are reported for aqueous solutions of lactose, sucrose, glucose, and fructose at various concentrations (0.001 to 0.1) mol‚dm-3 and temperatures (298.15 to 328.15) K. The hydrodynamic radius and activation energy for the diffusion of aqueous sugars are calculated from those results. In addition, the measured diffusion coefficients are used with the Hartley equation to estimate activity coefficients for aqueous lactose, sucrose, glucose, and fructose.
Binary mutual diffusion coefficients (interdiffusion coeffcients) have been measured for aqueous solutions of -cyclodextrin ( -CD) at concentrations from (0.002 to 0.008) mol‚dm -3 . The effect of temperature, from (298.15 to 312.15) K, was also analyzed. The concentration dependence of D is discussed on the basis of Hartley's equation. The activation energy for the diffusion process, 18719 J‚mol -1 , was calculated from data of D at different temperatures. This activation energy is in good agreement with that estimated using Stokes-Einstein equation (18644 J‚mol -1 ). Activity coefficients for aqueous -CD solutions were also estimated from Hartley equation and experimental D.
The interaction between the cationic HTMA-PFP (Poly-(9,9-bis(6′-N,N,N-trimethylammonium)hexyl-fluorene phenylene) bromide) and oppositely charged sodium n-alkyl sulfonate surfactants of different chain lengths has been studied in DMSO-water solutions (4% v/v) by UV-visible absorption, fluorescence spectroscopy, fluorescence lifetimes, electrical conductivity, and 1 H NMR spectroscopy. Polymer-surfactant interactions lead to complex spectroscopic behaviors which depends on surfactant concentration. At low surfactant concentrations, the observed strong static fluorescence quenching of fluorescence seems to be associated with formation of aggregates between polymer chains neutralized through interaction with surfactants. This is supported by conductivity and by analysis of absorption spectra deconvoluted at each surfactant concentration using an adapted iterative method. In contrast, above the surfactant critical micelle concentration, there is a strong fluorescence enhancement, leading in some cases to higher intensities than in the absence of surfactants. This is attributed to the transformation of the initially formed aggregates into some new aggregate species involving surfactant and polymer. These changes in HTMA-PFP fluorescence as a function of n-alkyl sulfonate concentration are important for the general understanding of polymer-surfactant interactions, and the aggregates formed may be important as novel systems for applications of these conjugated polyelectrolytes.
The interaction has been studied in aqueous solutions between a negatively charged conjugated polyelectrolyte poly{1,4-phenylene-[9,9-bis(4-phenoxybutylsulfonate)]fluorene-2,7-diyl} copolymer (PBS-PFP) and several cationic tetraalkylammonium surfactants with different structures (alkyl chain length, counterion, or double alkyl chain), with tetramethylammonium cations and with the anionic surfactant sodium dodecyl sulfate (SDS) by electronic absorption and emission spectroscopy and by conductivity measurements. The results are compared with those previously obtained on the interaction of the same polymer with the nonionic surfactant C12E5. The nature of the electrostatic or hydrophobic polymer-surfactant interactions leads to very different behavior. The polymer induces the aggregation with the cationic surfactants at concentrations well below the critical micelle concentration, while this is inhibited with the anionic SDS, as demonstrated from conductivity measurements. The interaction with cationic surfactants only shows a small dependence on alkyl chain length or counterion and is suggested to be dominated by electrostatic interactions. In contrast to previous studies with the nonionic C12E5, both the cationic and the anionic surfactants quench the PBS-PFP emission intensity, leading also to a decrease in the polymer emission lifetime. However, the interaction with these cationic surfactants leads to the appearance of a new emission band (approximately 525 nm), which may be due to energy hopping to defect sites due to the increase of PBS-PFP interchain interaction favored by charge neutralization of the anionic polymer by cationic surfactant and by hydrophobic interactions involving the surfactant alkyl chains, since the same green band is not observed by adding either tetramethylammonium hydroxide or chloride. This effect suggests that the cationic surfactants are changing the nature of PBS-PFP aggregates. The nature of the polymer and surfactant interactions can, thus, be used to control the spectroscopic and conductivity properties of the polymer, which may have implications in its applications.
The interaction between the water-soluble anionic conjugated copolymer poly{1,4-phenylene-[9,9-bis(4-phenoxy-butylsulfonate)]fluorene-2,7-diyl} (PBS-PFP) and various surfactants has been studied in aqueous solution by UV-vis absorption spectra, fluorescence and electrical conductivity. It is suggested from the linear dependence of absorbance, fluorescence and electrical conductivity on concentration that in the absence of surfactant, moderately stable dispersions are formed. These are affected in different ways on adding cationic, anionic or neutral surfactants. With the cationic cetyltrimethylammonium bromide, quenching of fluorescence intensity and lifetime, and formation of a new emission occurs at concentrations well below the critical micelle concentration (cmc). Electrical conductivity measurements indicate a discontinuity at surfactant/polymer ratio corresponding to electroneutrality, due to complexation. With the anionic sodium dodecyl sulfate, fluorescence quenching is also observed, but is attributed to formation of some mixed polymer/surfactant aggregate. The most striking changes are observed with the non-ionic pentaethyleneglycol monododecyl ether (C 12 E 5 ), where a blue shift in fluorescence emission, dramatic increases in lifetime and quantum yield, and changes in electrical around the cmc are interpreted in terms of incorporation of single polymer chains in elongated cylindrical micelles. This is supported by 1 H NMR spectroscopic measurements.
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