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1.
2.
Jean-Jacques Jutier Even Lemieux Robert E. Prud'homme 《Journal of Polymer Science.Polymer Physics》1988,26(6):1313-1329
The miscibility of polyester/nitrocellulose blends was investigated by differential scanning calorimetry and Fourier-transform infrared (FTIR) spectroscopy. Two nitrocelluloses (NC) derived from wood and having different nitrogen contents (12.62 and 13.42%) were used. On the basis of the glass transition temperature criterion, poly(?-caprolactone) (PCL), poly(valerolactone), poly(ethylene adipate), and poly(butylene adipate) are miscible with nitrocellulose, whereas poly(α-methyl α-propyl β-propiolactone) and poly(α-methyl β-proiolactone) are immiscible. The Tg versus composition curves of PCL/NC blends do not follow a monotone function but exhibit a singular point at a critical PCL volume fraction of 0.51 for NC-1342 and 0.45 for NC-1262 in agreement with Kovacs' theory. A shift of 17 cm-1 of the carbonyl stretching band was observed with PCL/NC blends and is taken as evidence for hydrogen bonding interaction between the PCL carbonyl group and NC hydroxyl group. The frequency difference between the free hydroxyl absorbance and the absorbances of the hydrogen-bonded species was found to be 85 cm-1 in pure NC and 125 cm-1 in PCL/NC blends; it indicates that the average strength of this interaction is stronger than the corresponding self-associated hydrogen bonding in pure NC. The presence of a dipole-dipole interaction between the nitrate-ester groups of NC and the carbonyl groups of the polyesters is reported. The relative strength of the hydrogen bonding and dipole-dipole interactions is discussed and correlated with polymer miscibility. 相似文献
3.
Patrick Pruja Sauveur Bnet Bernard Claudet Olivier Faugeroux Jean-Jacques Serra 《Superlattices and Microstructures》2004,35(3-6):409
Modeling the behavior of a protective coating during a thermal shock not only requires the knowledge of its own thermophysical characteristics, but also those of the coating–substrate discontinuity. According to its nature, this discontinuity can be modeled as a zero-thickness interface (thermal contact resistance) or a finite thickness layer (thermal third body). This paper presents an experimental device and two associated thermal transfer models developed in view of the microscale characterization of such discontinuities. 相似文献
4.
Martinho M Banse F Bartoli JF Mattioli TA Battioni P Horner O Bourcier S Girerd JJ 《Inorganic chemistry》2005,44(25):9592-9596
The green complex S=1 [(TPEN)FeO]2+ [TPEN=N,N,N',N'-tetrakis(2-pyridylmethyl)ethane-1,2-diamine] has been obtained by treating the [(TPEN)Fe]2+ precursor with meta-chloroperoxybenzoic acid (m-CPBA). This high-valent complex belongs to the emerging family of synthetic models of Fe(IV)=O intermediates invoked during the catalytic cycle of biological systems. This complex exhibits spectroscopic characteristics that are similar to those of other models reported recently with a similar amine/pyridine environment. Thanks to its relative stability, vibrational data in solution have been obtained by Fourier transform infrared. A comparison of the Fe=O and Fe=(18)O wavenumbers reveals that the Fe-oxo vibration is not a pure one. The ability of the green complex to oxidize small organic molecules has been studied. Mixtures of oxygenated products derived from two- or four-electron oxidations are obtained. The reactivity of this [FeO]2+ complex is then not straightforward, and different mechanisms may be involved. 相似文献
5.
The silver nitrate assisted cyclization of the entitled diols leads, depending on the substitution of the allenic linkage, specifically to dihydropyranes , when R is alkyl or to an equimolecular mixture of and its tetrahydrofuranyl isomer when R is hydrogen. 相似文献
6.
Yano J Sauer K Girerd JJ Yachandra VK 《Journal of the American Chemical Society》2004,126(24):7486-7495
The anisotropic g and hyperfine tensors of the Mn di-micro-oxo complex, [Mn(2)(III,IV)O(2)(phen)(4)](PF(6))(3).CH(3)CN, were derived by single-crystal EPR measurements at X- and Q-band frequencies. This is the first simulation of EPR parameters from single-crystal EPR spectra for multinuclear Mn complexes, which are of importance in several metalloenzymes; one of them is the oxygen-evolving complex in photosystem II (PS II). Single-crystal [Mn(2)(III,IV)O(2)(phen)(4)](PF(6))(3).CH(3)CN EPR spectra showed distinct resolved (55)Mn hyperfine lines in all crystal orientations, unlike single-crystal EPR spectra of other Mn(2)(III,IV) di-micro-oxo bridged complexes. We measured the EPR spectra in the crystal ab- and bc-planes, and from these spectra we obtained the EPR spectra of the complex along the unique a-, b-, and c-axes of the crystal. The crystal orientation was determined by X-ray diffraction and single-crystal EXAFS (Extended X-ray Absorption Fine Structure) measurements. In this complex, the three crystallographic axes, a, b, and c, are parallel or nearly parallel to the principal molecular axes of Mn(2)(III,IV)O(2)(phen)(4) as shown in the crystallographic data by Stebler et al. (Inorg. Chem. 1986, 25, 4743). This direct relation together with the resolved hyperfine lines significantly simplified the simulation of single-crystal spectra in the three principal directions due to the reduction of free parameters and, thus, allowed us to define the magnetic g and A tensors of the molecule with a high degree of reliability. These parameters were subsequently used to generate the solution EPR spectra at both X- and Q-bands with excellent agreement. The anisotropic g and hyperfine tensors determined by the simulation of the X- and Q-band single-crystal and solution EPR spectra are as follows: g(x) = 1.9887, g(y) = 1.9957, g(z) = 1.9775, and hyperfine coupling constants are A(III)(x) = |171| G, A(III)(y) = |176| G, A(III)(z) = |129| G, A(IV)(x) = |77| G, A(IV)(y) = |74| G, A(IV)(z) = |80| G. 相似文献
7.
