Organic nanoparticles from microemulsions: Formation and applications

Microemulsions have already been recognized as convenient templates for nanoparticle synthesis. Spontaneous formation of the compartmentalized domains within the microemulsions leads to facile and low-cost preparation processes.In the past, microemulsions were mainly explored as precursors for the synthesis of inorganic nanoparticles. However, there is a constantly growing number of publications offering to exploit these systems to produce organic nanoparticles, and in recent years, a variety of methods have emerged in this field. The aim of this review is to survey the methods recently used to produce organic nanomaterials from microemulsions, and to give a perspective on particle design possibilities that can be achieved by various techniques. The structure of the initial microemulsion system, the chemical and technical aspects of preparation, the nature of additives and surface active agents, as well as the possible outcomes in terms of final particle characteristics, will be discussed for the various methods.     

Special requirements for calculation methods for soil decontamination processes

Soil decontamination is one of the major problems of industrialized nations. Various soil purification processes together with their characteristic attributes are discussed. Some transport and equilibrium phenomena of the contaminant/soil system are covered and some research needs are outlined which will facilitate better process design and significantly reduce clean-up costs.     

Formation and characterization of self-assembling fish oil microemulsions

The novel fish oil O/W microemulsion system is formed with food-acceptable components, Tween 80, ethyl oleate, fish oil and water. We studied the influence of fish oil proportion in the oil phase on the microemulsion regions. We investigated this system using the dynamic light scattering and transmission electron microscopy; the rheological characteristics and release effect were also explored. The obtained results indicated that the particle sizes of spherical droplets in microemulsions depend significantly on the total oil phase content, varying from 5 to 198 nm. The rheological measurements showed that all studied microemulsions followed shear thinning behavior. Well-controlled release profile of the fish oil microemulsions was found in different dialyzate solutions.     

Reactivity of benzoyl chlorides in nonionic microemulsions: potential application as indicators of system properties

The solvolysis reactivity of benzoyl chlorides entails a high sensitivity on medium properties. A systematic study of the reaction of a series of these substrates, varying the electron-withdrawing character of the substituent, has been performed in nonionic microemulsions. The kinetic effects due to variation of microemulsion compositions can be assigned to modifications in system properties, to be precise, to modifications in interface properties. Microemulsion properties that are obtained from kinetic analysis of solvolysis show a good agreement with the characterization of the microemulsion that was made via 1H NMR and solvatochromic fluorescence probes. Benzoyl chlorides with electron-donating groups react through a dissociative mechanism, whereas electron-withdrawing groups favor an associative mechanism. A comparative analysis of reactivity between the different substrates at the interface shows a variation in the contributions of both reaction pathways, associative and dissociative, to the whole reaction mechanism. The confined media shift the point where the mechanism changes from an associative to a dissociative pathway, far away from the turning point in water. Furthermore, the change in mechanism can be modulated by modification of the microemulsion composition.     

Formation and characterization of microemulsions containing polymeric silicone

We have prepared microemulsions consisting of water/[40 wt % polyoxyethylene (20 mol) glycerin isostearate (abbreviated as POE-GIS) + 60 wt % random copolymer of polyoxyethylene (POE, 38 mol)/polyoxypropylene (POP, 10 mol) pentaerythritol tetramethyl ether {abbreviated as PEPTME (38/10)}]/[polyoxyethylene (POE, 19 mol)/polyoxypropylene (POP, 19 mol) polydimethylsiloxane copolymer (abbreviated as POE/POP-PDMS)] and water/[40 wt % POE-GIS + 60 wt % PEPTME (38/10)]/[95 wt % POE/POP-PDMS + 5 wt % oleic acid (abbreviated as OA)] systems and characterized them with optical observation, rheometry, and freeze-fracture transmission electron microscopy (FF-TEM) images. Bicontinuous and droplet-type O/W (oil-in-water) microemulsions are formed depending on the volume fraction of water. The bicontinuous structure observed in the oil-rich region, upon successive dilution with water, is transformed into a droplet-type microemulsion without phase separation.The prepared droplet-type microemulsion containing polymeric silicone and random copolymer PEPTME (38/10) as a cosurfactant in the water-rich region has potential applications in cosmetics.     

Solubilization in microemulsions and application to separations

Microemulsions possess distinct advantages in terms of phase behavior and droplet size over coarse emulsions as liquid membranes for separations. In order to achieve an efficient separation, the phase behavior of the microemulsion must fulfill several constraints. In an attempt to formulate microemulsions with the desired phase behavior, a solubilization study of a nonionic water-in-oil microemulsion system was conducted. One of the key attributes of the microemulsion system studied is the absence of a cosolvent. A simple geometric model is proposed to explain the observed effects of hydrocarbon chain length and electrolyte concentration on solubilization. This model is useful for optimization of microemulsion formulation. The microemulsion system developed was used to separate acetic acid from a dilute aqueous solution. The effect of mixing speed as well as treat ratio on separation rate and leakage were also investigated. Demulsification of the microemulsion to recover the separated acetic acid was successfully achieved.     

