Reverse micelles nanoparticles

Surfactants provide several types of well-organized self-assembhes, which can be used to control the physical parameters of synthesized nanoparticles, such as size, geometry and stability within liquid media. Estabhshed surfactant assembles that are commonly employed for nanoparticie fabrication are aqueous micelles, reversed micelles, microemulsions, vesicles [15,16], polymerized vesicles, monolayers, deposited organized multilayers (Langmuir-Blodgett (LB) films) [17,18] and bilayer Upid membranes [19](Fig. 2). 

Microemulsions with different structures, like micelles, reverse micelles or bicontinuous networks, can be used for several inorganic, organic [72] or catalytic reactions which require a large contact area between oil and water. Besides enzyme catalysis, this can be the formation of nanoparticles [54, 73, 74], hydro-formylation reactions [75] or polymerisations [76-78]. 

There are several oil-based formulations for the delivery of hydrophilic and lipophilic drugs, which maj orly include emulsions and gels (Figure 58.2). Apart from these, various other novel formulations may also be named under this category such as micelles, reverse micelles, solid lipid nanoparticles, and liposomes. - Based on the physicochemical properties of the drug and patient requirements, the vegetable oil-based formulations may be delivered by various routes like oral, parenteral, topical, transdermal, pulmonary, or ocular, etc., - ... 

Several types of nanoparticles can be envisaged as lubricant additives. The chapters of this book describe different possible nanolubricants nested nanoparticles (fuUerenes, onions and nanotubes) made on metal dichalcogenides or carbon, reverse overbased micelles, metallic nanoparticles and boron-based nanolubricants. In some cases, the authors chose to study these particles because their structure is close to well-known lamellar structures in tribology (for example inorganic fuUerenes of M0S2). However, dispersion of nanoparticles in oil is not always simple. Thus, in a first part, some rules will be shown about the dispersion of solid nanoparticles in a liquid. 

In 2000, the first example of ELP diblock copolymers for reversible stimulus-responsive self-assembly of nanoparticles was reported and their potential use in controlled delivery and release was suggested [87]. Later, these type of diblock copolypeptides were also covalently crossUnked through disulfide bond formation after self-assembly into micellar nanoparticles. In addition, the encapsulation of l-anilinonaphthalene-8-sulfonic acid, a hydrophobic fluorescent dye that fluoresces in hydrophobic enviromnent, was used to investigate the capacity of the micelle for hydrophobic drugs [88]. Fujita et al. replaced the hydrophilic ELP block by a polyaspartic acid chain (D ). They created a set of block copolymers with varying... 

Generation of nanoparticles under Langmuir monolayers and within LB films arose from earlier efforts to form nanoparticles within reverse micelles, microemulsions, and vesicles [89]. Semiconductor nanoparticles formed in surfactant media have been explored as photocatalytic systems [90]. One motivation for placing nanoparticles within the organic matrix of a LB film is to construct a superlattice of nanoparticles such that the optical properties of the nanoparticles associated with quantum confinement are preserved. If mono-layers of capped nanoparticles are transferred, a nanoparticle superlattice can be con-... 

As a result of their size and of specific interactions, hydrophilic macromolecules or solid nanoparticles cause strong changes in micellar size and dynamics, and their structural and dynamic properties are strongly affected. In these cases, the distribution among reversed micelles can be only described by ad hoc models [13,123]. 

Moreover, stable liquid systems made up of nanoparticles coated with a surfactant monolayer and dispersed in an apolar medium could be employed to catalyze reactions involving both apolar substrates (solubilized in the bulk solvent) and polar and amphiphilic substrates (preferentially encapsulated within the reversed micelles or located at the surfactant palisade layer) or could be used as antiwear additives for lubricants. For example, monodisperse nickel boride catalysts were prepared in water/CTAB/hexanol microemulsions and used directly as the catalysts of styrene hydrogenation [215]. 

In addition, it is of interest to note that investigations of the microscopic processes leading to nucleation, growth, oriented growth by the surfactant monolayer, and growth inhibition of nanoparticles in reversed micelles and of confinement and adsorption effects on such phenomena represent an intriguing and quite unexplored research field [218]. 

