Surface Potentials of Hydrophobic Microdomains in Aqueous Solutions of Poly(dimethyldiallylammonium-co-methyl-n-dodecyldiallylammonium salts) with Different Counterions. Evidence for the Existence of a Critical Aggregation Concentration

The solvatochromic acid-base indicator 1-hexadecyl-4-[(oxocyclohexadienylidene)ethylene]-1,4-dihydropyridine (HOED) was used to determine surface potentials (Y) of micelles formed from methyldiallyl-ndodecylammonium salts containing different counterions (MDDAX, X- = Cl, Br, I, benzoate, salicylate). Y decreased in the order Cl > Br > I > benzoate, salicylate consistent with conductometrically determined values for the counterion binding. HOED was also used to probe the microdomains formed in aqueous solutions of poly(dimethyldiallylammonium-co-methyl-n-dodecyldiallylammonium salts) containing different counterions (Copol C1-12 90/10 X). A similar dependence of Y on the nature of the counterion was found. Raising the temperature led to higher values of Y, while increasing the polysoap concentration appeared to lower the surface potentials for all polysoaps. With the exception of Copol C1-12 90/10 I and Sal, an additional peak in the UV-vis absorption spectrum of the probe was observed which was attributed to the aggregation of probe molecules on nondomain forming strains of the polysoap. Support for this conclusion was obtained from the observation that the intensity of the additional peak greatly decreased upon increasing the polysoap concentration. This behavior can be reconciled with the occurrence of a critical aggregation concentration. The sudden rise of the aggregation numbers of Copol C1-12 90/10 Br and benzoate at ca. 10 mM, leading to a constant value at higher concentrations, provides additional evidence for this conclusion

Synthesis of Hydrophobically and Electrostatically Modified Polyacrylamides and Their Catalytic Effects on the Unimolecular Decarboxylation of 6-Nitrobenzisoxazole-3-carboxylate Anion

A series of hydrophobically and electrostatically modified polyacrylamides (Copol(AM-C12)) has been synthesized by radical-initiated copolymerization of acrylamide with n-dodecylmethyldiallylammonium bromide as the hydrophobe in aqueous solution using ammonium persulfate as the initiator. The formation of hydrophobic microdomains of the copolymers was revealed by large hypsochromic shifts of the longwavelength absorption band of the solvatochromic probe Methyl Orange, noncovalently bound to the macromolecule. It was found that the microdomains formed by these copolymers in aqueous solution are more hydrophobic than those of the cationic polysoaps poly(alkylmethyldiallylammonium halides) containing the same n-dodecyl groups as the side chains as a result of the reduced electrostatic repulsions at the periphery of the microdomains. The reduced cationic character of the copolymers Copol(AM-C12) most likely also accounts for the observation that the anionic dye Methyl Orange does not induce microdomain formation in aqueous solution. The effect of the hydrophobically and electrostatically modified polyacrylamides on the unimolecular decarboxylation of 6-nitrobenzisoxazole-3-carboxylate anion (6-NBIC) has been investigated in aqueous solutions at pH 11.3 and 30 °C. It is suggested that the relatively modest catalytic effects induced by Copol(AM-C12) should be ascribed to hydrogen-bond stabilization of the initial state by NH groups in the macromolecules. The decarboxylation rates of 6-NBIC at binding sites in hydrophobic microdomains increase with increasing n-dodecyl group content in the copolymers.

Scholarship, community formation and book reviews: The Literarisches Centralblatt as arena and meeting place

