Chloride transport by a series of steroid-based "cholapod" receptors/carriers was studied in vesicles. The principal method involved preincorporation of the cholapods in the vesicle membranes, and the use of lucigenin fluorescence quenching to detect inward-transported Cl − . The results showed a partial correlation between anion affinity and transport activity, in that changes at the steroidal 7 and 12 positions affected both properties in concert. However, changes at the steroidal 3-position yielded irregular effects. Among the new steroids investigated the bis-p-nitrophenylthiourea 3 showed unprecedented activity, giving measurable transport through membranes with a transporter/lipid ratio of 1:250 000 (an average of <2 transporter molecules per vesicle). Increasing transporter lipophilicity had no effect, and positively charged steroids had low activity. The p-nitrophenyl monourea 25 showed modest but significant activity. Measurements using a second method, requiring the addition of transporters to preformed vesicle suspensions, implied that transporter delivery was problematic in some cases. A series of measurements employing membranes of different thicknesses provided further evidence that the cholapods act as mobile anion carriers.
Crystal tuning: Organic molecules can be xenophobic, preferring to crystallize with their own kind. Though useful for purification, this precludes the tuning of crystal properties by doping or mixing. Nanoporous steroids provide an exception, as their channels can accept a variety of termini (hexagons and spheres). The steroids can be cocrystallized in any ratio to give a wide range of chiral, potentially porous crystalline materials.
Cholapod anion receptors can achieve high affinities while maintaining compatibility with nonpolar media. Previously they have been shown to transport anions across cell and vesicle membranes. In the present work, the scope of the architecture is expanded and structure-selectivity relationships are investigated. Eight new receptors have been synthesized, with up to six H-bond donor centers. Using Cram's extraction method, these compounds plus five known examples have been tested for binding to seven monovalent anions (tetraethylammonium salts, wet chloroform as solvent). Association constants in excess of 10(10) M(-1) have been measured for several pairings. Selectivities vary with receptor geometry, as expected. More remarkably, they also depend on receptor strength: more powerful receptors show a wider range of binding free energies, and therefore a greater spread of Ka(X-)/Ka(Y-). This "affinity-selectivity" effect can be derived from empirical relationships for H-bond strengths, and could prove widely operative in supramolecular chemistry.
Like the first edition, this edition of Analysis of Surfactants covers the determination and characterization of commercially important surfactants as well as a variety of evaluation procedures and specifications. The sections on molecular spectroscopy have been expanded and the chapter on titrations was revised in this edition to include new developments. A new chapter on capillary electrophoresis was also added, as were sections on other surfactants, such as carboxylate and ester quats. This book is extensive in its coverage of the literature and contains over 2400 references.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.