Three approaches to preparing iron oxide nanoparticle-decorated microbubbles (NP-decoMBs) have been investigated. The size and stability characteristics of these microbubbles (MBs) were investigated by optical microscopy, laser light scattering and an acoustical method, and compared with those of non-decorated MBs. First, magnetite nanoparticles (Fe3O4NPs) grafted with dimyristoylphosphatidylcholine (DMPC) were synthesized and used to prepare MBs by brief sonication under an atmosphere of air saturated with perfluorohexane. These MBs had a rather large mean radius (r ~ 12 µm), and a moderate volume of encapsulated gas. Remarkably, a second approach that consisted of dispersing unbound DMPC molecules in the aqueous phase along with DMPC-grafted Fe3O4NPs prior to sonication was found to drastically change the situation, allowing the obtaining of monomodal populations of much smaller (r ~ 0.6 µm) NP-decoMBs. The latter were echogenic and stable for at least 10 days at room temperature, without significant variation of their size characteristics. In a third approach, NP-decoMBs were directly prepared from dispersions of naked Fe3O4NPs in the presence of DMPC. The resulting NP-decoMBs suspensions consisted of broadly distributed bubble populations mostly containing two populations (with r ~ 5 and ~ 15 µm). Control microbubbles made of DMPC only were small (r ~ 1.3 µm), although not as small as those formed from DMPC-grafted Fe3O4NPs in the presence of free DMPC, and were less stable, with a room temperature half-life of only ~1 day. These observations imply that there is a synergy between the Fe3O4NPs and the DMPC molecules in the air/water interfacial film stabilization process.
Over the past two decades, catanionic vesicles fabricated from mixtures of oppositely charged surfactants have attracted substantial attention because of their potential applications in drug delivery. This review focuses on the recent strategies in the development of novel catanionic vesicles, including eliminating excess salt in catanionic mixture systems, increasing the solubility of ion pair amphiphiles, improving drug loading contents, and enhancing the stability of catanionic vesicles. In addition, the gelation behavior of catanionic vesicles caused by polymers is also described.
Langmuir monolayers of amphiphilic molecules at an air-water interface can be compressed laterally to achieve high surface density. However, compression beyond a certain threshold causes the monolayer to become unstable, which may lead to the formation of collapsed states with topographical differences that are associated with the structures and mechanical properties of the constituent molecules of the monolayer. The mechanisms and collapsed structures can differ owing to differences in experimental conditions, i.e., temperature, ion-content, the pH of subphase, or compression rate; in addition, the type of constituent molecules, i.e., biological lipids or chemical surfactants, has an effect. In this review, we compare studies concerning several aspects of collapse, from basic concepts and theoretical mechanisms to experimental visualization of the monolayer topography. In addition, techniques often employed to study this subject are discussed in this review.
The physicochemical properties of large unilamellar vesicles (LUVs) were assessed with respect to lipid composition, pH, time, and temperature by monitoring their size, zeta potential, drug payload, and thermal behavior. A conventional thin film hydration technique was employed to prepare liposomes from soy phosphatidylcholine (SPC), dipalmitoylphosphatidylcholine (DPPC), dipalmitoylphosphatidylglycerol (DPPG), and a 7:3 (M/M) mixture of DPPC+DPPG along with 30 mole% cholesterol in each combination. While the size of liposomes depended on lipid composition, pH and temperature, the zeta potential was found to be independent of the pH of the medium, although it varied with liposome type. Spherical morphology and bilayer were observed by electron microscopy. The phase transition temperature increased with decreasing pH. Membrane micro-viscosity showed the highest value for SPC, and membrane rigidity increased with increasing pH. The entrapment efficiency of liposomes with reference to curcumin was as follows: DPPC>DPPC+DPPG>DPPG>SPC. Sustained release of curcumin was observed for all liposomes. Curcumin-loaded liposomes exhibited substantial antibacterial activity against the gram-positive bacteria Bacillus amyloliquefaciens. Additional studies are needed to improve the understanding of the effect of formulation variables on the physicochemical stability of liposomes.
Disulfide bond shuffling in the presence of the reducing agents dithiothreitol (DTT) or β-mercaptoethanol (BME) strongly affects the surface properties of lysozyme solutions. The addition of 0.32 mM DTT substantially alters the kinetic dependencies of the dynamic surface elasticity and surface tension relative to those of pure protein solutions. The significant increase in the dynamic surface elasticity likely relates to the cross-linking between lysozyme molecules and the formation of a dense layer of protein globules stabilized by intermolecular disulfide bonds at the liquid/gas interface. This effect differs from the previously described influence of chaotropic denaturants, such as guanidine hydrochloride (GuHCl) and urea, on the surface properties of lysozyme solutions. If both chaotropic and reducing agents are added to protein solutions simultaneously, their effects become superimposed. In the case of mixed lysozyme/GuHCl/DTT solutions, the dynamic surface elasticity near equilibrium decreases as the GuHCl concentration increases because of the gradual loosening of the cross-linked layer of protein globules but remains much higher than that of lysozyme/GuHCl solutions.