Tula Alev-Behmoaras Jean-Jacques Toulme Claude Hélène 《Photochemistry and photobiology》1979,30(5):533-539
Abstract— In order to test the ability of phosphate groups to quench the tyrosine fluorescence in nucleic acid-protein complexes, we have studied the effect of several phosphate ions on the fluorescence of tyrosine derivatives. Mono and bianions (H2 PO4 and HPO4 2– ) which are good proton acceptors quenched the fluorescence of all the phenolic compounds studied except that of O -methyl tyrosine. With the other derivatives (tyrosine, N -acetyl tyrosinamide and lysyl-tyrosyl-α lysine) fluorescence inhibition was accompanied by the appearance of a long wavelength emission (345 nm) attributed to tyrosinate anions. The quenching of tyrosine emission was due to the deprotonation of the phenolic group promoted in the excited state by phosphate ions and leading to the weakly fluorescent tyrosinate ion. Mono and dianions of phosphate mono ester inhibited tyrosine fluorescence as did unesterified phosphates. However, phosphate diester did not have any effect on the fluorescence of tyrosine derivatives. We conclude from this study that in nucleic acid-protein complexes phosphate groups are not able to quench tyrosine fluorescence except at the end of polynucleotide chains. Since monoester and diester monoanions have a different behavior, we propose that quenching of tyrosine fluorescence by monoanions requires the formation of two hydrogen bonds. This complex cannot form with diesters which consequently do not quench tyrosine fluorescence. 相似文献
8.
Mounir Maafi Belkacem Laassis Jean-Jacques Aaron M. Carmen Mahedero Arsenio Muñoz De La Peña Francisco Salinas 《Journal of inclusion phenomena and macrocyclic chemistry》1995,22(3):235-247
The photooxidation of Azure A and fluorescence properties of Azure A and its photoproduct have been investigated in aqueous media and in the presence of-cyclodextrin (-CD). The fluorescence intensity of the complex formed between the photoproduct and -CD was found to be three times higher than that of the uncomplexed Azure A photoproduct. A complex formation constant of 110±40 M–1 was calculated using the Benesi-Hildebrand treatment of the fluorescence emission data. Although the stoichiometry of the Azure A photoproduct: -CD complex was found to be 1: 1, it seems that the Azure A structure is only partially included. Calibration graphs were plotted for the free Azure A photoproduct and the photogenerated product included in -CD. The analytical parameters and quantification limits were determined. 相似文献
9.
Raboisson P Baurand A Cazenave JP Gachet C Schultz D Spiess B Bourguignon JJ 《The Journal of organic chemistry》2002,67(23):8063-8071
In our effort to identify potent purinergic P2Y(1) receptor antagonists as potent platelet aggregation inhibitors with enhanced metabolic stability, we developed an efficient route for the large-scale preparation of 2'-deoxy-C-nucleosides of pyrazolo[1,5-a]-1,3,5-triazine. The key strategic elements of this novel synthetic approach involved the following: (i) the use of a novel activating group, the N-methyl-N-phenylamino group, which was easily generated in high yield by treatment of the pyrazolo[1,5-a]-1,3,5-triazin-4-one (5) with phosphorus oxychloride and dimethylaniline under high pressure, (ii) a regio- and stereospecific palladium-mediated coupling reaction of the readily available unprotected glycal 1,4-anhydro-2-deoxy-D-erythro-pent-1-enitol (4b) and the 8-iodo derivative (16), and (iii) the stereoselective reduction of the ketone group of the furanosyl ring followed by the subsequent displacement of the N-methyl-N-phenylamino group upon treatment with methylamine. The beta configuration at the anomeric C-1' position of the glycal moieties was perfectly retained throughout this conversion. This procedure afforded 8-(2'-deoxy-beta-D-ribofuranosyl)-2-methyl-4-(N-methylamino)pyrazolo[1,5-a]-1,3,5-triazine (21) and 8-(2'-deoxy-beta-D-xylofuranosyl)-2-methyl-4-(N-methylamino)pyrazolo[1,5-a]-1,3,5-triazine (24) with an overall yield of 50% and 39%, respectively. Finally, the conversion of nucleosides 21 and 24 to the pyrazolotriazine C-nucleotides 3',5'-bisphosphate 2 and 3',5'-cyclophosphate 26 is also described herein and represents the first reported nucleotide derivatives within the pyrazolo[1,5-a]-1,3,5-triazine series. Preliminary biological testing has shown that compound 2 strongly inhibits ADP-induced human platelet aggregation and shape change and possesses significant efficacies 30 min after injection in rat, highlighting a strong P2Y(1)-receptor antagonist activity in vitro combined with a prolonged duration of action in vivo. 相似文献
10.
Renaud Barbeyron Jean-Jacques Vasseur Carine Baraguey Michael Smietana 《Tetrahedron》2017,73(17):2468-2475
The iminodiacetic acid and aminodiethanol moieties are known for their ability to generate with boronic acids bicyclic structures having a strong intramolecular NB coordination. We describe here the convergent synthesis of 3′-deoxy-3′-iminodiacetic acid and 3′-deoxy-3′-aminodiethanol thymidine analogues. The abilities of these compounds to form boronate complexes with aliphatic or aromatic boronic acids were established by 1D and 2D 1H and 13C NMR. Moreover, conformational analysis of the newly synthesized compounds revealed a marked preference for an N-type sugar puckering. 相似文献