Changes in wetting properties of alumina surface treated with DPPC in the presence of phospholipase A2 enzyme

Wetting properties of commercial Al(2)O(3) plates contacted with dipalmitoylphosphatidylcholine (DPPC) or DPPC+enzyme (phospholipase PLA(2)) in NaCl solution were determined by thin layer wicking and with the help of Washburn equation. Van Oss et al.'s approach to interfacial free energy interactions was applied to determining the solid surface free energy components. Wicking experiments were performed both for bare and alumina plates precontacted overnight with the probe liquid saturated vapours, as well as the untreated and DPPC (or DPPC+PLA(2)) treated alumina plates. For this purpose the penetration rates of n-octane, water and formamide were measured. From these experiments it resulted that original alumina surface is strongly polar with electron-donor interactions originating from the surface hydroxyl groups. Adsorption of DPPC on Al(2)O(3) plates slightly increased the hydrophobic character of the alumina surface (considerable decrease of the electron-donor, γ(s)(-) parameter and γ(s)(AB) component was visible) in such a way that the hydrocarbon chains were directed outwards and the polar part towards the alumina surface. However, after the enzyme action the products of DPPC hydrolysis by PLA(2) (palmitic acid and lysophosphatidylcholine) increased again the hydrophilic character of Al(2)O(3) surface (a minor increase in γ(s)(AB) component and drastic increase of the electron-donor γ(s)(-) parameter was noticeable). After treatment with DPPC or DPPC+enzyme PLA(2) solution the changes of the total surface free energy of alumina and its Lifshits-van der Waals (γ(s)(LW)) component were in the range 7-10 mJ/m(2), but the most considerable and delivering more interesting information were the changes of the electron-donor (γ(s)(-)) parameter ranging from 27 to 35 mJ/m(2). Moreover, the changes of the alumina surface wettability were dependent on the time of the enzyme contacting with DPPC in NaCl solution. On the basis of the obtained results it seems that the thin layer wicking method can be an additional useful tool in investigations of the effect of phospholipid and PLA(2) action on the hydrophilic-hydrophobic character of alumina surface.     

Forces between polyethylene surfaces in oxyethylene dodecyl ether solutions as influenced by the number of oxyethylene groups

The atomic force microscopy (AFM) colloidal probe technique was used to study the effect of oxyethylene dodecyl ethers, C12En (n = 1-7), on interactions between hydrophobic polyethylene (PE) surfaces in aqueous solutions. Long-range (colloidal) and contact (pull-off) forces were measured between 10 to 20 microm PE spheres and a flat PE surface at concentrations of surfactant of 1 x 10(-6) and 1 x 10(-4) M. The surface tension of the surfactant solutions and contact angles at PE surfaces were also studied. The influence of the number of oxyethylene groups in the surfactant molecule was examined. Initially, long-range attractive (hydrophobic) forces between the PE surfaces were observed that decreased in range and magnitude with an increase in the number of oxyethylene groups in 1 x 10(-4) M solutions. Above four oxyethylene groups per molecule, repulsive forces were observed. The measured pull-off force between PE surfaces decreased monotonically from approximately 500 mJ/m2 for C12E1 to 150 mJ/m2 for C12E7. The interfacial energy was calculated on the basis of the JKR model, taking into account long-range forces operating outside the contact area. The interfacial energies decreased from 43-47 mJ/m2 for PE-water and PE-C12E1 (1 x 10(-4) M) interfaces to approximately 18 mJ/m2 for PE-C12E7 (1 x 10(-4) M). The interfacial energy was also calculated from measured contact angles and surface tensions using Neumann's equation of state and Young's equation. A similar relationship between interfacial energy and the number of oxyethylene groups was observed on the basis of contact and surface tension measurements. However, interfacial energy values were smaller, within 15-20 mJ/m2, than those calculated from AFM pull-off force measurements.     

