Surfactant hydrogen-bonding interactions

Breslow studied the dimerisation of cyclopentadiene and the reaction between substituted maleimides and 9-(hydroxymethyl)anthracene in alcohol-water mixtures. He successfully correlated the rate constant with the solubility of the starting materials for each Diels-Alder reaction. From these relations he estimated the change in solvent accessible surface between initial state and activated complex " . Again, Breslow completely neglects hydrogen bonding interactions, but since he only studied alcohol-water mixtures, the enforced hydrophobic interactions will dominate the behaviour. Recently, also Diels-Alder reactions in dilute salt solutions in aqueous ethanol have been studied and minor rate increases have been observed Lubineau has demonstrated that addition of sugars can induce an extra acceleration of the aqueous Diels-Alder reaction . Also the effect of surfactants on Diels-Alder reactions has been studied. This topic will be extensively reviewed in Chapter 4. 

AOT is an anionic surfactant complexed to the counterion, usually sodium. The water molecules in the intramicellar water pool are either free or bound to the interface. The bound water can interact with various parts of the surfactant. These interactions include hydrogen-bonding interactions with oxygen molecules on the sulfonate and succinate groups, ion-dipole interactions with the anionic surfactant headgroup and counterion, dipole-dipole interactions with the succinate group, and dispersive forces with the hydrocarbon tails. 

One of the most important characteristics of micelles is their ability to enclose all kinds of substances. Capture of these compounds in micelles is generally driven by hydrophobic, electrostatic and hydrogen-bonding interactions. The dynamics of solubilization into micelles are similar to those observed for entrance and exit of individual surfactant molecules, but the micelle-bound substrate will experience a reaction environment different from bulk water, leading to kinetic medium effects308. Hence, micelles are able to catalyse or inhibit reactions. The catalytic effect on unimolecular reactions can be attributed exclusively to the local medium effect. For more complicated bimolecular or higher-order reactions, the rate of the reaction is affected by an additional parameter the local concentrations of the reacting species in or at the micelle. 

The measurement of the surface tension of SDS solutions at constant polymer additions was performed to investigate any possible interactions between SDS and the polymers used in these experiments. The results, shown in Figure 2, indicate no interaction between SDS and either PAA or PAM. Interactions between similarly charged surfactant and polyelectrolyte are not common as electrical effects frequently dominate to prevent any hydro-phobic or hydrogen bonding interaction. The hydrophilic nature of the amide dipole of polyacrylamides has been suggested (11) as a possible factor in preventing interaction with sodium dodecylsulfate,... 

A possible mechanism of the ammonia hydrothermal treatment for the acid-made sample is shown below. The predominant interaction between the silica wall and the surfactant of the acid-made products is the weak hydrogen bond interaction through an intermediate counterion (i.e. N03). Such weaker interaction eases the removals of organic template by hot water or organic solvent [6], Thus, when the acid-made materials are subjected to the ammonia hydrothermal treatment, the interactions between the surfactant and silicate framework would be transformed as ... 

PEO, EO ) hydrophilic headgroup. Through the proposed neutral N°I° assembly pathway, worm-like disordered mesoporous silica or amorphous silica are formed using nonionic PEO surfactants or triblock copolymers. The low structural order may be related to the absence of sufficiently strong electrostatic or hydrogen-bonding interactions. 

Li et al. [51] prepared monodisperse microspheres by distillation precipitation polymerization of DVB and NIPAM with 2,2-azobisisobutyronitrile (AIBN) as initiator in acetonitrile, in the absence of any surfactant. Next, latex particles of poly(EGDMA-co-AA) were assembled onto the microspheres to afford a corecorona composite polymer particle with a raspberry-like morphology, strengthened by hydrogen-bonding interaction. 

Wu and coworkers studied the silica-nanoparticle-stabilized emulsion polymerization of vinyl acetate, with the aid of a small amount of anionic reactive surfactant, 3-allyloxy-2-hydroxy-l-propanesulfonicacid sodium salt (HAPS) [118]. They argued that hydrogen bond interactions allowed for strong adhesion, and also commented on the mechanism of solids-stabilized emulsion polymerization. 

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