Synthesis and applications of porous spg (shirasu porous glass) microspheres

Fairly uniform porous microspheres of poly(styrene) (PS) and poly(methyl methacrylate) (PMMA) were synthesized using a particular microporous glass membrane (SPG). Average diameters of these spheres are from 2.5 to 38 μm with the coefficient of variation (CV) around 10%. A maximum specific surface area of 370 m² /g was achieved. Uniform dispersion of MMA droplets was successfully prepared only when the swelling process reported by Higuchi and Misra was adopted. Two potential applications, one as a packing material for column chromatography, and the other as a carrier of enzyme immobilization, were demonstrated.     

The effects of emulsifier type,phase ratio,and homogenization methods on stability of the double emulsion

The double emulsion technology has a potential effect on the development of diversity and quality of functional foods by means of decreasing oil or salt concentration, encapsulating and controlling release of valuable components. In this study, it was aimed to formulate stable double emulsions to be used in food systems. W1/O ratios of primary emulsions, stabilized by polyglycerol polyricinoleate (PGPR), were designed as 2:8 and 4:6, and (W1/O)/W2 ratios of the double emulsions were used as 2:8 and 4:6. W/O/W phase ratios, homogenization methods applied to primary emulsion (high-speed homogenization, ultrasonic homogenization), and emulsifier types used in W2 phase [sodium caseinate (SC), xanthan gum, lecithin-whey protein concentrate] were used as independent variables. Particle size and distributions, stability, encapsulation efficiency (EE), rheological properties, long-term stability, and morphological properties of the double emulsions were investigated.

The double emulsions prepared with SC and (W1/O)/W2 ratio of 4:6, were found to have the higher stability values, higher apparent viscosity, and lower particle size. High-speed homogenization applied to primary emulsion reduced particle size of the double emulsion and increased apparent viscosity, but did not affect stability and EE of the double emulsions, significantly.     

Effect of porous support fabric on osmosis through a Loeb-Sourirajan type asymmetric membrane

Commercially available asymmetric membranes of the Loeb-Sourirajan (L-S) type comprise a support fabric, bonded to the porous substructure. The influence of this fabric on osmotic permeation flux was examined, mostly with a Toray CA-3000 membrane from which, with care, it was possible to remove the support fabric. In osmosis experiments with 12% MgCl₂ solution on one side (either side) and 6% solution on the other, the permeation flux (J₁) was of the order of 0.01 and 0.06 m³/m² d with and without fabric, respectively. These results could be generalized by considering the resistivity to solute diffusion in the non-skin part of the membrane. This resistivity term averaged 104 and 17 d/m for membranes with and without fabric, respectively, and in further tests without fabric, it was between 15 and 25 d/m over a wide range of MgCl₂ concentrations. Four other L-S membranes, all with support fabric, were tested in osmosis experiments. Their resistivity values were similar to or higher than those of the Toray membrane with fabric, but, with one of the four, the results were affected by switching the location of the high and low concentration solutions. It was concluded that existing commercially available L-S membranes are not appropriate for large-scale osmosis applications because their support fabric decreases permeation flux excessively.     

Adsorption behavior of BSA in microfiltration with porous glass membrane

The fouling mechanism during dead-end microfiltration of bovine serum albumin (BSA) with porous glass membrane was investigated from the point of BSA adsorption onto the pore surface of membrane under the condition of pH 5.0 and ionic strength 0.01. The location of BSA retention was confirmed by comparing the filtration performance between dead-end mode and cross-flow mode. During the dead-end microfiltration BSA was retained only by the adsorption on the pore surface. The adsorption was irreversible and of multilayer type, which consists of the adsorption on clean pore surface, i.e. the primary adsorption, and that on preadsorbed pore surface, i.e. the secondary one. The adsorption isotherm was high affinity type. The adsorption rate was proportional to the feed rate of BSA, and the proportional coefficient was dependent on the adsorption process. The flux decline was correlated quantitatively with the amount of adsorbed BSA from the pore radius narrowing model by adsorption.     

