Microemulsions are highly versatile reaction media, which currently find many applications. In this review, we shall describe recent trends in the use of microemulsions as organic reaction media, and present models for their functioning, in particular the pseudophase model. This model allows a quantitative explanation of organic reactivity in these microheterogeneous media.
LuisiP.L., and StraubB.E. (eds.). (1984) Reverse micelles.Plenum Press, New York.
2.
PileniM.P. (ed.). (1989) Structure and reactivity in reverse micelles, Elsevier, Amsterdam.
3.
ZulaufM., and EickeH.F. (1979) Inverted micelles and microemulsions in the ternary system water/aerosol-OT/isooctane as studied by photon correlation spectroscopy.J. Phys. Chem., 83, 480–486.
4.
FendlerJ.H. (1987) Atomic and molecular clusters in membrane mimetic chemistry.Chem. Rev., 87, 877–899.
5.
MukerjeeP., and RayA. (1966) The specificity of counterion adsorption to micelles of dodecylpyridinium iodide and their critical concentrations.J. Phys. Chem., 70, 2144–2149.
6.
MukerjeeP., CardinalJ.R., and DesaiN.R. (1977) In: Micellization, solubilization and microemulsions, MittalK.L. (ed.), Plenum Press, New York.
7.
FunasakiN. (1979) Micellar effects on the kinetics and equilibrium of chemical reactions in salt solutions.J. Phys. Chem., 83, 1998–2003.
8.
FernándezM.S., and FromherzP. (1977) Lipoid pH indicators as probes of electrical potential and polarity in micelles.J. Phys. Chem., 83, 1755–1761.
9.
WongM., ThomasJ.K., and GräzelM. (1976) Fluorescence probing of inverted micelles. The state of solubilized water clusters in alkane/diisooctyl sulfosuccinate (aerosol OT) solution.J. Am. Chem. Soc., 98, 2391–2397.
10.
BakaleG., BeckG., and ThomasJ.K. (1981) Electron capture in water pools of reversed micelles.J. Phys. Chem., 85, 1062–1064.
11.
ZinsliP.E. (1979) Inhomogeneous interior of Aerosol OT microemulsions probed by fluorescence and polarization decay.J. Phys. Chem., 83, 3223–3231.
12.
KehE., and ValeurB. (1981) Investigation of water-containing inverted micelles by fluorescence polarization. Determination of size and internal fluidity.J. Colloid. Interface Sci., 79, 465–478.
13.
ThomasJ.K. (1980) Radiation-induced reactions in organized assemblies.Chem. Rev., 80, 283–299.
14.
MarcelW. (1986) Proteins and peptides in water-restricted environments.Proteins: Struct. Funct. Genet., 1, 4–15.
15.
LissiE.A., and EngelD. (1992) Incorporation of n-alkanols in reverse micelles in the AOT/n-heptane/water system.Langmuir, 8, 452–455.
16.
VerhaertR.M.D., and HilhorstR. (1991) Enzymes in reversed micelles. Theoretical analysis of a one-substrate/one-product conversion and suggestions for efficient application.Rec. Trav. Chim. Pays-Bas, 110, 236–2466.
17.
BlandamerJ.M., BurgessJ., and ClarkB. (1983) Enhancement of rates of reaction using neutral water/organic microemulsions as solvent media.J. Chem. Soc., Chem. Commun., 12, 659–660.
18.
HubigS.M., and RodgersM.A.J. (1990) Electron-transfer reactions between viologen radical cations and quinones in AOT reverse micelles studied by electron pulse radiolysis.J. Phys. Chem., 94, 1933–1936.
19.
El-SeoudO.A., Da SilvaM.J., BarburL.P.M., and MartineA. (1977) Kinetics of the reaction of p-nitrophenyl acetate with amines in the presence of dodecylammonium propionate and aerosol-OT aggregates in benzene.J. Chem. Soc., Perkin Trans. 2, 13, 1674–1678.
20.
IzquierdoC., and CasadoJ. (1991) Microemulsions as a medium in chemical kinetics: the persulfate-iodide reaction.J. Phys. Chem., 95, 6001–6004.
21.
MackayR.A. (1981) Chemical reactions in microemulsions.Adv. Colloid. Interface Sci., 15, 131–156.
