Photophysics and locations of IR125 and C152 in AOT reverse micelles

Many fluorescent chromophores have been employed to investigate the nature and dynamics of the water confined in reverse micelles (RMs). However, some questions remain as to the location of a probe in a RM and the diameter of the RM at which the physical characteristic of the water inside RMs becomes similar to that of bulk water. In this work, we systematically studied the photophysics of IR125 and C152 in AOT RMs at different w(0) by means of static absorption and fluorescence spectroscopy as well as time-resolved fluorescence spectroscopy. We obtained the absorption maxima, fluorescence emission maxima, fluorescence lifetime, and reorientation time of IR125 and C152 in AOT RMs at corresponding w(0). We found that all obtained photophysical parameters of IR125 and C152 in AOT RMs as a function of w(0) have a distinct changeover point around w(0) = 8, indicating that there is a dramatic change in the nature of the water confined in AOT RMs around w(0) = 8. The observed changeover point around w(0) = 8 is well in agreement with the Satpati's report (ChemPhysChem, 2009, 10, 2966). In addition, we observed that the measured reorientation time of IR125 in AOT RMs increases with the increase of w(0), which is opposite to the trend of change in the measured reorientation time of C152 in AOT RMs with the increase of w(0). We found that IR125 prefers to reside in the water pool of AOT RMs and that C152 prefers to reside in the outer side of the interfacial region or the nonpolar n-heptane phase of AOT RMs. Furthermore, we found that the time-resolved fluorescence anisotropy of IR125 in smaller w(0) AOT RMs primarily measures the reorientation of RMs and the time-resolved fluorescence anisotropy of IR125 in larger w(0) AOT RMs measures the reorientation of IR125 in the water pool confined in RMs. This work demonstrated that IR125 is an excellent probe to study the nature and dynamics of the water confined in AOT RMs.     

Fourier transform infrared spectroscopy of azide and cyanate ion pairs in AOT reverse micelles

Evidence for ion pair formation in aqueous bis(2-ethylhexyl) sulfosuccinate (AOT) reverse micelles (RMs) was obtained from infrared spectra of azide and cyanate with Li(+), Na(+), K(+), and NH(4)(+) counterions. The anions' antisymmetric stretching bands near 2000 cm(-1) are shifted to higher frequency (blueshifted) in LiAOT and to a lesser extent in NaAOT, but they are very similar to those in bulk water with K(+) and NH(4)(+) as the counterions. The shifts are largest for low values of w(o) = [water]/[AOT] and approach the bulk value with increasing w(o). The blueshifts are attributed to ion pairing between the anions and the counterions. This interpretation is reinforced by the similar trend (Li(+)>Na(+)>K(+)) for producing contact ion pairs with the metal cations in bulk dimethyl sulfoxide (DMSO) solutions. We find no evidence of ion pairs being formed in NH(4)AOT RMs, whereas ammonium does form ion pairs with azide and cyanate in bulk DMSO. Studies are also reported for the anions in formamide-containing AOT RMs, in which blueshifts and ion pair formation are observed more than in the aqueous RMs. Ion pairs are preferentially formed in confined RM systems, consistent with the well established ideas that RMs exhibit reduced polarity and a disrupted hydrogen bonding network compared to bulk water and that ion-specific effects are involved in mediating the structure of species at interfaces.     

Effect of the Cationic Surfactant Moiety on the Structure of Water Entrapped in Two Catanionic Reverse Micelles Created from Ionic Liquid‐Like Surfactants