Demulsification of water-in-oil emulsion by using porous glass membrane

The hydrophilic porous glass membranes were used to demulsify water-in-oil emulsion, and demulsification efficiency can reach more than 96.2%. Effects of pore size of the membrane, transmembrane pressure and volumetric ratio of oil phase to internal aqueous phase in the emulsion on demulsification were investigated. It was found that pore size of membrane and transmembrane pressure can significantly affect demulsification efficiency. The smaller the pore size of the membrane, the better the demulsification efficiency. However, smaller pore size of the membrane has to be exerted a greater transmembrane pressure in order to make internal aqueous phase enter the membrane pore. Correspondingly, effect of transmembrane pressure on permeation flux of the droplets was also studied. In addition, recovered-oil phase by the demulsification were reused five times to extract cadmium from simulated aqueous waste. The results indicated that the extracting efficiency could arrive at 96.5%.     

Preparation of water and alkali durable porous glass membrane coated on porous alumina tubing by sol-gel method

Composite porous glass membranes were prepared by the sol-gel method. A thin porous glass layer, about 2 μm thick, was coated on the surface of the porous ceramic tubing (Al₂O₃:99.9 wt.%, pore diameter: 200 nm). The composition of the porous glass layer of the composite membrane was SiO₂-ZrO₂. Considering from the fact that the desalination ratio of the feed aqueous NaCl solution (NaCl 0.5 wt.%) was about 90% by use of these membranes, they were defect-free. The best composition of the porous glass layer was 70 SiO₂-30 ZrO₂ from the standpoint of preparing membranes. These membranes had a large water and alkali durability. These membranes can be expected to apply to recovering dyes and paints from organic solvents and to be used as a gas separation membrane.     

Fabrication of nano-scale liposomes containing doxorubicin using Shirasu porous glass membrane

Nano-scale liposomes were successfully produced using a Shirasu porous glass (SPG) membrane emulsification technique. Primary liposomes prepared by a film-hydration method were treated using SPG membranes with different pore sizes (2.0, 1.0, 0.7, 0.5, and 0.2 μm) for control over the liposome size. The liposome sizes were evaluated using a dynamic light scattering method and their morphologies were observed by optical microscopy and transmission electron microscopy. As the passage number of liposomes through SPG membrane increased, the size and its distribution of the liposomes gradually decreased. A smaller pore size of the SPG membrane and a higher applied pressure resulted in liposomes with a smaller size. After the preparation of nano-scale liposomes containing ammonium sulfate (AS), doxorubicin (DOX) was encapsulated in the liposomes by a remote loading method, where AS served as a precipitant for DOX. The encapsulation efficiency of the DOX was maximized up to 94% when the concentrations of AS and DOX were 250 and 0.045 mM, respectively. We have obtained the release profiles of the liposomes with different sizes. As shown below, liposomes with smaller size exhibited a faster release profile of drug due to the large surface area. These nano-scale liposomes encapsulating an anti-cancer drug can potentially be employed as drug delivery vehicles for intravenous injection.     

多孔玻璃载体自转晶B-Al-MFI型沸石膜的原位合成

在乙胺和水的混合蒸汽相中,首次通过载体自转晶,在多孔玻璃表面原位合成了B-Al-MFI型沸石膜。X射线衍射和扫描电镜观察证明,膜中沸石晶体的取向是随机的。晶体尺寸约为15～25μm,单层晶体厚的膜约为10～20μm。在焙作去有机模板剂后的沸石膜上,O~2和N~2的透过性分别为0.095×10^-^8和0.15×10^-^8mol/(m^2·s·Pa)。计算的O~2/N~2的理想选择值(0.63)明显低于诺森扩散的理想选择性值(0.94)和透过原载体的理想选择性值(0.91)。     

