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Abstract: The importance of the linear aromatic density of polyelectrolytes on the ability to bind and influence the state of aggregation of dyes such as rhodamine 6G is highlighted. The corresponding complexes present different interaction patterns with metal ions such as Cu2+, undergoing different spectroscopic changes. The chemical bases of these changes are discussed. The different polyelectrolytes studied, poly(sodium 4-styrenesulfonate), poly(sodium 4-styrenesulfonate-co-sodium maleate) at two different comonomer compositions (3:1 and 1:1), and poly(sodium acrylate-co-sodium maleate), bear different linear aromatic density and induce different R6G binding patterns, as seen by diafiltration and UV–vis spectroscopy of absorbance and fluorescence. As the linear aromatic density increases, smaller dye aggregates are induced in the systems. Thus, in the presence of a large excess of the polyelectrolyte showing the highest linear aromatic density, the dyes disperse on the polymer domain and no aggregation is detected. The interaction is less sensitive to the cleaving effect produced by the addition of NaCl 0.1M for the complexes that include the polyelectrolytes with the highest linear aromatic density. In the presence of Cu2+, the complexes formed with the polyelectrolytes showing the lowest linear aromatic density tend to cleave, producing the release of the dye from the polymer domain. On the contrary, the complexes formed with the polyelectrolytes showing the highest linear aromatic density effectively retain the dye in the presence of the divalent metal ion. Based on fluorescence changes by the addition of different amounts of Cu2+ to the solution, the potential of the polyelectrolyte/R6G complexes in applications as sensing materials is discussed. [Copyright &y& Elsevier]

In the present work, microfibrillated cellulose (MFC) suspensions were produced by high-pressure homogenization and subsequently used to fabricate MFC membranes (C-1) by vacuum filtration followed by hot-pressing. A polyketone (PK50) was chemically modified by Paal-Knorr reaction to graft imidazole (IM) functional groups along its backbone structure. The resulting polymer is referred to as PK50IM80. By solution impregnation, C-1 was immersed in an aqueous solution of PK50IM80 and subsequently hot pressed, resulting in the fabrication of MFC/PK50IM80 composite membranes (C-IMP). Another method, referred to as solution mixing, consisted in adding MFC into an aqueous solution of PK50IM80 followed by vacuum filtration and hot-pressing to obtain MFC/PK50IM80 composite membranes (C-MEZC). C-IMP and C-MEZC were characterized by a wide range of analytical techniques including, X-ray photoelectron spectroscopy, Fourier-transform infrared chemical imaging, scanning electron microscopy, atomic force microscopy, dynamical mechanical analysis, tensile testing as well as streaming zeta potential, and compared to C-1 (reference material). The results suggested that C-IMP possess a more homogeneous distribution of PK50IM80 at their surface compared to C-MEZC. C-IMP was found to possess significantly enhanced Young's modulus compared to C-1 and C-MEZC. The tensile strength of C-IMP was found to improve significantly compared to C-1, whereas C-1 possessed significantly higher tensile index than C-IMP and C-MEZC. Furthermore, the presence of PK50IM80 at the surface of MFC was found to significantly shift the isoelectric point (IEP) of the membranes from pH 2.3 to a maximum value of 4.5 for C-IMP. Above the IEP, C-IMP and C-MEZC were found to possess significantly less negative electrical surface charges (plateau value of −25 mV at pH 10) when compared to C-1 (plateau value of −42 mV at pH 10). Our approach may have implication to broaden the range of filtration applications of MFC-based membranes. • Polyketone (PK50) was modified with imidazole (IM80) by Paal-Knorr reaction. • MFC/PK50IM80 composite membranes were produced by solution impregnation (SI). • FTIR 2D chemical imaging was used to assess PK50IM80 surface distribution. • Membranes with improved tensile mechanical properties were obtained by SI. • PK50IM80 affects the electrical surface charges of the composite membranes. [ABSTRACT FROM AUTHOR]

The association efficiency of oxytetracycline ( OTC) to pharmaceutical available, ionic oil-in-water nanoemulsions is studied. Theoretical mathematical developments allowed us to differentiate by diafiltration ( DF) between thermodynamically and kinetically controlled binding of the drug to the nanoemulsions, and relate these important magnitudes to the association efficiency. The nanoemulsions have been prepared by the solvent displacement technique in the presence of cationic and anionic surfactants. The resulting nanoemulsions were stable at 4°C and 25°C for 60 days, have a size of ∼200 nm, showing polydispersity indexes ranging between 0.11 and 0.23, and present zeta potentials ranging between −90 and +60 mV, depending on the charge of the surfactants used. The zeta potential of the nanoemulsions influenced the interaction with OTC, having three ionic forms at different pH, namely, cationic, zwitterionic, and anionic. DF proved to be a powerful tool for the quantification of the drug association efficiency, achieving values up to 84%. Furthermore, this technique allowed obtaining different values of the drug fractions reversibly bound (11%-57%) and irreversibly bound (10%-40%) to the nanoemulsions depending on the surfactants used and pH. These findings may be useful for the development of new drug delivery systems, and as routine assays in academia and pharmaceutical industries. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 104:1141-1152, 2015 [ABSTRACT FROM AUTHOR]

With the aim of achieving supramolecular structures containing dyes with controlled state of aggregation, the formation of ternary complexes between 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin, poly(decylviologen), and sulfobutylether- β -cyclodextrin at low excess of the cyclodextrin is described. By controlling the stoichiometry of the reactants, both non-fluorescent H-aggregates of the dye and stabilized fluorescent monomers may be obtained. The dye undergoes self-aggregation in the presence of the flexible, cationic polymer, and by addition of the negatively charged cyclodextrin the aggregates are cleaved. The cyclodextrin primarily induces the inclusion of 5,10,15,20-tetrakis-(4-sulfonatophenyl)-porphyrin in its cavity, and the ensemble is stabilized by the polymer by means of electrostatic, hydrophobic, and/or aromatic–aromatic interactions. The ternary complex thus produced tends to nanofiber formation, as seen by FE-TEM. [ABSTRACT FROM AUTHOR]