Surface tension of protein and insoluble lipids at the air-aqueous phase interface

The surface activity of bovine serum albumin (BSA) in water and aqueous solutions of ethanol (0.5, 1.0, and 2.0 M) and sucrose (0.5 and 1.0 M) has been investigated over a range of protein concentrations (5–1.10⁻⁵, % w/w). The surface tension data were determined by the Wilhelmy plate method. Surface data at low protein concentrations indicate a low surface activity, which rises to a plateau as the monolayer is saturated at higher protein concentrations. The protein concentration and surface tension at the plateau depend on the aqueous phase composition. The effect of aqueous phase composition on BSA-lipid interactions has been investigated by spreading an insoluble lipid (monostearin or monoolein) on a film of BSA previously adsorbed on the interface. The existence of protein-lipid interactions depends on the protein/lipid ratio. The surface activity of mixed BSA-lipid films is determined by the lipid because the surface pressure of the mixed film is the same as the lipid equilibrium spreading pressure, and the monolayer is not saturated by BSA. However, the surface activity of mixed BSA-lipid films is determined by BSA as the monolayer is saturated by the protein.     

Surface tension of bovine serum albumin and tween 20 at the air-aqueous interface

Interfacial properties (surface tension, σ, and critical micelle concentration, CMC) of aqueous solutions of Tween 20 (polyoxyethylene sorbitan monolaurate) and/or bovine serum albumin (BSA) were evaluated. Temperature, Tween 20 concentration in the aqueous phase, BSA/Tween 20 ratio, and aqueous phase composition [water, ethanol (0.5, 1.0, and 2.5 M), and sucrose (0.5 M)] were the variables studied. The CMC of Tween 20 was determined by surface tension measurements (Wilhelmy plate method). The existence of BSA-Tween 20 interactions was deduced from surface tension measurements. The results show that the effect of temperature on CMC depends on the aqueous phase composition, but the σ value at CMC, σ_CMC, does decrease as temperature is increased. The CMC and σ_CMC values also depend on the aqueous phase composition. In aqueous ethanol solutions, the CMC increases, but σ_CMC decreases. However, in sucrose aqueous solutions, the CMC decreases, but there is no significant effect on σ_CMC. The BSA-Tween 20 interactions at the interface depend on both Tween 20 concentration (C) and solute in the bulk phase. In water and aqueous solutions of ethanol and sucrose, σ values decrease in the presence of protein at C<CMC but are practically independent of C at C>CMC. This is an indication that the interfacial characteristics of the mixed film are determined by either the protein or the lipid at the higher and lower protein/lipid ratio, respectively. In the intermediate region, the existence of BSA-Tween 20 interactions dominates the interfacial characteristics of mixed films.     

Effect of additives on the adsorption of sodium bis(2-ethyl hexyl sulfosuccinate) at the air-water interface studied by equilibrium and dynamic surface tension measurements

Using equilibrium and dynamic surface tension measurements, we have studied the effect of the addition of poly(sodium 4-styrenesulfonate) (PSS), sodium chloride, and 1,4,7,10,13,16-hexaoxyacyclooctadecane (18-crown-6) on the surface properties of sodium bis(2-ethyl hexyl sulfosuccinate) (AOT). The addition of PSS or NaCl weakly increases the maximum packing of AOT, whereas the presence of 18-crown-6 slightly decreases the maximum surface coverage. The surfactant adsorption kinetics on the interface is a diffusion-controlled process. The two asymptotic solutions at long times and at short times to the classic Ward Tordai equation were used to fit dynamic results. At long times there is evidence of the existence of an electrostatic barrier at high surfactant concentration when using pure AOT and AOT mixed with PSS. In binary mixtures of AOT with sodium chloride or 18-crown-6, the electrostatic barrier is not observed over the surfactant concentration range studied.     