The behavior of water entrapped in reverse micelles (RMs) formed by two catanionic ionic liquid‐like surfactants, benzyl‐n‐hexadecyldimethylammonium 1,4‐bis‐2‐ethylhexylsulfosuccinate (AOT‐BHD) and cetyltrimethylammonium 1,4‐bis‐2‐ethylhexylsulfosuccinate (AOT‐CTA), was investigated by using dynamic (DLS) and static (SLS) light scattering, FTIR, and ¹H NMR spectroscopy techniques. To the best of our knowledge, this is the first report in which AOT‐CTA has been used to create RMs and encapsulate water. DLS and SLS results revealed the formation of RMs in benzene and the interaction of water with the RM interface. From FTIR and ¹H NMR spectroscopy data, a difference in the magnitude of the water–catanionic surfactant interaction at the interface is observed. For the AOT‐BHD RMs, a strong water–surfactant interaction can be invoked whereas for AOT‐CTA this interaction seems to be weaker. Consequently, more water molecules interact with the interface in AOT‐BHD RMs with a completely disrupted hydrogen‐bond network, than in AOT‐CTA RMs in which the water structure is partially preserved. We suggest that the benzyl group present in the BHD⁺ moiety in AOT‐BHD is responsible for the behavior of the catanionic interface in comparison with the interface created in AOT‐CTA. These results show that a simple change in the cationic component in the catanionic surfactant promotes remarkable changes in the RMs interface with interesting consequences, in particular when using the systems as nanoreactors.     

Inhibited phenol ionization in reverse micelles: confinement effect at the nanometer scale

We found that the absorption spectra of 2-acetylphenol (2-HAP), 4-acetylphenol (4-HAP), and p-nitrophenol (p-NPh) in water/sodium 1,4-bis(2-ethylhexyl)sulfosuccinate (AOT)/n-heptane reverse micelles (RMs) at various W(0) (W(0) = [H(2)O]/[surfactant]) values studied changed with time if (-)OH ions were present in the RM water pool. There is an evolution of ionized phenol (phenolate) bands to nonionized phenol absorption bands with time and this process is faster at low W(0) values and with phenols with higher bulk water pK(a) values. That is, in bulk water and at the hydroxide anion concentration used, only phenolate species are observed, whereas in AOT RMs at this fixed hydroxide anion concentration, ionized phenols convert into nonionized phenol species over time. Furthermore, we demonstrate that, independent of the (-)OH concentration used to prepare the AOT RMs, the nonionized phenols are the more stable species in the RM media. We explain our results by considering that strong hydrogen-bonding interactions between phenols and the AOT polar head groups result in the existence of only nonionized phenols at the AOT RM interface. The situation is quite different when the phenols are dissolved in cationic benzyl-n-hexadecyldimethylammonium chloride RMs. Therein, only phenolates species are present at the (-)OH concentrations used. The results clearly demonstrate that the classical definition of pH does not apply in a confined environment, such as in the interior of RMs and challenge the general idea that pH can be determined inside RMs.     

Photodetachment of ferrocyanide in reverse micelles

Solvated electrons have been generated in reverse micelles (RMs) through photodetachment of ferrocyanide (Fe(CN)(6)(4-)) in sodium bis(2-ethylhexyl) sulfosuccinate (AOT) RMs. We have measured both bleach recovery of the parent ferrocyanide CN stretch in the infrared and the decay of the solvated electron absorption at 800 nm. The bleach recovery has been fit to a diffusion model for the geminate recombination process. The fit parameters suggest a narrowing of the spatial distribution of ejected electrons due to confinement in the RMs when compared to bulk water. The diffusion coefficient of the solvated electron does not appear to be significantly affected by RM confinement. The decay of the solvated electron absorption exhibits an additional decay component that is not observed in bulk water and is smaller for larger RMs. No corresponding additional component is seen in the parent ferrocyanide IR bleach recovery, which supports our interpretation that the confinement-induced new decay process in RMs is due to electrons reacting with AOT headgroups.     

Physicochemical investigation of the solubilization of cobalt nitrate in sodium bis(2-ethylhexyl)sulfosuccinate reversed micelles