22.
BuntonC.A. (2005) Micellar charge effects as mechanistic criteria in spontaneous hydrolyses of acid chlorides.J. Phys. Org. Chem., 18, 115–120.
23.
BuntonC.A., GarreffaA., GermaniR., OnoriG., SantucciA., and SavelliG. (2001) Relation between the IR spectrum of water and decarboxylation kinetics in microemulsions.Prog. Colloid Polym. Sci., 118, 103–106.
24.
MackayR.A., and HermanskyC. (1981) Phosphate ester-nucleophile reactions in oil-in-water microemulsions.J. Phys. Chem., 85, 739–744.
25.
O'ConerC.J., FendlerE.J., and FendlerJ.H. (1973) Dramatic rate enhancement of the aquation of the tris(oxalato)chromate(III) anion by surfactant solubilized water in benzene.J. Am. Chem. Soc., 95, 600–602.
26.
MengerF.M., DonohueJ.A., and WilliamsR.F. (1973) Catalysis in water pools.J. Am. Chem. Soc., 95, 286–288.
27.
El-SeoudO.A., SilvaM.J., BarburL.P., and MartinsA. (1978) Kinetics of the reversible hydration of 1,3-dichloroacetone catalyzed by micellar Aerosol-OT in carbon tetrachloride.J. Chem. Soc. Perkin Trans. 2, 331–335.
28.
MartinC.A., McCrannP.M., WardM.D., AngelosG.H., and JaegerD.A. (1984) Reactions in microemulsion media. Nucleophilic substitution reactions of benzyl and p-alkylbenzyl chlorides.J. Org. Chem., 49, 4392–4396.
29.
Gómez-HerreraC., GracianiM.M., MuñozE., MoyáM.L., and SánchezF. (1991) Kinetics of the oxidation of iodide by peroxodisulfate in reverse micelles.J. Coll. Interface Sci., 141, 454–458.
30.
MoyáM.L., IzquierdoC., and CasadoJ. (1992) Microemulsions as a medium in chemical kinetics. II. The iodide + peroxydisulfate and crystal violet + hydroxide reactions in different surfactant/oil/water microemulsions.Int. J. Chem. Kin., 24, 19–30.
31.
MoyáM.L., IzquierdoC., and CasadoJ. (1991) Microemulsions as a medium in chemical kinetics: the persulfate-iodide reaction.J. Phys. Chem., 95, 6001–6004.
32.
LópezP., RodríguezA., Gómez-HerreraC., SánchezF., and MoyáM.L. (1992) Oxidation of hexacyanoferrate(II) by peroxodisulfate in AOT-oil-water microemulsions.J. Chem. Soc. Faraday Trans., 88, 2701–2704.
33.
BlandamerM.J., ClarkB., BurgessJ., and ScottJ.W.M. (1984) Kinetics of reactions involving three organic substrates in microheterogeneous systems.J. Chem. Soc. Faraday Trans. 1, 80, 1651–1655.
34.
ValienteM., and RodenasE. (1991) Reverse cetyltrimethylammonium bromide micelles in alkanols: influence on the basic hydrolysis of crystal violet.J. Phys. Chem., 95, 3368–3370.
35.
TamuraK., and NiiN. (1989) Fluorescence polarization study of Aerosol-OT reversed micelles at high pressures.J. Phys. Chem., 93, 4825–429.
36.
LeisJ.R., MejutoJ.C., and PeñaM.E. (1993) Comparison between the kinetics of the alkaline fading of carbocation dyes in water/sodium bis(2-ethylhexyl) sulfosuccinate/isooctane microemulsions and in homogeneous media.Langmuir, 9, 889–893.
37.
MineroC., and PramauroE. (1988) Electron-transfer reactions in micro-emulsions. Oxidation of benzenediols by hexachloroiridate(IV).Langmuir, 4, 101–105.
38.
RodenasE., and Pérez-BenitoE. (1991) Chromium(VI) oxidation of alkanol components of sodium dodecyl sulfate reverse micelles.J. Phys. Chem., 95(23), 9496–5000.
39.
Da Rocha PereiraR., ZanetteD., and NomeF. (1990) Application of the pseudophase ion-exchange model to kinetics in microemulsions of anionic detergents.J. Phys. Chem., 94, 356–361.
