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41.
The acid properties of pure and modified silica surfaces were studied by 2-phenylethylamine (PEA) desorption in a thermogravimetric (TGA) apparatus, carrying out the experiments at different heating rates (5 < beta/(degrees C.min(-1)) < 30). The samples, containing about 13 wt % alumina, titania, and zirconia, were prepared by the sol-gel route from molecular precursors. The textural, structural, and surface properties of the materials were studied by complementary techniques (ICP, XRD, N(2) physisorption, SEM-EDS, and XPS). The chemical modification of the silica surface by enrichment with Al, Ti, or Zr, in amounts of about 90, 50, and 60% of that introduced in the preparation as determined by XPS, justified the increase of acidity of the modified silica surfaces compared with that of pure silica. The total number of strong acid sites was found to be in the order of SZ > SA > ST > S. Two different kinetic approaches were applied to the thermogravimetric data to kinetically interpret the PEA desorption from the different types of acid sites. The classical differential Kissinger model was found to be inadequate in representing the very complex situation of the acid surfaces. A more complex model is proposed by simultaneously taking into account PEA desorption from the different acid sites by a set of parallel and independent desorption reactions following Arrhenius's kinetic law. The fraction of each type of acid site on each surface and the relevant activation parameters were optimized through a computational procedure. Very good fitting of the experimental-calculated desorption profiles corroborated the validity of the model. For each surface, the acid-site energy distribution is presented and discussed in relationship to the surface composition of the oxides. 相似文献
42.
Murphy CJ Sau TK Gole AM Orendorff CJ Gao J Gou L Hunyadi SE Li T 《The journal of physical chemistry. B》2005,109(29):13857-13870
This feature article highlights work from the authors' laboratories on the synthesis, assembly, reactivity, and optical applications of metallic nanoparticles of nonspherical shape, especially nanorods. The synthesis is a seed-mediated growth procedure, in which metal salts are reduced initially with a strong reducing agent, in water, to produce approximately 4 nm seed particles. Subsequent reduction of more metal salt with a weak reducing agent, in the presence of structure-directing additives, leads to the controlled formation of nanorods of specified aspect ratio and can also yield other shapes of nanoparticles (stars, tetrapods, blocks, cubes, etc.). Variations in reaction conditions and crystallographic analysis of gold nanorods have led to insight into the growth mechanism of these materials. Assembly of nanorods can be driven by simple evaporation from solution or by rational design with molecular-scale connectors. Short nanorods appear to be more chemically reactive than long nanorods. Finally, optical applications in sensing and imaging, which take advantage of the visible light absorption and scattering properties of the nanorods, are discussed. 相似文献
43.
** Email: giorgio.vittadini{at}unimib.it*** Email: simona.minotti{at}unicatt.it In this paper we propose a methodology for measuring the relativeeffectiveness of healthcare services (i.e. the effectof hospital care on patients) under general conditions, in which:) a healthcare outcome underlies qualitative and quantitativeobservable indicators; ß) we are interested in studyingthe simultaneous dependency of multiple outcomes on covariates(where the outcomes can also be correlated to each other); )the relative effectiveness is adjusted for hospital-specificcovariates; ) we hypothesise a general distribution for randomdisturbances and the random parameters of relative effectiveness.For this topic, a generalisation of the SURE (seemingly unrelatedregression equations) multilevel model is proposed. The solutionsare obtained by means of Bayesian inference methods. Since thereis currently no software available to estimate this model, anSAS procedure based on Markov Chain Monte Carlo methods hasbeen developed by the authors, in line with Goldstein &Spiegelhalter (1996, J. R. Stat. Soc. Ser. A, 159, 385443),Spiegelhalter et al. (1996, Bayesian Using Gibbs Sampling Manual.Cambridge: MRC Biostatistic Unit, Institute of Public Health)and Albert & Chib (1997, J. Am. Stat. Assoc., 92, 916925).In addition, a new theoretical result regarding the joint posteriordistribution for the parameters is provided. The model proposedhas been implemented for an effectiveness study of a selectionof Lombard hospitals. 相似文献
44.
Stazi F Palmisano G Turconi M Clini S Santagostino M 《The Journal of organic chemistry》2004,69(4):1097-1103
1,1,4,7,10,10-Hexamethyltriethylenetetramine (HMTTA) emerged from a limited parallel screening of selected polyamines as the most appropriate additive for an especially problematic Koenigs-Knorr glucuronidation. This initial finding rapidly evolved into a reliable and high-yielding procedure through the use of two sets of experimental designs. The detailed effect of the stoichiometry of reagents and the amount of amine additive on reaction yield was elucidated. The complexity of the response surface for product yield, described by a third-order polynomial equation, together with ancillary kinetic experiments evidenced the multiple role of HMTTA in the present glucuronidation process. 相似文献
45.
