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51.
Nearly all the available information on the transient flow behaviour of liquid crystalline polymers has been obtained on model systems, especially on solutions of polybenzylglutamate (PBG) and hydroxypropylcellulose (HPC). The assessment of rheological models has been based almost entirely on these model systems. It is not clear how much of the available theoretical and experimental knowledge can be applied to systems of industrial relevance, which have quite different molecular structures. Here, an industrial lyotropic system, poly(p-phenylenetherephthalamide) (PpPTA) in sulphuric acid (TWARON from AKZO), is investigated. Various techniques to study transient behaviour are used, these include measurements of transient shear and normal stresses after sudden changes in shear rate, dynamic moduli and stress relaxation after cessation of flow and elastic recoil. At all shear rates studied the PpPTA solution is shear thinning, and the first normal stress difference remains positive. For the stress transients a strain scaling applies reasonably well as it did in model systems. The moduli increase with time upon cessation of flow, indicating that the molecules become less oriented in the previous flow direction. This particular behaviour is similar to that of HPC. Transients also resemble more closely those of HPC rather than those of PBG. This latter difference might be attributed to the higher flexibility of HPC and PpPTA chains as compared with PBG molecules. 相似文献
52.
Berdeaux O Juaneda P Martine L Cabaret S Bretillon L Acar N 《Journal of chromatography. A》2010,1217(49):7738-7748
The retina is one of the vertebrate tissues with the highest content in polyunsaturated fatty acids (PUFA). A large proportion of retinal phospholipids, especially those found in photoreceptor membranes, are dipolyunsaturated molecular species. Among them, dipolyunsaturated phosphatidylcholine (PC) molecular species are known to contain very-long-chain polyunsaturated fatty acids (VLC-PUFA) from the n-3 and n-6 series having 24-36 carbon atoms (C24-C36) and four to six double bonds. Recent interest in the role played by VLC-PUFA arose from the findings that a protein called elongation of very-long-chain fatty acids 4 (ELOVL4) is involved in their biosynthesis and that mutations in the ELOVL4 gene are associated with Stargardt-like macular dystrophy (STD3), a dominantly inherited juvenile macular degeneration leading to vision loss. The aim of the present study was to develop an HPLC-ESI-MS/MS method for the structural characterisation and the quantification of dipolyunsaturated PC molecular species containing VLC-PUFA and validate this methodology on retinas from bovines and human donors. Successful separation of phosphatidylethanolamine (PE), phosphatidylinositol (PI), phosphatidylserine (PS), PC, lyso-phosphatidylcholine (LPC) and sphingomyelin (SM) was achieved using a silica gel column and a gradient of hexane/isopropanol/water containing ammonium formate as a mobile phase. A complete structural characterisation of intact phosphatidylcholine species was obtained by collision-induced dissociation (CID) in the negative mode. Fatty acid composition and distribution can be clearly assigned based on the intensity of sn-2/sn-1 fragment ions. The PC species were characterised on bovine retina, 28 of which were dipolyunsaturated PC species containing one VLC-PUFA (C24-C36) with three to six double bonds. VLC-PUFA was always in the sn-1 position while PUFA at the sn-2 position was exclusively docosahexaenoic acid (DHA, C22:6n-3). Most of these VLC-PUFA-containing dipolyunsaturated PCs were detected and quantified in human retinas. The quantitative analysis of the different PC molecular species was performed in the positive mode using precursor ion scanning of m/z 184 and 14:0/14:0-PC and 24:0/24:0-PC as internal standards. The relationship between the MS peak intensities of different PC species and their carbon chain length was included for calibration. The main compounds represented were those having VLC-PUFA with 32 carbon atoms (C32:3, C32:4, C32:5 and C32:6) and 34 carbon atoms (C34:3, C34:4, C34:5 and C34:6). Dipolyunsaturated PCs with 36:5 and 36:6 were detected but in smaller quantities. In conclusion, this new HPLC-ESI-MS/MS method is sensitive and specific enough to structurally characterise and quantify all molecular PC species, including those esterified with VLC-PUFA. This technique is valuable for a precise characterisation of PC molecular species containing VLC-PUFA in retina and may be useful for a better understanding of the pathogenesis of STD3. 相似文献
53.
Shape optimization methods, as commonly applied in aerodynamic design applications, have recently been adapted for use in nuclear fusion divertor target design. The resulting algorithms are very efficient compared to the standard use of numerical edge plasma simulations as analysis tools only. In this paper, we highlight some numerical aspects of the underlying algorithm, focusing on a correct, nine-point discretization of the fluxes and the need for an adjoint pressure correction equation. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
54.
