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1.
Spreading of partially crystallized oil droplets on an air/water interface   总被引:3,自引:0,他引:3  
The influence of crystalline fat on the amount and rate of oil spreading out of emulsion droplets onto either a clean or a protein-covered air/water interface was measured for β-lactoglobulin stabilized emulsions prepared with either anhydrous milk fat or a blend of hydrogenated palm fat and sunflower oil. At a clean interface, liquid oil present in the emulsion droplets was observed to completely spread out of the droplets unimpeded by the presence of a fat crystal network. Further, the presence of a fat crystal network in the emulsion droplets had no effect on the rate of oil spreading out of the droplets. At a protein-covered interface, the spreading behavior of emulsion droplets containing crystalline fat was evaluated in terms of the value of the surface pressure (ΠAW) at the point of spreading; ΠAW at spreading was unaffected by the presence of crystalline fat. We conclude it is unlikely that the role of crystalline fat in stabilizing aerated emulsions such as whipped cream is to reduce oil spreading at the air/water interface. However, the temperature of the system did have an effect: spontaneous spreading of emulsion droplets at clean air/water interfaces occurred for systems measured at 5 °C, but not for those measured at 22 or 37 °C. Thus, temperature may play a more important role in the whipping process than commonly thought: the entering and spreading of emulsion droplets was favored at lower temperatures because the surface pressure exerted by protein adsorbed at the air/water interface was reduced. This effect may facilitate the whipping process.  相似文献   

2.
Emulsions prepared with whey proteins, phospholipids and 10% of vegetable oil were used for a model typifying dressings, coffee whitener and balanced diets. For the present study, two whey proteins (partial heat-denatured whey protein concentrate (WPC) and undenatured whey protein isolate (WPI)) in combination with different phospholipids (hydrolysed and unmodified deoiled lecithin) were chosen to investigate the interactions between proteins, phospholipids and salt (sodium chloride) in such emulsion systems. Oil-in-water (o/w) emulsions (10 wt.% sunflower oil) containing various concentrations of commercial whey proteins (1-2%), phospholipids (0.39-0.78%) and salt (0.5-1.5%) were prepared using a laboratory high pressure homogeniser under various preparation conditions. Each emulsion was characterised by droplet size, creaming rate, flow behaviour and protein load. The dynamic surface activity of the whey proteins and lecithins at the oil-water interface was determined using the drop volume method. The properties of emulsions were significantly influenced by the content of whey protein. Higher protein levels improved the emulsion behaviour (smaller oil droplets and increased stability) independent of the protein or lecithin samples used. An increase of the protein content resulted in a lower tendency for oil droplet aggregation of emulsions with WPC to occur and emulsions tending towards a Newtonian flow behaviour. The emulsification temperature was especially important using the partial heat-denatured WPC in combination with the deoiled lecithin. A higher emulsification temperature (60 degrees C) promoted oil droplet aggregation, as well as an increased emulsion consistency. Emulsions with the WPC were significantly influenced by the NaCl content, as well as the protein-salt ratio. Increasing the NaCl content led to an increase of the droplet size, higher oil droplet aggregation, as well as to a higher creaming rate of the emulsions. An increase of the lecithin content from 0.39 to 0.78% in the emulsion system resulted in a small reduction of the single droplet size. This effect was more pronounced when using the hydrolysed lecithins.  相似文献   

3.
The entering and spreading of emulsion droplets at quiescent and expanding air/water interfaces was studied using a new apparatus consisting of a modified Langmuir trough in which the air/water interface can be continuously expanded by means of rollers in the place of traditional barriers. When sodium caseinate and whey protein isolate-stabilized emulsion droplets were injected under the surface of sodium caseinate and whey protein isolate solutions, respectively, it appeared that the droplets entered the air/water interface only if the air/water surface pressure did not exceed a threshold value of approximately 15 mN/m. This condition was satisfied either under quiescent conditions for low protein concentrations or by continuous expansion of the interface at higher protein concentrations. According to equilibrium thermodynamics, entering of the droplets and the formation of lenses should occur for all the systems investigated, but this was not observed. At surface pressures higher than approximately 15 mN/m, immersed emulsion droplets were metastable. This is probably due to a kinetic barrier caused by the formation of a thin water film bounded by protein adsorption layers between the emulsion droplet and the air/water interface.  相似文献   

