Cetyltrimethylammonium Bromide Microemulsion Research Articles

Chiral Biocatalytic Oxidations at 90 °C in Microemulsions Driven by Electrocatalytic Oxygen Reduction to Hydrogen Peroxide

AbstractChirality plays a significant role in the manufacture of pharmaceuticals and fine chemicals. The use of chemical catalysts to control stereoselectivity relies on the use of chiral catalysts with labor–intensive synthesis and purification. Natural enzymes offer inherent stereoselectivity, making them attractive catalysts for this purpose. We report here chiral biocatalytic oxidations in microemulsions driven by horseradish peroxidase coupled with a synthetic Cu2+‐polymer catalyst. This hybrid system features crosslinked layer–by–layer (LBL) films composed of polyions with Cu2+‐containing pyrene–labelled poly(2‐hydroxy‐3‐dipicolylamino) propyl methacrylate (Py−PGMADPA) to drive oxygen reduction to form hydrogen peroxide. Peroxide in turn activates horseradish peroxidase (HRP) crosslinked in LbL films on magnetic particle beads to biocatalytically oxidize styrene, ethylbenzene, and methyl phenylacetate to chiral products. R‐stereoisomers of these reactants were selectively formed with a high enantiomeric excess of ≥80 % at 90 °C. The enzyme films show high thermal stability at 90 °C in cetyltrimethylammonium bromide microemulsion. Reactions at 90 °C were essentially complete in 2 hr. This hybrid approach opens a door to new designs of biocatalytic syntheses using a separate electrocatalyst for enzyme activation.

An experimental investigation on the impact of divalent ions on the emulsification of oil: Comparison of biodegradable (green) and petroleum-based surfactants

Emulsification of oil with surfactants often yields in complex colloidal systems which require understanding their physicochemical properties prior to their use in industry. This study aims to investigate the effects of divalent ions (calcium and magnesium) on the emulsification performance of biodegradable (green) surfactants of Triton™ CG-110 (alkyl polyglycoside, APG) and GreenZyme (GZ) at two temperature conditions (25 °C and 70 °C). For this purpose, the phase behaviour, interfacial tension (IFT), stability, droplet size distribution and rheological properties of APG and GZ microemulsion were evaluated. The outcomes were then compared with the emulsification performance of petroleum-based (synthetic) surfactants of alpha-olefin sulfonate (AOS) and cetyltrimethylammonium bromide (CTAB). Furthermore, the impacts of alkalis (ethanolamine and sodium carbonate) on microemulsions and the demulsification performance of a zwitterionic demulsifier (cocobetaine) were explored. The results show that only APG and CTAB could produce water in oil (W/O) microemulsions in the presence of divalent ions. The stability of APG and CTAB microemulsions was affected by divalent ions since the water segregation rate (WSR) index of these microemulsions went up from ≈21% to ≈ 85% as salinity increased up to 15 wt%. Also, the average droplet size of these microemulsions went up from 50-64 nm to 220–255 nm as salinity increased to 9 wt%. This is because the negative charge density on the microemulsion droplet surface decreases as the salinity increases, thus the electrostatic repulsive force between the droplets becomes weaker. In addition, APG and CTAB microemulsions showed a shear thinning behaviour, and their viscosity value increased with the increase in salinity. It is speculated that the presence of divalent ions generates more friction between the molecules, which causes an increase in the viscosity of the microemulsions.

Stability and Aggregation Kinetics of Silver Nanoparticles in Water in Oil Microemulsions of Cetyltrimethylammonium Bromide and Triton X-100

Water in oil (W/O) microemulsions are simple preparative route for nanoparticles where water droplets dispersed in oil stabilized by surfactant or surfactant and cosurfactant monolayer act as nanoreactors to carry out chemical reactions. In this work, silver nanoparticles (AgNPs) were prepared in W/O microemulsions of cetyltrimethylammonium bromide (CTAB) and triton X-100 (TX-100) by using AgNO3 and NaBH4 as a precursor salt and reducing agent, respectively. To prepare microemulsions, CTAB or TX-100, 1-pentanol, cyclohexane and water were mixed with different molar ratio. AgNPs were prepared with different [AgNO3] in microemulsions of CTAB with fixed water to surfactant ratio (Wo). Average particle sizes were determined from dynamic light scattering (DLS) measurements. AgNPs prepared from microemulsions of CTAB were unstable while from TX-100, NPs were stable. Aggregation kinetics was investigated by measuring the absorbance at definite time intervals at the absorption maximum, ?max of AgNPs in different media under pseudo-first-order conditions. The aggregation behavior was studied at different [AgNO3]:[NaBH4] and Wo and the parameters were optimized to ensure formation of stable AgNPs without aggregation in microemulsions. This would help tuning the size, stability, and aggregation kinetics of AgNPs by controlling the nature of the surfactant and composition of the microemulsions.

