Determination of the rheological behavior of epoxy–amine thermosets by dynamic mechanical analysis: Isothermal methods versus nonisothermal methods

The reticulation process of an epoxy resin using an amine as a cure agent was studied at different temperatures and concentrations of the cure agent with dynamic mechanical thermal analysis. The study was performed under both isothermal and nonisothermal conditions, and a temperature–time–transformation diagram was obtained. The measurements from the two modes gave similar results, although the nonisothermal mode required fewer experiments. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1965–1977, 2003     

Controlling the agglomeration of anisotropic Ru nanoparticles by the microwave-polyol process

A rapid polyol process for the synthesis of ruthenium nanoparticles was developed using microwave irradiation. A colloidal solution of monodispersed anisotropic Ru metal nanoparticles (mean particle size 2-6 nm) with different aspect ratios was obtained first. Particles with different degrees of agglomeration have also been synthesized using monodisperse particles as seeds and PVP (poly-N-vinyl-2-pyrrolidone) as the stabilization reagent. The stabilization mechanisms of different protective reagents were studied by UV-vis spectra. The HRTEM images indicated that dendritic particles formed by controlling agglomeration consisted of single-crystal domains with a random crystalline orientation.     

Synthesis of alpha-MoTe2 nanorods via annealing Te-seeded amorphous MoTe2 particles

Semiconductor alpha-MoTe2 nanorods have been synthesized by annealing Te-seeded particles of an amorphous MoTe2 intermediate. This intermediate is prepared by a solution reaction between Mo(CO)6 and elemental Te in diphenylmethane. The as-synthesized products were characterized by structural, compositional, and morphological techniques of X-ray diffraction, selected area electron diffraction, selected area energy dispersive spectroscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, transmission electron microscopy, and high-resolution transmission electron microscopy. The results of the annealing process are MoTe2 nanorods with diameters of 50-200 nm and lengths ranging from 0.1 to 3.0 microm. Here, the rodlike structure of MoTe2 is reported for the first time, and added to the list as one kind of new morphology of MoTe2 nanomaterials. A mechanism for the formation of the nanorods is proposed. The sandwich-layered structure of Te-Mo-Te and the similarity in the structure between hexagonal alpha-MoTe2 and hexagonal Te are responsible for the formation of nanorods of MoTe2.     

Potentiometric, luminescence and NMR study of the interaction of Eu with glyceryl phosphates

Complexation of europium(III) with glyceryl-1- and -2-phosphates has been studied by metal ion luminescence, ¹H and ¹³C NMR spectroscopy and potentiometry. From the luminescence and NMR studies, the formation of a 1:1 inner-sphere complex, in which the glyceryl phosphate is directly bound to the metal, is confirmed. Similar apparent binding constants at pH 2 were obtained by the three methods. Values obtained by NMR at pH 2 are 53 M⁻¹ and 12 M⁻¹ for glyceryl-1- and -2-phosphate, respectively. By comparison with literature data on related systems it is suggested that the ligands bind through the phosphate group. To obtain structural information from the NMR data, complexation has also been studied with the lanthanide ions Dy(III), Er(III) and Gd(III) using both chemical shift and relaxation data. From this, metal-proton distance ratios have been calculated. Comparison of ¹H and ¹³C NMR spectral data in the presence of paramagnetic lanthanides suggests conformational equilibria in the solutions. From the potentiometric studies, global formation constants have been determined, and speciation diagrams obtained over the pH range 1.5pH7.0 for ligand/metal ratios of 1 and 30. Implications of these results on lanthanide induced fusion of phospholipid membranes are discussed.     

Synthesis and studies on metal coordination with a novel carboxyamide ligand

Novel complexes of Co(II), Ni(II), Cu(II) and Pd(II) with the new ligand [N,N'-bis(2-carboxy-1-oxo-phenelenyl)ethylenediamine] (H2L) have been synthesized and characterized on the basis of elemental analyses, magnetic susceptibility, thermal, infrared, electronic, 1H NMR and EPR spectral studies. Infrared and 1H NMR spectra show that H2L acts as a binegative tetradentate ligand. Coordination occurs through deprotonated carboxylate oxygens and nondeprotonated amido nitrogens in all the complexes. Electronic spectral studies and magnetic moment values suggest N2O2 coordination around each metal centre with strong field square planar chromophores. The probable structures of the complexes have been assigned on the basis of spectral studies. The complex formation between M(II) [M(II) = Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)] and (L2-) has also been studied potentiometrically in 75% aqueous DMF at 25 degrees C in 0.1 M NaClO4. The stability constants were found to follow the order: Mn(II) < Co(II) < Ni(II) < Cu(II) > Zn(II).     

Synthesis of 3-alkyl-8-substituted- and 4-hydroxy-8-substituted-2,3,4,5-tetrahydro-1H-2-benzazepines

Based on the Schmidt reaction and an iodolactone ring expansion reaction, two different synthetic routes to substituted 2,3,4,5-tetrahydro-1H-2-benzazepines were developed. The Schmidt reaction on 2,3-dihydro-2H-1-naphthalenone ( 1 ) gave 3 , the product resulting from the alkyl group migration, as the major product instead of the tetrazole 2. This prompted the investigation of the Schmidt reaction on aromatic ketones 8 and 12. The product 9 due to alkyl group migration was the major product of the Schmidt reaction on 2-methyl-3,4-dihydro-2H-1-naphthalenone ( 8 ). The β-keto diester 12 gave a mixture of decarb-oxylated lactams after the Schmidt reaction. In this case, the lactam 13 resulting from the migration of the aromatic ring dominated over the other lactam 14. When lactam 14 was subjected to nitration, a single regioisomer was produced and transformed to the bromo alcohol 19. The other approach was based on the single pot ring expansion of the iodolactone 22 to the lactam 23 in the presence of methanolic ammonia. The iodolactone 22 was readily prepared from 2-allylbenzoic acid.     

CFD evaluation of drop retraction methods for the measurement of interfacial tension of surfactant-laden drops

Drop retraction methods are popular means of measuring the interfacial tension between immiscible polymers. Experiments show that two different drop retraction methods, imbedded fiber retraction (IFR) and deformed drop retraction (DDR), give inconsistent results when a surfactant is present on the surface of the drop. These inconsistencies are deemed to be due to dilution of the surfactant and due to gradients in interfacial concentration of surfactant along the drop surface. This physical picture is quantified for the simple case of a Newtonian drop in a Newtonian matrix, with an insoluble, nondiffusive surfactant at the interface. The drop is deformed in computational fluid dynamics simulations by shearing the matrix, and then allowed to retract. Dilution and interfacial tension gradients effects are found to be especially large at the early stages of retraction, making IFR unsuitable for measuring the interfacial tension of surfactant-laden interfaces. The effects of surfactant dilution and gradients are found to persist even at late stages of retraction, causing the DDR method to underestimate the equilibrium interfacial tension significantly. The largest underestimates occur when the drop viscosity is lower than the matrix viscosity.     

Tandem and chemoselective synthesis of benzil derivatives from styrene and arene diazonium salts

A facile and practically applied protocol for synthesis of benzil derivatives using styrene and arene diazonium salts is reported. Pd(OAc)₂/SeO₂ catalytic system was found to be efficient for chemoselective synthesis of benzil. Selenium dioxide works well as an oxidant under milder reaction conditions. Moderate to very good yields of the desired products were obtained.