to react through its N-centered and O-centered nucleophilic groups to generate two isomeric products via 2H-pyran intermediates. The O-centered nucleophile reacted less rapidly to give the minor product. The surface reaction product was characterized in situ by surface enhanced Raman spectroscopy, and ex situ using mass spectrometry and H/D exchange, and found to be chemically the same as the major pyridinium solution-phase reaction product.     

Unusual coordination mode of tetradentate Schiff base cobalt(III) complexes

Contrary to the stereotype, Jacobsen's catalyst, chiral (salcy)Co(III)OAc adopts an unusual binding mode. The tetradentate {ONNO} ligand does not form a square plane but wraps cobalt in a cis-β fashion while acetate is chelating.     

Nanoparticles-chemistry, new synthetic approaches, gas phase clustering and novel applications

In this paper, an overview of the synthesis, chemistry and applications of nanosystems carried out in our laboratory is presented. The discussion is divided into four sections, namely (a) chemistry of nanoparticles, (b) development of new synthetic approaches, (c) gas phase clusters and (d) device structures and applications. In ‘chemistry of nanoparticles’ we describe a novel reaction between nanoparticles of Ag and Au with halocarbons. The reactions lead to the formation of various carbonaceous materials and metal halides. In ‘development of new synthetic approaches’ our one-pot methodologies for the synthesis of core-shell nanosystems of Au, Ag and Cu protected with TiO₂ and ZrO₂ as well as various polymers are discussed. Some results on the interaction of nanoparticles with biomolecules are also detailed in this section. The third section covers the formation of gas phase aggregates/clusters of thiol-protected sub-nanoparticles. Laser desorption of H₂MoO₄, H2WO₄, MoS₂, and WS₂ giving novel clusters is discussed. The fourth section deals with the development of simple devices and technologies using nanomaterials described above.     

Quantum Dots (QDs) Based Fluorescent Sensor for the Selective Determination of Nimesulide

Fluorescent PET (Photoinduced Electron Transfer) has been of particular growth in recent times. A novel PET based fluorescent sensor using unmodified CdSe quantum dots (QDs) has been developed for the trace determination of Nimesulide (NIM). The sensor is based on the selective fluorescence quenching of quantum dots by NIM in presence of other NSAIDs and is found that intensity of quenching is linearly related to NIM concentration in the range 8.2?×?10^?7 – 4.01?×?10^?5?M. The mechanism of interaction is discussed. Finally, the potential application of the proposed method for the trace determination of NIM in pharmaceutical formulation is demonstrated.     

Magnetic Moment and Susceptibility Measurements of Mixed Rare Earth Oxalate Crystals

The growth of double rare earth oxalate crystals with a general chemical formula AB(C₂O₄)₃ · 10 H₂O (where A and H are Nd, Pr and Sm) is reported. The variation of the magnetic moment of these crystals with an external field is studied and the magnetic susceptibility and the effective magnetic moment are calculated. The observed effective magnetic moment of the crystals are in good agreement with those calculated on theoretical grounds.     

Understanding the Photoluminescence Mechanism of Nitrogen‐Doped Carbon Dots by Selective Interaction with Copper Ions

Doped fluorescent carbon dots (CDs) have drawn widespread attention because of their diverse applications and attractive properties. The present report focusses on the origin of photoluminescence in nitrogen‐doped CDs (NCDs), which is unraveled by the interaction with Cu²⁺ ions. Detailed spectroscopic and microscopic studies reveal that the broad steady‐state photoluminescence emission of the NCDs originates from the direct recombination of excitons (high energy) and the involvement of defect states (low energy). In addition, highly selective detection of Cu²⁺ is achieved, with a detection limit of 10 μm and a dynamic range of 10 μm –0.4 mm . The feasibility of the present sensor for the detection of Cu²⁺ in real water samples is also presented.