Imidazolium-based zwitterionic surfactants: characterization of normal and reverse micelles and stabilization of nanoparticles.

This paper presents the physicochemical properties of micellar aggregates formed from a series of zwitterionic surfactants of the type 3-(1-alkyl-3-imidazolio)propane-sulfonate (ImS3-n), with n = 10, 12, 14, and 16. The ImS3-n dipolar ionic surfactants represent a versatile class of dipolar ionic compounds, which form normal and reverse micelles. Furthermore, they are able to stabilize nanoparticles in water and in organic media. Aqueous solubility is too low at room temperature to allow characterization of micellar aggregates but increases with addition of salts, allowing determination of aggregation number and cmc. As expected, these parameters depend on the length of the alkyl chain, and cmc values follow Klevens equation. In the presence of NaClO4, all ImS3-n micelles become anionoid by incorporating ClO4(-) on the micellar interface. A special feature of these surfactants is the ability to form reverse micelles and solubilize copious amounts of saline solutions in chloroform. (1)H NMR and infrared spectroscopic evidence showed that the maximum water to surfactant molar ratio w0 achievable depends on the concentration and type of salt dissolved. Reverse micelles of the ImS3-n surfactants can be used to stabilize metallic nanoparticles, whose size may be tuned by the amount of water dissolved.

Imidazolium-based zwitterionic surfactant: a new amphiphilic Pd nanoparticle stabilizing agent.

Palladium nanoparticles (NPs) with an average size of 3.4 nm were prepared in water using imidazolium-based surfactant 3-(1-dodecyl-3-imidazolio)propanesulfonate (ImS3-12) as a stabilizer. The Pd NPs are highly dispersible in water and chloroform and were characterized by transmission electron microscopy, energy-dispersive X-ray spectroscopy, powder X-ray diffraction, and dynamic light scattering. The results indicate that in water the NP surface is covered with a double layer of ImS3-12 molecules. The NPs were effective in the aqueous biphasic hydrogenation of cyclohexene, with easy recycling and no loss of catalytic activity after four successive runs.

The chameleon-like nature of zwitterionic micelles: effect of cation binding.

Addition of salts, especially perchlorates, to zwitterionic micelles of SB3-14, C(14)H(29)NMe(2)(+)(CH(2))(3)SO(3)(-), induces anionic character and uptake of H(3)O(+) by SB3-14 micelles. Thus, the addition of alkali metal perchlorates accelerates the acid hydrolysis of 2-(p-heptoxyphenyl)-1,3-dioxolane, HPD, in the presence of SB3-14 micelles, which depends on the local proton concentration at the micelle surface. The addition of metal chlorides to solutions of such perchlorate-modified SB3-14 micelles decreases both the negative zeta potential of the micelles and the observed rate constant for acid hydrolysis of HPD. The effect of the monovalent cations Li(+), Na(+), and K(+) is smaller than that of the divalent cations Be(2+), Mg(2+), and Ca(2+), and much smaller than that of the trivalent cations Al(3+), La(3+), and Er(3+). The major factor responsible for this cation valence dependence of these effects is shown to be electrostatic in nature, reflecting the strong dependence of the micellar surface potential on the cation valence. The fact that the salt effects are not identical after correction for the electrostatic effects indicates that additional secondary nonelectrostatic effects may contribute as well.

GPx-Like activity of selenides and selenoxides: experimental evidence for the involvement of hydroxy perhydroxy selenane as the active species.

The reaction mechanism of the GPx-like oxidation of PhSH with H(2)O(2) catalyzed by selenoxides proceeds via formation of the hydroxy perhydroxy selenane, which is a stronger oxidizing agent than selenoxide. A hydroxy perhydroxy selenane intermediate was observed by electrospray ionization mass spectrometry and (77)Se NMR spectroscopy in reactions of selenoxide 8 with H(2)O(2).The initial velocity of oxidation of PhSH by H(2)O(2) with selenoxide 8 is 4 orders of magnitude higher than that of 8 without peroxide. Selenoxide 8 is not reduced to selenide 6 by PhSH in the presence of H(2)O(2). While electronic substituent effects have minimal impact on the catalytic performance of selenoxides, chelating groups increase the rate of catalysis.

Synthesis of a new zwitterionic surfactant containing an imidazolium ring. Evaluating the chameleon-like behavior of zwitterionic micelles.

Synthesis of a new zwitterionic surfactant containing the imidazolium ring 3-(1-tetradecyl-3-imidazolio)propanesulfonate (ImS3-14) is described. The solubility of ImS3-14 is very low but increases on addition of a salt which helps to stabilize the micellized surfactant. Fluorescence quenching and electrophoretic evidence for ImS3-14 shows that the micellar aggregation number is only slightly sensitive to added salts, as is the critical micelle concentration, but NaClO(4) markedly increases zeta potentials of ImS3-14 in a similar way as in N-tetradecyl-N,N-dimethylammonio-1-propanesulfonate (SB3-14) micelles. The rate of specific hydrogen ion catalyzed hydrolysis of 2-(p-heptoxyphenyl)-1,3-dioxolane and equilibrium protonation of 1-hydroxy-2-naphthoate ion in zwitterionic micelles of ImS3-14 and SB3-14 are increased markedly by NaClO(4) which induces anionoid character and uptake of H(3)O(+), but NaCl is much less effective in this respect. Comparison of ImS3-14 with SB3-14 is based on experimental evidence, and computational calculations indicate similarities and differences in structures of both compounds.