Book reviews serve multiple functions. They are not only used to assess the merit of individual books but also contribute to the creation and maintenance of scholarly communities. This paper draws on nineteenth-century book reviews to outline three of their features that contributed to the selfdefinition of such communities: the assessment of books, the assessment of authors, and the use of positive and negative politeness strategies to address individual authors as well as a broader audience. The analysis will be based on the book reviews of the German Semitist Theodor Nöldeke and the experimental psychologist Wilhelm Wundt in the Literarisches Centralblatt in the eighteenseventies. In their book reviews they both criticized and praised their peers, which turned review journals like the Centralblatt in arenas for polemic debate as well as meeting places for likeminded scholars. To be more precise, book reviews were used to communicate standards of scholarly excellence, expectations of the character and skills of scholars, and the acknowledgement of the value of the continued existence of aims and interests shared among a large group of academically educated and employed scholars. By contributing to the establishment and maintenance of scholarly peer groups with shared values, book reviews also reinforced the dividing line between academic researchers and lay contributors to their fields.Wiedza, formacja społeczna i recenzje książek: Literarisches Centralblatt jako arena i miejsce spotkań Recenzje książek pełnią wiele funkcji. Służą nie tylko do oceny wartości poszczególnych książek, ale także przyczyniają się do tworzenia i utrzymywania społeczności naukowych. Artykuł ten, opierając się na dziewiętnastowiecznych recenzjach książek, przedstawia trzy ich cechy, które przyczyniły się do samookreślenia się społeczności naukowych: ocena książek, ocena autorów oraz stosowanie pozytywnych i negatywnych strategii uprzejmości w zwracaniu się do poszczególnych autorów a także szerszej publiczności. Analiza będzie oparta na recenzjach książek niemieckiego semitysty Theodora Nöldeke i eksperymentalnego psychologa Wilhelma Wundta w Literarisches Centralblatt z lat 70. XVIII w. W swoich recenzjach książek autorzy zarówno krytykowali, jak i chwalili swoich rówieśników, którzy zamieniali czasopisma przeglądowe, takie jak Centralblatt, na arenę polemicznych debat, a także miejsce spotkań dla podobnie myślących naukowców. Mówiąc ściślej, recenzje książek posłużyły do przekazania standardów doskonałości naukowej, oczekiwań co do charakteru i umiejętności naukowców oraz uznania przez nich wartości dalszego istnienia celów i zainteresowań podzielanych przez dużą grupę osób wykształconych i zatrudnionych uczonych. Przyczyniając się do tworzenia i utrzymywania naukowych grup rówieśniczych o wspólnych wartościach, recenzje książek również wzmocniły linię podziału między badaczami akademickimi a laikami w swoich dziedzinach

MICELLE TO LAMELLAR AGGREGATE TRANSITION OF AN ANIONIC SURFACTANT IN DILUTE AQUEOUS-SOLUTION INDUCED BY ALKALI-METAL CHLORIDE AND TETRAALKYLAMMONIUM CHLORIDE SALTS

Micelles of the anionic surfactant sodium dodecylbenzenesulfonate (NaDoBS) in dilute aqueous solution can be transformed into lamellar aggregates by the addition of alkali metal chloride (LiCl to CsCl) and tetraalkylammonium chloride (alkyl is methyl or n-butyl) salts. Depending on the type of cation, concentration of salt, and isomeric purity of the alkyl chain of the surfactant, different types of phases are observed: large unilamellar vesicles, multivesicular vesicles, and flocculated multilamellar vesicles (lamellar droplets). Over limited concentration ranges, some salts induce phase separation in a surfactant-rich and a surfactant-lean phase. The formation of the different phases was monitored by turbidity and fluorescence depolarization measurements, whereas the phases were characterized by light microscopy, freeze-fracture electron microscopy, and confocal scanning laser microscopy. Thermodynamic aspects of aggregation, in particular the counterion binding characteristics, were studied by microcalorimetry and conductivity. On a molecular level, the packing in a lamellar array can be explained largely in terms of a change in counterion binding and, to a lesser extent, by a decrease of the hydration of the headgroup and the. counterion. A better counterion binding is facilitated by a less hydrated cation or by an increase of the electrolyte concentration. The formation of different types of lamellar aggregates is due to different types of interactions between lamellar layers or between aggregates: largely repulsive for stable dispersions of unilamellar vesicles to attractive down to short distances for the flocculated lamellar droplets

Activity of water in aqueous systems; A frequently neglected property

In this critical review, the significance of the term ‘activity’ is examined in the context of the properties of aqueous solutions. The dependence of the activity of water(ℓ) at ambient pressure and 298.15 K on solute molality is examined for aqueous solutions containing neutral solutes, mixtures of neutral solutes and salts. Addition of a solute to water(ℓ) always lowers its thermodynamic activity. For some solutes the stabilisation of water(ℓ) is less than and for others more than in the case where the thermodynamic properties of the aqueous solution are ideal. In one approach this pattern is accounted for in terms of hydrate formation. Alternatively the pattern is analysed in terms of the dependence of practical osmotic coefficients on the composition of the aqueous solution and then in terms of solute–solute interactions. For salt solutions the dependence of the activity of water on salt molalities is compared with that predicted by the Debye–Hückel limiting law. The analysis is extended to consideration of the activities of water in binary aqueous mixtures. The dependence on mole fraction composition of the activity of water in binary aqueous mixtures is examined. Different experimental methods for determining the activity of water in aqueous solutions are critically reviewed. The role of water activity is noted in a biochemical context, with reference to the quality, stability and safety of food and finally with regard to health science.