香兰素基非离子表面活性剂的动态表面张力与气/液界面吸附行为

通过最大气泡压力法测定香兰素基聚氧乙烯醚(VAEO)的动态表面张力,利用Word-Tordai方程研究其在气/液界面的吸附行为。结果表明,质量浓度低于临界胶束浓度(cmc)时,VAEO在吸附前期为扩散控制吸附,在吸附后期为混合动力控制吸附;质量浓度大于cmc时,为混合动力控制吸附,胶束不影响吸附行为。VAEO_(10)和VAEO_(20)的扩散系数D的数量级为10~(-11)m~2/s,比文献报道的壬基酚聚氧乙烯醚(NPEO_9)低一个数量级。     

气固界面吸附团簇分布及相变机制研究

为了深入探讨气固界面吸附过程中团簇分布及其演化规律,结合实验测量和理论分析研究了水蒸气在二氧化硅和石墨表面的吸附特征,获取了不同压比下的团簇分布,确定了吸附相变及润湿转变的临界条件。结果表明,实验测量结果和Zeta吸附理论预测吸附曲线吻合很好,明确了气体分子以团簇形式吸附在固体表面,在低压比区,小分子团簇和零吸附单元占主导地位,随着压比的增加,吸附团簇类型增多,当压比达到某一临界值时,吸附熵达到极大值,界面发生吸附相变。确定了零吸附情况下石墨和二氧化硅表面张力及界面润湿临界条件,润湿压比下,性质均一的大分子团簇聚集,形成类液膜润湿界面。     

Effect of ethanol on monoglyceride monolayers at the air-aqueous phase interface

We have studied the behavior of monopalmitin and monoolein monolayers, spread at the air-aqueous phase interface, as a function of temperature and surface pressure. The subphases were aqueous ethanol solutions at 0.5 and 1 mol/L. The structural characteristics of these films at interface were deduced from the π-A isotherms, as measured with an automated Langmuir-type film balance. The monolayer structure and stability were functions of hydrocarbon chain length and the presence of a double bond. Generally, the factors that decreased monolayer stability produced transformations toward configurations with more expanded structures. Changes in the subphase composition had a direct influence on the monolayer molecular structure. This study showed the existence of interactions between film and ethanol molecules at the interface. As a consequence of these interactions, a contraction in the monolayer structure was observed. The magnitude of interactions between monoglyceride and ethanol molecules at the interface depends on the surface pressure, temperature, and surface composition. Stronger film-substrate interactions produced changes in monolayer stability. Relationships between film elasticity and structural characteristics are also discussed.     

Interaction of a Tat substrate and a Tat signal peptide with thylakoid lipids at the air-water interface

The Tat machinery enables folded proteins to be translocated across biological membranes. In vitro studies have shown that Tat substrates can interact with membranes prior to translocation. In this study we investigated the initial states of this interaction with thylakoid lipid monolayers at the air-water interface by using monolayer techniques combined with infrared reflection-absorption spectroscopy (IRRAS). We used enhanced green fluorescent protein (EGFP) as a model substrate and the signal peptide SP16 from the 16 kDa protein of the spinach oxygen-evolving complex (OEC16). We found that the signal peptide is essential for the interaction of the model substrate with lipid monolayers. IRRA spectroscopy showed an increased amount of α-helical secondary structure elements for the chimeric model substrate i16/EGFP (SP16 fused to EGFP) compared with EGFP; this can be attributed to the signal peptide.     

Adsorption of amphiphiles at an oil-water vs. an oil-metal interface

Studies were conducted to investigate whether adsorption of amphiphiles from oil onto a degreased metal can be predicted from knowledge about adsorption of the amphiphiles at the oil-water interface. The surface of a degreased metal comprises oxides, hydroxides, and adsorbed water vapor, which form from the reaction of the metal with air and moisture. If the behaviors of amphiphiles at water-oil and metal-oil interfaces are similar, this information can be useful in the development of cheaper and quicker methods of estimating amphiphile adsorption properties on degreased metals. The amphiphiles used were safflower oil (SA) and jojoba oil (JO), both of which are plant-based oils, and methyl palmitate (MP). SA is a triester whereas JO and MP are monoesters. The interfacial tension of water-hexadecane was measured as a function of amphiphile concentration in hexadecane and used to estimate an interfacial-based free energy of adsorption, ΔG _ads. The resulting interfacial-based ΔG _ads values for SA were identical to those reported from friction-based adsorption isotherms. The corresponding values for the monoesters were within the range reported from friction-based adsorption isotherms.     

