Mild and Efficient Tf2O-Mediated Synthesis of 3-Amino-1-benzofurans

Russian Journal of Organic Chemistry - A mild and efficient procedure has been developed for the synthesis of 3-amino-1-benzofurans by intramolecular cyclization of the corresponding...     

Spectral properties and emission efficiencies of GdVO4 phosphors

GdVO₄ with activators Eu, Dy, Sm and Bi has been synthesised by a solid-state reaction. GdVO₄:Eu³⁺ (3%) yielded the highest quantum efficiency of 95%. Interesting energy-transfer properties have been revealed in the mixed-activator phosphor (GdVO₄:Eu³⁺, Sm³⁺) when excited in the 4f shell of Sm³⁺ at 408 nm. Bismuth-activated GdVO₄ gives rise to a broad-band emission peaking at 525 nm in comparison to YVO₄:Bi³⁺, which gives an emission peak at 570 nm under UV excitation. The quantum efficiency of GdVO₄:Bi³⁺ increases gradually with bismuth concentration and reaches a maximum of 80% for a bismuth concentration of ≈0.5%. There is a shift in the excitation band of GdVO₄:Bi³⁺ towards longer wavelengths with increasing concentration of bismuth, which can lead to energy transfer from bismuth to europium in a phosphor with both these activators. Heat treatment of GdVO₄:Bi³⁺ at 1500 °C for 3–3.5 h resulted in a large percentage of bismuth being lost from the lattice as evaluated by X-ray fluorescence. However, if a large percentage of bismuth (of the order of 3% or more) is initially added, a sufficient quantity of bismuth can still be retained after heat treatment, which can lead to the development of ceramic scintillators for X-ray tomographic applications. Addition of 3–5% boron gives a white GdVO₄ phosphor without any chemical treatment. Received: 27 Feruary 2001 / Accepted: 1 August 2001 / Published online: 30 October 2001     

Structural damage assessment in a cantilever beam with a breathing crack using higher order frequency response functions

Vibration measurements offer an effective, inexpensive and fast means of non-destructive testing of structures and various engineering components. There are mainly two approaches to crack detection through vibration testing; open crack model with emphasis on changes in modal parameters and secondly, the breathing crack model focusing on nonlinear response characteristics. The open crack model based on linear response characteristics can identify the crack only at an advanced stage. Researchers have shown that a structure with a breathing crack behaves more like a nonlinear system, similar to that of a bilinear oscillator and the nonlinear response characteristics can very well be investigated to identify the presence of the crack. In the present study, the bilinear restoring force is approximated by a polynomial series and a nonlinear dynamic model of the cracked structure is developed using higher order frequency response functions. The effect of crack severity on the response harmonic amplitudes are investigated and a new procedure is suggested whereby the crack severity can be estimated through measurement of the first and second harmonic amplitudes.     

Use of ultrasonics in shear layer cavitation control

In this paper we report results from some investigations on the use of ultrasonics in controlling hydrodynamic cavitation in the shear layer downstream of a sudden expansion. Control of this type of cavitation has been achieved by modulating the local pressure that was experienced by a nucleus present in the shear layer. This modulation was made possible by using a piezoelectric device, termed as Ultrasonic Pressure Modulator (UPM). The performance of UPM has been studied at different dissolved gas concentrations with electrolysis bubbles as nuclei. Control of cavitation due to natural nuclei has also been attempted. Efficiency of UPM, in reducing cavitation, was seen to be dependent on the driving frequency employed. Experimental and numerical studies have been conducted to bring out the physics behind this approach of cavitation control. Different measures of cavitation control have been identified and some possible applications of this method have also been outlined.     

Understanding the role of surfactants on the preparation of ZnS nanocrystals

We have synthesized surface modified ZnS nanoparticles of size 2-3 nm using non-ionic surfactant-stabilized reverse emulsions. The non-ionic surfactants in the Span series, i.e. sorbitan monolaurate (Span 20) and sorbitan monooleate (Span 80) of hydrophilic-lipophilic balance (HLB) values of 8.6 and 4.3, respectively, have been used for the stabilization of emulsions. The role of these surfactants in controlling the size and properties of the ZnS nanoparticles has been discussed. The triethylamine (TEA) has been proved to be the effective surface modifying (capping) agent for the preparation of free-standing ZnS nanoparticles. The Span 20 with the higher HLB value of 8.6 has been found to be highly suitable in synthesizing TEA-capped ZnS nanoparticles of smaller size and higher photophysical characteristics compared to that of the Span 80 of lower HLB value of 4.3. A mechanism for the formation of TEA-capped ZnS nanoparticles from the surfactant-stabilized reverse emulsions has been proposed.     

