Emulsifying potency of new amino acid-type surfactant (II): stable water-in-oil (W/O) emulsions containing 85 wt% inner water phase

The ternary phase diagram for N-[3-lauryloxy-2-hydroxypropyl]-L-arginine L-glutamate (C12HEA-Glu), a new amino acid-type surfactant, /oleic acid (OA)/water system was established. The liquid crystal and gel complex formations between C12HEA-Glu and OA were applied to a preparation of water-in-oil (W/O) emulsions. Stable W/O emulsions containing liquid paraffin (LP) as the oil and a mixture of C12HEA-Glu and OA as the emulsifier were formed. The preparation of stable W/O emulsions containing 85 wt% water phase was also possible, in which water droplets would be polygonally transformed and closely packed, since the maximum percentage of inner phase is 74% assuming uniformly spherical droplets. Water droplets would be taken into the liquid crystalline phase (or the gel complex) and the immovable water droplets would stabilize the W/O emulsion system. The viscosity of emulsions abruptly increased above the 75 wt% water phase (dispersed phase). The stability of W/O emulsions with a lower weight ratio of OA to C12HEA-Glu and a higher ratio of water phase was greater. This unusual phenomenon may be related to the formation of a liquid crystalline phase between C12HEA-Glu and OA, and the stability of the liquid crystal at a lower ratio of oil (continuous phase). W/O and oil-in-water (O/W) emulsions containing LP were selectively prepared using a mixture of C12HEA-Glu and OA since the desirable hydrophile-lipophile balance (HLB) number for the emulsification was obtainable by mixing the two emulsifiers.     

Rheology of double emulsions

New equations for the viscosity of concentrated double emulsions of core-shell droplets are developed using a differential scheme. The equations developed in the paper predict the relative viscosity (eta(r)) of double emulsions to be a function of five variables: a/b (ratio of core drop radius to shell outer radius), lambda(21) (ratio of shell liquid viscosity to external continuous phase viscosity), lambda(32) (ratio of core liquid viscosity to shell liquid viscosity), phi(DE) (volume fraction of core-shell droplets in double emulsion), and phi(m)(DE) (the maximum packing volume fraction of un-deformed core-shell droplets in double emulsion). Two sets of experimental data are obtained on the rheology of O/W/O (oil-in-water-in-oil) double emulsions. The data are compared with the predictions of the proposed equations. The proposed equations describe the experimental viscosity data of double emulsions reasonably well.     

Application of fluorescence correlation spectroscopy: a study of flocculation of rigid rod-like biopolymer (schizophyllan) and colloidal particles

The flocculation between the rod-like biopolymer Schizophyllan and two types of colloidal particles (latex with diameter 40 nm and alumina with diameter 60 nm) has been investigated by means of fluorescence correlation spectroscopy (FCS). The concentration ratio of Schizophyllan/particle q was varied in the range 0.1 approximately 20. Under conditions of pH about 5.7, 1 mmol.L(-1) NaCl, and room temperature (22+/-0.5 degrees C), the particles are strongly charged (alumina particles positively charged, latex negatively), while Schizophyllan is neutral. We observed that Schizophyllan chains flocculate with both types of particles, which suggests that the charge neutralization does not play a decisive role in these interactions. The ratio of fluorescence intensity of one floc over that of one particle, Q(f)/Q(p), and the corresponding hydrodynamic radius (r(h)) of the flocs have been measured. For a Schizophyllan-latex system, Q(f)/Q(p) reached a maximum value of 5 for q=3 indicating that the flocs contained five particles on average. The corresponding value of r(h) was r(h)=455 nm. The flocculation kinetic of latex particles with Schizophyllan was too fast to be measurable by FCS. For the Schizophyllan-alumina system, Q(f)/Q(p) was stable at about 1 in the whole studied range of q but r(h) increased with q suggesting that many Schizophyllan chains are adsorbed on individual particles. The flocculation kinetic of this system was studied by FCS and the obtained results were compatible with those of photon correlation spectroscopy.     

Long-Term Cultured Hairy Roots of Chicory—A Rich Source of Hydroxycinnamates and 8-Deoxylactucin Glucoside

Foam fractionation is a promising method for separation and concentration of biochemicals. It is simple, easily scalable, inexpensive, and environment friendly. Foam fractionation thus represents an alternative to the traditional methods used for immunoglobulin enrichment. However, little, if any, literature exists documenting the utilization of foam fractionation in the enrichment of immunoglobulins. Milk were utilized as an immunoglobulin source to serve as examples of a real system in this study. The investigation examined the effects of varying five different process parameters: the initial pH value, the initial concentration of immunoglobulin, the nitrogen flow rate, the column height, and the foaming time. Experimental results demonstrated that immunoglobulin could effectively be enriched from milk by foam fractionation. The maximum enrichment ratio with pretreatment (using pH 4.6 precipitation) was 6.30 along with a more than 92 % recovery for IgG and an enrichment ratio of 5.1 with 85 % recovery for IgM.     

