A study of the thermodynamic stability and the related polymorphic transformations induced by thermal treatments of the mesomorphic form that crystallizes in stereodefective metallocene isotactic polypropylene (iPP) is presented. We show that the mesomorphic form of the more isotactic samples is stable at room temperature, whereas the mesomorphic form crystallizing in the more stereoirregular sample is unstable and crystallizes at room temperature in the crystalline α form. In any case, the mesomorphic form transforms during heating or by annealing at temperatures higher than 60–80 °C always in the α form, regardless of the stereoregularity, even in the case of stereoirregular samples generally crystallizing from the melt in the γ form. These data confirm the proposed model of structure of the mesomorphic form as small aggregates of chains in three-fold helical conformation packed with lateral correlations similar to the α form of iPP. 相似文献
We have prepared molecularly imprinted beads with molecular recognition capability for target molecules containing the penicillanic acid substructure. They were prepared by (a) grafting mesoporous silica beads with 6-aminopenicillanic acid as the mimic template, (b) filling the pores with a polymerized mixture of methacrylic acid and trimethylolpropane trimethacrylate, and (c) removing the silica support with ammonium fluoride. The resulting imprinted beads showed good molecular recognition capability for various penicillanic species, while antibiotics such as cephalosporins or chloramphenicol were poorly recognized. The imprinted beads were used to extract penicillin V, nafcillin, oxacillin, cloxacillin and dicloxacillin from skimmed and deproteinized milk in the concentration range of 5–100 μg·L−1. The extracts were then analyzed by micellar electrokinetic chromatography by applying reverse polarity staking as an in-capillary preconcentration step, and this resulted in a fast and affordable method within the MRL levels, characterized by minimal pretreatment steps and recoveries of 64–90 %.
Penicillanic acid-imprinted beads prepared in preformed porous silica by an imprinting &; etching approach show selectivity towards β-lactams antibiotics. Molecularly imprinted solid phase extraction/micellar electrokinetic chromatography coupled with in-capillary preconcentration resulted in a fast and affordable method for penicillins in milk at MRL levels.
We have prepared molecularly imprinted beads with molecular recognition capability for target molecules containing the penicillanic acid substructure. They were prepared by (a) grafting mesoporous silica beads with 6-aminopenicillanic acid as the mimic template, (b) filling the pores with a polymerized mixture of methacrylic acid and trimethylolpropane trimethacrylate, and (c) removing the silica support with ammonium fluoride. The resulting imprinted beads showed good molecular recognition capability for various penicillanic species, while antibiotics such as cephalosporins or chloramphenicol were poorly recognized. The imprinted beads were used to extract penicillin V, nafcillin, oxacillin, cloxacillin and dicloxacillin from skimmed and deproteinized milk in the concentration range of 5–100 μg·L?1. The extracts were then analyzed by micellar electrokinetic chromatography by applying reverse polarity staking as an in-capillary preconcentration step, and this resulted in a fast and affordable method within the MRL levels, characterized by minimal pretreatment steps and recoveries of 64–90 %.
Figure
Penicillanic acid-imprinted beads prepared in preformed porous silica by an imprinting & etching approach show selectivity towards β-lactams antibiotics. Molecularly imprinted solid phase extraction/micellar electrokinetic chromatography coupled with in-capillary preconcentration resulted in a fast and affordable method for penicillins in milk at MRL levels. 相似文献
β-Bromovinyl chalcogenides were conveniently prepared in good yields by reacting alkynyl chalcogenides with bromine or by addition of organochalcogenyl bromide to bromoacetylenes in the presence of zinc bromide. 相似文献
Enol ethers are reacted with mercaptanes to give the corresponding O/S- or S/S-acetals in medium to high yield. Either product can be formed selectively depending on the acid catalyst and the reaction time applied. 相似文献
Herein, it is shown that a medium-resolution solution structure of a protein can be obtained with the sole assignment of the protein backbone and backbone-related constriants if a derivative with a firmly bound paramagnetic metal is available. The proof-of-concept is provided on calbindin D9k, a calcium binding protein in which one of the two calcium ions can be selectively substituted by a paramagnetic lanthanide ion. The constraints used are HN (and Ha) nuclear Overhauser effects (NOEs), hydrogen bonds, dihedral angle constriants from chemical shifts, and the following paramagnetism-based constraints: 1) pseudocontact shifts, acquired by substituting one (or more) lanthanide(s) in the C-terminal calcium binding site; 2) N-HN residual dipolar couplings due to self-orientation induced by the paramagnetic lanthanide(s); 3) cross-correlations between the Curie and internuclear dipole-dipole interactions; and 4) paramagnetism-induced relaxation rate enhancements. An upper distance limit for internuclear distances between any two backbone atoms was also given according to the molecular weight of the protein. For this purpose, the paramagnetism-based constraints were collectively implemented in the program CYANA for solution structure determinations, similarly to what was previously done for the program DYANA. The method is intrinsically suitable for large molecular weight proteins. 相似文献
Summary We present a method for the numerical approximation of Navier-Stokes equations with one direction of periodicity. In this direction a Fourier pseudospectral method is used, in the two others a standard F.E.M. is applied. We prove optimal rate of convergence where the two parameters of discretization intervene independently.
Approximation des équations de Navier-Stokes par une méthode éléments finis-spectrale Fourier
Resumé On présente une méthode d'approximation numérique des équations de Navier-Stokes possédant une direction de périodicité. Dans cette direction une méthode pseudospectrale basée sur des développements en série de Fourier est utilisée, dans les deux autres on applique une méthode d'éléments finis standard. On montre que la convergence est optimale et que les deux paramètres de discrétisation peuvent être choisis de façon indépendante.
We present a review of recent work on the statistical mechanics of non equilibrium processes based on the analysis of large
deviations properties of microscopic systems. Stochastic lattice gases are non trivial models of such phenomena and can be
studied rigorously providing a source of challenging mathematical problems. In this way, some principles of wide validity
have been obtained leading to interesting physical consequences. 相似文献
Here we study zero-dimensional subschemes of ruled varieties, mainly Hirzebruch surfaces and rational normal scrolls, by applying
the Horace method and the Terracini method
This research is part of the T.A.S.C.A. project of I.N.d.A.M., supported by P.A.T. (Trento) and M.I.U.R. (Italy) 相似文献