Interfacial composition, structural parameters and thermodynamic properties of water-in-oil microemulsions

The formation and structural characteristics of water-in-oil microemulsions comprising hexadecylpyridinium chloride (CPC), alkanols (C₄–C₆) and alkanes (C₅, C₈–C₁₀) have been investigated by the method of dilution. The compositions of the surfactant and the cosurfactant in the interfacial region (interphase) of the microemulsion droplets have been determined. The thermodynamics of transfer of the cosurfactants (alkanols) from the continuous oil (alkane) phase to the interface have been evaluated from dilution measurements at different temperatures. The structural parameters, radii of the droplet and the waterpool, aggregation numbers of CPC and the alkanols in the interphase of a droplet, and the nanoparticle density of solution have been estimated assuming monodispersity of the droplets. The thermodynamics and structural parameters have been examined in terms of the chain lengths of the alkanols and alkanes. Received: 12 September 2000 Accepted: 27 October 2000     

Structure of biodiesel based bicontinuous microemulsions for environmentally compatible decontamination: A small angle neutron scattering and freeze fracture electron microscopy study

Most toxic industrial chemicals and chemical warfare agents are hydrophobic and can only be solubilized in organic solvents. However, most reagents employed for the degradation of these toxic compounds can only be dissolved in water. Hence, microemulsions are auspicious media for the decontamination of a variety of chemical warfare agents and pesticides. They allow for the solubilization of both the lipophilic toxics and the hydrophilic reagent. Alkyl oligoglucosides and plant derived solvents like rapeseed methyl ester enable the formulation of environmentally compatible bicontinuous microemulsions. In the present article the phase behavior of such a microemulsion is studied and the bicontinuous phase is identified. Small angle neutron scattering (SANS) and freeze fracture electron microscopy (FFEM) measurements are used to characterize the structure of the bicontinuous phase and allow for an estimation of the total internal interface. Moreover, also the influence of the co-surfactant (1-pentanol) on the structural parameters of the bicontinuous phase is studied with SANS.     

Application of microemulsions for the extraction of <Emphasis Type="Italic">o</Emphasis>-phthalate esters from soil with subsequent separation of microemulsions,simultaneous preconcentration,and gas chromatographic analysis of target components

The possible application of microemulsions as extractants for the extraction of o-phthalate esters from soils with the subsequent breakdown of microemulsions, simultaneous preconcentration of dialkhylphthalates in the organic phase, and their following gas chromatographic analysis with mass-spectrometric detection is demonstrated. The preconcentration factor was 18. The method is characterized by low detection limits, good selectivity, and reproducibility.     

Formation of zinc sulfide and hydroxylapatite nanoparticles in polyelectrolyte-modified microemulsions

The paper is focused on the formation of nanoparticles, i.e., zinc sulfide (ZnS) and hydroxylapatite, in a microemulsion template phase consisting of heptanol, water, and a surfactant with a sulfobetaine head group in the absence and presence of an added polyelectrolyte. In the absence of a polyelectrolyte, beside larger particles, spherical ZnS nanoparticles with a diameter below 10 nm can be redispersed after solvent evaporation. In the presence of the synthetic cationic polyelectrolyte poly(diallyldimethylammonium chloride), a reloading of the particle surface is observed, and cationic charged ZnS nanoparticles, of about 5 nm in size, can be redispersed as a main fraction. When hydroxylapatite is formed in the presence of the more stiff biopolymer chitosan hydroxylapatite, hybrid structures were formed. Transmission electron micrographs show fiber-like aggregate structures, consisting of individual small nanoparticles ordered along the polymer chain.     

Synthesis and properties of polyampholytes prepared in microemulsions

A series of polyampholytes of sodium 2-acrylamido-2-methylpropanesulfonate (NaAMPS) and 2-(methacryloyloxy)ethyltrimethylammonium chloride (MADQUAT) has been synthesized by polymerization in microemulsions. The reaction products are stable inverse latexes consisting of high molecular weight copolymers entrapped in water droplets of small size (d % 80 nm) and dispersed in an isoparaffinic oil. The optimization of the formulation was by a selection procedure based on the hydrophile-lipophile balance of the emulsifiers and solubility parameters of the different components. Both ionomers play an important role in the formulation owing to their amphiphilic and electrolyte characters. Reactivity parameter studies yield r_A and r_M values of 0.81 and 1.97 for NaAMPS and MADQUAT, respectively. The properties of polyampholytes in pure water and in salt solutions were investigated by turbidimetry and viscometry experiments. The results are compared with the recently developed theory of Higgs and Joanny (J. Chem. Phys. 94, 1543 (1991)).     

