Michael L. Hair

Study of the advancing and receding contact angles: liquid sorption as a cause of contact angle hysteresis

Two types of experiments were used to study the behavior of both advancing and receding contact angles, namely the dynamic one-cycle contact angle (DOCA) and the dynamic cycling contact angle (DCCA) experiments. For the preliminary study, DOCA measurements of different liquids on different solids were performed using an automated axisymmetric drop shape analysis-profile (ADSA-P). From these experimental results, four patterns of receding contact angle were observed: (1) time-dependent receding contact angle; (2) constant receding contact angle; (3) stick/slip; (4) no receding contact angle. For the purpose of illustration, results from four different solid surfaces are shown. These solids are: FC-732-coated surface; poly(methyl methacrylate/n-butyl methacrylate) [P(MMA/nBMA)]; poly(lactic acid) (DL-PLA); and poly(lactic/glycolic acid) 50/50 (DL-PLGA 50/50). Since most of the surfaces in our studies exhibit time dependence in the receding contact angle, a more extended study was conducted using only FC-732-coated surfaces to better understand the possible causes of decreasing receding contact angle and contact angle hysteresis. Contact angle measurements of 21 liquids from two homologous series (i.e. n-alkanes and 1-alcohols) and octamethylcyclotetrasiloxane (OCMTS) on FC-732-coated surfaces were performed. It is apparent that the contact angle hysteresis decreases with the chain length of the liquid. It was found that the receding contact angle equals the advancing angle when the alkane molecules are infinitely large. These results strongly suggest that the chain length and size of the liquid molecule could contribute to contact angle hysteresis phenomena. Furthermore, DCCA measurements of six liquids from the two homologous series on FC-732-coated surfaces were performed. With these experimental results, one can construe that the time dependence of contact angle hysteresis on relatively smooth and homogeneous surfaces is mainly caused by liquid retention/sorption. The results also suggested that the contact angle hysteresis will eventually approach a steady state, where the rate of liquid retention-evaporation or sorption process would balance out each other. If the existence of contact angle hysteresis can be attributed to liquid sorption/retention, one should only use the advancing contact angles (measured on a dry surface) in conjunction with Youngs equation for surface energetic calculations.

The effect of liquid properties to contact angle hysteresis

Abstract Low-rate dynamic advancing and receding contact angles of 21 liquids from two homologous series (i.e. n-alkanes and 1-alcohols) and octamethylcyclotetrasiloxane (OMCTS) on FC-732-coated silicon wafer surfaces were measured by an automated Axisymmetric Drop Shape Analysis-Profile (ADSA-P). The receding contact angle was found to decrease with time, suggesting surface swelling and sorption. An initial receding angle (θri), which theoretically represents the receding angle before sorption starts, was extrapolated back to time of zero contact (t0) by least-squares regression in each experiment. The contact angle hysteresis, i.e. the difference between advancing contact angle and θri, was found to decrease with increasing chain length of the liquid molecules for both the alkane and alcohol series. Contact angle hysteresis was found to vanish when the chain length was extrapolated to infinity. These results are plausible in terms of liquid sorption by the solid surface: very large molecules are unlikely to penetrate into the solid film. In order to reconfirm that contact angle hysteresis depends on molecular size of the liquid, contact angles of OMCTS, which is a bulky and quasi-spherical molecule, were measured. The hysteresis was found to be 4.1°, which is smaller than for any alkane or alcohol system. The molecular size-dependent hysteresis suggests that contact angle hysteresis phenomena are mainly due to liquid penetration and surface swelling, or at least liquid retention, even on this very hydrophobic surface. The fact that receding contact angles reflect liquid retention by the solid and are therefore not a property of the solid alone, supports the widespread practice of using only the advancing contact angles in studies of surface energetics of solids and disregarding the receding contact angles.

The effect of dextran to restore the activity of pulmonary surfactant inhibited by albumin.

Pulmonary surfactant is crucial to maintain the proper functioning of the respiration system. Certain types of blood proteins (e.g. albumin) were found to inhibit the activity of pulmonary surfactant. Axisymmetric Drop Shape Analysis (ADSA) was used to study the effect of dextran to restore the activity of an albumin-inhibited pulmonary surfactant. It was found that dextran could effectively restore surface tension properties of the inhibited surfactant in vitro. Furthermore, dextran improved the performance of pulmonary surfactants when albumin was absent. It was found that when a surfactant film was under high compression (e.g. above 70% surface area reduction), the presence of dextran increased film stability, so that the film could sustain high surface pressures without being collapsing.

The effect of concentration on the bulk adsorption of bovine lipid extract surfactant

The film adsorption of bovine lipid extract surfactant (BLES) onto the air–liquid interface was examined using axisymmetric drop shape analysis. In combination with a pendant drop constellation, BLES concentrations as high as 10 mg/ml were studied, i.e. concentrations far higher than those accessible with the captive bubble set-ups. ‘Adsorption clicks’, i.e. dynamic processes in which the interfacial tension of surfactant films decreases quickly in a stepwise fashion, were studied at concentrations below 1 mg/ml. Adsorption clicks with high magnitudes up to approximately 35 mJ/m2 (within 0.2 s) were observed. The rate of adsorption was investigated as a function of surfactant concentration. At concentrations below 1 mg/ml, the rate of adsorption is highly concentration dependent. Surfactant films formed on 1 mg/ml BLES solutions reached a surface tension of about 25 mJ/m2 in approximately 10 s, while 0.1 mg/ml BLES required more than 100 s to reach a similar value.

