Type Of Co-solvent Research Articles

Fractionation of Used Frying Oil by Supercritical CO2 and Cosolvents

Supercritical extraction with pure and modified CO2 has been used for the fractionation of waste frying oil at different temperature and pressure conditions (25−80 °C and 300−400 kg/cm2). The cosolvents used to modify the CO2 behavior were ethanol, methanol, acetone, and hexane. They were selected because of their capacity to form hydrogen bonds. Both extraction rate and oil yield were larger under high density conditions (high pressure and low temperature). Further, when cosolvents were used, higher values of both variables were attained at softer operating pressures. Regarding the effect of cosolvents on these variables, it was found to follow this order: ethanol > methanol > acetone > hexane. The relative separation efficiency (RSE) of triglycerides (TG) from polar compounds with molecular weight higher than triglycerides (HMWC) was not greatly dependent on the operating conditions (pressure, temperature, cosolvent type, and cosolvent concentration). However, better values of the separation efficiency ...

Narrowly Size-Distributed Cobalt Salt Containing Poly(2-hydroxyethyl methacrylate) Particles by Inverse Miniemulsion

Cobalt-containing hybrid particles have been prepared through the encapsulation of cobalt tetrafluoroborate hexahydrate (CoTFB) via inverse miniemulsion polymerization of 2-hydroxyethyl methacrylate (HEMA). We systematically varied the amount and type of cosolvent (water, methanol, ethanol, ethylene glycol), apolar continuous phase (cyclohexane, isooctane, isopar M, hexadecane), amount of cobalt salt, and molecular weight of the polymeric surfactant. The influence of those parameters on the particle size, size distribution, and particle morphology were investigated. Narrowly size-distributed hybrid particles with good colloidal stability could be obtained in a wide range of cobalt content between 5.7 and 22.6 wt % salt relative to the monomer. The addition of a cosolvent such as water not only promotes the loading of metal salt but also has a positive influence on narrowing the particle size distribution. We assume that generally narrowly size-distributed particles can be obtained for a large variety of combinations of polar/apolar phase by adjusting the balance between osmotic and Laplace pressure via the solubility of the metal salt in the continuous phase and lowering the interfacial tension by adjusting the hydrophilic-lipophilic balance (HLB) value of the surfactant. The results show a significant advantage of the inverse miniemulsion over the direct system with respect to the variability and total amount of metal salt without losing the narrow particle size distribution and colloidal stability.

Application of dispersive liquid–liquid microextraction for the determination of phenylurea herbicides in water samples by HPLC‐diode array detection

A simple dispersive liquid-liquid microextraction method combined with HPLC-photodiode array detection has been developed for the determination of phenylurea herbicides in water samples. The herbicides studied included tebuthiuron, diuron, propanil, fluometuron, siduron, linuron, thidiazuron, and diflubenzuron. Several factors influencing the extraction efficiency of the studied compounds, such as extraction and disperser solvent type and their volumes, co-solvent type and its fraction, and ionic strength were investigated and optimized. Under the optimum extraction conditions, the calibration graphs were linear in the range of 0.2-200 mug/L for target analytes. The enrichment factors were between 11 and 118. The LOD were in the range of 0.01-0.5 mug/L (S/N=3). The relative standard deviations obtained ranged from 3.0 to 7.8% (n=5).

Effect of Penetration Enhancers on Transdermal Delivery of Propofol

To develop a transdermal dosage form of propofol (PF), in vitro skin permeability and in vivo absorbability of PF were investigated in rats, and the effectiveness of enhancers on the transdermal delivery of PF was estimated. Propylene glycol (PG), isopropyl myristate and macrogol were used as co-solvent type enhancers. L(-)-Menthol (MEN), D(+)-limonene, oleic acid, stearic acid, sucrose fatty acid esters and sodium dodecyl sulfate (SDS) were used as membrane-acting type enhancers. Among the co-solvent type enhancers, PG showed the highest enhancing effect in vitro. Furthermore, the synergistic effect of the combined use of PG and membrane-acting type enhancers was confirmed. Higher values of permeation parameters were observed with the combined use of PG and MEN, sucrose fatty acid esters or SDS. For the in vivo experiment, the addition of a smaller amount of PG was preferable to the amount used in the in vitro experiment. The synergistic effect of enhancers was observed with the combined use of PG and MEN. Our findings suggest that the combination of PG and MEN was useful as enhancers for the transdermal absorption of PF. These results provide useful information to develop a transdermal dosage form of PF as a sedative or a hypnotic.