Development and validation of a high-performance thin-layer chromatographic method for determination of ofloxacin residues on pharmaceutical equipment surfaces

An HPTLC method with densitometric quantification using fluorescence at 313 nm was developed and validated for the determination of ofloxacin residue in controlling pharmaceutical equipment cleanliness. Simulated samples at a residue level of 1 mg/m2 were prepared by spreading the calculated amount of ofloxacin solution on 1, 5, and 10 dm2 stainless steel surfaces. After evaporation of the solvent, the residue was removed by two ethanol wetted cotton swabs, which were thereafter extracted with the mixture of ethanol and Na2EDTA-water solution at pH 11 for 15 min with sonication. The extract and standards were applied on HPTLC silica gel 60 plates and then developed in a horizontal developing chamber from both sides using ethanol-conc. ammonia (4+1, v/v) as the mobile phase. The mean recovery (n=6) at 1 mg/m2 from 1, 5, and 10 dm2 was 95.3, 88.6, and 89.7% with the CV values 3.78, 4.41, and 4.97%, respectively. The absolute detection limit was 0.6 ng and the quantitation limit was 2 ng, but it was shown that these can be improved by immersion of the developed plate into a solution of liquid paraffin-n-hexane (1+2, v/v) to approximately 0.25 and 0.9 ng, respectively. The LOD of the method using detection without paraffin-n-hexane was 3, 0.6, and 0.3 microg/m2 by swabbing 1, 5, and 10 dm2, respectively. The method can be applied to routine control of pharmaceutical equipment cleanliness by sampling from stainless steel surface areas of 1 to 10 dm2 with acceptable residue limit/surface of 1 mg/m2.     

Determination of anisotropic surface characteristics of different phyllosilicates by direct force measurements

To fundamentally understand the electrokinetic behavior of clay minerals, it is necessary to study the anisotropic surface charge properties of clay surfaces. In this study, two 2:1 layer natural minerals, talc and muscovite, were chosen as representatives of magnesium and aluminum phyllosilicate minerals, respectively. The molecularly smooth basal planes of both platy minerals were obtained by cleavage along the basal planes, while suitable edge surfaces were prepared by an ultramicrotome cutting technique. Silicon nitride atomic force microscopy tip was used as a probe to study the interaction forces between the tip and clay basal/edge surfaces in aqueous solutions of various pH values. The measured interaction force profiles between the tip and clay basal/edge surfaces were fitted with the classical DLVO (Derjaguin-Landau-Verwey-Overbeek) theory, which allows direct determination of electrical surface potential of talc and muscovite surfaces. The surface potential of muscovite basal planes was found to be significantly more negative than the basal plane of talc, both being pH insensitive. In contrast, the surface potential of edge surfaces was highly pH-dependent, exhibiting a point of zero charge (PZC) at pH 7.5 and 8.1 for edges of muscovite and talc, respectively. The observed differences in surface potential of basal planes and edge surfaces for both talc and muscovite are closely related to their crystal structure and ionization characteristics. The protonation reactivity and the contribution of each surface group to the surface charging behavior are modeled using their protonation constants.     

Interaction energy and surface reconstruction between sheets of layered silicates

Interactions between two layered silicate sheets, as found in various nanoscale materials, are investigated as a function of sheet separation using molecular dynamics simulation. The model systems are periodic in the xy plane, open in the z direction, and subjected to stepwise separation of the two silicate sheets starting at equilibrium. Computed cleavage energies are 383 mJ /m(2) for K-mica, 133 mJ /m(2) for K-montmorillonite (cation exchange capacity=91), 45 mJ /m(2) for octadecylammonium (C(18))-mica, and 40 mJ /m(2) for C(18)-montmorillonite. These values are in quantitative agreement with experimental data and aid in the molecular-level interpretation. When alkali ions are present at the interface between the silicate sheets, partitioning of the cations between the surfaces is observed at 0.25 nm separation (mica) and 0.30 nm separation (montmorillonite). Originally strong electrostatic attraction between the two silicate sheets is then reduced to 5% (mica) and 15% (montmorillonite). Weaker van der Waals interactions decay within 1.0 nm separation. The total interaction energy between sheets of alkali clay is less than 1 mJ /m(2) after 1.5 nm separation. When C(18) surfactants are present on the surfaces, the organic layer (>0.8 nm) acts as a spacer between the silicate sheets so that positively charged ammonium head groups remain essentially in the same position on the surfaces of the two sheets at any separation. As a result, electrostatic interactions are efficiently shielded and dispersive interactions account for the interfacial energy. The flexibility of the hydrocarbon chains leads to stretching, disorder, and occasional rearrangements of ammonium head groups to neighbor cavities on the silicate surface at medium separation (1.0-2.0 nm). The total interaction energy amounts to less than 1 mJ /m(2) after 3 nm separation.     