Effect of pore size on adsorption of a polyelectrolyte to porous glass

The adsorption of quaternized poly(vinylpyridine) (QPVP) on controlled pore glass (CPG) size, over the ionic strength range 0.001-0.5 M was found to display nonmonotonic behavior as a function of pore size. Both adsorption kinetics and ionic strength effects deviated dramatically from behavior typical of adsorption on flat surfaces when the ratio of the pore radius Rp to the polymer hydrodynamic radius Rh became smaller than ca. 2. Ionic strength enhancement of adsorption for small pore sizes was observed at much higher salt concentrations than is typical for polycation adsorption on flat surfaces. The amount of polymer adsorbed per unit surface area of glass GammaA, in 0.5 M NaCl, exhibited a shallow maximum at Rp/Rh approximately 5. Since the value of GammaA for small pore size CPG is strongly depressed by the large surface area, an alternative and more interesting observation is that the amount of polymer adsorbed per gram of CPG, Gammaw, displays a strong maximum when Rp is equal to or slightly smaller than Rh. The efficiency with which QPVP binds anionic micelles to (negatively charged) CPG (grams of surfactant/grams of QPVP) increases strongly with diminishing pore size, indicating that the configuration of polycation bound to small pores favors micelle binding. Since the micelles are larger than small pores, the results indicate that when Rp < Rh, adsorbed polycation molecules reside only partially within the pore. The results of this study are supported by simulations of polyelectrolytes within cylindrical cavities.     

Temperature-sensitive porous membrane production through radiation co-grafting of NIPAAm on/in PVDF porous membrane

N-isopropylacrylamide (NIPAAm) monomer was grafted on and in poly(vinylidene fluoride) (PVDF) micro-pore membrane by γ-irradiation. The influence of irradiation and reaction conditions on the grafting yield was investigated in detail. The chemical structure of NIPAAm-grafted PVDF (NIPAAm-g-PVDF) membrane was characterized by Fourier transform infrared spectra and X-ray photoelectron spectra measurements. The morphology of the sample surface as well as the cross-section before and after grafting was characterized by scanning electron microscope. The temperature sensitive properties of the membrane were monitored by measuring the conductance as well as the water flux through the sample thickness. The results show that the membrane exhibits clearly temperature-sensitive permeability to water as expected, i.e. the permeability of water changes dramatically as the temperature goes over the lower critical solution temperature of NIPAAm.     

An oxygen reduction sensor based on a novel type of porous carbon composite membrane electrode

The development of a simple, efficient and sensitive sensor for dissolved oxygen is proposed using a novel type of porous carbon composite membrane/glassy carbon electrode based on the low-cost common filter paper by a simple method. The resulting device exhibited excellent electrocatalytic activities toward the oxygen reduction reaction. Scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and electrochemical measurements demonstrated that the porous morphology and uniformly dispersed Fe₃C nanoparticles of the PCCM play an important role in the oxygen reduction reaction. A linear response range from 2μmol/L up to 110 μmol/L and a detection limit of 1.4 μmol/L was obtained with this sensor. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation, was 3.0%. The successful fabrication of PCCM/GC electrode may promote the development of new porous carbon oxygen reduction reaction material for the oxygen reduction sensor.     

Effect of solute polarity on the performance of porapak type porous polymers

Summary The breakthrough volume of ådsorbent traps made with porous polymer beads Porapak N, P. Q, R, S was evaluated by analysis of polarity reference substances proposed by Rohrschneider (ethanol, methyl ethyl ketone, nitrometane, benzene, pyridine) by McReynolds (butanol, methyl propyl ketone) and of the first term of some homologous series: alcohols, aldehides, carboxilic acids, nitrocompounds, iodoalkanes and nitriles.Adjusted retention times of the compounds were measured at 200°C and correlated with the physical properties and with polarity class according to Ewell.Trapping efficiency of the various Porapak types was evaluated and the theoretical breakthrough volumes at 25°C was calculated for the used test substances.Dedicated to Prof. Dr. A. Liberti on the occasion of his 70th birthday.     

Effects of type of adsorption isotherms on parallel diffusion of sulfonated dyes into porous cellulose membrane

Transport phenomenon of three sulfonated azo dyes, C.I. Acid Red 88, C.I. Direct Yellow 12, and C.I. Direct Blue 15 into water-swollen cellulose membranes has been analyzed on the basis of parallel transport theory by surface and pore diffusion. Langmuir equation was applied into the mass balance equation to estimate dye concentration in the pores. The results were compared with the results obtained by applying Freundlich equation in our previous papers. The surface diffusivity (D _s) and the pore diffusivity (D _p) for the parallel diffusion model obtained by applying Langmuir equation agreed with those obtained by applying Freudlich equation. The theoretical concentration profiles for parallel diffusion calculated usingD _s andD _p coincided accurately with the experimental data when we applied either Langmuir or Freundlich equations.     