Synergism and foaming properties in mixed nonionic/fatty acid soap surfactant systems

The synergism and foaming behavior of a mixed surfactant system consisting of a nonionic surfactant (polyethoxylated alkyl ether C(n)E(m)) and a fatty acid soap (sodium oleate) were studied. The micellar interaction parameter (the beta-parameter) was determined from the cmc following the approach of Rubingh's regular solution theory. For both the C(12)E(6)/sodium oleate and the C(14)E(6)/sodium oleate mixtures, the results indicate a fairly strong attractive interaction (negative beta-values), which were in agreement with previous data reported for other nonionic/anionic surfactant systems. The characteristics of the foam produced from the surfactants were evaluated using a glass column equipped with a series of electrodes measuring the conductance of the foam, which enabled the water content of the foam to be determined. From these measurements, since the total foam volume was almost the same for all concentrations and surfactants, we compared the amount of liquid in the foam produced under dynamic foaming and the ability of the foam to entrain the liquid after the airflow was switched-off (static foam stability). The amount of liquid in the foam 100 s after the air was switched-off followed the order NaOl > C(12)E(6) > C(14)E(6). Also, the mixtures had the same foam volumes as the pure surfactants at the same concentration. However, both mixtures had higher concentrations of liquid in the foam when the mole fraction of the nonionic surfactant in the mixed surfactant system was greater than about >0.3 in the solution.     

Affinity foam fractionation of Trichoderma cellulase

Cellulase could not be selectively collected from fermentation broth by simple foam fractionation, because of the presence of other more surface-active compounds. A new approach of affinity foam fractionation was investigated for improvement. A hardwood hydrolysate (containing cellulose oligomers, substrates to cellulase) and two substrate analogs, i.e., carboxymethyl cellulose (CMC) and xylan hydrolysate, were added before the foaming process. The substrates and substrate analogs were indeed found to bind the cellulase selectively and form more hydrophobic complexes that partition more readily onto bubble surfaces. In this study, the effects of the type and concentration of substrate/analog as well as the presence of cells at different growth stages were examined. The foam fractionation properties evaluated included foaming speed, foam stability, foamate volume, and enrichment of filter paper unit (FPU) and individual cellulase components (i.e., endoglucanases, exoglucanases, and β-glucosidases). Depending on the broth and substrate/analog employed, the foamate FPU could be more than fourfold higher than the starting broth FPU. Addition of substrate/analog also deterred the enrichment of other extracellular proteins, resulting in the desired cellulase purification in the foamate. The value of E/P (enzyme activity-FPU/g/L of proteins) in the foamate reached as high as 18, from a lactose-based fermentation broth with original E/P of 5.6. Among cellulase components, exoglucanases were enriched the most and β-glucosidases the least. The study with CMC of different molecular weights (MW) and degrees of substitution (DS) indicated that the CMC with low DS and high MW performed better in cellulase foam fractionation.     

Kinetics study of oil sorption with open‐cell polypropylene/polyolefin elastomer blend foams prepared via continuous extrusion foaming

The objective of the present work was to study the sorption kinetics of open‐cell polypropylene/polyolefin elastomer (PP/POE) blend foams. First, open‐cell PP/POE foams of different cell structures were prepared by controlling the foaming temperature via a continuous extrusion foaming process. Second, the effect of the cell structures on the sorption process, rate, and capacity was studied. Pseudo‐first order and pseudo‐second order models were applied to study the sorption kinetics of the PP/POE foams for cyclohexane. Third, the sorption rate and sorption capacity by both volume and weight of the PP/POE foam for different oils and solvents were studied to show how the intrinsic properties of the testing oils and solvents affected the sorption performance. The results showed that the sorption with the PP/POE foams followed the pseudo‐second order kinetics model. Both the cell structures of the foams and the intrinsic properties of the testing oils and solvents affected the sorption performance. For the same testing oil, a higher open‐cell content in the foam was favorable for a higher sorption rate, and a higher void fraction was favorable for a higher sorption capacity. For the same foam, a lower viscosity of the testing oil was favorable for a higher sorption rate. The sorption capacity by volume was closely related to the viscosity of the testing oil, while both the viscosity and the density of the testing oil determined the sorption capacity by weight.     