Efficient intramolecular general-acid catalysis of the reactions of alpha-effect nucleophiles and ammonia oxide with a phosphate triester.

The S(N)2(P) reactions with alpha-effect nucleophiles of the cationic form 1.H(+) of phosphate triester diethyl 8-(N,N-dimethylamino)-1-naphthyl phosphate are catalyzed by the neighboring dimethylammonium group, with accelerations as high as 10(6). Hydroxylamine and its N-methyl and N,N-dimethyl derivatives, which react through oxygen, we presume by way of the zwitterionic ammonia oxide tautomers, are of special interest. The alpha-effect and the efficient general-acid catalysis in this system are mutually reinforcing. The alpha-effect is greater for the reactions of the triester than for the corresponding mono- and diesters and qualitatively different for hydroxylamines RR'NOH, where the likely role of the ammonia oxide tautomer NH(3)(+)-O(-) is evaluated by ab initio calculations. The initial phosphorus-containing product NH(2)OPO(OEt)(2) reacts further with hydroxylamine to generate diethyl phosphate and diimide, identified by its disproportionation to hydrazine and N(2) and its reducing potential.

The chameleon-like nature of zwitterionic micelles: the intrinsic relationship of anion and cation binding in sulfobetaine micelles.

The rate of specific hydrogen ion-catalyzed hydrolysis of 2-( p-heptoxyphenyl)-1,3-dioxolane and acid-base equilibrium of 4-carboxy-1-n-dodecylpyridinium in zwitterionic micelles of SB3-14, C14H29NMe2+(CH2)3SO3(-) are controlled by NaClO4, which induces anionic character and uptake of H3O+ in the micelles. Other salts, e.g., NaF, NaCl, NaBr, NaNO3, NaI, NaBF4, have similar, but smaller, effects on the uptake of H3O+. Salt effects upon zeta potentials of SB3-14 micelles, estimated by capillary electrophoresis, are anion specific, and the anion order is similar to that of the rates of acid hydrolysis and of acid-base equilibria. Fluorescence quenching shows that the micellar aggregation number is not very sensitive to added salts, consistent with electrophoretic evidence. These specific anion effects follow the Hofmeister series and are related to anion hydration free energies.

The chameleon-like nature of zwitterionic micelles. Control of anion and cation binding in sulfobetaine micelles. Effects on acid equilibria and rates.

The rate of specific hydrogen ion catalyzed hydrolysis of 2-(p-heptoxyphenyl)-1,3-dioxolane and equilibrium protonation of 1-hydroxy-2-naphthoate ion in zwitterionic micelles of SB3-14, C14H29NMe2+(CH2)3SO3-, are increased markedly by NaClO4 which induces anionic character and uptake of H3O+ in the micelles. Other salts, for example, NaNO3, NaBr, and NaCl, have similar but much smaller effects on this uptake of H3O+.

Modeling protic to dipolar aprotic solvent rate acceleration and leaving group effects in S(N)2 reactions: A theoretical study of the reaction of acetate ion with ethyl halides in aqueous and dimethyl sulfoxide solutions.

The S(N)2 reactions between acetate ions and ethyl chloride, ethyl bromide, and ethyl iodide in aqueous and dimethyl sulfoxide (DMSO) solutions were theoretically investigated at an ab initio second-order Møller-Plesset perturbation level of theory for geometry optimizations and at a fourth-order Møller-Plesset perturbation level for energy calculations. The solvent effect was included by the polarizable continuum model using the Pliego and Riveros parametrization for DMSO and the Luque et al. scale factor for the water solution. The calculated DeltaG() values of 24.9, 20.0, and 18.5 kcal mol(-1) in a DMSO solution for ethyl chloride, ethyl bromide, and ethyl iodide are in good agreement with the estimated experimental values of 22.3, 20.0, and 16.6 kcal mol(-1), respectively. In an aqueous solution, the theoretical Delta G++ barriers of 26.9, 23.1, and 22.1 kcal mol(-1) are also in good agreement with the estimated experimental values of 26.1, 25.2, and 24.7 kcal mol(-1), respectively. The present ab initio calculations are reliable to predict the absolute and relative reactivities of ethyl halides in a DMSO solution, but in the aqueous phase, the results are less accurate. The protic to dipolar aprotic solvent rate acceleration is theoretically predicted, although this effect is underestimated. We suggest that further improvement of the present results could be obtained by including liquid-phase optimization in both solvents and treating specific solvation by water molecules for the reaction in the aqueous phase.