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排序方式: 共有190条查询结果,搜索用时 12 毫秒
1.
Alexander Semenov Aurélia Charlot Rachel Auzély-Velty Marguerite Rinaudo 《Rheologica Acta》2007,46(5):541-568
Dynamics of associating polymer solutions above the reversible gelation point are studied. Each macromolecule consists of
a soluble backbone (B) and a small fraction of specific strongly interacting groups (A or C stickers) attached to B. A mixture
of B–A and B–C associating polymers with 1:1 stoichiometric ratio is considered. As a result of AC association, the polymers
reversibly gelate above the overlap concentration. It is shown that (1) the network strands are linear complexes (double chains)
of B–A and B–C; (2) “diffusion” of the network junction points is characterized by an apparent activation energy, which can
be significantly higher than the energy of one AC bond; (3) most importantly, the randomness of sticker distribution along
the chain can significantly slow down the network relaxation leading to a markedly non-Maxwellian viscoelastic behavior. The
theory elucidates the most essential features of rheological behavior of polysaccharide associating systems (with A = adamantyl
moiety, C = β-cyclodextrin, B = either chitosan or hyaluronan) including similar behavior of G
′ and G
″ in a wide frequency range, strong temperature dependence of the characteristic frequency ω
x
, and an extremely strong effect of added free stickers (fC) on the dynamics.
This paper was presented at Annual European Rheology Conference (AERC) held in Hersonisos, Crete, Greece, April 27–29, 2006. 相似文献
2.
Hureau C Blondin G Charlot MF Philouze C Nierlich M Césario M Anxolabéhère-Mallart E 《Inorganic chemistry》2005,44(10):3669-3683
Two Mn(II) complexes are isolated and X-ray characterized, namely, cis-[(L(2))Mn(II)(Cl)(2)] (1) and [(L(3))Mn(II)Cl(OH(2))](ClO(4)) (2(ClO(4))), where L(2) and L(3) are the well-known tetradentate N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)ethane-1,2-diamine and N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)propane-1,3-diamine ligands, respectively. The crystal structure reveals that whereas the ligand L(2) is in the cis-alpha conformation in complex 1, the ligand L(3) is in the more unusual cis-beta conformation in 2. EPR spectra are recorded on frozen solutions for both complexes and are characteristic of Mn(II) species. Electrochemical behaviors are investigated on acetonitrile solution for both complexes and show that cation 2 exists as closely related Mn(II) species in equilibrium. For both complexes exhaustive bulk electrolyses of acetonitrile solution are performed at oxidative potential in various experimental conditions. In the presence of 2,6-lutidine and after elimination of chloride ligands, the formation of the di-mu-oxo mixed-valent complexes [(L(2))Mn(III)(mu-O)(2)Mn(IV)(L(2))](3+) (3a) and [(L(3))Mn(III)(mu-O)(2)Mn(IV)(L(3))](3+) (4) is confirmed by UV-vis and EPR spectroscopies and cyclic voltammetry. In addition crystals of 4(ClO(4))(3) were isolated, and the X-ray structure reveals the cis-alphaconformation of L(3). In the absence of 2,6-lutidine and without elimination of the exogenous chloride ions, the electrochemical oxidation of 1 leads to the formation of the mononuclear Mn(III) complex, namely, [(L(2))Mn(III)(Cl)(2)](+) (5), as confirmed by UV-vis as well as parallel mode EPR spectroscopy and cyclic voltammetry. In the same conditions, the electrochemical oxidation of complex 2 is more intricate, and a thorough analysis of EPR spectra establishes the formation of the binuclear mono-mu-oxo mixed-valent [(L(3))ClMn(III)(mu-O)Mn(IV)Cl(L(3))](3+) (6) complexes. Electrochemical conversion of Mn(II) complexes into mixed-valent Mn(2)(III,IV) oxo-bridged complexes in the presence of 2,6-lutidine is discussed. The role of the chloride ligands as well as that of L(3) in the building of oxo bridges is discussed. Differences in behavior between L(2) and L(3) are commented on. 相似文献
3.
Summary The reduction of nickel(II) halides with NaBH4 in the presence of different ligands, L=PPh3, AsPh3, SbPh3, has been studied. With a molar ratio L/Ni=3, new complexes NiX(SbPh3)3, X=Cl, Br, I, were obtained. With a molar ratio L/Ni=2, dimeric species [NiXL2]2, X=Cl, Br, I; L=PPh3, AsPh3, SbPh3, were isolated. They are unstable and decompose easily in the solid and rapidly in solution, so that pure samples were only identified for X=Cl, L=PPh3, AsPh3, SbPh3; X=Br, L=PPh3 and X=I, L=PPh3. With a molar ratio L/Ni=1, complexes [NiXL]n (probably polymeric) were obtained. They are very unstable and pure samples could only be isolated when X=Cl, L=PPh3. Impure substances containing variable amounts of decomposition products were obtained in all the remaining cases. The chemical and structural behaviour of these complexes is discussed. 相似文献
5.
G. Charlot T. W. Davis N. Kornblum R. Fabre T. G. Tomesco A. Ionesco-Matiu C. Popesco F. T. Jones und C. W. Mason 《Fresenius' Journal of Analytical Chemistry》1938,114(5-6):208-211
Ohne Zusammenfassung 相似文献
6.
The authors have formerly described a qualitative method for the analysis of Cations according to which separations were reduced to a minimum, each metal being detected by an independent test.They presently seek to improve this method, with special regard to the case when small quantities of an element are to be found in the presence of large proportions of one or more other cations.In this first paper are given the results for the following metals arsenic, tin, antimony, bismuth. 相似文献
7.
8.
A rapid titrimetric method is described for small quantities of chlorate by means of a standardised solution of helianthine. It is possible to determine 10 γ of NaClO3 to about 5 %. 相似文献
9.
Brönsted's definition of acids and bases presents the following advantages: One may reason along the lines of the acid-base couple and the proton exchange just as done in the case of an oxidation-reduction couple and the electron exchange. The force of the acid is connected with that of the corresponding base.The acid or basic character of certain compounds is evidenced by their tendency to exchange protons, something that does not necessitate the use of “hydrolytic” phenomena.Properties of “strong acids” and “strong bases” are explained.The formulas of the pH of acid solutions, basic solutions, or salt solutions are unified and their use simplified.In acidimetry the reasoning is simplified, and complex problems may be approached with more facility.In the case of non-aqeous solvents that offer great possibilities in acidimetry spbrönsted's theory permits predictions about limitations in the acidityscale. It furnishes an explanation of phenomena in inert solvents. 相似文献
10.
Mihaela Pascu Daniela-Elena Pascu Gina Alina Trăistaru Aurelia Cristina Nechifor Andrei A. Bunaciu Hassan Y. Aboul-Enein 《Journal of the Iranian Chemical Society》2014,11(2):315-321
The present study investigates the antioxidant activities of some Romanian plants, using different spectrophotometric methods (FRAP I, FRAP II, and CUPRAC). The plants investigated are hawthorn (Crataegus oxyacantha), bilberry (Vaccinium myrtillus L.), rosehip (Rosa canina), and chokeberries (Aronia melanocarpa). Hawthorn is used to treat a wide variety of inflammatory conditions, but the primary use is generally restricted for treating hypertension, ischemic heart disease, congestive heart failure, and arrhythmia. Investigations have proved the safe and reliable use of plant and plant extracts for treatment of cardiovascular disorders. 相似文献