40.
KhmeltnitskyY.L., PolyakovI.N., GrinbergV.Y., LevashovA.V., and MartinekK. (1990) Kinetic theory of enzymatic reactions in reversed micellar systems. Application of the pseudophase approach for partitioning substrates.Eur. J. Biochem., 190, 155–159.
41.
StamatisH., XenakisA., MengeU., and KolisiF.N. (1993) Kinetic study of lipase catalyzed esterification reactions in water-in-oil microemulsions.Biotechnol. Bioeng., 42, 931–937.
42.
StamatisH., XenakisA., DimitriadisE., MengeU., and KolisiF.N. (1995) Catalytic behavior of Pseudomonas cepacia lipase in w/o microemulsions.Biotechnol. Bioeng., 45, 33–41.
43.
LolisisF.N., ValisT.P., and XenakisA. (1990) Lipase-catalyzed esterification of fatty acids in nonionic microemulsions.Ann. New York Acad. Sci., 613, 674–680.
44.
García-RíoL., LeisJ.R., PeñaM.E., and IglesiasE. (1993) Transfer of the nitroso group in water/AOT/isooctane microemulsions: intrinsic and apparent reactivity.J. Phys. Chem., 97, 3437–3442.
45.
García-RíoL., HervésP., MejutoJ.C., Pérez-JusteJ., and Rodríguez-DafonteP. (2003) Pseudophase approach to reactivity in microemulsions: quantitative explanation of the kinetics of the nitroso group transfer reactions between N-methyl-N-nitroso-p-toluenesulfonamide and secondary alkylamines in water/AOT/isooctane microemulsions.Ind. Eng. Chem. Res., 42, 5450–5456.
46.
García-RíoL., LeisJ.R., and MejutoJ.C. (1996) Pseudophase approach to reactivity in microemulsions: quantitative explanation of the kinetics of nitrosation of amines by alkyl nitrites in AOT/isooctane/water microemulsions.J. Phys. Chem., 100, 10981–10988.
47.
García-RíoL., MejutoJ.C., and Pérez-LorenzoM. (2004) Modification of reactivity by changing microemulsion composition. Basic hydrolysis of nitrophenyl acetate in AOT/isooctane/water systems.New J. Chem., 28, 988–995.
48.
García-RíoL., MejutoJ.C., and Pérez-LorenzoM. (2005) Microheterogeneous solvation for aminolysis reactions in AOT-based water-in-oil microemulsions.Chem. Eur. J., 11, 4361–4373.
49.
FernándezE., García-RíoL., MejutoJ.C., and Pérez-LorenzoM. (2005) Michael addition and ester aminolysis in w/o AOT-based microemulsions.New J. Chem., 29, 1594–1600.
50.
García-RíoL., MejutoJ.C., and Pérez-LorenzoM. (2005) Aminolysis reactions by glycine in AOT-based water-in-oil microemulsions.Colloid Surface Sci. A, 270-271, 115–123.
51.
García-RíoL., MejutoJ.C., and Pérez-LorenzoM. (2006) Ester aminolysis by morpholine in AOT-based water-in-oil microemulsions.J. Colloid Interface Sci., 301, 624–630.
52.
García-RíoL., MejutoJ.C., and Pérez-LorenzoM. (2006) First evidence of simultaneous different kinetic behaviors at the interface and the continuous medium of w/o microemulsions.J. Phys. Chem. B, 110, 812–819.
53.
García-RíoL., LeisJ.R., and MoreiraJ.A. (2000) Reactivity in water/oil microemulsions. Influence of sodium bis(2-ethylhexyl)sulfosuccinate/isooctane/water microemulsions on the solvolysis mechanism of substituted benzoyl chlorides.J. Am. Chem. Soc., 122, 10325–10334.
54.
García-RíoL., LeisJ.R., and MejutoJ.C. (2003) Solvolysis of benzoyl halides in AOT/isooctane/water microemulsions. Influence of the leaving group.Langmuir, 19, 3190–3197.
FletcherP.D.I., HoweA.M., and RobinsonB.H. (1987) The kinetics of solubilisate exchange between water droplets of a water-in-oil microemulsion.J. Chem. Soc., Faraday Trans. 1, 83, 985–1006.