A wide investigation of the solubilization of the water-soluble salt Co(NO₃)₂ in water/sodium bis(2-ethylhexyl)sulfosuccinate (AOT)/n-heptane microemulsions and of some physicochemical properties of the Co(NO₃)₂/AOT/n-heptane and Co(NO₃)₂/AOT systems has been carried out. After saturation of water/AOT/n-heptane microemulsions with pure Co(NO₃)₂, the Co(NO₃)₂/AOT composites were prepared by complete evaporation under vacuum of the volatile components (water and apolar solvent) of the salt-containing microemulsions. It was observed that these composites could be totally dissolved in pure n-heptane, allowing the solubilization of a noticeable amount of Co(NO₃)₂ in a dry apolar organic solvent. By UV-vis-near-IR spectrophotometry, some information on the state of Co(NO₃)₂ within water-containing or dry AOT reversed micelles was acquired, whereas by small-angle X-ray scattering it the occurrence of small nanoparticles in the salt-containing dry AOT reversed micelles was ascertained. Surprisingly, the analysis of the X-ray diffraction spectra corroborated by UV-vis and X-ray photoelectron spectroscopy data of Co(NO₃)₂/AOT composites led to the hypothesis that nanoparticles are mainly constituted of sodium nitrate resulting from the metathesis reaction between AOT and Co(NO₃)₂. By transmission electron microscopy, information on the size and the size distribution of the nanoparticles in salt/AOT composites was gained.     

Vibrational relaxation of azide in formamide reverse micelles

Static and ultrafast infrared spectroscopy have been used to measure absorption spectra and vibrational energy relaxation (VER) times for the antisymmetric stretching vibrational band of azide, N(3)(-), in formamide-containing reverse micelles (RMs). RMs were formed in n-heptane using the surfactant AOT, sodium bis(2-ethylhexyl) sulfosuccinate. The VER times were found to be significantly longer than in bulk formamide. The VER times became longer as the molar ratio of formamide to AOT, omega(F), was decreased. Decreasing omega(F) also resulted in substantial blue shifts of the azide static absorption band compared to the frequency in bulk formamide. The omega(F) dependent studies are consistent with expected size trends, where a larger RM results in more bulklike polar solvent and faster VER rates. These results are in contrast to aqueous AOT RMs where VER times were indistinguishable from those in the bulk and the static spectral shifts were much smaller. The differences between the static and dynamic behavior in aqueous and formamide RMs are related to differences in structural changes upon confinement in RMs.     

Nanometer particles synthesis in reverse micelles: Influence of the size and the surface on the reactivity

In this paprr we are presenting the synthesss “in situ” of nanoparticles in reverse micelles. In the case of aggregates containing copper ions, it is possible to form metallic particles surrounded or not by an oxide layer. By mixing aggregates containing cadmium and sulphide ions, CdS particles are formed. The size and polydispersity of the particles are controlled. The photoelectron transfer reaction depends mainly on the surface composition. In the range of 1 to 5 nm, the efficiency in the electron transfer does not depend on the size of the particle. The reverse micelles are formed by using either sodium di(2-ethyl hexyl)sulfosuccinate, usually called {AOT} or mixed bivalent and sodium di(2-ethyl hexyl)sulfosuccinate {AOl/M(AOT)₂}.     

Influence of heterogeneity of confined water on photophysical behavior of acridine with amines: a time-resolved fluorescence and laser flash photolysis study

The photophysical behavior of acridine (Acr) shows facilitated water-assisted protonation equilibrium between its deprotonted (Acr* ～ 10 ns) and protonated forms (AcrH(+*) ～ 28 ns) within confined region of ordered water molecules inside AOT/H(2)O/n-heptane reverse micelles (RMs). The time-resolved-area-normalized-emission spectra confirm both Acr* and AcrH(+*), while time-resolved-emission spectra depict time evolution between them. Quenching of AcrH(+*) with N,N-dimethylaniline (DMA) is a purely diffusion-controlled bimolecular quenching with linear Stern-Volmer (S-V) plot, while nonlinearity arises with triethylamine (TEA) that forms ground state complex with AcrH(+) (AcrH(+)··H(2)O··TEA) indicating both static and dynamic quenching. Transient intermediates, DMA(?+) and AcrH(?) infer photoinduced electron transfer from DMA to Acr, while those from AcrH(+)··H(2)O··TEA complex suggest water mediated excited-state proton transfer (ESPT) between AcrH(+) and TEA. The ESPT becomes faster in larger RMs due to enhanced mobility of hydronium ions in AcrH(+)··H(2)O··TEA, which reduces in smaller RMs as water becomes much more constrained owing to stronger complexation by excess confinement.     

