Colloidal Stability of Emulsifier-free Oil-in-Water Emulsions: Effect of Oil Properties.

This study aims to determine the factors affecting the colloidal stabilization of emulsifier-free (EF) oil-in-water (O/W) emulsions prepared by mixing oil and water with a high-powered bath-type ultrasonicator (HPBath-US; 28 kHz, 300 W) in the absence of emulsifiers such as surfactants. The interrelation between the colloidal stability, oil properties (oil density, interfacial tension between oil and water, solubility parameter of oil, and oil viscosity), and emulsion properties (diameter and zeta-potential of oil droplets) of such EF-O/W emulsions were examined for this purpose. The colloidal stability of EF-vegetable oil-in-water emulsions (EF-VEG/W) was significantly higher than that of EF-hydrocarbon oil-in-water emulsions (EF-HDC/W) and EF-fatty acid-in-water emulsions (EF-FA/W). This can be attributed to the larger density of vegetable oils (VEG) (approximately 0.9 g cm-3), the formation of smaller-sized oil droplets (diameter of approximately 0.2 µm) in the EF-VEG/W emulsions, and the lower solubility parameter of VEG (δ around 1). Furthermore, the formation of smaller-sized oil droplets in the EF-O/W emulsions correlated with the physical properties of the oil.

Unimodal sized silica nanocapsules produced through water-in-oil emulsions prepared by sequential irradiation of kilo- and submega-hertz ultrasounds.

This study investigates the regulation of the size of 100 nm hollow-sphere silica particles using surfactant-free water-in-oil (W/O) emulsion. First, water droplets were dispersed in soybean oil via sequential ultrasound irradiation (28 kHz → 200 kHz → 950 kHz). A precursor of hollow silica particles was prepared using hydrolysis and polymerization of methylsilyl trichloride into a stable W/O emulsion. The final structure/morphology of the silica particles was influenced by the volume ratio of water/soybean oil, the cycle number of the sequential ultrasound irradiation, and the amount of organosilane added to the emulsion. The emulsion was stabilized by Ostwald ripening, as the size distribution at 5/103 (water/oil = v/v) was a bimodal split between a water droplet size of a few µm and some with a size of a few tens of nm. The most appropriate cycle number was 3 in this system. Further cycling to 5 resulted in a broad and bimodal size distribution of the final particles due to rapid coalescence of water droplets. Subsequent hydrolysis of methylsilyl trichloride consumed water with diminishing large droplets, forming fine and unimodal (0.12 ± 0.02 µm) hollow silica particles. Very fine and uniform-sized hollow particles (0.08 ± 0.01 µm) were successfully produced by decreasing the volume ratio to 1/103 (water/oil) because of a transparent stable emulsion as a homogeneous template of the hollow structures.

Enhanced podocyte vesicle transport in the nephrotic rat.

Albumin endocytosis is enhanced in the podocytes of minimal change nephrotic syndrome. We investigated that the endocytic vesicle transport in the podocyte using three-dimensional observation in a rat model of puromycin aminonucleoside (PAN)-induced nephrotic syndrome. At day 7, Evans Blue-labeled albumin was intravenously injected in PAN rats, and one kidney was fixed for a morphological analysis; the other was used for the isolation of glomeruli through sieving and protein analyses. Evans Blue-labeled albumin was found to accumulate in an increased number of vesicles in the podocytes of PAN rat. Continuous sections and its three-dimensional observation demonstrated that vesicles may be transported from the cytoplasm to the apical membrane of the podocytes. The increased protein bands in the gel electrophoresis of the sieved glomeruli of nephrotic rats were analyzed by mass spectrometry in comparison to the control rats. The major proteins increased in the nephrotic rats were cytoplasmic dynein 1 heavy chain, myosin IX, and myosin VIIb. In conclusion, the podocyte endocytic vesicles carrying albumin increased with glomerular cytoplasmic dynein and myosin in minimal change nephrotic rats.

A facile route of gold nanoparticle synthesis and surface modification using amino-terminated poly(ethylene oxide)-poly(propylene oxide) block copolymers.

We report here a facile synthetic method and surface modification of gold nanoparticles using amino-terminated poly(ethylene oxide)-poly(propylene oxide) block copolymers (CH3-[OCH2CH2]x-[OCH2CH(CH3)]y-NH2; EO(x)PO(y)NH2) (SURFONAMINE) as media, reducing agents, stabilizing agents and surface-modifying agents. Gold nanoparticles were synthesized through autoreduction of hydrogen tetrachloroaureate(III) hydrate (HAuCl4 x 3H2O) by SURFONAMINE as media and reducing agents at ambient conditions (approximately 25 degrees C). The AuCl4- reduction and gold nanoparticle formation were promoted by SURFONAMINE with longer PEO segment and heating. The enhanced-activity of SURFONAMINE for AuCl4- reduction contributed to particle growth due to the AuCl4- reduction by SURFONAMINE anchored on gold nanoparticles. Furthermore, amphiphilic property of the gold nanoparticle surface was controlled in terms of EO/PO unit ratio of SURFONAMINE. For example, gold nanoparticles synthesized in SURFONAMINE L-207 (EO33PO10NH2) homogeneously mixed with water but not with cyclohexane. On the other hand, gold nanoparticles synthesized in SURFONAMINE B-200 (EO6PO29NH2) were miscible with cylcohexane while immiscible with water.

Spontaneous formation of gold nanoparticles in poly(ethylene oxide)-poly(propylene oxide) solutions: solvent quality and polymer structure effects.