NMR study of the influence of n‐alkanol co‐surfactants on reverse micelles in quaternary microemulsions of cetyltrimethylammonium bromide (CTAB)

The effects of different n-alkanol co-surfactants on the size, shape, composition and dynamics of reverse micelles (RMs) in cetyltrimethylammonium bromide (CTAB)/n-alkanol/n-hexane/water and CTAB/n-alkanol/n-pentane/water microemulsions were investigated using T2 relaxation and pulsed gradient stimulated echo nuclear magnetic resonance (NMR) measurements and molecular modelling. NMR T2 relaxation times and diffusion coefficients were determined for the surfactant and co-surfactant in these CTAB quaternary reverse microemulsions, for a range of medium chain length alcohol co-surfactants, from 1-butanol to 1-heptanol. These data revealed a slight RM size dependency on co-surfactant chain length, with RM sizes tending to decrease with increasing alcohol chain length. Molecular modelling of CTAB/n-alkanol/n-hexane/water RMs suggested a variation in RM shape with co-surfactant chain length, where those formed with pentanol were found to be least spherical and those formed with heptanol the most spherical. The NMR data also revealed differences in the behaviour of the micellar structures in the CTAB/n-pentanol/n-hexane/water reverse microemulsion, compared with the other reverse microemulsions in this study, where CTAB was found to be distributed between two environments, which then combined to form larger micelles. The origins of these differences remain unclear. Copyright © 2016 John Wiley & Sons, Ltd.

Preparation of Pt/Al2O3 catalyst in CTAB microemulsion and kinetics of m-chloronitrobenzene hydrogenation

Pt/Al2O3 catalyst was prepared successfully by a microemulsion method using cetyltrimethylammonium bromide (CTAB) as the surfactant and N2H5OH as the reducing agent. Selective hydrogenation of m-chloronitrobenzene (m-CNB) was used as a probe to investigate how parameters affect the preparation of catalysts via the microemulsion method. Transmission electron microscope (TEM) and selected-area electron diffraction (SAED) show that Pt particles (mean size 3 nm) were distributed uniformly on the catalyst and were in polycrystalline structure. Experiments on m-CNB selective hydrogenation show that at 303 K and hydrogen pressure of 0.1 MPa, the turnover frequency (TOF) was 0.216 s–1, the m-CNB conversion was 99.6% and the m-CAN selectivity was 98.9%, indicating high dechlorination inhibition effect. The reaction was an approximately first-order process with apparent activation energy of 26.92 kJ mol–1.

Acid Hydrolysis of Bromazepam Catalyzed by Micelles, Reverse Micelles, and Microemulsions

Kinetics of the acid hydrolysis of bromazepam (Bz) has been investigated in micelles, reverse micelles, and microemulcions of cetyltrimethylammonium bromide (CTAB) by spectrophotometric method. The rate of the acid hydrolysis of Bz was found to be enhanced both below and above the critical micelle concentration (CMC) of CTAB in aqueous solution. The pseudo-first-order rate constant (k′) shows an initial decrease for both low and high H+concentrations. With further increase in [CTAB], at low [H+], thek′attains an almost constant value, while, at high [H+], thek′passes through a maximum and then decreases. The kinetic data for catalysis by micelles of CTAB was interpreted with the pseudophase ion exchange (PIE) model. In CTAB/cyclohexane/1-butanol/water microemulsions, as the water to surfactant ratio (wo) increases, the physicochemical properties and droplet sizes of microemulsions significantly change and distinct changes in reaction environment can be marked. The rate of the hydrolysis reaction exhibits excellent correlation with the physicochemical properties and droplet sizes of the microemulsions and reverse micelles of CTAB. At [H+] = 0.001 M, in reverse micelles and microemulsions of CTAB, thek′of the acid hydrolysis of Bz decreases sharply followed by a slight increase with increasingwo.

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.

