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81.
Landis CA Payne MM Eaton DL Anthony JE 《Journal of the American Chemical Society》2004,126(5):1338-1339
The cycloaromatization of acyclic enediynes typically requires very high temperatures (>160 degrees C) and dilute conditions to proceed in a synthetically useful yield. These conditions hinder reaction throughput, inhibiting the use of this reaction for the large-scale production of materials. The reaction of sodium telluride with acyclic arenediynes yields the corresponding tellurepine, which under gentle heating extrudes Te degrees to yield the cycloaromatization product. We have developed conditions that form sodium telluride from inexpensive tellurium metal in situ, and that also perform the desilylation of silylated arenediynes in the same process. Under our conditions, we are able to perform desilylation and cycloaromatization at temperatures as low as 40 degrees C and on a scale as large as 5 g in standard laboratory glassware. 相似文献
82.
This work emphasizes the important role of the synthetic parameters in the structure of the polymeric material obtained in the aniline polymerization. The polymers formed by the oxidative polymerization of aniline by copper(II) ions in acidic aqueous solution, acetonitrile/water medium, and also copper(II) acetate complex encapsulated into MCM-41 molecular sieve were characterized by resonance Raman spectroscopy using three exciting laser lines and other techniques such as UV-vis, FTIR, and XANES (Nitrogen K edge). Additionally the products were investigated by thermogravimetric analysis and powder X-ray diffraction. When Cu(II) ions in acidic aqueous medium are used, emeraldine salt (ES-PANI) is formed through the usual head-to-tail polymerization mechanism, while in acetonitrile/water medium a polymer is observed having mainly phenazine-like rings, quinonediimine, and/or phenylenediamine segments in the chains, suggesting that a distinct mechanism is operating. The average molecular weights of the free polymers synthesized in water and in acetronile/water were, respectively, ca. 37 300 and 16 900 Da. The encapsulated polymer synthesized in Cu(II)-MCM-41 is a polymeric mixture of (i) ES-PANI and (ii) the polymer obtained when this metal cation was used as oxidant in acetonitrile/water medium. All the characterization data were compared to those ones obtained for standard free polyaniline and also for the encapsulated polymer into mesoporous MCM-41 formed by using persulfate in acidic aqueous medium as oxidant. 相似文献
83.
Luiz Claudio de Santa Maria Marcia C.A.M. Leite José M.S. Ribeiro Manoel R. Silva 《European Polymer Journal》2003,39(4):843-846
Iron composite materials based on styrene/divinylbenzene network hosts were produced using aqueous suspension polymerization. The effects of different kinds of porogen agent, toluene, toluene/n-heptane mixture or a toluene solution of polyphenyleneoxide on the bulk density, swelling in toluene and ferromagnetic properties of these materials were evaluated. The specific area and average porous diameter of network resins were characterized by BET and BJH methods, while the iron content was determined by atomic absorption spectrometry. The morphology of the composites was studied by both optical microscopy and scanning electron microscopy with energy dispersive X-ray analysis. All the spherical beads, irrespective of their sizes, have agglomerated iron particles located only on their surface. The particles have exhibited ferromagnetic behavior, with a coercivity of 328.69 Oe. The porogen agents used affect the iron particle distribution on the bead surfaces. 相似文献
84.
Gustavo F. S. Andrade Marcia L. A. Temperini 《Journal of Solid State Electrochemistry》2007,11(11):1497-1503
The adsorption and faradaic processes of formylferrocene thiosemicarbazone (TFF) on gold electrode in 0.1 mol L−1 NaClO4 acetonitrile solution were monitored by surface-enhanced Raman scattering (SERS) and ultraviolet-visible (UV-VIS) techniques.
SERS data indicate that TFF adsorbs through the iminic N(2′) and S atoms on the gold electrode. The reduction product formed
on the gold surface was aminomethylferrocene, whose experimental spectrum was supported by density functional theory calculations.
In solution, thiourea was detected by the UV-VIS technique. Although there was an oxidation wave in the TFF cyclic voltammogram,
no spectral changes were observed after the oxidation process.
This work is dedicated to the memory of Prof. Francisco C. Nart. 相似文献
85.
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87.