4.
Π/A isotherms of spread β-lactoglobulin and β-casein at the air–water interface are measured under different spreading conditions. While the isotherms do not show drastic effects of the spreading concentration and the compression rate the interfacial shear rheological behaviour is significantly influenced. In particular, the shear viscosity of β-lactoglobulin layers depend directly on the spreading concentration. Significant viscosity increase is obtained at larger surface pressures when the spreading concentration is increased. In contrast the shear rheology of the spread β-casein layers can be normalised by plotting the viscosities as a function of the surface pressure Π. The different behaviour is discussed in terms of denaturation of the β-lactoglobulin during the monolayer formation process by adsorption from the spread thin protein solution layer.  相似文献   

5.
The proline-rich N-Terminal domain peptides of γ-zein (VHLPPP)n with n = 1 and 3 (peptides I and II) are shown to form stable Langmuir films at air/water interface and the films have been characterized using surface pressure–molecular area (πA), surface potential–molecular area (ΔVA) isotherms, respectively. The longer peptide sequence does not show dramatic increase in surface or interfacial properties suggesting that the minimum length of n = 1 is sufficient to achieve the necessary surface properties. Brewster angle micrographs also agreed with these results. The high surface-active nature of the peptide suggests a fairly non-polar character at air/water interface and at solid/air interface when coated expresses a high surface energy.

Additives such as isopropyl alcohol (IPA) and polyvinyl alcohol (PVA) with the peptides showed more homogenous films at the air/water interface and also improved mechanical and tensile properties. The organized assembly of peptide I at the air/water and solid/air interface suggests that even thin layer of the peptide could play an important role in coating the inner surface of protein body membrane in storage proteins. Composite films of such short peptides with biocompatible polymers may find applications as surface coatings and in biomaterials.  相似文献   


6.
Wood polymer composites (WPC) were prepared by impregnating an Australian softwood, Pinus radiata with methyl methacrylate which subsequently underwent in situ polymerisation utilising either γ radiation or the catalyst–accelerator method. Novel additives including thermal initiator, crosslinking agents, an inclusion compound and oxygen scavenger were incorporated to improve the polymer loading and properties of the resulting WPC. Polymer loadings of WPC obtained utilising the accelerator–catalyst method corresponded well with those obtained using γ radiation with 20 kGy radiation dose. The mechanistic significance of the current work in analogous radiation grafting and curing processes is discussed.  相似文献   

7.
Edelfosine (1-O-octadecyl-2-O-methyl-rac-glycero-3-phosphocholine, Et-18-OCH3), an anticancer drug based on a phospholipid-like structure, was spread and investigated at the aqueous solution/air interface by means of surface pressure–area (πA) and electric surface potential–area (ΔVA) isotherms in addition to Brewster angle microscopy (BAM). The influence of such factors as subphase temperature, ionic strength, speed of compression and number of molecules spread at the surface on the characteristics of the πA isotherms was studied. Edelfosine was found to form stable Langmuir monolayers which are nearly not influenced by the experimental conditions. The relative reflectivity measurements proved that the thickness of monolayer in the vicinity of collapse is 2.4 nm, which corresponds to length of a vertically oriented molecule. Perpendicular orientation of edelfosine molecules just before the film collapse has been confirmed with the apparent dipole moment value, which attains the maximum value in this region.  相似文献   

8.
To be suitable for reducing water evaporation, monolayers need to be easy to apply and also spread quickly across the surface of water. However, the choice of monolayer often involves a compromise between spreading rate and evaporation resistance. Because emulsions of the monolayer material have been suggested as a way to improve spreading, emulsions were made with the long-chain alcohols hexadecanol, octadecanol and eicosanol using the non-ionic surfactants Brij 78 and Tween 60 as emulsifying agents. The emulsions of octadecanol and eicosanol spread faster than the corresponding powder. However there was no improvement in the spreading of hexadecanol emulsion due to a significant amount of the material dispersing into the bulk water instead of spreading at the interface. The choice of emulsifier to stabilise the emulsions is critical for effective evaporation resistance. Whereas the octadecanol emulsion made with Brij 78 showed improved evaporation resistance, the emulsion with Tween 60 had an appreciably lower evaporation resistance than powdered octadecanol. One limitation of the emulsion application method is the poor spreading on surfaces with an already high surface pressure.  相似文献   