Electrochemical Behavior of Anthraquinone in Reverse Micelles and Microemulsions of Cetyltrimethylammonium Bromide

The electrochemical behavior of an anthraquinone (AQ) was studied in aqueous solutions at a glassy carbon electrode, using the sodium salt of anthraquinone-2-sulfonic acid (AQS), by employing cyclic voltammetry. AQ undergoes a two-electron reduction in aqueous media. The electrochemical behavior of AQ was also investigated in micelles, reverse micelles (CTAB/1-butanol/water), and microemulsions (CTAB/1-butanol/water/cyclohexane) of cetyltrimethylammonium bromide (CTAB). The electrode reactions of AQ in reverse micelles and microemulsions are nearly reversible at low oil (cyclohexane) content. However, at higher oil content, the reversibility is gradually lost. In the case of reverse micelles, the reduction current, as well as the reduction potential, of AQ depend on the transition from a micellar solution to a stable solution of reverse micelles that occurs with added 1-butanol. In microemulsions, the change in cyclohexane content was found to cause a linear increase in the peak current for AQ reduction as well as a linear decrease in the corresponding reduction potential. As the cyclohexane content is increased, the o/w microemulsions dominated by micelles undergo a transition to a w/o microemulsion dominated by reverse micelles, which causes changes in the electrochemical behavior.

GNP confinement at the interface of cationic reverse micelles: influence in improving the lipase activity

The present work reports thiol-assisted confinement of gold nanoparticles (GNPs) at the interface of reverse micelles with the aim to enhance the interfacial area and thereby the efficiency of surface-active Chromobacterium viscosum lipase. The strong gold capping ability of optimally hydrophobic thiols (1-dodecanethiol and 1,6-hexanedithiol) was aptly utilized to pull GNPs (∼3–5 nm) from the water pool to the oil/water interface of cetyltrimethylammonium bromide (CTAB) reverse micelles. These small sized GNPs were fitted at the microscopic interface of CTAB reverse micelles possibly because of the comparable thickness of the interface (∼1–2 nm) to that of the GNP diameter. Lipase solubilized within this augmented interface enjoys a flexible conformation, which resulted in the improvement of its activity (∼2.5 fold) with respect to only CTAB microemulsion. The activity of lipase within CTAB reverse micelles was thoroughly studied in the presence of mono and dithiols with varying chain length, where a greater improvement in activity was observed with dithiols. Bidentate ligand property of dithiols led to firm localization of higher number of GNPs at the interface which enhanced the total space in vicinity of enzyme at the interfacial domain. Fitting fusion of small sized GNPs within CTAB reverse micellar interface was confirmed by microscopic and spectroscopic studies. Smooth localization of lipase at the enhanced interface was also confirmed from the improvement in its secondary structure (α-helical content) in circular dichroism spectroscopic analysis. Interestingly, large sized GNPs (∼8 and 20 nm) were found to be well fitted at the interface of bigger head group-containing surfactants, cetyltriethylammonium bromide (CTEAB) and cetyltripropylammonium bromide (CTPAB). The hydrolytic efficiency of lipase in 1,6-hexanedithiol included GNP (∼20–25 nm)-doped CTPAB reverse micelles improved by ∼3.4 fold compared to that observed in only CTAB.

Radiation Induced Formation of Acrylated Palm Oil (APO) Nanoparticles Using Cetyltrimethylammonium Bromide Microemulsion System

In this study, we report the preparation of Acrylated Palm Oil (APO) nanoparticles using aqueous Cetyltrimethylammonium bromide (CTAB) microemulsion system. This microemulsion system which contains the dispersed APO nanodroplets was subjected to the gamma irradiation to induce the formation of the crosslinked APO nanoparticles. The dynamic light scattering (DLS), the Fourier Transform Infrared (FTIR) spectrocospy and the Transmission Electron Microscopy (TEM) were used to characterize the size and the chemical structure of the nanoparticle. Sized of the APO nanoor microparticle can be varied depended on the volumes of the modified palm oil and the irradiation doses. Their size is in the range of 73 to 100 nanometer (nm) after irradiation using gamma irradiator. This radiation-induced method provides a free initiator induced and easy to control process as compared to the classical or chemical initiator process.

Effect of the thermodynamic properties of W/O microemulsions on samarium oxide nanoparticle size

In this work, we report the preparation of the Sm 2O 3 nanoparticle precursors (Sm(OH) 3) via a simple W/O microemulsion process, in which microemulsions of cetyltrimethylammonium bromide (CTAB)/alkanol/1-octane/Sm(NO 3) 3 aqueous solution were added into sodium hydroxide (NaOH) aqueous solutions. The Sm 2O 3 nanoparticles were then prepared by calcining the precursors at 900 °C. Particularly, Δ G c → i , which is the change in standard Gibbs free energy for transferring cosurfactant from the continuous phase to the microemulsion interface and can be used to estimate the thermodynamic properties of microemulsions, was determined using the dilution method. The effects of alkanol carbon chain length (1-pentanol, 1-hexanol, 1-heptanol and 1-octanol) and the reaction temperatures (298, 308, 318 and 328 K) on both Δ G c → i and Sm 2O 3 nanoparticle size have been investigated. Specifically, the Sm 2O 3 nanoparticle size, when calcined at 900 °C, was found to be mainly controlled by Δ G c → i , and was thereby affected by the thermodynamic properties of microemulsions. The obtained products were characterized by DSC–TGA, XRD, TEM and UV–Vis. The results showed that Δ G c → i decreased with the increase in both the length of alkanol carbon chain and the reaction temperature, and the average size of Sm 2O 3 nanoparticles decreased as Δ G c → i decreased. The effect of microemulsion thermodynamic properties on Sm 2O 3 nanoparticle size reported here can provide some insights in controllable preparation of other rare earth oxide nanoparticles via the microemulsion route.

