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91.
Use of gel-permeation chromatography in the determination of the composition of two-polymer mixtures
Jean-Pierre Menin Ren Roux 《Journal of polymer science. Part A, Polymer chemistry》1972,10(3):855-866
The possibility of evaluating with acceptable accuracy the composition of a two-polymer mixture which is well separated by GPC, was studied by using mixtures of high molecular weight polybutadiene (M?w = 4.5 × 105) and low molecular weight polyiso-butylene (M?n in the range of 103). It was concluded that a satisfactory evaluation of the composition of a polymer mixture can be achieved, provided that the variations of the refractive index with the molecular weight are taken into account for the low molecular weight polymer (the polyisobutylene). 相似文献
92.
The tetranuclear [Ni4(pypentO)(pym)(mu 3-OH)2(mu-Oac)2(NCS)2(OH2)] cubane-like complex has been prepared, and its structure and magnetic properties have been studied (pypentO and pym are the deprotonated forms of 1,5-bis[(2-pyridylmethyl)amino]pentane-3-ol and 2-pyridylmethanol, respectively). The X-ray diffraction analysis of this novel nickel complex (C61H74N14O25.5S4Ni8, monoclinic, P2(1), a = 13.9375(14) A, b = 20.6604(18) A, c = 16.6684(19) A, beta = 110.619(12) degrees, Z = 2) showed a Ni4O4 cubane arrangement of four nickel atoms, four mu 3-O bridging ligands (one pypentO, one pym, and two OH-), two syn-syn bridging acetates, and three terminal monodentate ligands (two NCS- and one OH2). In this low-symmetry elongated cubane, the four Ni-Ni long distances (3.18 A) correspond to the faces of the cube including two mu 3-OR bridges, and the two Ni-Ni short distances (2.94 A) correspond to the faces including two mu 3-OR and one acetate bridges. The temperature dependence of the magnetic susceptibility was fitted with J1 = -3.09 cm-1, J2 = 15.0 cm-1, J3 = 6.72 cm-1, and g = 2.27. The differences in sign among the J1, J2, and J3 superexchange interactions is in good agreement with the different types of faces present in this Ni4O4 cubane core. The two faces of the cube, including two mu 3-OR bridges associated with one acetate bridge, exhibit ferromagnetic interactions, while the four faces which include only mu 3-OR bridges exhibit antiferromagnetic interactions. The very small zero field splitting may be attributed to the fact that the ground state is diamagnetic. The nature of the ground state is confirmed by the good simulation of the magnetization curves at 2 and 5 K (diagonalization of the full matrix taking into account all energy levels obtained with the parameter set resulting from the fit of the susceptibility curve). The large differences in J values resulting from small differences in Ni-O-Ni angles in this Ni4O4 core of very low symmetry reflect a quite strong magnetostructural correlation. 相似文献
93.
Herv Bouchard Jean-Pierre Pulicani Marc Vuilhorgne Jean-Dominique Bourzat Alain Commer on 《Tetrahedron letters》1994,35(52):9713-9716
A new route to semisynthetic 19-nor-7β, 8β-methylene taxoids, such as compound 8, from the 7-O-trifluoromethanesulfonyl derivative 6 is reported. Evidence for a dissociation of the triflate to form a carbocation at C-7 under the reaction conditions is presented. Electrochemical reduction of the cyclopropane taxoid 8 gives, besides the expected 10-dehydroxy-cyclopropane analog 10, the 7-membered C-ring derivative 11. 相似文献
94.
Siham El FangourAlexandre Guy Jean-Pierre VidalJean-Claude Rossi Thierry Durand 《Tetrahedron letters》2003,44(10):2105-2108
The first synthesis of the two enantiomers of phytoprostane F1 methyl ester 1 and 2 is described using the syn-anti-syn alcoxy ester 3 as starting material. 相似文献
95.