The effect of ultrasonic agitation on the stripping of photoresist using supercritical CO 2 and co-solvent formulation

A novel technology for removing high-dose ion-implanted photoresist (HDI PR) from semiconductor wafers using supercritical carbon dioxide (scCO 2) and several co-solvent formulations have been described. A combination of ultrasonic agitation with scCO 2/co-solvent stripping was found to be an effective method for photoresist removal. Ultrasonic agitation was an efficient technique for achieving higher stripping rates. The effects of temperature, pressure, reaction time and the type of organic co-solvent on the stripping rate of HDI PR were investigated. The microstructures of sample wafers after stripping were characterized by scanning electron microscopy and energy dispersive X-ray spectrometer.

Acetic Acid Recovery from Fast Pyrolysis Oil. An Exploratory Study on Liquid-Liquid Reactive Extraction using Aliphatic Tertiary Amines

Flash pyrolysis oil or Bio-oil (BO), obtained by flash pyrolysis of lignocellulosic biomass, is very acidic in nature. The major component responsible for this acidity is acetic acid, present in levels up to 2–10 wt%. Here, we report an exploratory study on BO upgrading by reactive extraction of acetic acid using long-chain tertiary amines in a batch set-up. Factors affecting the extraction efficiency, such as the type and concentration of tertiary amine and co-solvents, were investigated. More than 90 wt% of the acetic acid could be extracted in a single equilibrium step (BO diluted in THF (26 wt% BO), trioctylamine (TOA) in octane as the extractant phase, T = 20°C). However, the amine has considerable affinity for the BO phase and about 10 wt% on initial intake was transferred to the BO. A considerable improvement was obtained when using the aqueous phase of a thermally treated BO containing 6 wt% acid of acetic acid. In a single extraction step, acetic acid extraction efficiencies up to 75 wt% were achieved without significant amine transfer to the aqueous phase.

Hollow-fibre liquid-phase microextraction: A simple and fast cleanup step used for PAHs determination in pine needles

A new, fast and simple cleanup procedure, based on hollow-fibre liquid-phase microextraction (HF-LPME) is described here, used for the determination of 13 polycyclic aromatic hydrocarbons (PAHs) in complex pine needle samples. Initially, pine needle samples were sonicated in a 20 mL aqueous solution having a 20% (v:v) acetone content and 5 mL of the sonicated liquid extract was then used for the HF-LPME cleanup step. Different experimental parameters (namely: type of organic solvent used as acceptor phase, effect and type of co-solvent, salt addition, sample agitation and sampling time) were controlled and optimized based on the response of GC–MS instrument under the SIM mode. Under the optimized experimental conditions found the typical chromatograms obtained revealed that despite the very complex matrix of pine needles the HF-LPME cleanup step greatly reduced if not eliminated the presence of interferents, resulting in chromatograms which contained very cleanly separated and readily evaluable PAH peaks. In addition, the proposed method was found to be linear in the concentration 10–2000 ng g −1 for most target analytes and the limits of detection for a S/N = 3 ranged between 0.01 and 0.95 ng g −1 (dry weight). Furthermore, the repeatability and reproducibility were also found good. Finally, the proposed method was applied for the analysis of real pine needle samples taken for different parts of the island of Crete.

