2‐Pyrazolines from 1,3 ‐ dipolar cycloaddition of diazomethane to arylsulfonylethenes

Novel 2‐pyrazolines were obtained by the cycloaddition of diazomethane to bis(arylsulfonylethenyl)‐sulfones ( 3 ) and 1‐arylsulfonyl‐2‐styrylsulfonylethenes (7). Dehydrogenation of 2‐pyrazolines with chloranil gave pyrazoles.     

Immobilization of single-strand specific nuclease (S1 nuclease) fromAspergillus oryzae

S1 nuclease fromAspergillus oryzae (EC 3.1.30.1) was coupled to gelatin-alginate composite matrix using the residual free aldehyde groups on the surface of glutaraldehyde crosslinked matrix. The immobilized enzyme retained approximately 10% activity of the soluble enzyme. When partially purified enzyme was bound to the matrix, the immobilized preparation did not show any detectable enzyme activity. However, the activity could be restored when the coupling was carried out in the presence of a coprotein or substrate. The optimum pH of the immobilized S1 nuclease shifted to 3.8 from 4.3 for the soluble enzyme. Also, optimum temperature increased to 65°C after immobilization. Bound S1 nuclease showed increased pH and temperature stabilities. Immobilization brought about a twofold decrease in the Michaelis-Menton constant (K _m).     

Direct spectrophotometric method for the determination of cobalt with indane 1,2,3-trionetrioxime in aqueous medium

A simple, sensitive and selective Spectrophotometric method has been developed for the determination of cobalt using indane 1,2,3-trionetrioxime (ITT): The method is based on the colour reaction between ITT and cobalt(II) in sodium acetate-acetic acid buffer (pH 4.5–7.5) medium. The calibration graph for measurement at 320 nm is linear in the range 1.18–23.60g of cobalt per 25 ml, with molar absorptivity of 5.32×10⁴1mol^–1 cm^–1. The effect of interfering ions has been studied and the method was applied to the determination of cobalt in alloys, with good results.     

Synthesis and characterization of polyesters containing heterocyclic thiaxanthone units

Several polyesters containing thiaxanthone rings were prepared from 2,7-dichloroformylthiaxanthone-5,5′-dioxide ( IVa ), 2,8-dichloroformylthiaxanthone-5,5′-dioxide ( IVb ), and bisphenols by solution polycondensation. The 2,8-diethoxycarbonylthiaxanthone-5,5′-dioxide ( V ) was prepared and characterized by spectral methods to confirm the formation of 2,8-thiaxanthonedicarboxylic acid-5,5′-dioxide ( IVb ). Prior to polymer synthesis two model compounds,2,7-diphenoxycarbonylthiaxanthone-5,5′-dioxide (MDE-1) and 2,8-diphenoxycarbonylthiaxanthone-5,5′-dioxide (MDE-2), were synthesized and characterized by spectral methods. The polyesters were obtained in 62–78% yield and had inherent viscosities in the range 0.42–0.90 dL/g. The effect of thiaxanthone rings on solubility, crystallinity, and thermal stability of the polyesters are also discussed. The polyesters have decomposition temperatures in the range 372–438°C.     

Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H2O Vapor Sorption

In this work we report a strategy for generating porosity in hybrid metal halide materials using molecular cages that serve as both structure-directing agents and counter-cations. Reaction of the [2.2.2] cryptand (DHS) linker with Pb^II in acidic media gave rise to the first porous and water-stable 2D metal halide semiconductor (DHS)₂Pb₅Br₁₄. The corresponding material is stable in water for a year, while gas and vapor-sorption studies revealed that it can selectively and reversibly adsorb H₂O and D₂O at room temperature (RT). Solid-state NMR measurements and DFT calculations verified the incorporation of H₂O and D₂O in the organic linker cavities and shed light on their molecular configuration. In addition to porosity, the material exhibits broad light emission centered at 617 nm with a full width at half-maximum (FWHM) of 284 nm (0.96 eV). The recorded water stability is unparalleled for hybrid metal halide and perovskite materials, while the generation of porosity opens new pathways towards unexplored applications (e.g. solid-state batteries) for this class of hybrid semiconductors.     

Conformationally Locked Cyclo[2]Dipyrrins Linked with Anthracene Subunits: Synthesis and Chiroptical Properties

Herein, we report the synthesis of anthracene-containing twisted cyclo[2]dipyrrin 1 by utilizing a non-planar building block, 1,5-dipyrrylanthracene (1,5-DPA). The non-planar nature of the macrocycle enhanced the solubility and helped in structural characterization. Macrocycle 1 adopts a twisted ‘figure of eight’ conformation stabilized by strong intramolecular H-bonding interactions and exists as a pair of helical enantiomers, as revealed by X-ray crystallographic analysis. More importantly, the sterically locked structure enabled facile optical resolution using chiral HPLC. The (P,P) and (M,M) enantiomers show moderate chiroptical properties, such as absorption dissymmetry factors |g_abs| in the order of 10⁻³, and luminescence dissymmetry factors |g_lum| of 3.8×10⁻³ and 2.9×10⁻³ at 702 nm, respectively.     

Energy dispersive X-ray fluorescence (EDXRF) determination of lanthanides after preconcentration on 1-(2-pyridylazo)-2-naphthol modified naphthalene

A method is described for the simultaneous multielement determination of yttrium and lanthanides at microgram level. This is based on the preconcentration of these lanthanides on to 1-(2-pyridylazo)-2-naphthol (PAN) modified naphthalene. The optimal conditions for quantitative preconcentration viz., pH, amount of PAN modified naphthalene, time of stirring and aqueous phase volume were systematically evaluated. The quantitation of lanthanides was carried out by energy dispersive X-ray fluorescence analyzer, employing²⁴¹Am annular source, via their characteristic K X-rays. The developed procedure gave reliable results in the analysis of xenotime samples.