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1.
J. P. S. Farinha J. M. G. Martinho H. Xu M. A. Winnik R. P. Quirk 《Journal of Polymer Science.Polymer Physics》1994,32(9):1635-1642
Cyclization of a polystyrene chain (Mn = 10,600; Mw/Mn = 1.09) both ends labeled with 4-(1-pyrenyl)butanoamide groups was studied in cyclohexane between 25 and 95°C. The amide groups (peptide bonds) at both ends can form an intrachain hydrogen bond between the amide hydrogen at one chain end and the carbonyl oxygen at the other. The presence of two sets of conformers, random coils, and chains cyclized through hydrogen bonding, complicates the data analysis. The pyrene excimer kinetics of this polymer is well described by a model composed of two monomers (hydrogen bonded and nonbonded chains) and one excimer, in equilibrium. The cyclization rate constant for hydrogen-bonded chains is larger than the one for nonhydrogen-bonded chains. The pyrene excimer binding energy (ca. 1.6 kcal/mol) is lower than the published value for nonhydrogen-bonded chains (~ 9 kcal/mol), suggesting that intrachain hydrogen bonding hinders the stabilization of the excimer. © 1994 John Wiley & Sons, Inc. 相似文献
2.
A.M. Mota M.L.Simes Gonalves J.P. Farinha J. Buffle 《Colloids and surfaces. A, Physicochemical and engineering aspects》1994,90(2-3):271-278
In order to study the influence of the adsorption of fulvic compounds on voltammetric signals and to understand better the adsorption of these compounds on hydrophobic natural water interfaces, adsorption studies of macromolecules such as poly(ethylene glycol) (HO(CH2CH2O)n) with molecular weight of 8000 were done on the mercury/water interface by a.c. voltammetry at the potential of zero charge. The maximum surface concentration, adsorption equilibrium constant and adsorption rate constant have been determined from the global adsorption mechanism, controlled by two determining steps: diffusion and kinetics of adsorption at the interface. 相似文献
3.
M. C. Freitas M. M. Farinha A. M. G. Pacheco M. G. Ventura S. M. Almeida M. A. Reis 《Journal of Radioanalytical and Nuclear Chemistry》2005,263(3):710-720
Summary Selenium is determined by instrumental neutron activation analysis (INAA), based on measurement of the long-lived 75Se nuclide. In the urban and industrialized areas of Portugal selenium contents have been found of the order of of 0.5-1 ng/m3 in PM10 and PM2.5, according to the data collected since 1994. From November 12, 2001 and for not more than 3 months, the Se contents in PM10 and PM2.5 increased by a factor of 1000 in the northern area of Lisbon. More than other nutrients, selenium illustrates the dichotomy between essentiality and toxicity. There is no legislation on Se for ambient air and on indoor ambient point threshold limit values (US and Germany legislation), were 100 times higher than the abnormal values found that winter. The increase was also visible for mercury although not to such an extent. Attempts were made to understand the trend, going into a study of the emission sources located in the area using both INAA and PIXE. It was concluded that the observation occurred due to abnormal meteorological wind direction, which pushed the pollutants towards the populated area, when usually they flow into the Tagus estuary. 相似文献
4.
Dr. Flávio Figueira Igor Marques Dr. Andreia S. F. Farinha Prof. Dr. Augusto C. Tomé Prof. Dr. José A. S. Cavaleiro Prof. Dr. Artur M. S. Silva Prof. Dr. Jonathan Sessler Prof. Dr. Vítor Félix Prof. Dr. João P. C. Tomé 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14349-14355
A novel sapphyrin derivative was obtained from the reaction between a free‐base sapphyrin and dimethyl acetylenedicarboxylate (DMAD). The formation of the new compound involved a double aza‐Michael addition of two pyrrolic NH groups to a DMAD molecule, with the formation of a disubstituted ethano bridge. The NMR spectral data reveal a product with an unsymmetrical structure; DFT calculations provided support for a structure in which the ethano bridge links two adjacent pyrrole units. The present study provides a seemingly unprecedented example of an N,N′‐dinucleophile reacting with DMAD to form a heterocyclic compound in which the two N‐atoms are linked to the two sp3 carbon atoms derived from a substituted acetylene. 相似文献
5.