Effect of Temperature, Pressure, and Cosolvents on Structural and Dynamic Properties of the Hydration Shell of SNase: A Molecular Dynamics Computer Simulation Study

It is now generally agreed that the hydration water and solvational properties play a crucial role in determining the dynamics and hence the functionality of proteins. We present molecular dynamics computer simulation studies on staphylococcal nuclease (SNase) at various temperatures and pressures as well as in different cosolvent solutions containing various concentrations of urea and glycerol. The aim is to provide a molecular level understanding of how different types of cosolvents (chaotropic and kosmotropic) as well as temperature and high hydrostatic pressure modify the structure and dynamics of the hydration water. Taken together, these three intrinsic thermodynamic variables, temperature, pressure, and chemical potential (or activity) of the solvent, are able to influence the stability and function of the protein by protein-solvent dynamic coupling in different ways. A detailed analysis of the structural and dynamical properties of the water and cosolvents at the protein surface (density profile, coordination numbers, hydrogen-bond distribution, average H-bond lifetimes (water-protein and water-water), and average residence time of water in the hydration shell) was carried out, and differences in the structural and dynamical properties of the hydration water in the presence of the different cosolvents and at temperatures between 300 and 400 K and pressures up to 5000 bar are discussed. Furthermore, the results obtained help understand various thermodynamic properties measured for the protein.

Supercritical Fluid Processing of Drug Nanoparticles in Stable Suspension

Significant effort has been directed toward the development of drug formulation and delivery techniques, especially for the drug of no or poor aqueous solubility. Among various strategies to address the solubility issue, the reduction of drug particle sizes to the nanoscale has been identified as a potentially effective and broadly applicable approach. Complementary to traditional methods, supercritical fluid techniques have found unique applications in the production and processing of drug particles. Here we report the application of a newly developed supercritical fluid processing technique, Rapid Expansion of a Supercritical Solution into a Liquid Solvent, to the nanosizing of potent antiparasitic drug Amphotericin B particles. A supercritical carbon dioxide-cosolvent system was used for the solubilization and processing of the drug. The process produced well-dispersed nanoscale Amphotericin B particles suspended in an aqueous solution, and the suspension was intrinsically stable or could be further stabilized in the presence of water-soluble polymers. The properties of the drug nanoparticles were found to be dependent on the type of cosolvent used. The results on the use of dimethyl sulfoxide and methanol as cosolvents and their effects on the properties of nanosized Amphotericin B particles are presented and discussed.

Physicochemical basis for cosolvent modulation of β-lactoglobulin functionality: Interfacial tension study

Abstract The impact of neutral cosolvents on the thermal stability of globular proteins in aqueous solutions depends on the nature of the cosolvent, e . g ., sorbitol causes a pronounced increase in the thermal denaturation temperature ( T m ) of β-lactoglobulin (β-lg), whereas glycerol does not. When a protein unfolds there is a change in the exposed surface area and in the type of molecular interactions that occur at the protein–solvent–cosolvent interface. These changes contribute to the free energy change associated with protein denaturation and depend on cosolvent type. In this study we measured the equilibrium interfacial tensions of aqueous glycerol (0–70% w/w) and sorbitol (0–55% w/w) solutions as a function of temperature to provide insights into the role of the interfacial energy on the thermal stability of β-lg. There was a slight increase in interfacial tension with increasing sorbitol concentration, indicating its preferential exclusion from the oil–water interface. On the other hand, there was an appreciable decrease in interfacial tension with increasing glycerol concentration, indicating its preferential accumulation at the oil–water interface. These changes were largely independent of the measurement temperature (30–80 °C). Our results suggest that sorbitol increases the T m of β-lg mainly through a steric exclusion effect, whereas glycerol has little effect on T m because the steric exclusion effect is counter-balanced by a differential interaction effect.