A concise synthesis of quinazolinone TGF-β RI inhibitor through one-pot three-component Suzuki-Miyaura/etherification and imidate-amide rearrangement reactions

A simple and efficient synthesis of dihydropyrrolopyrazole boronic acid intermediate (5) has been developed. Utilization of a three-component Suzuki-Miyaura/etherification with microwave heating led to advanced compound 11 in high yield and with easy purification. Reaction of compound 11 with methanesulfonyl chloride at room temperature furnished the 1,3 O-N rearranged product (12), which is postulated to proceed via an intramolecular mechanism. The outlined synthesis provides a highly efficient and high-yielding route that is amenable to rapid analog synthesis.     

Reaction of [RuIII(edta)(H2O)]- with H2O2 in aqueous solution. Kinetic and mechanistic investigation

The reaction of [Ru(III)(edta)(H(2)O)](-) (1) (edta = ethylenediaminetetraacetate) with hydrogen peroxide was studied kinetically as a function of [H(2)O(2)], temperature (5-35 degrees C) and pressure (1-1300 atm) at a fixed pH of 5.1 using stopped-flow techniques. The reaction was found to consist of two steps involving the rapid formation of a [Ru(III)(edta)(OOH)](2-) intermediate which subsequently undergoes parallel heterolytic and homolytic cleavage to produce [(edta)Ru(V)=O](-) (45%) and [(edta)Ru(IV)(OH)](-) (55%), respectively. The water soluble trap, 2,2'-azobis(3-ethylbenzithiazoline-6-sulfonate) (ABTS), was employed to substantiate the mechanistic proposal. Reactions were carried out under pseudo-first conditions for [ABTS] > [HOBr] > [1], and were monitored as a function of time for the formation of the one-electron oxidation product ABTS* (+). A detailed mechanism in agreement with the rate and activation parameters is presented, and the results are discussed with reference to data reported for the corresponding [Fe(III)(edta)(H(2)O)](-)/H(2)O(2) system.     

Radioanalytical separation and size-dependent ion exchange property of micelle-directed titanium phosphate nanocomposites

Nanocomposite titanium-phosphate (TiP) of different sizes was synthesized using Triton X-100 (polyethylene glycol-p-isooctylphenyl ether) surfactant. The materials were characterized by FTIR and powdered X-ray diffraction (XRD). The structural and morphological details of the material were obtained by scanning electron microscopy (SEM) and transmission electron microscopy. The SEM study was followed by energy dispersive spectroscopic analysis for elemental analysis of the sample. The important peaks of the XRD spectra were analyzed to determine the probable composition of the material. The average size distribution of the particles was determined by dynamic light scattering method. Ion exchange capacity was measured for different metal ions with sizes of the TiP nanocomposite and size-dependent ion exchange property of the material was investigated thoroughly. The nanomaterial of the smallest size of around 43 nm was employed to separate carrier-free ^137mBa from ¹³⁷Cs in column chromatographic technique using 1.0 M HNO₃ as eluting agent at pH 5.     

Studies on ceric–thiol-initiated aqueous vinyl polymerization with particular reference to end groups in poly(methyl methacrylate)

Ceric-thiol systems are good initiators for the acid aqueous polymerization of some water-soluble Vinyl monomers although not for styrene (in aqueous emulsion) and vinyl acetate. Thiols used are 2-mercaptoethanol, thioglycolic acid, 2-mercaptoethylamine hydrochloride, and L -cysteine hydrochloride. The polymerization proceeds through a radical mechanism. End-group analysis of poly(methyl methacrylate) obtained by initiation with various ceric-thiol systems has been carried out using Palit's dye testes. Hydroxyl, carboxyl, and amine end groups (to the extent of about one per polymer molecule) were incorporated in poly(methyl methacrylate)s obtained by initiation with 2-mercaptoethanol, thioglycolic acid, and 2-mercaptoethylamine hydrochloride, respectively, each in combination with Ce⁴⁺ ions; both amine and carboxyl end groups were obtained using C⁴⁺/L -cysteine hydrochloride initiator system. From the end-group results, the initiating species have been identified and the initiation mechanism prooposed. The probable termination mechanism also has been discussed.     

Selective Interpolymer Complexation between Acrylic Copolymers and Nonionic Polymers

Abstract

Selective interpolymer complexation has been studied between methacrylic acid-methacrylamide copolymer and some complementary polymers such as poly(methacrylamide), poly(vinyl pyrrolidone), and poly(ethylene oxide). The relative order of complexation ability of the various nonionic polymers has been interpreted on the basis of the nature of interactions between different units of polymers. Configurational environment and neighboring group influences seem to affect interpolymer complex formation.