9.
Spreading of a droplet of a concentrated oil-in-water emulsion over a water surface has been monitored. At the initial moment, this process proceeds at a high rate like an explosion. The stationary spreading is soon followed by the development of instability with the formation of a flower-shaped structure. At the final stage, the spot of the spread liquid may somewhat shrink. The characteristic times of these three stages are about 0.1, 1, and 10 s. The explosive character of the initial stage of spreading may be explained by the loss of dimensionality (3D → 2D) and the passage of the dispersion medium into the aqueous substrate with the release of a high free energy, while the subsequent spreading of the oil spot is explained by the Marangoni effect. A decrease in the energy of the interaction between dispersed phase (“oil”) particles in the emulsion leads to the phase separation. The final shrinkage of the oil spot may be due to the surface wave disturbance, which arises upon the explosive phase separation in the emulsion.  相似文献   

10.
Response surface methodology was applied to study the effect of different heating temperature/time treatments on whey protein denaturation and its effect on κ-carrageenan gelation in milk. The path of gel formation was followed using small deformation rheology and the extent of whey protein denaturation was determined by gel permeation chromatography. κ-Carrageenan did not influence the rate of whey protein denaturation and it was unlikely that whey protein denaturation played a significant role on κ-carrageenan gelation in milk. In skim milk serum or skim milk ultrafiltrate the path of gel formation and gel strength were not influenced by the severity of heat treatment but increasing the concentration of whey proteins enhanced the gel strength. Heat treatment became important for carrageenan gelation in skim or recombined milks (i.e. in the presence of casein micelles) by influencing the gelation temperature and gel strength. Increasing the concentration of whey proteins in the recombined milks had a beneficial effect on gel strength.  相似文献   

11.
以天然三萜皂苷七叶皂素为研究对象, 分别采用吊片法、 悬滴法和高速摄像机动态拍摄法探究了七叶皂素分子在气-液、 液-液、 固-液界面的界面行为. 考察了以七叶皂素为乳化剂制备乳液的性质, 以及七叶皂素对液滴在疏水固体表面润湿铺展行为的调控规律, 并从分子层次角度分析了作用机理. 结果表明, 七叶皂素能在气-液界面发生吸附, 将水的表面张力降低至42.1 mN/m, 临界胶束浓度为5×10?4 mol/L. 七叶皂素还可以在油-水界面吸附, 将亲油端插入油相, 亲水端插入水相, 形成稳定的界面膜, 降低界面张力. 以七叶皂素为乳化剂所制备的乳液, 随着浓度增大可以达到较小的粒径和较大的Zeta电势, 短时间内表现出较好的稳定性. 高浓度的七叶皂素可以很好地抑制液滴在疏水固体表面的弹跳和回缩, 达到很好的铺展效果, 有利于拓展其在诸多领域的应用.  相似文献   

12.
The distribution of proteins and lipids in food emulsions and foams is determined by competitive and cooperative adsorption between the two types of emulsifiers at the fluid-fluid interfaces, and by the nature of protein-lipid interactions, both at the interface and in the bulk phase. The existence of protein-lipid interactions can have a pronounced impact on the surface rheological properties of these systems. Therefore, these results are of practical importance for food emulsion formulation, texture, and stability. In this study, the existence of protein-lipid interactions at the interface was determined by surface dynamic properties (interfacial tension and surface dilational modulus). Systematic experimental data on surface dynamic properties, as a function of time and at long-term adsorption, for protein (whey protein isolate (WPI)), lipids (monoglycerides), and protein-lipid mixed films at the oil-water interface were measured in an automated drop tensiometer. The dynamic behaviour of protein+lipid mixed films depends on the adsorption time, the lipid and the protein/lipid ratio in a rather complicated manner. The protein determined the interfacial characteristics of the mixed film as the protein at WPI>/=10(-2)% wt/wt saturated the film, no matter what the concentration of the lipid. However, there exists a competitive or cooperative adsorption of the emulsifier (WPI and monoglycerides), as the concentration of protein in the bulk phase is far lower than that for interfacial saturation.  相似文献   