Ion-beam-induced reduction of iron oxide supported on porous glass

When ferric oxide supported on porous glass was irradiated by 40 keV He⁺ ions, the reduction of Fe³⁺ to Fe²⁺ species occurred. The yield of Fe²⁺ species, which was monitored by the Mössbauer spectroscopic measurement, increased with increasing total dose, and went up to ca. 80%. This unexpectedly large yield meant that the effect was exerted beyond the range of the incident He⁺ ions. Clear dose rate dependence of the Fe²⁺ yield was also observed. We examined the possibility that the reduction of the Fe³⁺ species was caused by some type of gaseous reductant produced by radiolysis of surface chemical species such as physisorbed water molecules and surface hydroxyls.     

Immobilization of several multienzyme systems on porous glass beads

Equimolar concentrations of malate dehydrogenase (EC 1.1.1.37) and fumarase (EC 4.2.1.2) and equimolar concentrations of malate dehydrogenase and citrate synthase (EC 4.1.3.7) were simultaneously immobilized to alkylamine porous silica beads with gluteraldehyde. The activity of each enzyme in the two-enzyme immobilized systems was determined and exact concentrations of the free nonimmobilized enzymes were prepared. The activities of the coupled free and coupled immobilized systems were measured, and it was observed that there was a 10-fold enhancement in the catalysis of the immobilized enzymes.     

Effects of emulsifier type and environmental stress on the stability of curcumin emulsion

The objective of this study was to investigate the effects of environmental stress and emulsifier types on the stability of curcumin emulsions. Results showed that Lecithin and Tween 80 presented good emulsifying capacity. The Tween 80 emulsion was the most stable among the four emulsions.

The particle sizes of Tween 80 and whey protein emulsion were relatively smaller than gum arabic and lecithin. Extensive droplet aggregation appeared in whey protein-stabilized emulsions when the pH was approximately isoelectric point (pI) with salt concentration >200?mM. Lecithin emulsion was unstable when pH?≤?6 with salt concentration >100?mM. There was little impact of pH and ionic strength on gum arabic and Tween 80 emulsions. All of the emulsions were stable at temperatures from 30 to 90°C in the absence of salt. These results help characterize the emulsifying and stabilizing abilities of emulsifier types intended for applications in the food industry.     

Effect of confinement on droplet breakup in sheared emulsions

The breakup of Newtonian droplets in a Newtonian matrix during shear flow is investigated in a counterrotating parallel plate device. For bulk conditions, the critical capillary number for breakup is known to be only determined by the viscosity ratio. Here, we show that the critical capillary number is also affected by the degree of confinement: for low viscosity ratios, confinement suppresses breakup, whereas for high viscosity ratios, confinement promotes breakup. This way, above a critical value for the degree of confinement, even droplets with a viscosity ratio larger than 4, which are unbreakable by shear in a bulk situation, can be broken in a simple shear flow field.     

Influence of dynamic interfacial tension on droplet formation during membrane emulsification

Membrane emulsification is a promising and relatively new technique for producing emulsions. The purpose of this study was to better understand the influence of interfacial tension on droplet formation during membrane emulsification. Droplet formation experiments were carried out with a microengineered membrane; the droplet diameter and droplet formation time were studied as a function of the surfactant concentration in the continuous phase. These experiments confirm that the interfacial tension influences the process of droplet formation; higher surfactant concentrations lead to smaller droplets and shorter droplet formation times (until 10 ms). From drop volume tensiometer experiments we can predict the interfacial tension during droplet formation. However, the strong influence of the rate of flow of the to-be-dispersed phase on the droplet size cannot be explained by the predicted values. This large influence of the oil rate of flow is clarified by the hypothesis that snap-off is rather slow in the studied regime of very fast droplet formation.     

Fluorescence of rare earth ions adsorbed on porous vycor glass

Fluorescence of rare earth (RE) ions arising from f—f transitions in Pr³⁺, Eu³⁺, Tb³⁺, Dy³⁺, Ho³⁺, Er³⁺ and Tm³⁺ was observed front the ions adsorbed on porous Vycor glass or on pressed discs of fumed silica. The non-radiative relaxations of the excited states were depressed as a result of a strong chemical bond between the ions and silica acting as a ligand.