Synthesis and Fluorescence Properties of Eu 2+-Doped KMgF 3 Nanoparticles

The phase diagram of a cetyltrimethyl ammonium bromide( CTAB)/n-butanol/n-octane/KNO3-Mg( NO3)(2) system was drawn. Nanoparticles of Eu2+-doped KMgF3 were prepared from the quaternary microemulsions of cetyltrimethyl ammonium bromide(CTAB), n-butanol, n-octane and water. The X-ray diffraction(XRD) patterns were indexed to a pure KMgF3 cubic phase. The environmental scanning electron microscopic (ESEM) images show the presence of spherical Eu2+-doped KMgF3 nanoparticles with a diameter of ca. 20 nm. The emission of KMgF3: Eu2+ nanoparticles peaks at 360 mn. The excitation band was observed at 250 nm with a blue shift of ca. 70 nm compared with that of KMgF3: Eu2+ single crystal. The preparation method of nano-KMgF3: Eu2+/PMMA composite films was inquired into.

Structural properties of microheterogeneous surfactant-based catalytic systems: Multicomponent self-diffusion NMR approach

The possibilities of the Fourier transform pulsed-gradient spin-echo1H nuclear magnetic resonance approach in the structural study of surfactant-based microheterogeneous liquid systems are examined by the example of cetyltrimethylammonium bromide microemulsions under a large scale alterations in the water-to-oil ratio. The advantages of this approach to study the structure of microcompartmentalized systems with different phase manifestations are shown. The obtained structural information is used to analyze the microenvironment of the reacting species and the kinetic data on the basic hydrolysis of carbon acids esters in the microemulsion reaction medium.

Novel synthesis of well-dispersed crystalline SnO2 nanoparticles by water-in-oil microemulsion-assisted hydrothermal process.

Well-dispersed crystalline tin dioxide (SnO2) nanoparticles were synthesized by a novel and simple water-in-oil (w/o) microemulsion-assisted hydrothermal process, using low-cost tin chloride as the starting material. The typical quaternary microemulsions of cetyltrimethylammonium bromide (CTAB)/n-pentanol/n-hexane/water were used as space-confined microreactors for the nucleation, growth, and crystallization of SnO2 nanoparticles under hydrothermal conditions. The techniques of XRD, TEM, HRTEM, SAED, EDS, FTIR, XPS, and N2 adsorption measurement were used to characterize the compositions and structures of obtained samples. The results show that the SnO2 nanoparticles have high specific areas (107-169 m2 g(-1)), small particle sizes (ca. 3.0 nm), high crystallinity, and narrow size distributions. The well-dispersed, uniform, and well-crystallized powders with microporous texture are favorable for gas-sensing applications. The as-developed microemulsion-assisted in situ crystallizing process can be extended to prepare other oxide, metal, and sulfide nanoparticles.

Solvation dynamics of coumarin 480 in neutral (TX-100), anionic (SDS), and cationic (CTAB) water-in-oil microemulsions

The steady state spectra and time resolved studies indicate that the Coumarin 480 (C-480) molecules are located at the interfacial region in TritonX-100(TX-100)/cyclohexane/1-hexanol/water, sodium dodecyl sulfate(SDS)/1-hexanol/water, and cetyltrimethylammonium bromide(CTAB)/isooctane/1-hexanol/water microemulsions. The retardation of solvation dynamics of C-480 in these three microemulsions is observed. Moreover, the solvent relaxation times in these three microemulsions are independent of water loading. The close resemblance of solvation dynamics results among TX-100, SDS, and CTAB microemulsions imply that ionic solvation has no role in the slow solvation processes occurring in these microemulsions.