13.
We studied the whipping of artificial creams composed of a blend of sunflower oil and hydrogenated palm fat stabilized by protein or a mixture or protein and low molecular weight (lmw) surfactant. It was found that an increased whipping speed, decreased protein concentration, and the addition of lmw surfactant leads to shorter whipping times. Further, shorter whipping times were observed for WPI-stabilized cream compared to cream stabilized by sodium caseinate. In all cases, the decrease in whipping time was due to a decrease in the length of the second stage of whipping, the stage characterized by the adhesion of fat droplets to the air bubble surface. The decrease in whipping time could be accounted for by considering the influence of the experimental variables on the fraction of bubble surface area at which fat droplet spreading is possible. The same changes in parameters that promote droplet spreading at the air/water interface cause a decrease in the whipping time of our model creams. Correlating the whipping time of cream with the spreading behavior of fat droplets at the air/water interface represents a new insight into the mechanisms involved in the whipping of cream.  相似文献   

14.
Casein is well known to be a good protein emulsifier and β-casein is the major component of casein and commercial sodium caseinate. This work studies the behaviour of β-casein at the interface. The interfacial characteristics (structure and stability) of β-casein spread films have been examined at the air–water interface in a Langmuir-type film balance, as a function of temperature (5–40°C) and aqueous phase pH (pH 5 and 7). From surface pressure–area isotherms (πA isotherms) as a function of temperature we can draw a phase diagram. β-Casein spread films present two structures and the collapse phase. That is, there is a critical surface pressure and a surface concentration at which the film properties change significantly. This transition depends on the temperature and the aqueous phase pH. The film structure was observed to be more condensed and β-casein interfacial density was higher at pH 5. β-Casein films were stable at surface pressures lower than equilibrium surface pressure. In fact, no hysteresis was observed in πA isotherms after continuous compression-expansion cycles or over time. The relative area relaxation at constant surface pressure (10 or 20 mN m−1) and the surface pressure relaxation at constant area near the monolayer collapse, can be fitted by two exponential equations. The characteristic relaxation times in β-casein films can be associated with conformation–organization changes, hydrophilic group hydration and/or surface rheology, as a function of pH.  相似文献   

15.
The wettability of the solid powder of silica gel was determined via a modified Washburn equation expressed as contact angles. The interfacial tension (γ) between the dodecane and the dilute sodium dodecyl benzene sulfonate (SDBS) aqueous solution was obtained using the spinning drop (γ<10 mN m−1) or drop volume methods (γ>10 mN m−1). Contact angle changes for SDBS aqueous solutions on the surface of a silica gel powder were studied. The average aggregation number of SDBS micelles in aqueous solution was determined using the fluorescence quenching method. The relationship between the wettability of the powder surface, the critical micelle concentration (CMC) of SDBS and the mimic oil recovery of the resident oil on the powder surface has been explored. It has been found that good residual oil recovery was achieved by surface wettability changes at the interfacial tensions around 4–5 mN m−1, which is far from the ‘ultra low’ condition (≤10−3 mN m−1).  相似文献   

16.
The emulsifying and stabilizing ability of several hydrophobic (insoluble in water and soluble in volatile organic solvents) polymers, such as Eudragit RL, Eudragit RS, PLGA, PCL, and their mixtures, with regard to the methylene chloride (MC)-in-water mini-emulsions, has been compared to the viscosity of MC solutions and to the properties of adsorption and spread monolayers of these polymers.