Functional hybrid nanostructures for nanophotonics: Synthesis, properties, and application

The review considers the potential of hybrid nanostructures in creating smart materials with optically controlled properties. The goals and technologies of development of stable hybrid nanostructures are analyzed. Some experimental results concerning smart materials with optically controlled properties, including those based on a unique photochromic material bacteriorhodopsin, which have a great potential in the development of a new type information systems, are summarized.     

Porphyrazines: synthesis,properties, application

The data on the synthesis, properties, and practical application of porphyrazines (tetraazaporphines), the nearest structural analogs of porphyrins and phthalocyanines, have been systematized.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2320–2336, December, 1995.This work was financially supported by the Russian Government and the International Science Foundation (Grant No. MEY300).     

Carbonates in zeolites: Formation,properties, reactivity

Two possible schemes of carbonate formation (with and without water participation) in cationic form zeolites are considered. Activation energy for the formation of hydrogen carbonate in NaX zeolite from water and carbon dioxide is calculated at the DFT level with periodic boundary conditions, while the problems of modeling the formation of symmetric carbonate in the same zeolite are discussed. The formation of copper carbonate is studied using binuclear CuOCu clusters from CO₂ where the influence of water on the barrier is discussed. The questions related to DFT application to binuclear copper clusters are also considered by comparison with the data obtained at the MP2 level. The reactivity of copper carbonate is tested in the reaction with methanol. © 2015 Wiley Periodicals, Inc.     

Carbonyl materials: Preparation,properties, and application

The synthesis of powders, films, and coatings obtained by CVD during thermal decomposition of metal carbonyl vapors is considered. The conditions for obtaining them, as well as their main properties and fields of application, are shown.     

The thiomethyl anion: Formation,reactivity, and thermodynamic properties

The thiomethyl anion (1) has been generated by fluorodesilylation of trimethylsilylmethanethiol in a variable-temperature flowing afterglow device. The proton affinity (1649 ± 12 kJ mol^?1) and electron affinity (0.67 ± .13 eV) were determined and compared to a previously reported molecular orbital calculation. Isomerization via a 1,2-proton shift does not take place between ?40° and 100°C despite a 156 kJ mol^?1 driving force. Ion-molecule reactions of 1 were examined with a number of reagents including N₂0, O₂, CS₂, COS, and CO₂, Hydride ion transfer was observed in every case, along with other products, and thermodynamic information has been derived.     

Wet foams: Formation,properties and mechanism of stability

Overall picture of phenomena occuring during formation and existence of the wet foams is presented. Properties and mechanism of stability are discussed on the example of the wet foams obtained from solutions of two homologous series of surface active substances; the fatty acids and n-alkanols. In general three physical processes which contribute to foam stability can be distinguished: drainage of liquid out of the foam, coalescence and/or rupture of bubbles, and disproportionation (which may be called Ostwald ripening or gas diffusion from one bubble to another). Dynamic and non-equilibrium character of the wet foams is stressed.Motion of a bubble through the solution causes disequilibration of the surface concentration alongside the bubble surface. The surface concentration on the upstream part of the bubble is much smaller than the equilibrium concentration. Thus, the bubbles arrive at the solution surface with non-equilibrium surface concentration, and these actual non-equilibrium surface coverages determine possibility of formation and properties of the foams.Solution content ϕ in the volume of wet foam is high (of an order 307.), while in top foam layer it is much smaller (ϕ≅5%) . It shows that rupture of the wet foam takes place practically only in the top layer of bubbles and durability of these top foam films determine stability and volume of the whole foam column. On the basis of measurements of liquid content ϕ and lifetimes of bubbles in the top foam layer it was estimated that thicknesses of rupture of these top films were of an order of a few micrometers. At such thicknesses the force of disjoining pressure do not attain yet any meaningful value.Influence of kinetics of adsorption, frequency of external disturbances, surface activity of the solute and lifetime of the foam films on magnitude of the surface elasticity forces induced in the systems studied is discussed. It is shown that stability of the wet foams can be explained in terms of the effective elasticity farces, i.e. the surface elasticity forces which are induced at an actual non-equilibrium surface coverage. There is agreement between the courses of the dependences of the foamability parameter (retention time, rt) and the effective elasticity forces as a function of the number n of carbon atoms in the fatty acid and n-alkanol molecule. This shows that the effective elasticity forces are decisive parameter in formation and stability of the wet foams. It also explains why the foamability of a substance with a stronger surface activity can be lower than that of a substance with a weaker surface activity. The foamability, especially under dynamic conditions, cannot simply be correlated with the surface activity.     

