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1.
F. Rubio F. García H. D. Burrows A. A. C. C. Pais A. J. M. Valente M. J. Tapia J. M. García 《Journal of polymer science. Part A, Polymer chemistry》2007,45(9):1788-1799
The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H2O and D2O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H2O and D2O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007 相似文献
2.
Vicenç Branchadell Roser Pleixats Claude Commandeur Max Malacria 《Journal of organometallic chemistry》2003,687(2):337-345
Regioselectivity of the Tsuji-Trost reaction on allyl acetates and carbonates substituted with silyl groups at the olefinic moiety has been analyzed. Silicon atom in the central carbon atom increases the stability of the intermediate π-allylpalladium cation with respect to the isomeric π-allylpalladium cation featuring the silicon in a terminal carbon atom. 相似文献
3.
Summary A new gas chromatographic method using an automatic purge-and-trap system coupled to a GC with mass selective detection to analyze styrene at the parts-per-trillions (ng kg–1) level is described. The method shows a good sensitivity and the detection limit is 10 ng kg–1 with a relative standard deviation (RSD) of 4.7% for 164 ng kg–1 styrene in olive oil. This analytical method has been successfully applied to the analysis of styrene in extra-virgin olive oil from the European market. 相似文献
4.
A. Fernndez-Mateos E.M. Martín de la Nava R. Rabanedo Clemente R. Rubio Gonzlez M.S.J. Simmonds 《Tetrahedron》2005,61(52):12264-12274
A diastereoselective synthesis of the model insect antifeedant 29 a CDE molecular fragment of 12-ketoepoxyazadiradione has been achieved in ten steps from indenone 9 in 44% overall yield. Several of the compounds obtained along the synthesis related to model compound 29 show significant antifeedant activity against Spodoptera littoralis and Spodoptera frugiperda. 相似文献
5.
I. M. Shmyt’ko A. N. Izotov N. S. Afonikova S. Vieira G. Rubio 《Physics of the Solid State》1998,40(4):687-690
The formation of polytypic modifications is observed in dislocation-free silicon single crystals under directional plastic
deformation. It is shown that the deformation-stimulated phase appears on the surface of the sample in the form of small grains
ranging from several hundred to several thousand angstroms in size. A twin structure in the individual grains is observed.
Fiz. Tverd. Tela (St. Petersburg) 40, 746–749 (April 1998) 相似文献
6.
Roser Cervellera Xavier Ramis Josep Maria Salla Ana Mantecn Angels Serra 《Journal of polymer science. Part A, Polymer chemistry》2006,44(9):2873-2882
N,N‐Dimethylaminopyridine (DMAP) was used as initiator to cure mixtures of diglycidylether of bisphenol A (DGEBA) and 1,3‐dioxan‐2‐one (TMC) or 5,5‐dimethyl‐1,3‐dioxan‐2‐one (DMTMC). The curing was studied by differential scanning calorimetry (DSC) and Fourier transform infrared in the attenuated‐total‐reflection mode (FTIR/ATR). FTIR/ATR was used to monitor the competitive reactive processes and to quantify the evolution of the groups involved in the curing. We observed the formation of five‐membered cyclic carbonates and anionic carbonate groups that remain unreacted at the chain ends. The formation of these groups was explained by the attack of the anionic propagation species on the methylene carbon of the carbonate group, which leads to an alkyl‐oxygen rupture. By performing the cure in the thermobalance we could evaluate the loss of CO2 produced in the samples containing carbonates. The kinetics were studied by DSC and analyzed with isoconversional procedures. The addition of carbonates slows down the curing rate. Thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA) experiments were used to evaluate the properties of the materials obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2873–2882, 2006 相似文献
7.
The knowledge of the chemical forms of metals is used to assess their availability and uptake by plants, and in sediments the forms of metals determine their transport and mobility in the aquatic media. This information may be obtained by determining chemical forms of metals (speciation) or different phases in which the metals are bound, obtained by applying extraction schemes. The analytical methods used include different steps and all of them must be validated. We report here the recommendations to minimize the errors in this kind of analysis. For validation the use of Certified Reference Materials (CRMs) and the participation in interlaboratory exercises are highly recommended. 相似文献
8.
9.
The combined effects of micellar and chemical catalysis were studied with a view to improving the features of catalytic kinetic determinations. For this purpose we chose the reaction between N,N-dimethyl-p-phenylenediamine (DPD) and N,N-dimethylaniline (DA) to form Bindschedler's Green leuco base, which is oxidized by hydrogen peroxide in a reaction catalysed by Cu(II). This reaction was found to be accelerated by anionic sodium dodecylsulphate (SDS) and cationic dodecyltrimethylammonium bromide (DTAB) micelles. Several advantages were gained in relation to the analytical features of the kinetic photometric determination of Cu(II) when the reaction was developed in the presence of micelles compared to that occurring in an aqueous medium. Such advantages include a lower detection limit, higher sensitivity, precision and solubility of DPD and DA, and substantially increased selectivity in some cases. A detailed study of the parameters which influence both reactions is reported. Some observations on the effect of SDS and DTAB on the reaction are also commented on. 相似文献
10.
The degradation process of TEOS-PDMS Ormosils containing different amounts of γ -APS has been studied by means of DTA, TG, FTIR and 29Si-NMR measurements. It has been found that the amount of γ -APS improved the thermal properties of Ormosil materials. The increase in γ -APS content causes the increment on the decomposition temperatures and activation energies of the studied Ormosils. These results have been attributed to the favourable effect of γ -APS in the copolymerisation reaction between TEOS and PDMS molecules. 29Si-NMR analyses have shown that the incorporation of γ -APS increases the concentration of D(Q) units in the Ormosil structure, i.e., increases the number of TEOS molecules bonded to PDMS ones. Initial decomposition temperature (IDT), temperature of maximum weight loss rate (Tmax), integral procedure decomposition temperature (IPDT) and activation energy values (E) were calculated from different equations which described the degradation of these materials. Addition of 10 wt% γ -APS produced an increase of 63∘C in the IDT and of 115 and 110∘C, respectively, for Tmax and IPDT (up to 478 and 610∘C) compared to the free γ -APS Ormosil. Activation energy values also rise up to 69.4 kJ⋅ mol−1 by introducing 10 wt% of γ -APS. 相似文献