Effect of Confinement on the Properties of Sequestered Mixed Polar Solvents: Enzymatic Catalysis in Nonaqueous 1,4‐Bis‐2‐ethylhexylsulfosuccinate Reverse Micelles

The influence of different glycerol, N,N‐dimethylformamide (DMF) and water mixtures encapsulated in 1,4‐bis‐2‐ethylhexylsulfosuccinate (AOT)/n‐heptane reverse micelles (RMs) on the enzymatic hydrolysis of 2‐naphthyl acetate by α‐chymotrypsin is demonstrated. In the case of the mixtures with DMF and protic solvents it has been previously shown, using absorption, emission and dynamic light‐scattering techniques, that solvents are segregated inside the polar core of the RMs. Protic solvents anchor to the AOT, whereas DMF locates to the polar core of the aggregate. Thus, DMF not only helps to solubilize the hydrophobic substrate, increasing its effective concentrations but surprisingly, it does not affect the enzyme activity. The importance of ensuring the presence of RMs, encapsulation of the polar solvents and the corrections by substrate partitioning in order to obtain reliable conclusions is highlighted. Moreover, the effect of a constrained environment on solvent–solvent interactions in homogenous media and its impact on the use of RMs as nanoreactors is stressed.     

Thermochemical study of silver halide nanoparticles formation conditions in AOT inverted micelles

AgCl and AgBr nanoparticles formation conditions were studied by a thermochemical method in AOT (sodium bis(2-ethylhexyl)sulfosuccinate) inverted micellar systems, in AOT—dioctyl sulfide (DOS) mixed micelles, and (for comparison) in aqueous solutions. The heats of formation of AgCl and AgBr nanoparticles in AOT micelles in exchange reactions with potassium halides are, respectively, −55.5 × (1 ± 0.07) and −68.6 × (1 ± 0.07) kJ/mol, that is, smaller in magnitude than the values obtained for aqueous solutions (−68 × (1 ± 0.07) and −88 × (1 ± 0.07) kJ/mol). This difference arises from the existence of particle interactions causing the formation of coagulation contacts between halide particles followed by precipitation in an aqueous phase and the absence of such interactions in a micellar medium. DOS interacts with AOT (to form mixed micelles) and with silver ions (in long-term contact), thus reducing the heats of reactions.     

New insights on the photophysical behavior of PRODAN in anionic and cationic reverse micelles: from which state or states does it emit?

6-propionyl-2-(N,N-dimethyl)aminonaphtahalene, PRODAN, is widely used as a fluorescent molecular probe because of its significant Stokes shift in polar solvents. It is an aromatic compound with intramolecular charge-transfer states (ICT) that can be particularly useful as a sensor. The nature of the emissive states has not yet been established despite the detailed experimental and theoretical investigations done on this fluorophore. In this work, we performed absorption, steady-state, time-resolved fluorescence (TRES) and time-resolved area normalized emission (TRANES) spectroscopies on the molecular probe PRODAN in the anionic water/sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT)/n-heptane and the cationic water/benzyl-n-hexadecyl dimethylammonium chloride (BHDC)/benzene reverse micelles (RMs). The experiments were done by varying the surfactant concentrations at a fixed molar ratio (W = [H2O]/[Surfactant]) and changing the water content at a constant surfactant concentration. The results obtained varying the surfactant concentration at W = 0 show a bathochromic shift and an increase in the intensity of the PRODAN emission band due to the PRODAN partition process between the external solvent and the RMs interface. The partition constants, Kp, are quantified from the changes in the PRODAN emission spectra and the steady-state anisotropy () with the surfactant concentration in both RMs. The Kp value is larger in the BHDC than the AOT RMs, probably due to the interaction between the cationic polar head of the surfactant and the aromatic ring of PRODAN. The partition process is confirmed with the TRES experiments, where the data fit to a continuous model, and with the time-resolved area normalized emission spectroscopy (TRANES) spectra, where only one isoemissive point is detected. On the other hand, the emission spectra at W = 10 and 20 show a dual fluorescence with a new band that emerges in the low-energy region of the spectra, a band that was previously assigned to the PRODAN emission from the water pool of RMs. Our studies demonstrate that this band is due to the emission from an ICT state of the molecular probe PRODAN located at the interface of the RMs. These results are also confirmed by the lifetime measurements, the TRES experiments where the results fit to a two-state model, and the time-resolved area normalized emission spectroscopy (TRANES) spectra where three or two isoemissive points are detected in the AOT and BHDC RMs, respectively. In the AOT RMs, Kp values obtained at W = 10 and 20 are almost independent of the water content; the values are higher for the BHDC RMs due to the higher micropolarity of this interface.     