Organization of amphiphiles VI. A comparative study of the orientation of polyoxyethylated alkyl phenols at the air-water and the silica-water interface

The adsorption behavior on silica of a series of polyoxyethylated alkyl phenols of varying hydrophobicities and hydrophilicities was studied by determining the adsorption isotherm along with the zeta potential of silica. An increase in the concentration of each of the surfactants caused the zeta potential to become less negative and ultimately to reach a plateau; similarly, the adsorption isotherm also plateaued. These results were attributed to the flat orientation of the surfactants caused by hydrogen bonding of the oxygen atom of the oxyethylene group with the silanol group of the silica, which led to the formation of a thin oxyethylene layer at the silica-water interface. This layer masked a constant fraction of the silica surface. A model for the orientation of the surfactants at the silica-water interface was proposed, based on a “molecular parking area” (i.e., space occupied by the molecule during adsorption at the silica-water interface) of the surfactants on the silica surface.     

Spectroelectrochemical analysis of ion-transfer and adsorption of the PAMAM dendrimer at a polarized liquid|liquid interface

The interfacial behavior of the fourth generation polyamidoamine (G4 PAMAM) dendrimer at a water|1,2-dichloroethane (DCE) interface was studied by cyclic voltammetry and potential modulated fluorescence (PMF) spectroscopy. Irregular voltammetric responses were observed at positively polarized interfaces. The cyclic voltammogram was strongly dependent on pH and on the concentrations of the G4 PAMAM dendrimer and the organic supporting electrolyte. PMF spectroscopy was successfully used to analyze the interfacial mechanism of the dendrimer by adding an anionic porphyrin derivative as a fluorescent probe. The results of the PMF measurements demonstrated that the G4 PAMAM dendrimer was transferred across the interface, a process that was accompanied by an adsorption step at pH 7. In contrast, under alkaline conditions, the adsorption process did not seem to be involved in the interfacial behavior.     

Aggregation of hydrophobically modified chitosan in solution and at the air–water interface

Oleoyl‐chitosans (O‐chitosans), with three degrees of substitution (DS), were synthesized by reacting chitosan with oleoyl chloride. The chemical structures of these polymers were characterized by ¹H NMR and FTIR. The results suggested the formation of an amide linkage between amino groups of chitosan and carboxyl groups of oleic acid. These O‐chitosans exhibited poor solubility in aqueous acidic solution. The solubility of O‐chitosans decreased as the DS values increased. The transmittance of O‐chitosans (2 g/L) with DS 5%, 11%, 27% in 1% (v/v) HCl solution were 69.5%, 62.7%, 48.6%, respectively. These O‐chitosans were not soluble at neutral or alkali pH. Formation of self‐aggregation was observed using pyrene as a fluorescent probe in the O‐chitosans aqueous solution. The increase of DS of O‐chitosans resulted in significant decrease of critical aggregation concentration (CAC). The CAC of the O‐chitosans with DS 5%, 11%, 27% were 79.43, 31.6, 10 mg/L, respectively. The surface tension of solution could be reduced slightly by all of the O‐chitosans. The surface tension of O‐chitosans solution decreased with the increase of DS values. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1968–1973, 2006     

Structuring of 2-oleodipalmitin at the air interface from all-atom,united-atom,and coarse-grained molecular dynamics simulations