55.
Abstract The synthesis and crystal structure of the complex formed by the all-cis epimer of C-methylcalix[4]resorcinarene (1) and triethylammonium nitrate are reported. “1.(HNEt+ 3)4. (NO? 3)4(2)”, crystallizes in the monoclinic space group P21/n, a=25.796(2), b=16.6048(11), c=29.5659(10) Å, β=94.636(4)°, V=12623(2) Å3, Z=8. Refinement led to a final conventional R1 value of 0.128 for 12428 reflections and 1473 parameters. The resorcinarene displays the usual bowl-type shape, with four hydroxyl protons involved in intramolecular hydrogen bonds, whereas the remaining four make hydrogen bonds with four bridging nitrate ions, which results in the formation of infinite chains. Those chains are arranged so as to form layers, between which the triethylammonium ions and the remaining nitrate ions are hydrogen-bonded one to another. 相似文献
56.
Pierre Thury Martine Nierlich Bernardo Masci 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(2):m84-m86
Uranyl nitrate hexahydrate reacts with bis[2‐(2‐hydroxyphenoxy)ethoxy]ethane (C18H22O6), denoted LH2 hereafter, in the presence of triethylamine to give triethylammonium aqua[2,2′‐(3,6‐dioxaoctane‐1,8‐diyldioxy)diphenolato‐κ2O,O′](nitrato‐κ2O,O′)dioxouranium(VI), (Et3NH)[UO2(H2O)L(NO3)], which possesses a symmetry plane. The uranyl ion is coordinated to the two phenoxide O atoms, a nitrate ion and a water molecule (first sphere); the water molecule is itself held in the crown ether chain by hydrogen‐bonding interactions, thus ensuring second‐sphere coordination by the ligand L. 相似文献
57.
G. Balducci L. Bencivenni G. De Rosa R. Gigli B. Martine S.Nunziante Cesaro 《Journal of Molecular Structure》1980
The infrared and Raman spectra of some cyclopentadienyl compounds of the transition metals, namely Ti(C5H5)Cl3 and M(C5H5)2Cl2 (M = Ti, Zr and Hf), are reported and discussed. The infrared spectra of the gaseous species isolated in argon matrices at 10 K provide structural information about the single molecules. Particular attention has been paid to the low-frequency region in order to achieve more reliable assignments for the internal-rotation modes. The structural data and the fundamental frequencies derived from the spectra are employed in a calculation of the thermodynamic functions for these compounds in the ideal gas state. 相似文献
58.
Approximate inertial manifolds for reaction-diffusion equations in high space dimension 总被引:4,自引:0,他引:4
Martine Marion 《Journal of Dynamics and Differential Equations》1989,1(3):245-267
The concept of approximate inertial manifolds was introduced by Foiaset al. (1987) in the case of the two-dimensional Navier-Stokes equations. These manifolds are finite dimensional smooth manifolds such that the orbits enter a very thin neighborhood of the manifold after a transient time; this concept replaces the one of inertial manifold when either an inertial manifold does not exist or its existence is not known. Our aim in this paper is to prove that approximate inertial manifolds exist for reaction-diffusion equations in high space dimension by opposition with exact inertial manifolds whose existence has only been proved in low dimension and for which nonexistence results have been obtained in space dimensionn=4. 相似文献
59.
Nonlinear Galerkin methods and mixed finite elements:
two-grid algorithms for the Navier-Stokes equations 总被引:14,自引:0,他引:14
Summary.
A nonlinear Galerkin method using mixed finite
elements is presented for the two-dimensional
incompressible Navier-Stokes equations. The
scheme is based on two finite element spaces
and for the approximation of the velocity,
defined respectively on one coarse grid with grid
size and one fine grid with grid size and
one finite element space for the approximation
of the pressure. Nonlinearity and time
dependence are both treated on the coarse space.
We prove that the difference between the new
nonlinear Galerkin method and the standard
Galerkin solution is of the order of $H^2$, both in
velocity ( and pressure norm).
We also discuss a penalized version of our algorithm
which enjoys similar properties.
Received October 5, 1993 / Revised version received November
29, 1993 相似文献
60.
In this work, a two-phase film-flow model in a hygroscopic capillary tube is developed and extended to describe the two-phase capillary viscous transport in a network of parallel capillary tubes in terms of relative permeabilities. This film-flow approach is further considered to predict the longitudinal moisture transport in oak wood during drying. Numerical results obtained from this prediction are compared with data of convective drying experiments performed on samples of this wood. The comparison seems to confirm the physical relevance of a film-flow model to correctly represent the moisture transfer until the hygroscopic regime is reached. 相似文献