Nonionic surfactants with linear and branched hydrocarbon tails: compositional analysis, phase behavior, and film properties in bicontinuous microemulsions

Nonionic alcohol ethoxylates are widely used as surfactants in many different applications. They are available in a large number of structural varieties as technical grade products. This variety is mainly based on the use of different alcohols, which can be linear or branched and contain primary, secondary, or tertiary OH groups. Technical grade products are poorly defined as they are composed of alcohol mixtures being different in chain length and structure. On the other hand, monodisperse alcohol ethoxylates are commercially available; however, these surfactants exist only with primary and linear alcohols. In the field of microemulsion research the monodisperse alcohol ethoxylates are widely used. The phase behavior and film properties of these surfactants were studied intensively with respect to the size of the hydrophilic and hydrophobic moieties. Due to the lack of appropriate model surfactants until now, there is little information on how the structure of the hydrocarbon tail influences the microemulsion behavior. To examine structural influences, we synthesized a series of surfactants with the composition C10E5 and having different linear and branched hydrocarbon tails. The surfactants were monodisperse with respect to the hydrocarbon tail but polydisperse with respect to the ethoxylation degree. However, a detailed characterization showed that they were similar concerning the average ethoxylation degree and EO chain length distribution. The phase behavior was investigated for bicontinuous microemulsions, and the film properties were analyzed by small-angle neutron scattering (SANS). Our results show that the structure of the hydrocarbon tail strongly influences the microemulsion behavior. The most efficient surfactant is obtained if the hydrocarbon tail is linear and the hydrophilic group is attached in the C-1 position. Surfactants having the hydrophilic group bound to the C-2 or C-4 position or which contain a branched hydrocarbon tail are less efficient and exhibit in most cases visibly lower phase inversion temperatures. Both the efficiency and temperature behavior mainly can be explained on the basis of increased bulkiness of the branched structures compared to the fully linear version. The phase behavior results are largely confirmed by the SANS investigations. Those results show that the fully linear surfactant exhibits the most rigid interfacial film. In additional experiments this surfactant was compared with its monodisperse analogue. According to the phase diagrams, the surfactant having the polydisperse hydrophilic moiety is drastically more efficient although the film stiffnesses are almost identical.     

New star-like polydimethylsiloxanes: synthesis,properties, and application

Russian Chemical Bulletin - New star-like polydimethylsiloxanes with a cis-tetraphenylcyclotetrasilsesquioxane fragment as the core (branching center) were synthesized and characterized. The...     

Biocompatible microemulsions based on limonene: formulation, structure, and applications

The preparation of biocompatible (w/o) microemulsions based on R-(+)-limonene, water, and a mixture of lecithin and either 1-propanol or 1,2-propanediol as emulsifiers was considered. The choice of the compositions of the microemulsions used was based on the pseudo-ternary phase diagrams of the four-component system determined at 30 degrees C for different weight ratios of the components. When 1-propanol was considered as co-surfactant, the area of the microemulsion zone was remarkably increased. Interfacial properties and the dynamic structure of the emulsifier's monolayer were studied by electron paramagnetic resonance (EPR) spectroscopy using the spin-labeling technique. The rigidity and polarity of the interface were affected by the nature of the alcohol used as co-surfactant. When 1-propanol was used, the emulsifier's interface was much more flexible, indicating a less tight packing of lecithin molecules than in the case of 1,2-propanediol. In addition, the membrane's polarity was decreased when the diol was added as co-surfactant in the microemulsion system. To evaluate the size of the dispersed aqueous domains as a function of water content and other additives concentration, dynamic light scattering (DLS) measurements were carried out. Radii in the range from 60 to 180 nm were observed when 1-propanol was used as co-surfactant, and the water content varied from 0 to 12% w/w. Electrical conductivity measurements of R-(+)-limonene/lecithin/1-propanol/water microemulsions with increasing weight fractions of water indicated the appearance of a percolation threshold at water content above 4% w/w. Lipase from Rhizomucor miehei was solubilized in the aqueous domains of the biocompatible microemulsions, and the esterification of octanoic, dodecanoic, and hexadecanoic acids with the short-chained alcohols used as co-surfactants for the formulation of microemulsions was studied. The enzyme efficiency was affected by the chain length of the carboxylic acids and the nature of the alcohol. In the case of 1-propanol, a preference for the long-chain carboxylic acids was observed. On the contrary, when 1,2-propanediol was used formulation of the corresponding esters was not observed. This behavior could be possibly attributed to either the specificity of the lipase toward the alcohol employed for the esterification of the acids or the structural changes induced in the system when 1-propanol was replaced by 1,2-propanediol.