Drop deformation in polymer blends during uniaxial elongational flow

The deformation in uniaxial elongational flow of dispersed droplets in immiscible molten polymer blends was studied for negligible interfacial tension and for viscosity ratio p = η(drop)/η(matrix) between 0.005 and 13, with an original method based on quenching elongated specimens. Although drop deformation (drop major axis over initial diameter) was in the range 1 < λ_d < 5, a good overall agreement was found with the small deformation Newtonian theory, which predicts that the drop versus matrix deformation ranges from 5/3 to 0 when p increases from 0 to infinity. The theoretical prediction that for p lower than 1, the droplet should deform more than the faraway surrounding matrix, with a limiting ratio of 5/3 at vanishing droplet viscosity, was experimentally verified.     

泡沫的稳定性及液晶对它的影响

泡沫体系的表面张力、粘度,表面粘度以及液晶相的存在对泡沫的稳定性皆有影响。消泡剂可改变上述性质。本文报导聚氧乙烯辛基酚(TritonX-100),十二烷基硫酸钠(SDS),油酸三乙醇胺(TEAOL)和卵磷脂等起泡剂在均相溶液及有液晶存在时产生泡沫的稳定性,观察硅油的消泡作用。     

A multi point conductivity measurement system for characterisation of protein foams

Protein foams play an important role in both food and biotechnological processes. A sound understanding of foaming properties of proteins relevant to such processes is useful e.g. to allow adequate control of unwanted foams and appropriate choice of protein-physical system when foams of certain characteristics are required. In general, measurements of changes in foam volume (volumetric method) are used for foam characterisation. However, recently there has been increased interest in the use of measurement methods based on conductivity and capacitance. Simple relative techniques based on electrical conductivity measurements provide information on both foamability and foam stability. A multi point conductivity measurement system has been designed and used for characterisation of model protein foams (0.1 and 1.0 mg ml⁻¹ Bovine serum albumin, BSA). The solution of BSA was sparged with nitrogen or carbon dioxide gas at constant flow rate (90 cm³ min⁻¹) via a stainless steel sinter (0.5 or 2.0 μm in pore size). A comparison of foaming properties determined by volumetric and conductimetric techniques is provided. Both methods show that more stable foams are obtained for solutions at higher BSA concentrations. At all BSA concentrations, higher foamability and stability are achieved with a smaller sinter pore size. When nitrogen rather than carbon dioxide is used as a dispersed phase, higher foamability and foam stability are obtained. The conductivity measurements indicate that foamability is dependent on gas type, whereas, volumetric measurements do not show such differences.     

Investigation of aqueous foam stability containing pigment colorant using polyoxyethylene nonionic surfactant

To improve foam stability in pigment foaming dispersions, a series of fatty alcohol polyoxyethylene ether (CmEOn) with different alkyl chain and ethylene oxide (EO) chain length (m = 12, 14, 16 and n = 5, 7, 9) were used as foam stabilizer to select the most superior structure for stabilizing foam. The effects of CmEOn on surface tension were investigated which revealed that the CMC of CmEOn in the pigment foaming dispersion decreased with the increase of surfactant hydrophobicity or the decrease of hydrophilicity. Compared to the alkyl chain, EO chain length influenced foam more significantly. C₁₄EO₅ in the pigment foaming dispersion showed lowest CMC and equilibrium surface tension. The presence of wormlike micelles and lamellar liquid crystal of SDS and C₁₄EO₅ endowed the C₁₄EO₅ pigment foaming dispersion with highest viscosity which was distinctly different with other CmEOn. C₁₄EO₅ showed the most superior stabilization effects with foam half-life of 172.9 min at 9 wt%. To further analyze the stabilization mechanism of C₁₄EO₅, the foam volume and bubble diameter change were observed with a digital microscope. The results demonstrated that the superior stabilization effects of C₁₄EO₅ were closely related to its high viscosity, which mainly resulted in the decrease of foam drainage and gas permeability. C₁₄EO₅, the optimal CmEOn structure for stabilizing foam, shows excellent foam stabilization capability in pigment foaming dispersions, which is a promising tool to realize pigment foam coloring.     