Taking into account that the state of nanoparticles is thermodynamically unstable against an unlimited growth, the physicochemical processes allowing reversed micelles to lead to stable dispersions and to a size control of nanoparticles are ... 

It must be pointed out that formation and stabihzation of nanoparticles in reversed micelles are the result of a delicate equilibrium among many factors. In addition, lacking a general theory enabling the selection a priori of the optimal conditions for the synthesis of nanoparticles of a given material with the wanted properties, stable nanoparticles containing w/o microemulsions can be achieved only in some system-specific and experimentally selected conditions. 

Figure 11. Size- and shape-control of nanoparticles via salt reduction in (a) the hydrophobic core of a surfactant oil in water micelle and (b) the hydrophilic core of a water-in-oil reverse micelle.

To control the formation of nanoparticles with desired size, composition, structure, dispersion, and stability, a multifunction nanoagent is used. The active metals (Pd and Pt) react with the functional groups of the nanoagent, i.e., a pol5mier template. The polymer template determines the size, monodisperity, composition, and morphology of the particles (which is somewhat reminiscent of the reversed micelles technique mentioned above). 

Kitchens, C.L., McLeod, M.C. and Roberts, C.B. (2003) Solvent effects on the growth and steric stabilization of copper metallic nanoparticles in AOT reverse micelle systems. Journal of Physical Chemistry B, 107 (41), 11331-11338. 

Lee, Y Lee, J., Bae, C.J., Park, J.G., Noh, H.J., Park, J.H. and Hyeon, T. (2005) Large-scale synthesis of uniform and crystalline magnetite nanoparticles using reverse micelles as nanoreactors under reflux conditions. Advanced Functional Materials, 15 (3), 503-509. 

Fluorescent silica nanoparticles, called FloDots, were created by Yao et al. (2006) by two synthetic routes. Hydrophilic particles were produced using a reverse micro-emulsion process, wherein detergent micelles formed in a water-in-oil system form discrete nanodroplets in which the silica particles are formed. The addition of water-soluble fluorescent dyes resulted in the entrapment of dye molecules in the silica nanoparticle. In an alternative method, dye molecules were entrapped in silica using the Stober process, which typically results in hydrophobic particles. Either process resulted in luminescent particles that then can be surface modified with... 

Figure 14.23 Silica nanoparticles containing fluorescent dye molecules can be prepared using a reverse micelle suspension process (a) The water-in-oil emulsion is formed with the aqueous phase droplets containing TEOS and dye molecules in detergent, (b) The final particles contain entrapped dye within the silica particle matrix, creating highly fluorescent particles.

PS-PEO reverse spherical micelles have been used as nanoreactors for the synthesis of metallic nanoparticles, as shown by the works of Moller and coworkers [102] and Bronstein et al. [103]. 

Various metallic nanoparticles have been prepared in the case of PS-P2(4) VP reverse micelles, as illustrated by the works of Moller et al. [ 109-111 ] and Antonietti and coworkers [112]. Very recently, Bronstein et al. reported on the synthesis of bimetallic colloids formed in PS-P4VP micelles and their catalytic behavior for the selective hydrogenation of dehydrolinalool [113]. 

The reverse microemulsion method can be used to manipulate the size of silica nanoparticles [25]. It was found that the concentration of alkoxide (TEOS) slightly affects the size of silica nanoparticles. The majority of excess TEOS remained unhydrolyzed, and did not participate in the polycondensation. The amount of basic catalyst, ammonia, is an important factor for controlling the size of nanoparticles. When the concentration of ammonium hydroxide increased from 0.5 (wt%) to 2.0%, the size of silica nanoparticles decreased from 82 to 50 nm. Most importantly, in a reverse microemulsion, the formation of silica nanoparticles is limited by the size of micelles. The sizes of micelles are related to the water to surfactant molar ratio. Therefore, this ratio plays an important role for manipulation of the size of nanoparticles. In a Triton X-100/n-hexanol/cyclohexane/water microemulsion, the sizes of obtained silica nanoparticles increased from 69 to 178 nm, as the water to Triton X-100 molar ratio decreased from 15 to 5. The cosurfactant, n-hexanol, slightly influences the curvature of the radius of the water droplets in the micelles, and the molar ratio of the cosurfactant to surfactant faintly affects the size of nanoparticles as well. 

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