Impregnation of silk sericin into polyester fibers using supercritical carbon dioxide

AbstractSilk sericin was impregnated into polyester fabric using supercritical carbon dioxide (SCCO2) to overcome polyester hydrophobicity. The effects of sericin molecular weight, pH of sericin, solution and cosolvent types on sericin impregnation were investigated. Enzyme‐hydrolyzed, acid‐, based‐hydrolyzed sericin in SCCO2, and a 30 kDa sericin in SCCO2 modified with cosolvents such as water, methanol, 1‐propanol, and acetone; and a modifier: sodium hydroxide solution were used in this work. Impregnation of sericin in polyester was indicated by Fourier transform infrared spectrophotometry (FTIR) and dyeing with acid dye. Degradation of polyester fibers during SCCO2 process was indicated by scanning electron microscopy (SEM). Methylene blue dyeing was used to realize carboxyl group in polyester. The results showed no impregnation of sericin into polyester by using SCCO2 modified with cosolvents. However, sericin was impregnated into modified surface polyester since hydrophilic groups such as carboxyl and hydroxyl groups were regenerated by alkaline hydrolysis. Samples impregnated with hydrolyzed sericin showed high color strength of Supranolechtbordeaux B acid dye. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007

Synthesis and properties of new thermosensitive polymer systems

AbstractThe controlled thermal release of aqueous solvent mixtures from polymeric gel particles was investigated. A new type of a polymeric gel consisting of a maleic anhydride/poly(ethylene glycol) condensation product as a crosslinking macromonomer and acrylamides was synthesized by solution or inverse emulsion polymerization for the investigation. Afterward a shell of crosslinked polystyrene was coated to stabilize this new kind of “microcontainer” for the application. This concept was shown as generally useful for various mixtures of organic solvents and water. The cloud point temperature of the polymer gel strongly depended on the following parameters: the type and content of organic cosolvent, the degree of polymerization and constituents of the polyester moiety, and the type and content of the comonomers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007

Towards an Understanding of the Temperature/ Pressure Configurational and Free-Energy Landscape of Biomolecules

Besides temperature, we used hydrostatic pressure as a physical parameter for studying the stability and energetics of biomolecular systems. High pressure is also an important feature of certain natural environments, and the high-pressure phase behaviour of biomolecules is of increasing biotechnological interest. By using thermodynamic, spectroscopic, and scattering techniques, the temperature and pressure-dependent structure and phase behaviour of model biomembrane systems and proteins have been studied. The results demonstrate that combined temperature–pressure-dependent studies can help delineate the conformational and free-energy landscape of biomolecules and hence help to elucidate which features and thermodynamic parameters are essential in determining their stability. Moreover, we present data on the effect of various types of cosolvents on the temperature- and pressure-dependent structure and stability of proteins. We also introduce pressure as a kinetic variable. Applying the pressure-jump relaxation technique in combination with time-resolved synchrotron X-ray diffraction and spectroscopic techniques, the kinetics of lipid phase transitions and un/refolding reactions of proteins have been studied. Finally, recent advances in using the pressure axis for studying misfolding, aggregation, and amyloid fibril formation of proteins and its potential biotechnological and biomedical relevance will be discussed. We conclude with an outlook of the perspectives of high pressure research.

Encapsulation of hydrophobic drugs in polymeric micelles through co-solvent evaporation: The effect of solvent composition on micellar properties and drug loading

This study was designed to develop an optimized co-solvent evaporation procedure for the efficient encapsulation of hydrophobic drugs in polymeric micelles of methoxy poly(ethylene oxide)- block-poly(ɛ-caprolactone) (MePEO- b-PCL). MePEO- b-PCL block copolymers having varied MePEO and PCL molecular weights were synthesized, assembled to polymeric micelles, and used for the encapsulation of cyclosporine A (CyA) by a co-solvent evaporation method. The co-solvent composition was varied by changing the type of organic co-solvent (using acetone, acetonitrile and tetrahydrofuran), the ratio of organic to aqueous phase, and their order of addition. Carrier size, morphology and encapsulated CyA levels were defined by dynamic light scattering (DLS), transmission electron microscopy (TEM) and HPLC, respectively, and the effect of co-solvent composition on micellar properties and loaded CyA levels was evaluated. Application of acetone and acetonitrile as the selective co-solvent for the core-forming block led to a decrease in the average diameter of self-assembled structures. When acetone was added to water, a decrease in the ratio of organic to aqueous phase led to an increase in the loading efficiency of CyA in MePEO- b-PCL micelles. A similar trend in CyA loading was observed for MePEO- b-PCL micelles of varied MePEO and PCL block lengths. The ratio of organic to aqueous phase did not affect CyA loading when water was added to acetone. Irrespective of the order of addition, the decrease in the organic to aqueous phase ratio caused a reduction in the average diameter of the empty and CyA loaded micelles. We conclude that the co-solvent evaporation method may be optimized to improve the efficiency of drug encapsulation in polymeric micelles. For CyA encapsulation in MePEO- b-PCL micelles, addition of acetone to water at lower organic to aqueous phase ratio is shown to be the optimum procedure leading to higher drug encapsulation and smaller average diameter for the self-assembled structures.