Axisymmetric drop shape analysis-constrained sessile drop (ADSA-CSD): a film balance technique for high collapse pressures

Collapse pressure of insoluble monolayers is a property determined from surface pressure/area isotherms. Such isotherms are commonly measured by a Langmuir film balance or a drop shape technique using a pendant drop constellation (ADSA-PD). Here, a different embodiment of a drop shape analysis, called axisymmetric drop shape analysis-constrained sessile drop (ADSA-CSD) is used as a film balance. It is shown that ADSA-CSD has certain advantages over conventional methods. The ability to measure very low surface tension values (e.g., <2 mJ/m2), an easier deposition procedure than in a pendant drop setup, and leak-proof design make the constrained sessile drop constellation a better choice than the pendant drop constellation in many situations. Results of compression isotherms are obtained on three different monolayers: octadecanol, dipalmitoyl-phosphatidyl-choline (DPPC), and dipalmitoyl-phosphatidyl-glycerol (DPPG). The collapse pressures are found to be reproducible and in agreement with previous methods. For example, the collapse pressure of DPPC is found to be 70.2 mJ/m2. Such values are not achievable with a pendant drop. The collapse pressure of octadecanol is found to be 61.3 mJ/m2, while that of DPPG is 59.0 mJ/m2. The physical reasons for these differences are discussed. The results also show a distinctive difference between the onset of collapse and the ultimate collapse pressure (ultimate strength) of these films. ADSA-CSD allows detailed study of this collapse region.     

Spreading dynamics and dynamic contact angle of non-Newtonian fluids

The spreading dynamics of power-law fluids, both shear-thinning and shear-thickening fluids, that completely or partially wet solid substrate was investigated theoretically and experimentally. An evolution equation for liquid-film thickness was derived using a lubrication approximation, from which the dynamic contact angle versus the contact line moving velocity relationship was evaluated. In the capillary spreading regime, film thickness h is proportional to xi3/(n+2) (xi is the distance from the contact line), whereas in the gravitational regime, h is proportional to xi1/(n+2), relating to the rheological power exponent n. The derived model fit the experimental data well for a shear-thinning fluid (0.2% w/w xanthan solution) or a shear-thickening fluid (7.5% w/w 10 nm silica in polypropylene glycol) on a completely wetted substrate. The derived model was extended using Hoffmann's proposal for partially wetting fluids. Good agreement was also attained between model predictions and the shear-thinning fluid (1% w/w cmc solution) and shear-thickening fluid (10% w/w 15 nm silica) on partially wetted surfaces.     

Molding block copolymer micelles: a framework for molding of discrete objects on surfaces

Soft lithography based on photocurable perfluoropolyether (PFPE) was used to mold and replicate poly(styrene-b-isoprene) block-copolymer micelles within a broad range of shapes and sizes including spheres, cylinders, and torroids. These physically assembled nanoparticles were first formed in a selective solvent for one block then deposited onto substrates having various surface energies in an effort to minimize the deformation of the micelles due to attractive surface forces. The successful molding of these delicate nanoparticles underscores two advantages of PFPE as a molding material. First, it allows one to minimize particle deformation due to adsorption by using low energy substrates. Second, PFPE is not miscible with the organic micelles and thus prevents their dissociation. For spherical PS-b-PI micelles, a threshold value of the substrate surface energy for the mold to lift-off cleanly, that is, the particles remain adhered to the substrate after mold removal was determined to be around gamma congruent with 54 mJ/m2. For substrates with higher surface energies (>54 mJ/m2), the micelles undergo flattening which increase the contact area and thus facilitate molding, although at the expense of particle deformation. The results are consistent with theoretical predictions of a molding range for substrate surface energies, which depends on the size, shape, and mechanical properties of the particles. In a similar fashion, cylindrical PS-b-PI micelles remain on the substrate at surface energies gamma>or=54 mJ/m2 after a mold removal. However, cylindrical micelles behaved differently at lower surface energies. These micelles ruptured due to their inability to slide on the surfaces during mold lift-off. Thus, the successful molding of extended objects is attainable only when the particle is adsorbed on higher energy substrates where deformation can still be kept at a minimum by using stronger materials such as carbon nanotubes for the master.     

