Interfacial and Micellar Properties of Bolaform Electrolytes

Menger, Fredric M.; Wrenn, Simeon M.

doi:10.1021/j100607a600

Cited by 145 publications

(124 citation statements)

References 8 publications

(8 reference statements)

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“…This is nicely illustrated by a study of ours on bolaform electrolytes at an air-water interface (Ref. 5). A bolaform electrolyte is an organic molecule having two positive or negative sites separated by relatively great distances.…”

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confidence: 60%

Chemistry of interfacial organic processes

Menger¹

1979

Pure and Applied Chemistry

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-This article summarizes our work with (1) reaction mechan~sms at hydrocarbon-water interfaces, (2) the use of emulsifying agents in synthetically useful interfacial systems, (3) the conformations of bolaform electrolytes at air-water interfaces, (4) the analysis of reaction kinetics at micellar surfaces, (5) the rotamer population at a micelle interface, (6) mechanisms of fast proton transfers at a micelle interface, (7) the properties of organic and enzymatic reactions occurring inside water pools, (8) the design of a polymeric reducing agent and (9) the pyrochromatography of structurally related steroids using hot quartz and platinum surfaces in the absence of 0 2 • If people climb mountains because they are there, then chemists study interfaces because they are everywhere.Interfacial processes range from enzymecatalyzed reactions in cells to emulsion polymerizations in vats. Yet interfacial systems have been, relatively speaking, barely touched by the blossoming of physical organic chemistry. Experimental problems are the major cause of this. A heterogeneaus mixture does not provide a spectrum or rate constant as readily as does a homogeneous solution. These, however, who endure the complexities of interfacial systems are rewarded by something not often found with compounds sequestered in solution: molecular order. Whereas the orientation of reactants in solution is usually random, molecules at a phase boundary have well-defined orientations which can impact critically upon their behavior.In this article, I summarize concisely our experiences with liquid-liquid interfaces, interfaces of normal micelles in water, interfaces of inverted micelles in hydrocarbons, and solid-liquid interfaces. For an older but less egocentric account of reactivity at phase boundaries, I refer the reader to a Chemical Society review (Ref. 1). Liquid-Liquid InterfacesOnly a few mechanistic studies have ever been carried out on reactions at a hydrocarbon-water interface. We have probed this type of reaction by stirring rapidly a solution of p-nitrophenyl laurate in heptane with a larger volume of imidazole in water (Ref. 2).Since the ester is insoluble in water and the imidazole is insoluble in the heptane, we hoped that an imidazole-catalyzed hydrolysis would occur at the heptane-water boundary of the dispersed heptane droplets. This expectation was realized as borne out by the following Observations:(1) Partitioning of ester from heptane to water was not detectable by sensitive spectrophotometric methods. Hydrolysis rates are too fast to be explained by minute amounts of ester dissolving into bulk water prior to hydrolysis in that medium.(2) The hydrolysis rate does not change when the chain-length (and presumably water-insolubility) of the ester is increased.(3) Previous work had demonstrated a great sensitivity of colloidal or sub-colloidal esters in water to precipitation by sodium chloride (Ref. 3).If ester hydrolysis occurs only in the bulk water phase of the heptane-water mixture, then addition of salt should drasti...

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confidence: 60%

Chemistry of interfacial organic processes

Menger¹

1979

Pure and Applied Chemistry

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“…Also, the traditional method involving pyrene as a fluorescent probe for hydrophobic environment [23] could not be used, due The contributions from the two phenomena are difficult to separate, making the CAC determination through the Stern-Volmer approach very complicated [25]. An analysis of previous literature shows that in some instances it is not possible to determine a critical micellar concentration (cmc) or a CAC for bolaamphiphilic molecules in solution [26,27].…”

Section: Aqueous Solution Behavior Of [12-bis-tha]cl2mentioning

confidence: 99%

Interaction between a cationic bolaamphiphile and DNA: The route towards nanovectors for oligonucleotide antimicrobials

Mamusa

Resta

Barbero³

et al. 2016

Colloids and Surfaces B: Biointerfaces

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“…Defined "oligomeric" surfactant structures obviously have stimulated the imagination of many colloid chemists, as a number of imaginative names were suggested for them: bola-surfactants [410][411][412], gemini-surfactants [413][414][415], tentacle molecules [416][417], octopus molecules [418], hexapus [419], multiarmed amphiphiles [420][421][422]. .…”

Section: Defined Oligomeric Surfactantsmentioning

confidence: 99%

Molecular concepts, self-organisation and properties of polysoaps

Laschewsky

Polysoaps/Stabilizers/Nitrogen-15 NMR

223

126

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The article reviews water-soluble polymers characterized by surfactant side chains, and related amphiphilic polymers. Various synthetic approaches are presented, and rules for useful molecular architectures are given. Models for the self-organization of such polymers in water are presented comparing them with the micellization of low molecular weight surfactants. Highlighting key properties of aqueous polysoap solutions such as viscosity, surface tension and solubilization power, some structure-property relationships are established. Further, the formation of mesophases and of superstructures in bulk is addressed. Finally, the functionalization of polysoaps, and potential applications are discussed.

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Interfacial and Micellar Properties of Bolaform Electrolytes

Cited by 145 publications

References 8 publications

Chemistry of interfacial organic processes

Chemistry of interfacial organic processes

Interaction between a cationic bolaamphiphile and DNA: The route towards nanovectors for oligonucleotide antimicrobials

Molecular concepts, self-organisation and properties of polysoaps

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