Rheological properties of binary associating polymers

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.     

Synthesis, structure, and characterization of new mononuclear Mn(II) complexes. Electrochemical conversion into new oxo-bridged Mn(2)(III,IV) complexes. Role of chloride ions

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.     

Photon channelling in foams

Experiments by Gittings, Bandyopadhyay and Durian (Europhys. Lett. 65, 414 (2004)) demonstrate that light possesses a higher probability to propagate in the liquid phase of a foam due to total reflection. The authors term this observation photon channelling which we investigate in this article theoretically. We first derive a central relation in the work of Gitting et al. without any free parameters. It links the photon's path-length fraction f in the liquid phase to the liquid fraction ɛ. We then construct two-dimensional Voronoi foams, replace the cell edges by channels to represent the liquid films and simulate photon paths according to the laws of ray optics using transmission and reflection coefficients from Fresnel's formulas. In an exact honeycomb foam, the photons show superdiffusive behavior. It becomes diffusive as soon as disorder is introduced into the foams. The dependence of the diffusion constant on channel width and refractive index is explained by a one-dimensional random-walk model. It contains a photon channelling state that is crucial for the understanding of the numerical results. At the end, we shortly comment on the observation that photon channelling only occurs in a finite range of ɛ.     

Dosage de petites quantités de chlorate

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 %.     

M/'ethode d'analyse qualitative des cations sans s/'eparations syst/'ematiques

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.     

Utilité de la définition de brönsted des acides et des bases en chimie analytique

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.     

Synthesis of thermosensitive guar‐based hydrogels with tunable physico‐chemical properties by click chemistry

Thermosensitive guar‐based hydrogels are obtained in water solutions by copper‐catalyzed 1,3‐dipolar cycloaddition between alkyne‐functionalized guars and α,ω‐diazido‐poly[(ethylene glycol)‐co‐(propylene glycol)]. Characterization by TGA, HR‐MAS ¹H NMR, and rheology have shown that hydrogels with tunable physico‐chemical properties, such as crosslinking density, viscoelasticity, swelling ratio, and so forth, could be obtained by varying the guar molar mass, the degree of alkyne functionality, the guar/crosslinker weight ratio, and the reaction temperature. Based on swelling measurements, it has been shown that the thermal sensitiveness of guar‐based hydrogels is fast, reversible, and intimately related to the weight fraction of the thermosensitive crosslinker in the network. Finally, the monitoring of doxorubicin hydrochloride release has demonstrated the potential of these hydrogels as temperature‐dependent drug release devices. The robust, efficient, and orthogonal approach described herein represents a general approach towards the development of well‐controlled guar‐based hydrogels using α,ω‐diazido crosslinkers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2733–2742, 2010     

Efficient electron transfer through a triazole link in ruthenium(II) polypyridine type complexes

Spectroscopic, electrochemical and theoretical characterisations of photoactive systems readily assembled via click-chemistry show an efficient bi-directional charge shift through the triazole link.