Marcia Nitschke Siddhartha G. V. A. O. Costa Jonas Contiero 《Applied biochemistry and biotechnology》2010,160(7):2066-2074
Soybean oil soapstock was utilized as an alternative carbon source for the production of rhamnolipids by Pseudomonas aeruginosa LBI strain. The chemical composition and properties of the rhamnolipid mixture obtained were determined to define its potential
applications. The chemical characterization of the rhamnolipid has revealed the presence of ten different homologues. The
monorhamnolipid RhaC10C10 and the dirhamnolipid Rha2C10C10 were the main components of the mixture that showed predominance of 44% and 29%, respectively, after 144-h of cultivation.
The biosurfactant was able to form stable emulsions with several hydrocarbons and showed excellent emulsification for soybean
oil and chicken fat (100%). The rhamnolipid removed 67% of crude oil present in sand samples and presented antimicrobial activity
against Bacillus cereus and Mucor miehei at 64 μg/mL and inhibition of Neurospora crassa, Staphylococcus aureus, and Micrococcus luteus at 256 μg/mL. The results demonstrated that the rhamnolipid produced in soybean oil soapstock can be useful in environmental
and food industry applications. 相似文献
88.
The influence of matrix viscosity and polarity on ethylene‐vinyl acetate copolymer (EVA) nanocomposites was studied. Five different EVA grades, with different melt flow indexes (MFIs) and/or vinyl acetate (VA) contents, were mixed with two montmorillonite (MMT) nanoclays: pristine and modified with a polar surfactant, producing 75/25 w/w% masterbatches which were subsequently diluted in the EVA matrix to obtain 5 wt% MMT nanocomposites. Although the same VA content, WAXS results, rheological measurements and TEM analysis showed that the lower the EVA viscosity, the greater the tendency to obtain exfoliated and well dispersed nanocomposites with the organically modified clay. On the other hand, the high viscosity EVA nanocomposites showed that the (001) organoclay diffraction peak was shifted to higher values of 2θ, suggesting lamellae collapsing. TGA and FTIR measurements were used to probe the thermal degradation of organoclay; furthermore, it was not possible to identify, by the techniques used, any reaction between the VA groups and hydroxyl surfactant groups. Thus, it was inferred that the organic surfactant was removed (or ejected) from the clay galleries as a consequence of huge shear tensions developed during processing of the masterbatches/nanocomposites with high viscosity EVA matrices. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
89.
Silalahi AR Boschitsch AH Harris RC Fenley MO 《Journal of chemical theory and computation》2010,6(12):3631-3639
The ion size-modified Poisson Boltzmann equation (SMPBE) is applied to the simple model problem of a low-dielectric spherical cavity containing a central charge, in an aqueous salt solution to investigate the finite ion size effect upon the electrostatic free energy and its sensitivity to changes in salt concentration. The SMPBE is shown to predict a very different electrostatic free energy than the nonlinear Poisson-Boltzmann equation (NLPBE) due to the additional entropic cost of placing ions in solution. Although the energy predictions of the SMPBE can be reproduced by fitting an appropriatelysized Stern layer, or ion-exclusion layer to the NLPBE calculations, the size of the Stern layer is difficult to estimate a priori. The SMPBE also produces a saturation layer when the central charge becomes sufficiently large. Ion-competition effects on various integrated quantities such the total number of ions predicted by the SMPBE are qualitatively similar to those given by the NLPBE and those found in available experimental results. 相似文献
90.
Yan X Deinzer ML Schimerlik MI Broderick D Leid ME Dawson MI 《Journal of the American Society for Mass Spectrometry》2006,17(11):1510-1517
Several different agonists of the retinoic X receptor alpha (hRXRalpha) were examined for their effects on the amide H/D exchange kinetics of the homodimeric protein using mass spectrometry. Some agonists, LG 100268, SR11246, and DHA, bind such that slower deuterium exchange-in occurs compared with 9-cis-retinoic acid (9-cis-RA), whereas others, fenretinide and methoprenic acid, result in poorer protection during binding and hence faster exchange-in. Protection against H/D exchange by different agonists and the inhibition of H/D exchange kinetics relative to 9-cis-RA varies markedly in different regions of the protein. Agonists LG 100268, SR11246, and DHA generally inhibit faster exchange processes in the ligand binding regions of hRXRalpha than does the native ligand 9-cis-RA. In at least half of these regions, the level of protection by 9-cis-RA lags behind the agonists even after 60 min. Methoprenic acid did not significantly protect hRXRalpha against amide hydrogen exchange. An efficient method is described for comparing the effects of different agonists on the protein structure of the agonist-RXRalpha complex. 相似文献