Cristina R. Dias Rodica Zãvoianu M. Farinha Portela 《Reaction Kinetics and Catalysis Letters》2002,77(2):317-324
The acid-base properties of several NiMoO4 catalysts supported on two silicas and prepared by different methods have been studied by temperature-programmed desorption of NH3. The catalytic behavior in the oxidative dehydrogenation of isobutane for two NiMoO4 catalysts with different acid-base properties are compared. 相似文献
6.
Pissarra LS Farinha CM Xu Z Schmidt A Thibodeau PH Cai Z Thomas PJ Sheppard DN Amaral MD 《Chemistry & biology》2008,15(1):62-69
Cystic fibrosis (CF) is caused by mutations in the CF transmembrane conductance regulator (CFTR) Cl(-) channel. F508del, the most frequent CF-causing mutation, disrupts both the processing and function of CFTR. Recently, the crystal structure of the first nucleotide-binding domain of CFTR bearing F508del (F508del-NBD1) was elucidated. Although F508del-NBD1 shows only minor conformational changes relative to that of wild-type NBD1, additional mutations (F494N/Q637R or F429S/F494N/Q637R) were required for domain solubility and crystallization. Here we show that these solubilizing mutations in cis with F508del partially rescue the trafficking defect of full-length F508del-CFTR and attenuate its gating defect. We interpret these data to suggest that the solubilizing mutations utilized to facilitate F508del-NBD1 production also assist folding of full-length F508del-CFTR protein. Thus, the available crystal structure of F508del-NBD1 might correspond to a partially corrected conformation of this domain. 相似文献
7.
Maria Helena Godinho Assis Farinha Martins Mohamed Naceur Belgacem Luís Gil Nereida Cordeiro 《Macromolecular Symposia》2001,169(1):223-228
This paper deals with the use of cork powder, a by‐product from cork industry, as a filler to reinforce hydroxypropyl cellulose (HPC) matrix. Several films were prepared using HPC, as a matrix, filled with different amounts of cork powder (average diameter < 50 μm) (0.0; 0.5; 1.0 and 10.0% w/w) and in the presence or not of 1,4‐diisocyanatobutane (BDI) (7.0% w/w). Before the elaboration of these films, the surface properties of cork powder as well as that of suberin (main component of cork) were determined by Inverse Gas Chromatography (IGC). The tensile properties of the solid films obtained were studied and, as expected, for the films with BDI but without cork powder, the Young's modulus and the tensile strength increased, while the elongation decreased. However with the filled films it seemed that the Young's modulus decreased and the elongation increased. The Scanning Electron Microscopy showed that the fractured plane of samples with cross‐linking agent and cork powder displayed some nucleation points (0.3 μm) which indicates a strongly bonded interface and which could be considered as a responsible for the high mechanical properties observed. 相似文献
8.
Rodica Zvoianu Cristina R. Dias M. Farinha Portela 《Reaction Kinetics and Catalysis Letters》2001,72(2):201-208
The acid-base properties of a series of SiO2-supported NiMoO4 catalysts were investigated by temperature-programmed desorption of NH3 and CO2. Results show that supported catalysts with ca. one monolayer of the active phase are less acidic than the unsupported stoichiometric NiMoO4. 相似文献
9.
J.P.S. Farinha J.M.G. Martinho Lionello Pogliani 《Journal of mathematical chemistry》1997,21(2):131-139
The least squares fitting of experimental results with a non‐linear model can result in a serious loss of accuracy in the
model parameters estimation if the statistical nature of the method is not correctly considered. This occurs when the experimental
data is fitted to a set of functional parameters that depend in the model parameters to be estimated in the end. A realistic
example can be found in the two state model of monomer‐excimer kinetics. The decay curves of the monomer and excimer are a
sum and a difference of two exponentials, respectively. It is usual to fit the experimental decays in order to obtain the
pre‐exponential factors and decay constants, thus using a reparametrization that is non‐linear with respect to the model parameters.
This procedure is thoroughly discussed and a new method to analyse the decay curves that circumvents the problem of reparametrization
is presented. The proposed method yields improved results with less than 7% bias in the recovered rate constants. Monte Carlo
simulations have been performed in order to obtain confidence intervals for the fitting and model parameters.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
10.