p-Iodinations in hydrocarbon media: continuous flow reactor application

Regiospecific iodination of aryl amines, that is, aryl compounds possessing strong electron donating groups (EDG’s) in the p-position, is described. This procedure features not only the unique use of hydrocarbon media for such substitutions but also the absence of any oxidants aside from iodine itself. Further potential of this hydrocarbon media based electrophilic aromatic substitution is demonstrated by the coupling of the iodination with an in situ halogen/lithium exchange and product forming nucleophilic addition in a batch process. The protocol was ultimately scaled to a continuous flow reactor using an isolated p-iodoarylamine. Constituted as described, these procedures possess enhanced atom-economical, green and safety aspects compared to existing literature protocols.     

Development of the suzuki-miyaura cross-coupling reaction: use of air-stable potassium alkynyltrifluoroborates in aryl alkynylations

The palladium-catalyzed cross-coupling reaction of potassium alkynyltrifluoroborates with aryl halides or triflates proceeds readily with moderate to excellent yields. The potassium alkynyltrifluoroborates are air- and moisture-stable crystalline solids that can be stored indefinitely, which will provide an advantage in applications to combinatorial chemistry. The alkynyl cross-coupling reaction can be effected using 9 mol % of PdCl2(dppf).CH2Cl2 as catalyst in THF or THF-H2O in the presence of Cs2CO3 as the inorganic base. A variety of functional groups are tolerated in both partners.     

Application of an extended solvation theory to study on the binding of magnesium ion with myelin basic protein

Binding properties of myelin basic protein (MBP) from bovine central nervous system due to the interaction by divalent magnesium ion (Mg²⁺) was investigated at 27°C in aqueous solution using isothermal titration calorimetry (ITC) technique. An extended solvation model was used to reproduce the enthalpies of Mg²⁺-MBP interaction over the whole Mg²⁺ concentrations. It was found that there is a set of two identical and noninteracting binding sites for Mg²⁺ ions. The dissociation equilibrium constant is K _d=45.5 μM. The molar enthalpy of binding site is identical for both sites; ΔH=−15.24 kJ mol⁻¹. The solvation parameters recovered from the solvation model were attributed to the structural change of MBP due to the metal ion interaction.     

Synthesis and Crystal Structure of a Novel Self-assembled 2D Coordination Polymer of Chloridobis(imidazolidine-2-thione)thiocyanato dicopper(I)

Abstract  A copper(I) complex, poly(chloridobis(imidazolidine-2-thione)thiocyanato dicopper(I)), [Cu₂(Imt)₂(SCN)Cl] _n (1) (Imt = Imidazolidine-2-thione) has been prepared by the reaction of CuCl₂ with imidazolidine-2-thione and potassium thiocyanate in the ratio of 1:1:2. Compound 1 crystallizes in the monoclinic space group P2₁/a in the form of a coordination polymer, consisting of 2D layers. The solid-state structure is composed of dinuclear units having each copper(I) ion tetrahedrally coordinated. These units aggregate through bridging Imt and thiocyanate leading to a supramolecular 2D-network. Index Abstract  The title complex, poly(chloridobis(imidazolidine-2-thione)thiocyanato dicopper(I)), [Cu₂(Imt)₂(SCN)Cl] _n (Imt = Imidazolidine-2-thione) was prepared by the reaction of CuCl₂ with imidazolidine-2-thione and potassium thiocyanate in the ratio of 1:1:2. The crystal structure consists of dinuclear units having each copper(I) ion tetrahedrally coordinated. These units aggregate through bridging Imt and thiocyanate leading to a supramolecular 2D-network.      

Facile Non‐enzymatic Lactic Acid Sensor Based on Cobalt Oxide Nanostructures

In this study, we have investigated the effect of counter anions on the morphology of cobalt oxide nanostructures. The nanostructures of cobalt oxide are prepared by a low temperature aqueous chemical growth method. The morphology of cobalt oxide nanostructure material was investigated by scanning electron microscopy and the crystalline structure was studied by powder X‐ray diffraction technique. The cobalt oxide nanostructures exhibit the nanowire, lump, bundle of the nanowire and flower‐like morphologies. The XRD study has revealed a cubic phase of cobalt oxide nanostructures. The electro‐catalytic properties of cobalt oxide nanostructures were explored through cyclic voltammetry and amperometric techniques by sensing of lactic acid in the alkaline media. The cobalt oxide nanostructures prepared from cobalt nitrate have shown a well‐resolved redox peak. The proposed mechanism for the non‐enzymatic lactic acid sensor is elucidated by considering the morphology and cyclic voltammetry response. The limit of detection for the sensor was found to be 0.006 mM and it exhibits a linear range from 0.05–3 mM of lactic acid as shown by cyclic voltammetry. The amperometric response has shown the excellent current‐concentration response and the linear range of sensor was found to be 0.1 mM to 5.5 mM. The lactic acid sensor is stable, selective and can be used for practical applications. This study provides an excellent alternative analytical tool for the determination of lactic acid.     