Ion pairs of crystal violet in sodium bis(2-ethylhexyl)sulfosuccinate reverse micelles

The interfacial localization and the ion pair formation of the positively charged dye crystal violet (CV) in sodium bis(2-ethylhexyl)sulfosuccinate reverse micelles (AOT RMs) were studied by several structural and spectroscopic techniques and by quantum chemical calculations. The size and shape of the AOT RMs in the presence of CV were investigated by small-angle X-ray scattering, showing that CV does not significantly change the RM structure. CV localization as a function of the water to surfactant molar ratio (w(0)) was characterized by H(1) and (13)C NMR, indicating the close proximity of CV to the sulfosuccinate group of AOT at small and large w(0) values. These results were confirmed by calculation of magnetic shielding constants using the gauge-independent atomic orbital method with the HF/6-31G(d) basis set. Two different types of ion pairs between AOT and CV, i.e., contact ion pair (CIPs) and solvent-separated ion pair (SSIPs), were characterized by UV-vis spectroscopy and quantum chemical calculations using the semiempirical ZINDO-CI method. In nonpolar isotropic solvents CIPs are formed with an association constant (K(ASSOC)) of 2 x 10(4) mol(-1) L in isooctane and 750 mol(-1) L in chloroform. In AOT RMs at low w(0), CV-AOT CIPs are also formed. By increasing w(0), there is a sharp decrease in the CIP association free energy, and SSIPs are formed. (CV(+))(H(2)O)(AOT(-)) SSIPs are stable in the AOT RM up to the largest w(0) tested (w(0) = 33).     

On the possibility that cyclodextrins' chiral cavities can be available on AOT n-heptane reverse micelles. A UV-visible and induced circular dichroism study

The formation of reverse micelles (RMs) of sodium 1,4-bis(2-ethylhexyl)sulfosuccinate (AOT) in n-heptane including two different beta-cyclodextrin (beta-CD) derivatives (hydroxypropyl-beta-CD, hp-beta-CD, and decenyl succinyl-beta-CD, Mod-beta-CD) is reported. Both cyclodextrins can be incorporated into AOT RMs in different zones within the aggregate, while beta-CD cannot. Using UV-vis and induced circular dichroism (ICD) spectroscopy and different achiral molecular probes (some azo dyes, p-nitroaniline and ferrocene), it was possible to determine that Mod-beta-CD is located with its cavity at the oil side of the AOT RM interface, while for hp-beta-CD the cavity is inside the RM water pool. Among the molecular probes used, methyl orange (MO) was the only one which gave the ICD signal when dissolved in the AOT RMs with hp-beta-CD, so a detailed study of MO behavior in homogeneous media was also performed to compare with the microheterogeneous media. The solvatochromic behavior of the dye depends not only on the polarity of the media but also on other specific solvent properties. A Kamlet-Taft analysis shows that the MO absorption spectrum shifts to longer wavelength with an increase in the solvent polarity-polarizability (pi*) and the hydrogen donor ability (alpha) of the medium. MO appears to be almost 3 times more sensitive to the pi* parameter than to the alpha parameter. In addition, from the MO absorption spectral changes with the hp-beta-CD concentration, the association equilibrium constants in pure water (K11W) and inside the RMs (K11RM) were computed. The results show that K11W is almost 10 times larger than the value inside the RMs. The latter can be explained considering that MO resides anchored to the RM interface through hydrogen bond interaction with the hydration bound water. This study shows for the first time that the cyclodextrin chiral cavity is available for a guest in an organic medium such as the RMs; therefore, we have created a potentially powerful nanoreactor with two different confined regions in the same aggregate: the polar core of the RMs and the chiral hydrophobic cavity of cyclodextrin.     