This study employs classical molecular dynamics (MD) simulations to investigate the behavior of 1,3-dipalmitoyl-2-oleoyl glycerol (POP), a typical triglyceride found in food at the air interface. The investigation utilizes three force fields (FF) with varying levels of detail, including all-atom, united-atom, and coarse-grained simulations, to elucidate the structural evolution of POP at the air interface. The results confirm that the structuring processes observed in nonfood triglyceride systems also occur in POP. Aliphatic chains orient toward the air phase, while glycerol backbones face the inner triglyceride phase. Additionally, the study observes the formation of clusters of glycerol head groups at the interface, and the choice of the FF significantly affects the simulated morphological structure. The Berger FF exhibits the most substantial structuring effects after 200 ns of simulation, followed by the General AMBER FF, while the Martini FF shows the weakest effects. Number density plots of aliphatic chains and glycerol backbones at different temperatures monitor the evolution of structuring effects over time and determine the approach toward equilibrium conditions. The temperatures investigated include the solid state of POP at ambient temperature (293 K), the liquid state at human body temperature (310 K), and a typical processing temperature of the chocolate conching process (333 K). Practical Applications: Tailored molecular design of interfaces according to their purpose in food.     

Mechanism of the enhanced spreading of some mixtures of anionic and cationic hydrocarbon chain surfactants on a highly hydrophobic polyethylene surface

The objective of this investigation was to measure the interfacial properties and interactions among mixtures of different cationic and anionic surfactants at the hydrophobic solid/aqueous solution interface to explain the different spreading factors or behavior of the mixed surfactants on a highly hydrophobic polyethylene (PE) film. A synergistic effect in the spreading of the mixed surfactant solutions on the PE film was observed when the surfactants were added sequentially. Other interfacial phenomena related to this surfactant spreading, such as interaction parameters at the solid/liquid (S/L) and liquid/air (L/A) interfaces in the mixtures adsorbed at various interfaces and dynamic contact angles of the mixed surfactant solutions during the process of spreading on the PE substrate, were investigated to obtain insight into this enhanced spreading. All the interaction parameters were more negative than −20, indicating very strong interaction between these cationic and anionic surfactants. The interaction parameters at the S/L interface were more negative than at the L/A interface, showing that the attractive interaction at the S/L interface was stronger than at the L/A interface. The spreading was related to the difference in the interaction parameters at the S/L and L/A interfaces and to the dynamic contact angle.     

Interactions between fat crystal networks and sodium caseinate at the sunflower oil-water interface

A Couette-type torsion wire surface shear viscometer was used to measure the apparent interfacial shear viscosity of pH 7 (I=0.05 M) buffered solutions of sodium caseinate in contact with sunflower oil. The sunflower oil contained 1% fat crystals in either the β or β′ polymorphic form, or was crystal free. In all cases, the fat crystals increased the interfacial shear viscosity synergistically, with the β′ crystals causing the biggest increase. Substituting the protein for a small-molecule surfactant (Tween-40) showed that this was not simply due to the protein lowering the interfacial tension. Sedimentation studies of the different fat crystal slurries suggested that the extent of the interfacial shear viscosity increase was related to the strength of crystal-crystal interactions in the oil phase. It seems likely that when protein is present at the interface, it fixes the adsorbed layer of fat crystals to the cross-linked protein film at the interface. When this film was sheared, the strength of the crystal-crystal interactions in the oil phase became important. However, when Tween-40 was in the aqueous phase instead of the protein, the crystal-crystal interactions were not relevant, presumably because the Tween-40 interfacial film simply flowed around the adsorbed crystals     

Lecithins in oil-continuous emulsions. Fat crystal wetting and interfacial tension