The surface energy of talc

The determination of an average value for the surface energy of talc (gammaS) via solid-water interfacial interactions is described. It is based on a formula obtained by the combination of the Young equation with a general equation of pair interaction. Important features of the method are (a) the use of the Young equation to determine the range where the value of the surface energy lies and (b) the determination of the mean value within this range using a probability function. The value found is 217.31 mJ m(-2) in the range 193.36-257.43 mJ m(-2).     

Understanding suspension rheology of anisotropically-charged platy minerals from direct interaction force measurement using AFM

Based on the classical DLVO (Derjaguin–Landau–Verwey–Overbeek) theory, the maximum coagulation of fine particle suspensions would be predicated to occur at the point of zero charge (pzc) of the particles. Although this prediction has been fairly accurate for isotropic particles, the mismatch has been frequently reported for suspensions of anisotropically-charged or charge-mosaic particles, such as talc. Followed by successful preparation of sufficiently smooth talc edge surfaces using the ultramicrotome method for the colloidal force measurements using atomic force microscope (AFM), the anisotropic surface charge properties, i.e., surface charge characteristics of basal planes and edge surfaces of talc at different pH values were determined by fitting the measured force profiles between the AFM tip and both basal plane and edge surfaces to the DLVO theory. The talc basal planes were found to carry a permanent negative charge, while the charge on its edge surfaces was highly pH-dependent. The AFM-derived surface (Stern) potential values of talc basal planes and edge surfaces enable us to calculate the interaction energy for various associations between different charge-mosaic surfaces. The attractive interaction between talc basal planes and edge surfaces was found to dominate the rheological behavior. This study clearly demonstrates the necessity of determining anisotropic surface charge characteristics to improve the understanding of rheological properties and hence to better control their process performance.     

On the maximum spreading diameter of impacting droplets on well-prepared solid surfaces

This paper presents a systematic study of liquid droplet impact on three polymer surfaces: poly(methyl methacrylate), poly(methyl methacrylate/n-butyl methacrylate), and poly(n-butyl methacrylate). Changing from one surface to the next represents an incremental variation in solid surface tensions of 5-6 mJ/m2. These surfaces were prepared through careful experimental procedures that were used for the determination of solid surface tensions from contact angles. Our data for the maximum spreading diameter of water and formamide impacting on these surfaces were compared with those predicted from literature models. Of the models selected, we modified the model of Pasandideh-Fard et al. [Phys. Fluids 1996, 8, 650] and the results yielded a least error of only 5.09 +/- 5.05% in the determination of the maximum spreading diameter. The improved model was also compared with literature data, and good agreement was found. Of course, any such comparisons would rely on accurate experimental impact dynamics data on carefully prepared surfaces.     

Wettability of the morphologically and compositionally varied surfaces prepared from blends of well ordered comb-like polymer and polystyrene

Phase-separated surfaces of blends of polystyrene (PS) and well ordered comb-like polymer, poly[(oxy(decylsulfonylmethyl)ethylene)] (CH(3)-10SE), were prepared by spin casting polymer mixtures. Various surface morphologies, such as holes, islands, connected islands and pillars, were prepared by changing the blend compositions. Due to the influence of the CH(3)-10SE domain with a well ordered molecular conformation, a very low energy surface (≈22mN/m) was created, which is close to the value of the pure polymer (≈20mN/m), even when the blends contained only 20wt.% of the pure polymer. Furthermore, by selective etching the PS domain in the blend surfaces, the advancing contact angles of water and n-hexadecane were highly increased from 113.5° and 43.2° for the pure CH(3)-10SE surface to 133.3° and 67.2° for the CH(3)-10SE structural surfaces with holes prepared using the solvent etching method, respectively. The result of the water advancing contact angles measured on the samples immersed in water over 20days showed that the film stability of CH(3)-10SE could be improved considerably by even adding small amounts of PS.     