The effect of different interfaces and confinement on the structure of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide entrapped in cationic and anionic reverse micelles

The behavior of the ionic liquid (IL) 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf(2)N]) entrapped in two reverse micelles (RMs) formed in an aromatic solvent as dispersant pseudophase: [bmim][Tf(2)N]/benzyl-n-hexadecyldimethylammonium chloride (BHDC)/chlorobenzene and [bmim][Tf(2)N]/sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT)/chlorobenzene, was investigated using dynamic light scattering (DLS), FT-IR and (1)H NMR spectroscopies. DLS results reveal the formation of RMs containing [bmim][Tf(2)N] as a polar component since the droplet size values increase as the W(s) (W(s) = [[bmim][Tf(2)N]]/[surfactant]) increases. Furthermore, it shows that the RMs consist of discrete spherical and non-interacting droplets of [bmim][Tf(2)N] stabilized by the surfactants. Important differences in the structure of [bmim][Tf(2)N] entrapped inside BHDC RMs, in comparison with the neat IL, are observed from the FT-IR and (1)H NMR measurements. The electrostatic interactions between anions and cations from [bmim][Tf(2)N] and BHDC determine the solvent structure encapsulated inside the nano-droplets. It seems that the IL structure is disrupted due to the electrostatic interaction between the [Tf(2)N](-) and the cationic BHDC polar head (BHD(+)) giving a high ion pair degree between BHD(+) and [Tf(2)N](-) at a low IL content. On the other hand, for the AOT RMs there is no evidence of strong IL-surfactant interaction. The electrostatic interaction between the SO(3)(-) group and the Na(+) counterion in AOT seems to be stronger than the possible [bmim](+)-SO(3)(-) interaction at the interface. Thus, the structure of [bmim][Tf(2)N] encapsulated is not particularly disrupted by the anionic surfactant at all W(s) studied, in contrast to the BHDC RM results. Nevertheless, there is evidence of confinement in the AOT RMs because the [bmim](+)-[Tf(2)N](-) interaction is stronger than in bulk solution. Thus, the IL is more associated upon confinement. Our results reveal that the [bmim][Tf(2)N] structure can be modified in a different manner inside RMs by varying the kind of surfactant used to create the RMs and the IL content (W(s)). These facts can be very important if these media are used as nanoreactors because unique microenvironments can be easily created by simply changing the RM components and W(s).     

Sizing of Reverse Micelles in Microemulsions using NMR Measurements of Diffusion

This paper reports the size of reverse micelles (RMs) in AOT/octane/H(2)O and CTAB/hexanol/H(2)O microemulsions using magnetic resonance (MR) pulsed field gradient (PFG) measurements of diffusion. Diffusion data were measured using the pulsed gradient stimulated echo (PGSTE) experiment for surfactant molecules residing in the RM interface. Inverse Laplace transformation of these data generated diffusion coefficients for the RMs, which were converted into hydrodynamic radii using the Stokes-Einstein relation. This technique is complementary to those previously used to size RMs, such as dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS), but also offers several advantages, which are discussed. RM sizes, determined using the PGSTE method, in the AOT (sodium bis(2-ethylhexyl) sulfosuccinate) and CTAB (cetyltrimethylammonium bromide) microemulsions were compared with previous DLS and SAXS data, showing good agreement. Methods for determining number distributions from the PGSTE data, through the use of scaling factors, were investigated.     

Controlled production of ZnO nanoparticles from zinc glycerolate in a sol-gel silica matrix

The controlled production of ZnO nanoparticles within an amorphous silica matrix is achieved using a new methodology consisting of four stages. First, precursor zinc glycerolate nanoparticles are produced within reversed micelles of glycerol in heptane stabilized by the surfactant Aerosol-OT (bis-ethylhexyl sodium sulfosuccinate, AOT). The surface of these nanoparticles is then modified by exchanging AOT with bis-trimethoxysilyl-ethane (BTME). The surface-modified nanoparticles are copolymerized with tetramethoxysilane (TMOS) to provide a composite silica material, in which the nanoparticles are apparently dissolved, producing a uniform distribution of zinc in the silica matrix. Finally, the conversion of zinc to ZnO is achieved by heating the material at 700 degrees C, leading to a uniform dispersion of very small (<10 nm) ZnO particles within the amorphous matrix. The fluorescence spectrum of the ZnO particles within the matrix is blue-shifted, as expected from the strong quantum confinement achieved. The properties of the system at all stages in this synthetic process are monitored using TEM, XRD, fluorescence and FT-IR spectroscopy. Glycerol forms complexes with many metal ions, so the present procedure may be generalized to provide uniform distributions of metal ions and subsequently metal oxide nanoparticles in amorphous silica.     