Microbubble generation in a co-flow device operated in a new regime

A new regime of operation of PDMS-based flow-focusing microfluidic devices is presented. We show that monodisperse microbubbles with diameters below one-tenth of the channel width (here w = 50 μm) can be produced in low viscosity liquids thanks to a strong pressure gradient in the entrance region of the channel. In this new regime bubbles are generated at the tip of a long and stable gas ligament whose diameter, which can be varied by tuning appropriately the gas and liquid flow rates, is substantially smaller than the channel width. Through this procedure the volume of the bubbles formed at the tip of the gas ligament can be varied by more than two orders of magnitude. The experimental results for the bubble diameter d(b) as function of the control parameters are accounted for by a scaling theory, which predicts d(b)/w ∝ (μ(g)/μ(l))(1/12)(Q(g)/Q(l))(5/12), where μ(g) and μ(l) indicate, respectively, the gas and liquid viscosities and Q(g) and Q(l) are the gas and liquid flow rates. As a particularly important application of our results we produce monodisperse bubbles with the appropriate diameter for therapeutic applications (d(b) ? 5 μm) and a production rate exceeding 10(5) Hz.     

Ionic liquid foam floatation coupled with ionic liquid dispersive liquid–liquid microextraction for the separation and determination of estrogens in water samples by high‐performance liquid chromatography with fluorescence detection

An ionic liquid foam floatation coupled with ionic liquid dispersive liquid–liquid microextraction method was proposed for the extraction and concentration of 17‐α‐estradiol, 17‐β‐estradiol‐benzoate, and quinestrol in environmental water samples by high‐performance liquid chromatography with fluorescence detection. 1‐Hexyl‐3‐methylimidazolium tetrafluoroborate was applied as foaming agent in the foam flotation process and dispersive solvent in microextraction. The introduction of the ion‐pairing and salting‐out agent NH₄PF₆ was beneficial to the improvement of recoveries for the hydrophobic ionic liquid phase and analytes. Parameters of the proposed method including concentration of 1‐hexyl‐3‐methylimidazolium tetrafluoroborate, flow rate of carrier gas, floatation time, types and concentration of ionic liquids, salt concentration in samples, extraction time, and centrifugation time were evaluated. The recoveries were between 98 and 105% with relative standard deviations lower than 7% for lake water and well water samples. The isolation of the target compounds from the water was found to be efficient, and the enrichment factors ranged from 4445 to 4632. This developing method is free of volatile organic solvents compared with regular extraction. Based on the unique properties of ionic liquids, the application of foam floatation, and dispersive liquid–liquid microextraction was widened.     

Stability and shear thixotropy of multilayered film foam

Understanding of foam rheology is significant for the study of foam stabilization. In fact, the foam thixotropy is an important factor to foam stability, but the study about it has not attached great importance. Shear viscosity of different foam stabilizer solutions were investigated as well as microstructure, shear viscosity thixotropy, and stability of different foam systems prepared by the different foam stabilizers. The results show that high shear viscosity of foaming agent solution contributes to decreasing drainage of foam. Collapse of foam depends on the compact degree of molecular alignment. Reaction between the hydrophilic groups of foam stabilizer molecule and accessory ingredient molecule determines shear viscosity of foaming agent solution. Thixotropy of the foam can be used to evaluate the recoverability after sheared by high speed. Strong interaction forces and compact arrangement between the foam stabilizer molecule and accessory ingredient molecule contributes to improving stability and recoverability of foam. Foam stability increases with shear thixotropic recoverability of foam.     

Enhancing cellulase foam fractionation with addition of surfactant

Foam fractionation cannot be used to recover cellulase from an aerated water solution effectively because cellulase by itself can produce only a small amount of foam. The addition of a surfactant can, however, increase the foamate volume and enhance the concentration of cellulase. We studied three detergents individually added to a 200 mg/L cellulase solution to promote foaming. These detergents were anionic, cationic, and nonionic surfactants, respectively. Although contributing to foam production, it was observed that nonionic surfactant (Pluronic F-68) barely concentrated cellulase, leaving the enrichment ratio unchanged, near 1. With anionic surfactant, sodium dedecyl sulfate, and cationic surfactant, cetyltrimethylammonium bromide (CTAB), the enrichment ratio became much larger, but cellulase denaturation occurred, reducing the activity of the enzyme. When CTAB was used to help foam cellulase, β-cyclodextrin was subsequently added to the foamate to help restore the enzyme activity.     