Eudragits RS and RL contain 2.5 and 5 mol% of pendent cationic trimethylammonium (TMA) groups per 164 g/mol segments, whereas PLGA and PCL contain 1 and 2 polar carbonyl groups per 130 and 114 g/mol, respectively. The electrostatic attraction between the dipoles, formed by TMA groups and the condensed counter ions in the MC solutions, leads to the contraction of macromolecular coils of Eudragits, whereas the PLGA and PCL macromolecules, interacting by low polar carbonyl groups (with dipole moment μ = 2.7 D) retain more extended conformation in MC. This explains why the characteristic viscosities [η] of MC solutions are much lower for the former polymers (0.1 dL/g) with regard to PLGA and PCL solutions whose [η] is equal to 0.3 and 0.6 dL/g, respectively.

The ionization of TMA groups in contact with the water phase leads to the irreversible adsorption of Eudragits at the MC/water interface and to high decrease of the interfacial tension γ (down to 4 mN/m for the 5% MC solutions). Whereas PLGA and PCL possessing low polar carbonyl groups adsorb poorly at the MC/water interface exhibiting γ  28 mN/m. Higher stability of spread monolayers of Eudragits (π*  40 mN/m) with regard to PLGA and PCL (π* < 20 mN/m) correlates well with higher interfacial activity of the former with regard to the later. The higher surface potential ΔV of Eudragits (0.9 V) with regard to PLGA (0.3 V) and PCL (0.4 V) is explained by the formation of electric double layer (DL) by the former, whereas the later contribute to the ΔV only by cumulative dipole moments of carbonyl groups. The experimental values of surface potentials correlate well with the Gouy–Chapman model of the DL and the Helmholtz model of the monolayer.

The ensemble of experimental results leads to the conclusion that higher emulsifying and stabilizing ability of Eudragits with regard to PLGA and PCL is due to higher adsorption activity of the former which form the corona of polymeric chains with ionized TMA groups around the droplets. It can be postulated that Eudragit polymers have good surface active properties which may allow manufacturing of biocompatible nanoparticles by emulsification–solvent evaporation method without surfactants.  相似文献   


17.
Super-spreading trisiloxane surfactants are a class of amphiphiles which consist of nonpolar trisiloxane headgroups ((CH3)3-Si-O)2-Si(CH3)(CH2)3-) and polar parts composed of between four and eight ethylene oxides (ethoxylates, -OCH2CH2-). Millimeter-sized aqueous drops of trisiloxane solutions at concentrations well above the critical aggregate concentration spread rapidly on very hydrophobic surfaces, completely wetting out at equilibrium. The wetting out can be understood as a consequence of the ability of the trisiloxanes at the advancing perimeter of the drop to adsorb at the air/aqueous and aqueous/hydrophobic solid interfaces and to reduce considerably the tensions of these interfaces, creating a positive spreading coefficient. The rapid spreading can be due to maintaining a positive spreading coefficient at the perimeter as the drop spreads. However, the air/aqueous and solid/aqueous interfaces at the perimeter are depleted of surfactant by interfacial expansion as the drop spreads. The spreading coefficient can remain positive if the rate of surfactant adsorption onto the solid and fluid surfaces from the spreading aqueous film at the perimeter exceeds the diluting effect due to the area expansion. This task is made more difficult by the fact that the reservoir of surfactant in the film is continually depleted by adsorption to the expanding interfaces. If the adsorption cannot keep pace with the area expansion at the perimeter, and the surface concentrations become reduced at the contact line, a negative spreading coefficient which retards the drop movement can develop. In this case, however, a Marangoni mechanism can account for the rapid spreading if the surface concentrations at the drop apex are assumed to remain high compared to the perimeter so that the drop is pulled out by the higher tension at the perimeter than at the apex. To maintain a high apex concentration, surfactant adsorption must exceed the rate of interfacial dilation at the apex due to the outward flow. This is conceivable because, unlike that at the contact line, the surfactant reservoir in the liquid at the drop center is not continually depleted by adsorption onto an expanding solid surface. In an effort to understand the rapid spreading, we measure the kinetic rate constants for adsorption of unaggregated trisiloxane surfactant from the sublayer to the air/aqueous surface. The kinetic rate of adsorption, computed assuming the bulk concentration of monomer to be uniform and undepleted, represents the fastest that surfactant monomer can adsorb onto the air/aqueous surface in the absence of direct adsorption of aggregates. The kinetic constants are obtained by measuring the dynamic tension relaxation as trisiloxanes adsorb onto a clean pendant bubble interface. We find that the rate of kinetic adsorption is only of the same order as the area expansion rates observed in superspreading, and therefore the unaggregated flux cannot maintain very high surface concentrations at the air/aqueous interface, either at the apex or at the perimeter. Hence in order to maintain either a positive spreading coefficient or a Marangoni gradient, the surfactant adsorptive flux needs to be augmented, and the direct adsorption of aggregates (which in the case of the trisiloxanes are bilayers and vesicles) is suggested as one possibility.  相似文献   