Pressure perturbation calorimetric studies of the solvation properties and the thermal unfolding of proteins in solution—experiments and theoretical interpretation

We used pressure perturbation calorimetry (PPC), a relatively new and efficient technique, to study the solvation and volumetric properties of amino acids and peptides as well as of proteins in their native and unfolded state. In PPC, the coefficient of thermal expansion of the partial volume of the protein is deduced from the heat consumed or produced after small isothermal pressure jumps, which strongly depends on the interaction of the protein with the solvent or cosolvent at the protein-solvent interface. Furthermore, the effects of various chaotropic and kosmotropic cosolvents on the volume and expansivity changes of proteins were measured over a wide concentration range with high precision. Depending on the type of cosolvent and its concentration, specific differences were found for the solvation properties and unfolding behaviour of the proteins, and the volume change upon unfolding may even change sign. To yield a molecular interpretation of the different terms contributing to the partial protein volume and its temperature dependence, and hence a better understanding of the PPC data, molecular dynamics computer simulations on SNase were also carried out and compared with the experimental data. The PPC studies introduced aim to obtain more insight into the basic thermodynamic properties of protein solvation and volume effects accompanying structural transformations of proteins in various cosolvents on one hand, as these form the basis for understanding their physiological functions and their use in drug designing and formulations, but also to initiate further valuable applications in studies of other biomolecular and chemical systems.

New drug salt formation in biodegradable microspheres

Purpose. To investigate the effects of inorganic salts in the external phase of an oil-in-water (O/W) emulsion method during microsphere preparation. Methods. An O/W emulsion method was used to prepare poly( d, l-lactic acid) microspheres containing quinidine sulfate. Different inorganic salts were used in the external phase during microsphere preparation. Microsphere drug loading was determined by UV and the drug salt anions inside the microspheres were determined by ion chromatography. Results. New drug salts were formed during encapsulation in the microspheres when salts with non-common anions to the drug salt were used. Drug loading increased when NaClO 4 or NaSCN were used. The fraction of drug as the new salt in microspheres increased non-linearly with the salt concentration in the external phase, however, the fraction of drug as the new encapsulated salt was linearly related to drug loading. Drug loading decreased and new salt fraction increased with increasing organic solvent volume or with decreasing cosolvent polarity. Conclusions. Introducing salts containing non-common anions to the drug salt employed in the external phase of O/W emulsion microsphere method leads to new salt formation. The extent of new drug salt formation is affected by salt levels added, cosolvent type and polymer concentration.

Effect of Alcohols on the Retention Mechanisms of Cd and Zn on Wyoming Bentonite and Illite

The effects of ethanol- and methanol-water mixtures on Zn and Cd sorption onto bentonite and illite were investigated at low initial metal concentration (< or =10(-5) M) and low ionic strength (2.5 mM Ca(NO3)2). For all cosolvent fractions, the percent coverage of Zn and Cd to clay minerals was low (<5%) and independent of the solution dielectric constant, epsilon, except for Zn at 10 microM. Cadmium sorption to bentonite and illite was independent of epsilon. Zinc sorption varied significantly between clay types, cosolvent type, and cosolvent fraction. The partitioning of Zn to bentonite increased from 0 to 10% alcohol-water fraction and decreased after 10%. The same pattern was observed for the partitioning of Zn on illite in methanol-water mixtures. In ethanol-water mixtures, Kf for Zn on illite increased continuouslyfrom 0 to 50% ethanol. The decreased partitioning and hence mobility of Zn to bentonite and illite after 10% alcohol (only in methanol-water mixtures for illite) suggests a potential environmental threat resulting from increased transport of this metal in subsurface environments where these cosolvents are present.