Interaction between hydrogen peroxide and cobalt(II) acetylacetonate in the system of reverse micelles of triton X-100 nonionic surfactant in cyclohexane

The yield of free radicals upon the decomposition of hydrogen peroxide catalyzed by cobalt acetylacetonate (Co(acac)₂) in the systems of reverse micelles of TX-100/n-hexanol and AOT in cyclohexane at 37°C was studied with the inhibitor method using a stable nitroxyl radical as a spin trap. It is shown that, in micellar AOT solutions in cyclohexane as well as in n-decane, H₂O₂ and Co(acac)₂ in practice do not react, because H₂O₂ is localized in a micelle water pool and Co(acac)₂, in the organic phase. Therefore, the generation of radicals is not observed in AOT solutions in cyclohexane, whereas, in aqueous solution, Co(acac)₂ catalyzes the radical decomposition of H₂O₂. In the system of mixed reverse micelles of TX-100 and n-hexanol in cyclohexane, at equal overall concentrations of H₂O₂ and Co(acac)₂, the rate of radical formation is much higher than in aqueous solution; i.e., the micellar catalysis of the radical decomposition of H₂O₂ takes place. It follows from measurements of UV and ESR spectra and the kinetics of changes in the content of peroxides in the reaction mixture that TX-100 and n-hexanol react with free radicals formed upon H₂O₂ decomposition and with atmospheric oxygen.     

Calorimetric study of the solubilization of cholesterol,retinol and retinal by reversed AOT micelles

Distribution constants and standard enthalpies of transfer of cholesterol, retinol and retinal partitioned between n-heptane and water containing reversed sodium bis(2-ethylhexyl) sulfosuccinate (AOT) micelles as a function of the molar concentration ratio (R=[water]/[AOT]) were evaluated by a calorimetric method. The results indicate that, in spite of the bulky hydrocarbon radical, these solubilizates behave like alcohols with a short alkyl chain. Moreover, cholesterol is always solubilized in the palisade layer of the reversed micelles whereas retinol and retinal are preferentially solubilized in the aqueous pseudophase. The influence of the enthalpic and the entropic contributions to the transfer of the solubilizates from n-heptane to reversed AOT micelles are also considered.     

Influence of negatively charged interfaces on the ground and excited state properties of methylene blue

Properties of the ground and excited states of methylene blue (MB) were studied in negatively charged vesicles, normal and reverse micelles and sodium chloride solutions. All these systems induce dimer formation as attested by the appearance of the dimer band in the absorption spectra (lamdaD approximately 600 nm). In reverse micelles the dimerization constant (KD) corrected for the aqueous pseudophase volume fraction is two-three orders of magnitude smaller than KD of MB in water, and it does not change when W0 is increased from 0.5 to 10. Differences in the fluorescence intensity as a function of dimer-monomer ratio as well as in the resonance light scattering spectra indicate that distinct types of dimers are induced in sodium dodecyl sulfate (SDS) micelles and aerosol-OT (sodium dioctyl sulfoxinate, AOT) reversed micelles. The properties of the photoinduced transient species of MB in these systems were studied by time-resolved near infrared (NIR) emission (efficiency of singlet oxygen generation), by laser flash photolysis (transient spectra, yield and decay rate of triplets) and by thermal lensing (amount of heat deposited in the medium). The competition between electron transfer (dye*-dye) and energy transfer (dye*-O2) reactions was accessed as a function of the dimer-monomer ratio. The lower yield of electron transfer observed for dimers in AOT reverse micelles and intact vesicles compared with SDS micelles and frozen vesicles at similar dimer-monomer ratios is related with the different types of aggregates induced by each interface.