57.
RobinsonB.H., SteytlerD.C., and TackR.D. (1979) Ion reactivity in reversed-micellar systems. Kinetics of reaction between micelles containing hydrated nickel(II) and murexide-containing micelles in the system aerosol-OT + water + heptane.J. Chem. Soc., Faraday Trans. 1, 75, 481–496.
58.
ClarkS., FletcherP.D.I., and YeX. (1990) Interdroplet exchange rates of water-in-oil and oil-in-water microemulsion droplets stabilized by pentaoxy-ethylene monododecyl ether.Langmuir, 6, 1301–1309.
59.
JainT.K., CassinG., BadlaliJ.P., and PileniM.P. (1996) Relation between exchange process and structure of AOT reverse micellar system.Langmuir, 12, 2408–2411.
60.
García-RíoL., MejutoJ.C., and Pérez-LorenzoM. (2007) Microemulsions as microreactors in physical organic chemistry.Pure Appl. Chem., 79, 1111–1123.
61.
SilberJ.J., BiasuttiM.A., AbuinE., and LissiE. (1999) Interactions of small molecules with reverse micelles.Adv. Colloid Interface Sci., 82, 189–252.
OnoriG., and SantucciA. (1993) IR investigations of water structure in Aerosol OT reverse micellar aggregates.J. Phys. Chem., 97, 5430–5434.
65.
TemsamaniM.B., MaeckM., El HassaniI., and HurwithH.D. (1998) Fourier transform infrared investigation of water states in aerosol-OT reverse micelles as a function of counterionic nature.J. Phys. Chem. B, 102, 3335–3340.
66.
FioretoD., FredaM., MannaioliS., and OnoriG. (1999) Santucci, A. Infrared and dielectric study of Ca(AOT)2 reverse micelles.J. Phys. Chem. B, 103, 2631–2635.
67.
DeT.K., and MaitraA. (1995) Solution behavior of Aerosol OT in non-polar solvents.Adv. Colloid Interface Sci., 59, 95–193.
68.
KuriharaK., KizlingJ., SteniusP., and FendlerJ.H. (1983) Laser and pulse radiolytically induced colloidal gold formation in water and in water-in-oil microemulsions.J. Am. Chem. Soc., 105, 2574–2579.
69.
PetitC., LixonP., and PileniM.P. (1993) In situ synthesis of silver nanocluster in AOT reverse micelles.J. Phys. Chem., 97, 12974–12983.
70.
KortanA.R., HullR., OpilaR.L., BawendiM.G., SteigerwaldM.L., CarrollP.J., and BrusL.E. (1990) Nucleation and growth of cadmium selenide on zinc sulfide quantum crystallite seeds, and vice versa, in inverse micelle media.J. Am. Chem. Soc., 112, 1327–1332.
71.
HaramS.K., MahadeshwarA.R., and DixitS.G. (1996) Synthesis and characterization of copper sulfide nanoparticles in Triton-X 100 water-in-oil microemulsions.J. Phys. Chem., 100, 5868–5873.
72.
AyyubP., MaitraA.N., and ShahD.O. (1990) Formation of theoretical-density microhomogeneous yttrium barium copper oxide (YBa2Cu3O7-x) using a microemulsion-mediated process.Phys. C, 168, 571–579.
73.
JoselevichE., and WillnerI. (1994) Photosensitization of Quantum-Size TiO2 Particles in water-in-oil microemulsions.J. Phys. Chem., 98, 7628–7635.
74.
ChangC.L., and FoglerH.S. (1997) Controlled formation of silica particles from tetraethyl orthosilicate in nonionic water-in-oil microemulsions.Langmuir, 13, 3295–3307.
75.
FernándezE., García-RíoL., MejutoJ.C., and Pérez-LorenzoM. (2007) Evidence for compartmentalization of reagents in w/o microemulsions.Coloids Surf. A, 295, 248–287.
76.
FernándezE., García-RíoL., MejutoJ.C., and Pérez-LorenzoM. (2006) Modification of crystal violet - sulfite ion equilibrium induced by SDS micelles.J. Chem. Res., 1, 52–55.