Lecithin is a powerful emulsifier widely used in foods, feeds and pharmaceuticals. Several analytical methods have been proposed to characterize lecithins, but they are often inadequate to determine the industrial functionality. The purpose of this study was to find a relationship between the interfacial properties of lecithins (adsorption to oil/water and fat crystal/oil/water interfaces), phospholipid composition and functionality. Results show that all lecithins adsorb to fat crystals at the triglyceride oil/water interface, making their surface more polar (observed as an increase in the contact angle measured through the oil at the interface: fat crystal/oil/water). This adsorption process is quick (less than five minutes) for relatively polar lecithins, such as soybean phosphatidylcholine (PC), and results in highly polar surfaces (contact angle ∼180°). Less polar lecithins give slow adsorption (some hours) and less polar crystals (contact angle ≤90°). The adsorption of different lecithins to the oil/water interface, observed as a decrease in interfacial tension, follows the adsorption pattern to the fat crystals. We found a relation between high-fat crystal polarity and poor lecithin functionality in margarine (margarines spatters during frying), and also between high-fat crystal polarity and a high polar to nonpolar phospholipids [Σ(PI + PA + LPC)/ΣPE; PI, phosphatidylinositol; PA, phosphatidic acid; LPC, lysoPC, PE, phosphatidylethanolamine] ratio in lecithin. The correlations might bevia aggregation properties of lecithin in the oil. We found also that monoolein shifted the adsorption kinetics of lecithin (soybean PC) to fat crystals and the hydrophilicity of adsorbed layers probably due to formation of mixed aggregates between monoolein and soybean PC.     

Correlation between physical bonding and mechanical properties of wood–plastic composites: part 2: effect of thermodynamic factors on interfacial bonding at wood–polymer interface

Abstract

The main objective of this study was to find out if there is any significant correlation between physical properties and interfacial bonding of interphases in wood–plastic composites. To this end, high-density polyethylene (HDPE), mixture of 3% maleic anhydride grafted polyethylene (MAPE) and HDPE (coded as MHDPE) and polylactic acid (PLA) were separately interacted with veneers to identify factors underlying interfaces. Plastics were first melted at 180?°C and dispensed on wood surfaces so that the contact angle (CA) could be directly measured. Wood sanding moderately decreased the CAs of plastics in order of PLA, MHDPE, and HDPE. The treatment of veneers with MAPE comprehensively improved wetting, as the CA of HDPE was significantly reduced on the wood surface after the treatment. Thereafter, the interfacial shear strengths (IFSS) of the wood–polymer interface were determined using the automated bonding evaluation system. PLA had the highest IFSS both for unsanded and sanded veneers. Comparing both parts of this research finally revealed that applying sanding or/and MAPE treatments resulted in lower surface free energy and higher IFSS at the wood–polymer interface. However, our observations support the idea that, at higher temperatures, wetting of composites is mainly influenced by polymer properties rather than interfacial tension at the wood–polymer interface.     

Interfacial and foaming characteristics of milk whey protein and polysaccharide mixed systems

Protein‐polysaccharide (PS) interactions find many applications in food engineering and new foam formulations. In this article, we have studied the effect of anionic nonsurface active PSs [sodium alginate (SA) and lambda‐carrageenan (λ‐C)] in aqueous solution on interfacial and foaming characteristics of milk whey proteins [whey protein concentrate (WPC) and whey protein isolate (WPI)]. Whey protein concentration (1.0% wt), temperature (20°C), pH (7), and ionic strength (0.05 M) of the aqueous media were kept constant, while PS influence was evaluated within a 0.0–1.0% wt concentration range. The dynamic properties (dynamics of adsorption and surface dilatational properties) of WPC/PS and WPI/PS adsorbed films were considered in order to correlate the foaming characteristics of the biopolymer mixed systems. Foaming characteristics of the biopolymer mixed systems depended on the PS relative concentration in the aqueous phase and on the whey protein‐PS interactions in solution and at the air–water interface. Dynamic surface properties of the adsorbed films at short adsorption time had a significant effect on foaming capacity. For a particular system, the overall foam destabilization (foam half‐life time) and the individual destabilization processes (drainage, disproportionation, and bubble coalescence) depend on the nature of the PS, its relative bulk concentration, and whey protein‐PS interactions in the vicinity of the air–water interface. The viscosity of the aqueous phase has an effect on the rate of drainage while the rate of disproportionation/collapse is more dependent on the interfacial characteristics of the adsorbed film. © 2009 American Institute of Chemical Engineers AIChE J, 2010