We report here on the effects that the solution properties of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers have on the reduction of hydrogen tetrachloroaurate(III) hydrate (HAuCl4.3H2O) and the size of gold nanoparticles produced. The amphiphilic block copolymer solution properties were modulated by varying the temperature and solvent quality (water, formamide, and their mixtures). We identified two main factors, (i) block copolymer conformation or structure (e.g., loops vs entanglements, nonassociated polymers vs micelles) and (ii) interactions between AuCl4- ions and block copolymers (attractive ion-dipole interactions vs repulsive interactions due to hydrophobicity), to be important for controlling the competition between the reactivities of AuCl4- reduction in the bulk solution to form gold seeds and on the surface of gold seeds (particles) and the particle size determination. The particle size increase observed with increased temperature in aqueous solutions is attributed to enhanced hydrophobicity of the block copolymer, which favors AuCl4- reduction on the surface of seeds. The lower reactivity and higher particle sizes observed in formamide solutions are attributed to the shielding of ion-dipole interaction between AuCl4- ions and block copolymers by formamide, which overcomes the beneficial effects of formamide on the block copolymer conformation (lower micelle concentration).

A patient with TP53 germline mutation developed Bowen's disease and myelodysplastic syndrome with myelofibrosis after chemotherapy against ovarian cancer.

Here we report a case of myelodysplastic syndrome (MDS) with myelofibrosis associated with Bowen's disease. A female patient had undergone an operation and chemotherapy for ovarian cancer when she was 65 years old, and she developed MDS at the age of 70 years old. PCR-single strand conformation polymorphism (SSCP) analysis of peripheral blood mononuclear cells, a Bowen's disease lesion, and normal skin showed an abnormal peak in TP53 exon5. Direct sequencing revealed that they all had missense mutation in codon 175 (G to A) of arginine switched to histidine, suggesting a germline mutation of TP53. It was speculated that p53 function was lost by TP53 germline mutation with the loss of a wild type allele induced by the chemotherapy against ovarian cancer, leading to the development of MDS. No therapeutic effects of low dose melphalan or cyclosporine A on MDS were observed, however one month of 30 mg/day prednisolone administration induced a hematological response.

Size- and shape-controlled synthesis of colloidal gold through autoreduction of the auric cation by poly(ethylene oxide)-poly(propylene oxide) block copolymers in aqueous solutions at ambient conditions.

Gold nanoparticles with an average diameter in the range 5-20 nm have been synthesized from hydrogen tetrachloroaureate (III) hydrate (HAuCl(4)·3H(2)O) in air-saturated aqueous PEO-PPO-PEO block copolymer solutions at ambient temperature in the absence of any other reducing agent (PEO: poly(ethylene oxide), PPO: poly(propylene oxide)). The particle size was controlled by the block copolymer concentration and PEO and PPO block lengths. Our findings indicate that longer PEO blocks lead to an increase in particle size because of an increase in reaction activity. Adsorption of PO segments on gold nanoparticles seems to prevent particle growth from aggregation, and results in small particle size and high colloidal stability. An increase of the HAuCl(4) concentration causes a change in the particle shape from spherical to triangular or hexagonal nanoplates.

Mechanism of gold metal ion reduction, nanoparticle growth and size control in aqueous amphiphilic block copolymer solutions at ambient conditions.

Spontaneous formation and efficient stabilization of gold nanoparticles with an average diameter of 7 approximately 20 nm from hydrogen tetrachloroaureate(III) hydrate (HAuCl4.3H2O) were achieved in air-saturated aqueous poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymer solutions at ambient temperature in the absence of any other reducing agent. The particle formation mechanism is considered here on the basis of the block copolymer concentration dependence of absorption spectra, the time dependence (kinetics) of AuCl4- reduction, and the block copolymer concentration dependence of particle size. The effects of block copolymer characteristics such as molecular weight (MW), PEO block length, PPO block length, and critical micelle concentration (cmc) are explored by examining several PEO-PPO-PEO block copolymers. Our observations suggest that the formation of gold nanoparticles from AuCl4- comprises three main steps: (1) reduction of metal ions by block copolymer in solution, (2) absorption of block copolymer on gold clusters and reduction of metal ions on the surface of these gold clusters, and (3) growth of metal particles stabilized by block copolymers. While both PEO and PPO blocks contribute to the AuCl4- reduction (step 1), the PEO contribution appears to be dominant. In step 2, the adsorption of block copolymers on the surface of gold clusters takes place because of the amphiphilic character of the block copolymer (hydrophobicity of PPO). The much higher efficiency of particle formation attained in the PEO-PPO-PEO block copolymer systems as compared to PEO homopolymer systems can be attributed to the adsorption and growth processes (steps 2 and 3) facilitated by the block copolymers. The size of the gold nanoparticles produced is dictated by the above mechanism; the size increases with increasing reaction activity induced by the block copolymer overall molecular weight and is limited by adsorption due to the amphiphilic character of the block copolymers.

Surface properties of surfactant-free oil droplets dispersed in water studied by confocal fluorescence microscopy.

The fluorescence spectrum of dye molecules, 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyron (DCM), dissolved in surfactant-free n-decane droplets (average diameters of approximately 300 and approximately 2000 nm) dispersed in water was measured by a confocal microscope. The fluorescence spectra for 300- and 2000-nm droplets are found to exhibit a peak at 640 and 625 nm, respectively, and the peak red shifts with a decrease in the droplet diameter (solvatochromic shift of DCM molecules). It is concluded that (1) DCM molecules are located in a polar surface region of n-decane droplets and (2) the polarity increases with decreasing the droplet diameter.