Characteristics of AOT Microemulsion Structure: a Small Angle X-ray Scattering Study

The structure of micelles has attracted renewed attention during the past decade years due to the widespread use of microemulsions in technology1 and life science1,2. To obtain information of the micellar structure, using X-ray scattering (SAXS) whose wavelength is close to the size of the micellar aggregates is one of the most direct method3-5 and SAXS has been proved to be very sensitive for the change of micellar composition6,7. SAXS experiments have been carried out to compare the st…     

Unified scaling behavior of physical properties of clays in alcohol solutions

This paper reports observation of universal scaling of physical properties of clay particles, Laponite (aspect ratio=30) (L) and Na Montmorillonite (MMT, aspect ratio=200), in aqueous alcohol solutions (methanol, ethanol and 1-propanol) with solvent polarity, defined through reaction field factor f(OH)(?(0),n)=[(?(0) - 1/?(0) + 2) - (n(2) - 1/n(2) + 2)], at room temperature (20°C). Here, ?(0) and n are the static dielectric constant and refractive index of the solvent concerned. Physical properties (Z) such as zeta potential, effective aggregate size, viscosity and surface tension scaled with the relative solvent polarity as Z～δf(α); δf=(f(w)(?(0),n) - f(OH)(?(0),n)), where f(w)(?(0),n) is the reaction field factor for water, Z is the normalized physical property, and α is its characteristic scaling exponent. The value of this exponent was found to be invariant of aspect ratio of the clay but dependent on the solvent polarity only.     

High-speed, clinical-scale microfluidic generation of stable phase-change droplets for gas embolotherapy

In this study we report on a microfluidic device and droplet formation regime capable of generating clinical-scale quantities of droplet emulsions suitable in size and functionality for in vivo therapeutics. By increasing the capillary number-based on the flow rate of the continuous outer phase-in our flow-focusing device, we examine three modes of droplet breakup: geometry-controlled, dripping, and jetting. Operation of our device in the dripping regime results in the generation of highly monodisperse liquid perfluoropentane droplets in the appropriate 3-6 μm range at rates exceeding 10(5) droplets per second. Based on experimental results relating droplet diameter and the ratio of the continuous and dispersed phase flow rates, we derive a power series equation, valid in the dripping regime, to predict droplet size, D(d) approximately equal 27(Q(C)/Q(D))(-5/12). The volatile droplets in this study are stable for weeks at room temperature yet undergo rapid liquid-to-gas phase transition, and volume expansion, above a uniform thermal activation threshold. The opportunity exists to potentiate locoregional cancer therapies such as thermal ablation and percutaneous ethanol injection using thermal or acoustic vaporization of these monodisperse phase-change droplets to intentionally occlude the vessels of a cancer.     

Foam formation and stabilisation by pre-denatured ovalbumin

Various mild heat-treatments of ovalbumin solutions were applied to produce molecular species with different conformational states, and having different kinetics of adsorption to the air/water interface and different foaming properties. Molecular species with a higher degree of shear-induced deformation and a low degree of thermal conformational stability showed a slight enhancement of the rate of decrease of surface tension, 5 min after the creation of the fresh interface, and decreasing long-term values of surface tension. Solutions of ovalbumin molecular species exhibiting such initial structural patterns were shown to have enhanced foam capacity and stability against liquid drainage. Ovalbumin molecules with some degree of secondary and tertiary structural changes and increased viscosity, before adsorption at the air/water interface, were shown to be relevant to produce more or less hydrated foams with more or less stability against liquid drainage.     

The influence of the pore size, the foaming temperature and the viscosity of the continuous phase on the properties of foams produced by membrane foaming

Membrane foaming is a new method of foaming. To enlarge the knowledge about the influencing factors and to know how to vary the structure of the resulting foam, different factors were evaluated. A whey protein solution with 10% protein was foamed as a model solution by means of a tubular cross-flow filtration membrane. The pore size of the membrane was varied. The smaller the pore size, the smaller the bubbles produced. As a result, the foam firmness increases and less drainage was observed when smaller pore sizes were applied.

An important factor is that the added amount of gas must be stabilised as completely as possible in the foam. In order to achieve this, both the process and the product parameters were varied. Raising the foaming temperature increased the quantity of stabilised gas. The whey proteins then diffuse faster to the bubble surfaces and stabilise these by unfolding and networking reactions to prevent the coalescence of the bubbles.

The product parameter viscosity was found to influence the foaming result in such a way that up to a viscosity of 40 mPa s the incorporated gas bubbles are stabilised by the higher viscosity. At viscosities higher than 40 mPa s it is difficult to incorporate in the bubbles, and the foam structure becomes coarser due to increased coalescence at the pores of the membrane. The foam stability is enhanced with higher viscosities.