Effect of n-alkyl and sulfonyl groups on the wetting properties of comblike poly(oxyethylene)s and stick-slip behavior

The influence of side chain length and sulfonyl moiety on the molecular structures and wettability behavior of poly(oxyethylene)s with alkyl sulfonyl side chains (CH(3)-nSE, n = 1, 2, 3, 4, 5, 6, 8, 10), where n is the number of the carbon atom in the n-alkyl side group, was investigated. CH(3)-nSEs having shorter side chains (n < 5) do not have ordered structures, and their surfaces were found to be more polar than those of CH(3)-nSEs having longer side chains (n ≥ 5). The CH(3)-nSEs having longer side chains show double-layered lamellar structures (n ≥ 5) with well-aligned side chains and low surface energies in the range 21.2-25.8 mN/m. Interestingly, stick-slip behavior was observed only on the surfaces of CH(3)-3SE and CH(3)-4SE when water was used as the test liquid. The surface deformation at the three-phase line was generated from interactions between water and sulfonyl groups, and the optimum side chain lengths were believed to cause the stick-slip behavior.     

A comparison of spreading behaviors of Silwet L-77 on dry and wet lotus leaves

Trisiloxane surfactants are widely used in pesticide applications as adjuvants to promote spray drop spreading on leaves. The efficacy of the spray is related to the wetting of plant surfaces. The surface (composite or wetted) formed by the liquid drop instantly contacting with the substrate is vital to the spreading. In this paper the spreading behaviors of surfactant solutions on dry and previous wet lotus leaf surfaces were studied. It was found that the drop spreading on the wet surface was obviously easier than on the dry surface, which was rational to the existence of water in the grooves of the wet surface. The spreading of Silwet L-77 aqueous drops on the wet lotus leaf surface is mainly controlled by the surface tension gradient along the air-liquid interface.     

Topography of dipalmitoyl-phosphatidyl-choline monolayers penetrated by β-casein

In this work we have analyzed the topography by atomic force microscopy (AFM) of dipalmitoyl-phosphatidyl-choline (DPPC) monolayers previously spread at the air–water interface and penetrated by β-casein. AFM images of β-casein–DPPC monolayers were taken from Langmuir–Blodgett films deposited onto hydrophilic mica substrates at different initial surface pressures (π_i) and after the compression of the mixed films. The monolayer topography depends on the initial structure of the phospholipid:liquid expanded (LE) at 3 mN/m, coexistence between LE and liquid condensed (LC) structures at 7 mN/m, at the end of the LE–LC transition at 10 mN/m, and with a LC structure at 15 mN/m. The area occupied by DPPC domains in the mixed film increases with the π_i value, especially for DPPC with a LC structure at 15 mN/m. At this surface pressure the thickness of the film is at a maximum. After the film compression at 25 mN/m, which is above the equilibrium spreading pressure of β-casein (), this protein is displaced from the interface by DPPC and the topography of the mixed monolayer depends on the initial structure of the DPPC monolayer. A notable feature of the topography of these mixed monolayers is the presence of multilayers of β-casein and DPPC of high thickness (50–70 nm) at the lower π_i values. Although the film is dominated by DPPC at the highest surface pressures (at 25 mN/m), β-casein is not displaced totally from the interface and coexists as β-casein collapsed domains within the network of the DPPC structure.     