A double injection ADSA-CSD methodology for lung surfactant inhibition and reversal studies

This paper presents a continuation of the development of a drop shape method for film studies, ADSA-CSD (Axisymmetric Drop Shape Analysis-Constrained Sessile Drop). ADSA-CSD has certain advantages over conventional methods. The development presented here allows complete exchange of the subphase of a spread or adsorbed film. This feature allows certain studies relevant to lung surfactant research that cannot be readily performed by other means. The key feature of the design is a second capillary into the bulk of the drop to facilitate addition or removal of a secondary liquid. The development will be illustrated through studies concerning lung surfactant inhibition. After forming a sessile drop of a basic lung surfactant preparation, the bulk phase can be removed and exchanged for one containing different inhibitors. Such studies mimic the leakage of plasma and blood proteins into the alveolar spaces altering the surface activity of lung surfactant in a phenomenon called surfactant inhibition. The resistance of the lung surfactant to specific inhibitors can be readily evaluated using the method. The new method is also useful for surfactant reversal studies, i.e. the ability to restore the normal surface activity of an inhibited lung surfactant film by using special additives. Results show a distinctive difference between the inhibition when an inhibitor is mixed with and when it is injected under a preformed surfactant film. None of the inhibitors studied (serum, albumin, fibrinogen, and cholesterol) were able to penetrate a preexisting film formed by the basic preparation (BLES and protasan), while all of them can alter the surface activity of such preparation when mixed with the preparation. Preliminary results show that reversal of serum inhibition can be easily achieved and evaluated using the modified methodology.

DETERMINATION OF SOLID SURFACE TENSION FROM CONTACT ANGLES: THE ROLE OF SHAPE AND SIZE OF LIQUID MOLECULES

Accurate surface tension of Teflon® AF 1600 was determined using contact angles of liquids with bulky molecules. For one group of liquids, the contact angle data fall quite perfectly on a smooth curve corresponding to γsv = 13.61 mJ/m2, with a mean deviation of only ±0.24 degrees from this curve. Results suggest that these liquids do not interact with the solid in a specific fashion. However, contact angles of a second group of liquids with fairly bulky molecules containing oxygen atoms, nitrogen atoms, or both deviate somewhat from this curve, up to approximately 3 degrees. Specific interactions between solid and liquid molecules and reorientation of liquid molecules in the close vicinity of the solid surface are the most likely causes of the deviations. It is speculated that such processes induce a change in the solid–liquid interfacial tension, causing the contact angle deviations mentioned above. Criteria are established for determination of accurate solid surface tensions.

Restoring the activity of serum-inhibited bovine lung extract surfactant (BLES) using cationic additives.

In this work four cationic additives were used to improve the surface activity of lung surfactants, particularly in the presence of bovine serum that was used as a model surfactant inhibitor. Two of those additives were chitosan in its soluble hydrochloride form with average molecular weights of 113kDa and 213kDa. The other two additives were cationic peptides, polylysine 50kDa and polymyxin B. These additives were added to bovine lipid extract surfactant (BLES) and the optimal additive-surfactant ratio was determined based on the minimum surface tension upon dynamic compression, carried out in a constrained sessile drop (CSD) device in the presence of 50 microl/ml serum. At the optimal ratio all the BLES-additive mixtures were able to achieve desirable minimum surface tensions. The optimal additive-surfactant ratios for the chitosan chlorides are consistent with a previously proposed patch model for the binding of the anionic lipids in BLES to the positive charges in chitosan. For the peptides, the optimal binding ratios were consistent with ratios established previously for the binding of these peptides to monolayers of anionic lipids. The optimal formulation containing these peptides were able to reach low minimum surface tension in systems containing 500 microl/ml of serum, matching the effectiveness of a lung surfactant extract that had not undergone post-separation processes and therefore contained all its proteins and lipids (complete lung surfactant).

Restoring the charge and surface activity of bovine lung extract surfactants with cationic and anionic polysaccharides.

Chitosan, a cationic polysaccharide, has been found to improve the surface activity of lung surfactant extracts in the presence of various inhibitors. It has been proposed that chitosan binds to anionic lipids (e.g. phosphatidyl glycerols) in lung surfactants, producing stable lipid films at the air-water interface. This binding also reverses the net charge of the surfactant aggregates, from negative to positive. Unfortunately, positively charged aggregates may adsorb or interact with the negatively charged epithelial tissue, leading to poor surfactant performance. To address this issue an anionic polysaccharide, dextran sulfate (dexS), was used as a secondary coating to reverse the charge of chitosan-lung surfactant extracts without affecting the surface activity of the preparation. The dynamic surface tension and zeta potential of bovine lipid extract surfactant (BLES) containing chitosan chloride (chiCl) and dexS were evaluated as a function of dexS concentration. These studies were conducted in the absence and presence of sodium bicarbonate buffer, and in the absence and presence of bovine serum used as model inhibitor. It was determined that using an appropriate concentration of dexS, especially at physiological pH, it is possible to restore the negative charge of the surfactant aggregates, and retain their surface activity, even in the presence of bovine serum. High concentrations of dexS affect the binding of chiCl to BLES, and the surface activity of the preparation.