Application of polyionic magnetic nanoparticles as a catalyst for the synthesis of carbonitriles with both indole and triazole moieties via a cooperative geminal-vinylogous anomeric-based oxidation

Molecular Diversity - Three-component reaction of aldehydes with 3-(1H-indol-3-yl)-3-oxopropanenitrile and 1H-1,2,4-triazol-5-amine under the solvent-free condition at 70 °C was...     

New Synthetic Routes towards Soluble and Dissymmetric Triphenodioxazine Dyes Designed for Dye‐Sensitized Solar Cells

New π‐conjugated structures are constantly the subject of research in dyes and pigments industry and electronic organic field. In this context, the triphenodioxazine (TPDO) core has often been used as efficient photostable pigments and once integrated in air stable n‐type organic field‐effect transistor (OFET). However, little attention has been paid to the TPDO core as soluble materials for optoelectronic devices, possibly due to the harsh synthetic conditions and the insolubility of many compounds. To benefit from the photostability of TPDO in dye‐sensitized solar cells (DSCs), an original synthetic pathway has been established to provide soluble and dissymmetric molecules applied to a suitable design for the sensitizers of DSC. The study has been pursued by the theoretical modeling of opto‐electronic properties, the optical and electronic characterizations of dyes and elaboration of efficient devices. The discovery of new synthetic pathways opens the way to innovative designs of TPDO for materials used in organic electronics.     

Investigating the Thermostability of Succinate: Quinone Oxidoreductase Enzymes by Direct Electrochemistry at SWNTs‐Modified Electrodes and FTIR Spectroscopy

Succinate: quinone reductases (SQRs) are the enzymes that couple the oxidation of succinate and the reduction of quinones in the respiratory chain of prokaryotes and eukaryotes. Herein, we compare the temperature‐dependent activity and structural stability of two SQRs, the first from the mesophilic bacterium Escherichia coli and the second from the thermophilic bacterium Thermus thermophilus, using a combined electrochemical and infrared spectroscopy approach. Direct electron transfer was achieved with full membrane protein complexes at single‐walled carbon nanotube (SWNT)‐modified electrodes. The possible structural factors that contribute to the temperature‐dependent activity of the enzymes and, in particular, to the thermostability of the Thermus thermophilus SQR are discussed.     

New 2-in-1 polyelectrolyte step-by-step film buildup without solution alternation: from PEDOT-PSS to polyelectrolyte complexes

Although never emphasized and increasingly used in organic electronics, PEDOT-PSS (poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate)) layer-by-layer (lbl) film construction violates the alternation of polyanion and polycation rule stated as a prerequisit for a step-by-step film buildup. To demonstrate that this alternation is not always necessary, we studied the step-by-step construction of films using a single solution containing polycation/polyanion complexes. We investigated four different systems: PEDOT-PSS, bPEI-PSS (branched poly(ethylene imine)-poly(sodium 4-styrene sulfonate)), PDADMA-PSS (poly(diallyl dimethyl ammonium)-PSS), and PAH-PSS (poly(allylamine hydrochloride)-PSS). The film buildup obtained by spin-coating or dipping-and-drying process was monitored by ellipsometry, UV-vis-NIR spectrophotometry, and quartz-crystal microbalance. The surface morphology of the films was characterized by atomic force microscopy in tapping mode. After an initial transient regime, the different films have a linear buildup with the number of deposition steps. It appears that, when the particles composed of polyanion-polycation complex and complex aggregates in solution are more or less liquid (case of PEDOT-PSS and bPEI-PSS), our method leads to smooth films (roughness on the order of 1-2 nm). On the other hand, when these complexes are more or less solid particles (case of PDADMA-PSS and PAH-PSS), the resulting films are much rougher (typically 10 nm). Polycation/polyanion molar ratios in monomer unit of the liquid, rinsing, and drying steps are key parameters governing the film buildup process with an optimal polycation/polyanion molar ratio leading to the fastest film growth. This new and general lbl method, designated as 2-in-1 method, allows obtaining regular and controlled film buildup with a single liquid containing polyelectrolyte complexes and opens a new route for surface functionalization with polyelectrolytes.     

Generalized Second Bargmann Transforms Associated with the Hyperbolic Landau Levels on the Poincaré Disk

We deal with a family of generalized coherent states associated to the hyperbolic Landau levels of the Schrödinger operator with uniform magnetic field on the Poincaré disk. Their associated coherent state transforms constitute a class of generalized second Bargmann transforms.