Mutual miscibility of soylecithin, tristearin, fatty acids (FAs), and curcumin was assessed by means of surface pressure–area isotherms at the air-solution interface in order to formulate modified solid lipid nanoparticles (SLN). Appearance of minima in the excess area (Aex) and changes in free energy of mixing (∆G0ex) were recorded for systems with 20 mole% FAs. Modified SLNs, promising as topical drug delivery systems, were formulated using the lipids in combination with curcumin, stabilized by an aqueous Tween 60 solution. Optimal formulations were assessed by judiciously varying the FA chain length and composition. Physicochemical properties of SLNs were studied such as the size, zeta potential (by dynamic light scattering), morphology (by freeze fracture transmission electron microscopy), and thermal behavior (by differential scanning calorimetry). The size and zeta potential of the formulations were in the range 300–500 nm and –10 to –20 mV, respectively. Absorption and emission spectroscopic analyses supported the dynamic light scattering and differential scanning calorimetry data and confirmed localization of curcumin to the palisade layer of SLNs. These nanoparticles showed a sustained release of incorporated curcumin. Curcumin-loaded SLNs were effective against a gram-positive bacterial species, Bacillus amyloliquefaciens. Our results on the physicochemical properties of curcumin-loaded SLNs, the sustained release, and on antibacterial activity suggest that SLNs are promising delivery agents for topical drugs.
Molecular self-assembly has become a popular tool to prepare nanomaterials with potential applications, such as ion-responsive detection of Hg2+ in aqueous solutions. In this study, FFACD aromatic pentapeptides, whose N-terminuses were protected by carboxyl (Ac-FFACD) or a 9-fluorenylmethoxycarbonyl group (Fmoc-FFACD), were chosen as building blocks to produce nanostructures in solutions. Based on the preliminary determination of the critical aggregation concentration (CAC) of Ac-FFACD and Fmoc-FFACD aromatic pentapeptides in water, the order of magnitude of which is 10–5 mol·L–1, self-assembled spiral and networked nanowires can be easily obtained over a range of concentrations. These nanowires were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The self-assembled spiral and networked nanowires were designed to be used as templates for preparing CdS quantum dots (QDs) in-situ at room temperature. The peptide-functionalized, nanowire-encapsulated CdS QDs can be used for rapid, sensitive, and selective detection of trace amounts of mercuric ions (Hg2+) in aqueous solutions. This method enables rapid, linear detection (the linear correlation coefficients are 0.9972 of ΔF = 257.09 + 3.58 cHg2+ for Ac-FFACD and 0.9994 of ΔF = 48.13 + 32.96 cHg2+ for Fmoc-FFACD) with the Hg2+ limit of detection at 300.85 ng·L–1 and 32.09 ng·L–1 for Ac-FFACD and Fmoc-FFACD, respectively. The supramolecular, self-assembled nanowires, fabricated from the two aromatic pentapeptides and having encapsulated QDs, exhibit superior properties attributable to the large loading capacity and the coordination sites of these peptides with Hg2+. These structures can serve as novel Hg2+ sensors and have possible applications for detection of various targets in scientific and engineering systems.
Non-catalytic esterfication of free fatty acids (FFA) present in vegetable oils is an alternative pretreatment process for the biodiesel production. Biodiesel, consists of long-chain fatty acid methyl esters (FAME) and is obtained from renewable sources such as vegetable oils or animal fat. This study presents kinetics of thermal esterification of free fatty acids present in jatropha oil with methanol. The effect of process parameters like reaction time (1-5 h), temperature (170-190°C) and oil to methanol ratio (1:3-1:5) at constant pressure was investigated. The optimal conditions were found to be oil to methanol ratio of 1:4, 190°C, at 27.1 bar and 5 h which gave a maximum conversion of 95.1%. A second order kinetic model for both forward and backward reactions was proposed to study the reaction system. A good agreement was observed between the experimental data and the model values. The activation energy for forward reaction and the heat of reaction were found to be 36.364 Kcal/mol and 1.74 Kcal/mol respectively.
A beany and green off-odor is developed in soy bean oil (SBO) under light-induced oxidative conditions. 3-Methyl-2,4-nonanedione (3-MND) was inferred as the compound responsible for the off-odor. In this study, we designed a simple quantification method for 3-MND in SBO, and evaluated the relationship between the 3-MND concentration and the intensity of the off-odor. 3-MND was analyzed by GC/MS with a thermal desorption unit system. By our method, the 3-MND concentration was found to increase with storage days and the SBO content under light exposure, and there was a high correlation between the measured 3-MND concentration and the intensity of the light-induced off-odor in SBO (R = 0.9586).
In this paper, a novel magnetic mesoporous Pd catalyst is used to catalyse selective hydrogenation of sunflower oil at a mild temperature of 50°C. Effects of reaction temperature, stirring speed, time, catalyst loading and hydrogen pressure on the reaction activity, trans fatty acid (TFA) and stearic acid formation were studied. Under the condition of 3.2 mg Pd/100 g oil, 50°C, 1300 rpm stirring speed and 19.0 atm of H2, the lowest amount of TFA generated during the reaction (IV = 80) was 14.9 ± 0.4% while 11.4 ± 0.4% of stearic acid was produced. And this magnetic Pd-catalyst can be reused easily for at least six times without significant catalyst deactivation, the amount of TFA almost remained unchanged. Moreover, this Pd-catalyst shows a good magnetic separation, which provides a potential method for the facile oil modification.
Important Announcement for the Contributors of the Journal of Oleo Science;
At 0:00 AM on April 1, 2016 (Japan time), the Journal of Oleo Science will start charging Publication Charge for each case; 1: 20,000 yen (within 8 pages. /more than 8 pages, additional charge is necessary; 2,000 yen per page) for Members of Japan Oil Chemists’ Society (JOCS) (including Asian Members and Support Members), 2: 40,000 yen (within 8 pages. /more than 8 pages, additional charge is necessary; 4,000 yen per page) for Non-Members of JOCS.
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