Pressure-assisted cold denaturation of hen egg white lysozyme: the influence of co-solvents probed by hydrogen exchange nuclear magnetic resonance

COSY proton nuclear magnetic resonance was used to measure the exchange rates of amide protons of hen egg white lysozyme (HEWL) in the pressure-assisted cold-denatured state and in the heat-denatured state. After dissolving lysozyme in deuterium oxide buffer, labile protons exchange for deuterons in such a way that exposed protons are substituted rapidly, whereas "protected" protons within structured parts of the protein are substituted slowly. The exchange rates k obs were determined for HEWL under heat treatment (80 degrees C) and under high pressure conditions at low temperature (3.75 kbar, -13 degrees C). Moreover, the influence of co-solvents (sorbitol, urea) on the exchange rate was examined under pressure-assisted cold denaturation conditions, and the corresponding protection factors, P, were determined. The exchange kinetics upon heat treatment was found to be a two-step process with initial slow exchange followed by a fast one, showing residual protection in the slow-exchange state and P-factors in the random-coil-like range for the final temperature-denatured state. Addition of sorbitol (500 mM) led to an increase of P-factors for the pressure-assisted cold denatured state, but not for the heat-denatured state. The presence of 2 M urea resulted in a drastic decrease of the P-factors of the pressure-assisted cold denatured state. For both types of co-solvents, the effect they exert appears to be cooperative, i.e., no particular regions within the protein can be identified with significantly diverse changes of P-factors.

Development of a Universal Group Contribution Equation of State. 5. Prediction of the Solubility of High-Boiling Compounds in Supercritical Gases with the Group Contribution Equation of State Volume-Translated Peng−Robinson

In recent years, supercritical extraction processes, reactions in supercritical fluids, and rapid expansion of supercritical solutions processes for the generation of microparticles have become of great interest for different industrial applications. For the design of such processes, the solubility of the various compounds (high-boiling substances, educts, products, and catalysts) as a function of the pressure, temperature, type, and amount of cosolvents in the supercritical fluid (SCF) is the most important quantity. In most cases, the solubilities are correlated using cubic equations of state (EoS). Because the experimental database is limited, predictive models would be desirable. In this paper, the potential of the group contribution EoS volume-translated Peng−Robinson (VTPR), which was already successfully applied for the prediction of vapor−liquid equilibria, gas solubilities, activity coefficients at infinite dilution, and excess enthalpies, was investigated for the prediction of solubilities of various solids and liquids in supercritical carbon dioxide, ethane, and ethylene. Besides the influence of pressure, temperature, and SCF, in particular how suitable the VTPR model is to predict the effect of cosolvents on the phase equilibrium behavior was examined.

Effects of chaotropic and kosmotropic cosolvents on the pressure-induced unfolding and denaturation of proteins: an FT-IR study on staphylococcal nuclease.

FT-IR spectroscopy was used to study the effects of various chaotropic and kosmotropic cosolvents (glycerol, sucrose, sorbitol, K(2)SO(4), CaCl(2), and urea) on the secondary structure and thermodynamic properties upon unfolding and denaturation of staphylococcal nuclease (Snase). The data show that the different cosolvents have a profound effect on the denaturation pressure and the Gibbs free energy (DeltaG(o)) and volume (DeltaV(o) change of unfolding. Moreover, by analysis of the amide I' infrared bands, conformational changes of the protein upon unfolding in the different cosolvents have been determined. An increase, a reduction, or an independence of the volume change of unfolding is observed, depending on the type of cosolvent, which can at least in part be attributed to the formation of a different unfolded state structure of the protein. The data are compared with the corresponding thermodynamic values of DeltaV(o) for the temperature-induced unfolding process of Snase as obtained by pressure perturbation calorimetry, and significant differences are observed and discussed.