Pichini S Pellegrini M Pacifici R Marchei E Murillo J Puig C Vall O García-Algar O 《Rapid communications in mass spectrometry : RCM》2003,17(17):1958-1964
A high-performance liquid chromatography (HPLC) method with mass spectrometric detection is described for determination of arecoline in newborn meconium, urine and cord serum, using pilocarpine as internal standard. The analytes were extracted from neonatal biological matrices with chloroform/isopropanol (95:5, v/v) at alkaline pH. Extracts were analyzed by HPLC coupled to an electrospray (ESI) interface and a quadrupole mass spectrometer. Chromatography was performed on a C(8) reversed-phase column using 10 mM ammonium acetate (pH 4.3)/acetonitrile (90:10, v/v) as mobile phase. The mass spectrometer was operated in selected ion monitoring mode. The method was validated over the concentration range 0.005-1.00 micro g/g meconium, 0.004-1.00 micro g/mL cord serum and 0.001-1.00 micro /mL urine. Mean recoveries ranged between 86.5 and 90.7% for arecoline in the different biological matrices, with precision always better than 10%. The quantification limits of arecoline were 0.005 micro g/g meconium, 0.004 micro g/mL cord serum, and 0.001 micro g/mL urine. The method was applied to the analysis of neonatal biological matrices to assess eventual fetal exposition to arecoline. Two newborns from Asian mothers who declared areca nut consumption presented arecoline in meconium with concentrations in the range 0.006-0.008 micro g/g; also the urine from one neonate tested positive for the drug. 相似文献
46.
47.
Rodolphe AbdayemGraziano Baccolini Carla BogaMagda Monari Simona Selva 《Tetrahedron letters》2003,44(13):2649-2653
The reaction between 4-nitroalkoxybenzenes 7 and PCl3/AlCl3, when carried out in appropriate molar ratio, gives a prevalent formation of diazenes 8 and 2,7-dialkoxyphenazines 9 with their new chlorinated derivatives 10-13. These compounds are obtained, in satisfactory yield, in a one-pot procedure, in mild conditions, from commercially available and safe starting materials. In this reaction both the reagents PCl3 and AlCl3 play a fundamental role in obtaining the products, and this method might be applicable to other 4-alkoxynitrobenzenes. 相似文献
48.
Masciocchi N Ardizzoia GA Brenna S Castelli F Galli S Maspero A Sironi A 《Chemical communications (Cambridge, England)》2003,(16):2018-2019
Two new 3D homoleptic binary imidazolates, Cd(im)2 and Hg(im)2 (Him = imidazole), as well as [Hg(im)]NO3, containing 1D polycations of [Hg(im)]n(n+) formulation, have been prepared and characterized by ab-initio XRPD methods. 相似文献
49.
50.
Valeria Angeli Simona Biagi Silvia Ghimenti Massimo Onor Alessandro D'Ulivo Emilia Bramanti 《Spectrochimica Acta Part B: Atomic Spectroscopy》2011,66(11-12):799-804
Monomethylmercury and ethylmercury were determined on line using flow injection-chemical vapor generation atomic fluorescence spectrometry without neither requiring a pre-treatment with chemical oxidants, nor UV/MW additional post column interface, nor organic solvents, nor complexing agents, such as cysteine. Inorganic mercury, monomethylmercury and ethylmercury were detected by atomic fluorescence spectrometry in an Ar/H2 miniaturized flame after sodium borohydride reduction to Hg0, monomethylmercury hydride and ethylmercury hydride, respectively. The effect of mercury complexing agent such as cysteine, ethylendiaminotetracetic acid and HCl with respect to water and Ar/H2 microflame was investigated.The behavior of inorganic mercury, monomethylmercury and ethylmercury and their cysteine-complexes was also studied by continuous flow-chemical vapor generation atomic fluorescence spectrometry in order to characterize the reduction reaction with tetrahydroborate. When complexed with cysteine, inorganic mercury, monomethylmercury and ethylmercury cannot be separately quantified varying tetrahydroborate concentration due to a lack of selectivity, and their speciation requires a pre-separation stage (e.g. a chromatographic separation). If not complexed with cysteine, monomethylmercury and ethylmercury cannot be separated, as well, but their sum can be quantified separately with respect to inorganic mercury choosing a suitable concentration of tetrahydroborate (e.g. 10? 5 mol L? 1), thus allowing the organic/inorganic mercury speciation.The detection limits of the flow injection-chemical vapor generation atomic fluorescence spectrometry method were about 45 nmol L? 1 (as mercury) for all the species considered, a relative standard deviation ranging between 1.8 and 2.9% and a linear dynamic range between 0.1 and 5 μmol L? 1 were obtained. Recoveries of monomethylmercury and ethylmercury with respect to inorganic mercury were never less than 91%. Flow injection-chemical vapor generation atomic fluorescence spectrometry method was validated by analyzing the TORT-1 certificate reference material, which contains only monomethylmercury, and obtaining 83 ± 5% of monomethylmercury recovered, respectively. This method was also applied to the determination of monomethylmercury in saliva samples. 相似文献