Thermodynamic characteristics and Langmuir-Blodgett deposition behavior of mixed DPPA/DPPC monolayers at air/liquid interfaces

The role of dipalmitoylphosphatic acid (DPPA) as a transfer promoter to enhance the Langmuir-Blodgett (LB) deposition of a dipalmitoylphosphatidylcholine (DPPC) monolayer at air/liquid interfaces was investigated, and the effects of Ca2+ ions in the subphase were discussed. The miscibility of the two components at air/liquid interfaces was evaluated by surface pressure-area per molecule isotherms, thermodynamic analysis, and by the direct observation of Brewster angle microscopy (BAM). Multilayer LB deposition behavior of the mixed DPPA/DPPC monolayers was then studied by transferring the monolayers onto hydrophilic glass plates at a surface pressure of 30 mN/m. The results showed that the two components, DPPA and DPPC, were miscible in a monolayer on both subphases of pure water and 0.2 mM CaCl2 solution. However, an exception occurs between X(DPPA)=0.2 and 0.5 at air/CaCl2-solution interface, where a partially miscible monolayer with phase separation may occur. Negative deviations in the excess area analysis were found for the mixed monolayer system, indicating the existence of attractive interactions between DPPA and DPPC molecules in the monolayers. The monolayers were stable at the surface pressure of 30 mN/m for the following LB deposition as evaluated from the area relaxation behavior. It was found that the presence of Ca2+ ions had a stabilization effect for DPPA-rich monolayers, probably due to the association of negatively charged DPPA molecules with Ca2+ ions. Moreover, the Ca2+ ions may enhance the adhesion of DPPA polar groups to a glass surface and the interactions between DPPA polar groups in the multilayer LB film structure. As a result, Y-type multilayer LB films containing DPPC could be fabricated from the mixed DPPA/DPPC monolayers with the presence of Ca2+ ions.     

On Neglecting the Polar Nature of Halogenated Hydrocarbons in the Surface Energy Determination of Polar Solids from Contact Angle Measurements

The generally accepted strategy of neglecting the polar nature of halogenated liquids in the surface energy determination using the Lifshitz-van der Waals/Lewis acid-base (LW/AB) approach may lead to erroneous and inconsistent results for polar solids. This was demonstrated in a simulation study carried out on monopolar basic surfaces using water, glycerol, and hypothetical liquids whose surface energy characteristics (gamma(L)(LW)=50 mJ/m(2), gamma(L)(-)=0, and gamma(L)(+)=0-1 mJ/m(2)) were chosen to approximate halogenated hydrocarbons. Neglect of the liquid polarity overestimates the LW component and underestimates the basic parameter of the solid surface energy. This effect increases rapidly with an increase in the actual (nonzero) gamma(L)(+) value of supposedly apolar liquid. Consequently, results with an appropriate level of precision can be obtained only with liquids having gamma(L)(+)<0.02 mJ/m(2). For liquids having gamma(L)(+) approximately 0.5 mJ/m(2) (diiodomethane, s-tetrabromoethane, and, probably, other halogenated hydrocarbons), neglect of the liquid polarity causes errors up to 15% in the LW component and up to 100% in the basic parameter of the solid surface energy. The quantitative trends established in the simulation study were indeed observed in an experimental study performed on the surfaces of poly(methyl methacrylate) and polystyrene using water, glycerol, and diiodomethane or s-tetrabromoethane as the test liquids. Copyright 2000 Academic Press.     

Effects of albumin and erythrocyte membranes on spread monolayers of lung surfactant lipids