Leclaire J Dagiral R Fery-Forgues S Coppel Y Donnadieu B Caminade AM Majoral JP 《Journal of the American Chemical Society》2005,127(45):15762-15770
The synthesis of a new family of phosphorus dendrimers built from an octasubstituted metal-free phthalocyanine core is described up to generation 5. This core is used as a sensor and a probe for analyzing the properties of the internal structure and the influence of each structural part (core, branches, surface) upon the whole structure. UV-visible spectra show both a hyperchromic and bathochromic effect on the Q-bands with increasing generation, indicating that the chromophore is more isolated, and that the dendritic shell mimics a highly polar solvent. There is no evidence for aggregation, except for generation 0, showing again the isolation of the core. However, the dendritic shell is permeable to aqueous acids and bases, as demonstrated by the reversible splitting of the Q-band in an acidic medium (neutral form of the phthalocyanine) and the single Q-band in a basic medium (dianionic form), even for generation 4. The fluorescence quantum yield for the neutral form increases with increasing generation. The dianionic form of generation 0 is poorly fluorescent, whereas generations 3 and 4 (G3 and G4) exhibit better fluorescence. The cores of G3 and G4 are highly sensitive optical sensors for H3O+ and OH-. These experiments are carried out in THF/water mixtures, and the influence of water on the structure has been checked. The hydrodynamic radius of generation 4 is measured by NMR diffusion (pulse gradient spin-echo) experiments. R(H) varies from 35.4 A at 4 mol % of water to 32.5 A at 64 mol % of water in THF, indicating the hydrophobic nature of these dendrimers. 相似文献
96.
Anne-Marie Caminade Jean-Pierre Majoral Valérie Maraval Rosa-Maria Sebastián 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1493-1497
Several series of phosphorus-containing dendrimers have been designed to study the variation of their properties, depending on the type, the location (surface, branches, core, and cavities), and the number of functions implied. 相似文献
97.
Foaming constitutes one of the most important industrial activities in polymer engineering to produce efficient thermal insulating materials. In particular, rigid insulating boards are produced worldwide on a large scale using blowing agents which eventually are released in the environment where they adversely impact the natural friendly stratospheric ozone layer. Concomitantly, the chemicals used as blowing agents contribute to the creation of the unfriendly tropospheric ozone layer generating the disastrous green house effect around our planet. The traditional foaming intermediates currently named freons, like chlorofluorocarbons (CFCs) currently used as blowing agents as well as the hydrochlorofluorocarbons (HCFCs) often considered as alternative blowing agents, must be banned from industrial processes and new (friendly) foaming agents have to be suggested and evaluated in terms of both easy engineering and environmental neutrality. Undoubtedly thermodynamics plays a major role in assessing the effective capability of those chemicals. Some CFCs still accepted and other possible simple gases like carbon dioxide and nitrogen have been considered. The in-depth thermodynamic investigation has been made possible thanks to new experimental developments to determine gas solubility in polymers and associated swelling as well as the thermodynamic properties of (gas + polymer) systems, including the thermophysical properties of polymers under gas sorption. Pertinent data have been generated for such properties over extended T and p ranges. 相似文献
98.
Jean-Pierre Aubin 《Journal of Evolution Equations》2012,12(1):99-117
We assume that the evolution of the population is governed by a controlled McKendrick age-structured partial differential
equation where the mortality rate and immigrated population levels are no longer known coefficients, but contingent regulation
parameters chosen for a given purpose, for instance, for requiring that the population satisfies prescribed viability constraints
depending on time and age. The Lotka renewal equation relating the boundary condition (number of births) to the integral with
respect to age of the population is replaced by the introduction of another regulation parameter in the boundary condition,
regarded as a natality policy. We may control it by its derivative, regarded as a natality decision. We then construct a regulation map, associating with the population level, the time and the age the subset of natality policies,
a mortality rates and an immigration levels needed for governing viable evolutions of the population. 相似文献
99.
Rané Mathieu Anne-Marie Caminade Jean-Pierre Majoral 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4)
Abstract One of the possible ways of getting phosphacumulene complexes could be the complexation of phosphinoalkynes, which might induce the migration of hydrogen from phosphorus to the β carbon of the alkynyl group. 相似文献
100.
Jean-Pierre Majoral René Mathieu Anne-Marie Caminade Serge Attali Michel Sanchez 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):443-446
Abstract A new entry to non classical phosphorus complexes is reported. 相似文献