Calorimetric study of CdS nanoparticle formation in w/o microemulsions

The formation of CdS nanocrystals in ternary w/o microemulsions of sodium bis(2-ethylhexyl) solfosuccinate/water/isooctane and in quaternary w/o microemulsions of cetyltrimethylammonium bromide (CTAB)/ n-pentanol/water/ n-hexane was studied by calorimetric measurements. In order to gain information on the role played by the various factors governing the formation of nanoparticles, the enthalpy of formation of CdS nanocrystals in microemulsion was investigated as a function of W 0, the molar ratio between water and surfactant and P 0, the molar ratio between alcohol and surfactant. Different energetic states of CdS nanocrystals in microemulsions and in water and a dependence of them on the composition and nature of the microemulsive system are evidenced.

Extraction and recovery of gold from KAu(CN)2 using cetyltrimethylammonium bromide microemulsions

Extraction and recovery of gold from KAu(CN)2 using cetyltrimethylammonium bromide microemulsions

Extraction and recovery of gold from KAu(CN)2 using cetyltrimethylammonium bromide microemulsions

AbstractExtraction and stripping of KAu(CN)2 from alkaline solution by a w/o microemulsion formed with cetyltrimethylammonium bromide (CTAB) using 198Au(I) tracer has been investigated. Various parameters, such as the Au(I) concentration in aqueous phase, concentrations of halide ions, NH4SCN and thiodiethylene glycol in stripping solution as well as the relationship between water and Au(I) concentration in the organic phase in the extraction and stripping of Au(I) were studied. The results show that almost all of the Au(I) in the aqueous phase was extracted into the organic phase. The water content decreased significantly with an increase in Au(I) concentration in the organic phase, contrary to the results of a system with tributyl phosphate (TBP) as cosolvent. Almost all of the extracted Au(I) (∼98%) can be recovered with pure thiodiethylene glycol as the stripping agent, and ∼93% of the Au(I) is stripped with high concentrations of NH4SCN(>3.0 mol dm−3) or KI (>2.0 mol dm−3).© 2001 Society of Chemical Industry

Klenow fragment and DNA polymerase α-primase fromserva calf thymus in water-in-oil microemulsions

The activity of DNA polymerase α-primase complex from calf thymus and Klenow fragment of E. coli DNA polymerase 1 has been studied in reverse microemulsions formed by sodium bis(2-ethylhexyl) sulfosuccinate (AOT), sodium dodecylsulfate (SDS), cetyl trimethyl ammonium bromide (CTAB), polyoxyethylene 20 cetyl ether (Brij 58), and Triton X-114 in decane. DNA polymerases were not active in AOT, CTAB, and SDS reverse microemulsions, but these enzymes catalyzed DNA synthesis in Brij 58 and its mixture with other surfactants. We have also found the system composed from the Triton X-114, SDS, CTAB, and Brij 58 (concentration of 128, 25, 15, and 10 mM, respectively) in hexanol–decane (1:12 v/v), in which DNA polymerases revealed maximum activity. The above system was optically transparent, fluid, and stable during a few hours with a water-surfactants molar ratio up to 160. The pH dependence of DNA polymerase activity was not significantly different in comparison with water; however, DNA polymerase was sensitive to ionic strength in microemulsions. The dependence of DNA polymerase activity on w 0 was the curve with a few optima. DNA polymerases synthesized more products in water than in reverse microemulsions, and the processivity of Klenow fragment decreased. An increase of the water content resulted in an increase of DNA polymerase processivity.

Formations of polyvinyltoluene microlatexes in quaternary oil in water cetyltrimethylammonium bromide microemulsions

Polymerization of vinyltoluene (VT) in quaternary microemulsions containing cetyltrimethylammonium bromide (CTAB) as the cationic surfactant is studied using laser Raman spectroscopy (LRS) and dilatometry. The influences of water soluble (potassium peroxodisulphate, ammonium peroxodisulphate) and oil soluble (azobisisobutyronitrile, benzoyl peroxide) initiators, monomer, surfactant, cosurfactants (n-alcohol and bifunctional alcohols) and temperature on the rates of polymerization (R p), energy of activation (Ea), particle diameter (D), number of polymer particles (N p), molecular weight of polyvinyltoluene (M v) and number of polymer chains per latex particle (N pc) are investigated. The dependencies of the kinetic and latex size parameters on the initiators and cosurfactants are discussed in terms of the efficiency of the initiators in initiating the polymerization and on the interfacial partitioning behavior of various cosurfactants. The polymerization mechanism seems to follow Smith Ewart Case II hypothesis with two distinct rate regions. Final polymer microlatexes are found to lie within 10–50 nm as observed by transmission electron microscopy (TEM). Molecular weights are in the range of (1 to 5)×106. Each latex particle contains one to three polymer chains.