Dipalmitoyl phosphatidylcholine (DPPC), one of the main constituents of lung surfactant is mainly responsible for reduction of surface tension to near 0 mN/m during expiration, resisting alveolar collapse. Other unsaturated phospholipids like palmitoyloleoyl phosphatidylglycerol (PG), palmitoyloleoyl phosphatidylcholine (POPC) and neutral lipids help in adsorption of lung surfactant to the air-aqueous interface. Lung surfactant lipids may interact with plasma proteins and hematological agents flooding the alveoli in diseased states. In this study, we evaluated the effects of albumin and erythrocyte membranes on spread films of DPPC alone and mixtures of DPPC with each of PG, POPC, palmitoyloleoyl phosphatidylethanolamine (PE), cholesterol (CHOL) and palmitic acid (PA) in 9:1 molar ratios. Surface tension-area isotherms were recorded using a Langmuir-Blodgett (LB) trough at 37 degrees C with 0.9% saline as the sub-phase. In the presence of erythrocyte membranes, DPPC and DPPC+PA monolayers reached minimum surface tensions of 7.3+/-0.9 and 9.6+/-1.4 mN/m, respectively. Other lipid combinations reached significantly higher minimum surface tensions >18 mN/m in presence of membranes (Newman Keul's test, p<0.05). The relative susceptibility to membrane inhibition was [(DPPC+PG, 7:3)=(DPPC+PG, 9:1)=(DPPC+POPC)=(DPPC+PE)=(DPPC+CHOL)]>[(DPPC+PA)=(DPPC)]. The differential response was more pronounced in case of albumin with DPPC and DPPC+PA monolayers reaching minimum surface tensions less than 2.4 mN/m in presence of albumin, whereas DPPC+PG and DPPC+POPC reached minimum surface tensions of around 20 mN/m in presence of albumin. Descending order of susceptibility of the spread monolayers of lipid mixtures to albumin destabilization was as follows: [(DPPC+PG, 7:3)=(DPPC+PG, 9:1)=(DPPC+POPC)]>[(DPPC+PE)=(DPPC+CHOL)]>[(DPPC+PA)=(DPPC)] The increase in minimum surface tension in presence of albumin and erythrocyte membranes was accompanied by sudden increases in compressibility at surface tensions of 15-30 mN/m. This suggests a monolayer destabilization and could be indicative of phase transitions in the mixed lipid films due to the presence of the hydrophobic constituents of erythrocyte membranes.     

Competitive adsorption of fibrinogen and dipalmitoylphosphatidylcholine at the air/aqueous interface

The competitive adsorption of fibrinogen (FB) and DPPC at the air/aqueous interface, in phosphate buffer saline at 25 degrees C, was studied with tensiometry, infrared reflection absorption spectroscopy (IRRAS), and ellipsometry. For FB/DPPC mixtures with 750 ppm (0.075 wt%) FB and 1000 ppm (0.10 wt%) DPPC, the tension behavior was found to be similar to that of FB when alone, even with DPPC and FB being at the interface. Thus, FB interferes with adsorption of DPPC and inhibits its surface tension lowering ability. When FB protein is introduced in the solution after a DPPC monolayer has formed, the adsorption of FB is inhibited by the DPPC monolayer. When a DPPC monolayer is spread onto a solution with a preadsorbed FB layer, the DPPC monolayer excludes FB from the surface and controls the tension behavior with little inhibition by FB. When a DPPC dispersion is introduced with the Trurnit method, or sprayed dropwise, onto an aqueous FB/DPPC surfaces, the DPPC layer formed on the surface prevents the adsorption of FB and dominates the surface tension behavior. These results have implications in controlling the inhibition of lung surfactant tension behavior by serum proteins, when they leak at the alveolar lining layer, and in developing surfactant replacement therapies for alveolar respiratory diseases.     

Directed assembly of binary monolayers with a high protein affinity: infrared reflection absorption spectroscopy (IRRAS) and surface plasmon resonance (SPR)

Infrared reflection absorption spectroscopy (IRRAS) and surface plasmon resonance (SPR) techniques have been employed to investigate human serum albumin (HSA) binding to binary monolayers of zwitterionic dipalmitoylphosphatidylcholine (DPPC) and cationic dioctadecyldimethylammonium bromide (DOMA). At the air-water interface, the favorable electrostatic interaction between DPPC and DOMA leads to a dense chain packing. The tilt angle of the hydrocarbon chains decreases with increasing mole fraction of DOMA (X(DOMA)) in the monolayers at the surface pressure 30 mN/m: DPPC ( approximately 30 degrees ), X(DOMA) = 0.1 ( approximately 15 degrees ), and X(DOMA) = 0.3 ( approximately 0 degrees ). Negligible protein binding to the DPPC monolayer is observed in contrast to a significant binding to the binary monolayers. After HSA binding, the hydrocarbon chains at X(DOMA) = 0.1 undergo an increase in tilt angle from 15 degrees to 25 approximately 30 degrees , and the chains at X(DOMA) = 0.3 remain almost unchanged. The two components in the monolayers deliver through lateral reorganization, induced by the protein in the subphase, to form multiple interaction sites favorable for protein binding. The surfaces with a high protein affinity are created through the directed assembly of binary monolayers for use in biosensing.