18.
In this work we have analyzed the structural and topographical characteristics of mixed monolayers formed by an adsorbed whey protein isolate (WPI) and a spread monoglyceride monolayer (monopalmitin or monoolein) on the previously adsorbed protein film. Measurements of the surface pressure (pi)-area (A) isotherm were obtained at 20 degrees C and at pH 7 for protein-adsorbed films from water in a Wilhelmy-type film balance. Since the surface concentration (1/A) is actually unknown for the adsorbed monolayer, the values were derived by assuming that the A values for adsorbed and spread monolayers were equal at the collapse point of the mixed film. The pi-A isotherm deduced for adsorbed WPI monolayer in this work is practically the same as that obtained directly by spreading. For WPI-monoglyceride mixed films, the pi-A isotherms for adsorbed and spread monolayers at pi higher than the equilibrium surface pressure of WPI are practically coincident, a phenomenon which may be attributed to the protein displacement by the monoglyceride from the interface. At lower surface pressures, WPI and monoglyceride coexist at the interface and the adsorbed and spread pi-A isotherms (i.e., the monolayer structure of the mixed films) are different. Monopalmitin has a higher capacity than monoolein for the displacement of protein from the air-water interface. However, some degree of interactions exists between proteins and monoglycerides and these interactions are higher for adsorbed than for spread films. The topography of the monolayer corroborates these conclusions.  相似文献   

19.
We have investigated the dynamic rheological properties of concentrated multiple emulsions to characterize their amphiphile composition at interfaces. Multiple emulsions (W1/O/W2) consist of water droplets (W1) dispersed into oil globules (O), which are redispersed in an external aqueous phase (W2). A small-molecule surfactant and an amphiphilic polymer were used to stabilize the inverse emulsion (W1 in oil globules) and the inverse emulsion (oil globules in W2), respectively. Rheological and interfacial tension measurements show that the polymeric surfactant adsorbed at the globule interface does not migrate to the droplet interfaces through the oil phase. This explains, at least partly, the stability improvement of multiple emulsions as polymeric surfactants are used instead of small-molecule surfactants.  相似文献   

20.
The interfacial behavior of the hypoglycemia lectin BmoLL purified from the leaves of Bauhinia monandra, and its ability to interact with lipid monolayers has been studied by surface tension (γ) measurements. The results of these experiments revealed that in the solution concentration range comprised between 0.2 and 1.0 mg/ml, there was an extremely pronounced increase in the BmoLL adsorption at the interface with the air phase. This adsorption at the higher studied BmoLL concentrations gave rise to a more gradual increase in the surface pressure (π = γ0γ). The results showed also that the surface pressure of adsorbed films was pH dependent and it substantially increased at low pHs (between pH 4.0 and pH 2.5). Independently carried out ξ potential measurements demonstrated that BmoLL was negatively charged at all pHs and borne the highest charge at the pH around 5.5. The penetrant ability of BmoLL into the two different in chemical nature monolayers: (dioleoylphosphatidylcholine and octadecylamine) have been assessed measuring Δπ increments at constant area. It was observed that, whereas the monolayers of either pure dioleoylphosphatidylcholine (DOPC) or pure octadecylamine (ODA) stimulated BmoLL adsorption, the lectin adsorption within their mixtures strongly depended on both the content of positively charged octadecylamine in a mixture and on the monolayer compressibility. These findings are discussed in terms of both the electrostatic interaction involved in adsorption of BmoLL and of changes in monolayer compressibilities brought up by the addition of ODA molecules to the phospholipid. The relevance of this work to liposome preparations is indicated in the concluding remarks.  相似文献   

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