Fatty acid monolayers adsorption

We have examined the behavior of the adsorption fatty acid monolayer at the air bubble surface in respect to coexistence of ionized and neutral molecules and surface-inactive ions. We can write the dissociation equation for fatty acid, which is the object of the study, as follows ... 

As the counterion penetrates the plane of the interfacial head groups, the surface pressure will be affected as a first-order effect thus, the expansion of the 7r-A isotherms for the fatty acid monolayers is in the same sequence as the cation sizes noted above. The penetrated counterions must be held with an energy at least comparable to KT since they are not expelled during the kinetic movement of the film molecules, but remain in place and increase the surface pressure. To penetrate the plane of the head groups in the monolayer, the counterions must possess sufficient adsorption energy to overcome the work against the kinetic surface pressure 7tK, such that, according to Davies and Rideal (10) ... 

Electron Microscopic Investigation of the Adsorption of Long-Chain Fatty Acid Monolayers on Glass... 

Recently, it was also shown that the adsorption forces could be adjusted by covering HOPG with a long-chain fatty acid monolayer prior to sample deposition [40], as this led to improvements in the dragging and imaging of the dendronized polymers. 

In a further study, DiMasi and colleagues investigated the kinetics of amorphous CaCOs formation at a fatty acid monolayer interface using synchrotron X-ray reflectivity measurements [173]. In-situ experiments found three different parameters that control CaCOs mineralization in the presence of arachidic acid monolayers, PAA, and Mg + ions. Firstly, the crystal growth rate depends on the concentration of counterions and not on the polymer concentration in solution. Secondly, the soluble polymer only affects the lifetime of the amorphous calcium carbonate. And finally, the sole effect of Mg + is to delay the mineral film formation. These data thus suggest that competitive adsorption (e.g. Mg + vs. Ca +) is another parameter to consider in controlled mineralization processes. 

Most LB-forming amphiphiles have hydrophobic tails, leaving a very hydrophobic surface. In order to introduce polarity to the final surface, one needs to incorporate bipolar components that would not normally form LB films on their own. Berg and co-workers have partly surmounted this problem with two- and three-component mixtures of fatty acids, amines, and bipolar alcohols [175, 176]. Interestingly, the type of deposition depends on the contact angle of the substrate, and, thus, when relatively polar monolayers are formed, they are deposited as Z-type multilayers. Phase-separated LB films of hydrocarbon-fluorocarbon mixtures provide selective adsorption sites for macromolecules, due to the formation of a step site at the domain boundary [177]. 

The adsorbed layer at G—L or S—L surfaces ia practical surfactant systems may have a complex composition. The adsorbed molecules or ions may be close-packed forming almost a condensed film with solvent molecules virtually excluded from the surface, or widely spaced and behave somewhat like a two-dimensional gas. The adsorbed film may be multilayer rather than monolayer. Counterions are sometimes present with the surfactant ia the adsorbed layer. Mixed moaolayers are known that iavolve molecular complexes, eg, oae-to-oae complexes of fatty alcohol sulfates with fatty alcohols (10), as well as complexes betweea fatty acids and fatty acid soaps (11). Competitive or preferential adsorption between multiple solutes at G—L and L—L iaterfaces is an important effect ia foaming, foam stabiLizatioa, and defoaming (see Defoamers). 

Fig. 3.5 Representation of a scheme of an experiment (upper set of drawings) and the obtained experimental results presented as AFM images (middle part) and cross-sectional profiles (bottom) that provides evidence of silica nucleation and shell formation on biopolymer macromolecules. Scheme of experiment. This includes the following main steps. 1. Protection of the mica surface against silica precipitation. It was covered with a fatty (ara-chidic) acid monolayer transferred from a water substrate with the Langmuir-Blodgett technique. This made the mica surface hydrophobic because of the orientation of the acid molecules with their hydrocarbon chains pointing outwards. 2. Adsorption of carbohydrate macromolecules. Hydrophobically modified cationic hydroxyethylcellulose was adsorbed from an aqueous solution. Hydrocarbon chains of polysaccharide served as anchors to fix the biomacromolecules firmly onto the acid monolayer. 3. Surface treatment by silica precursor. The mica covered with an acid mono-...

The combination of the LB technique and the neutron activation method of analysis was used to determine the stoichiometry of the interaction between fatty acid (arachidic acid) and metal ions dissolved in the subphase. The experimental data were used to estimate the stability constants of arachidic acid and bivalent metal ions (Cd and Ba). The data were explained as an interaction between metal ions and the monolayer as an adsorption process ... 

The adsorption of amphiphilic molecules at the surface of a liquid can be so strong that a compact monomolecular film, abbreviated as monolayer, is formed. There are amphiphiles which, practically, do not dissolve in the liquid. This leads to insoluble monolayers. In this case the surface excess T is equal to the added amount of material divided by the surface area. Examples of monolayer forming amphiphiles are fatty acids (CH3(CH2) c 2COOH) and long chain alcohols (CH3(CH2)nc iOH) (see section 12.1). 

Pyrene-labeled SA mixed monolayers were prepared by adsorption from solutions of the desired concentration of a particular fatty acid, along with a small fraction (1-5%) of the probe Py-C16. All solutions used were of total acid concentration of 5xl0 3M. 

The Langmuir equation has been used to describe adsorption of p carotene from solution onto activated bleaching clays (8) and free fatty acid from isooctane solution by acid-washed rice hull ash (9). Likewise, isotherm analysis of the commercial bleaching of rubber and melon seed oil by Fullers earth, activated carbon, and Fullers earth/activated carbon mixture (10) followed Langmuir behavior at 55°C and 80°C, suggesting the possibility of monolayer adsorption with little competition. This behavior was not observed at 30°C where the isotherm no longer applies, because of desorption. The amount of adsorbent was kept constant while varying... 

Organic adsorbates that are more hydrophobic exhibit different adsorption behavior, particularly at higher concentrations. Long-chain fatty acids adsorb to oxide surfaces in part through surface complexation, as shown by electron spin resonance spectroscopy (32). At higher concentrations at the surface, however, favorable interactions between sorbed molecules (hemimicelle formation) appear to dominate and result in greater than monolayer adsorption (40, 41). Because humic substances (like the fatty acids) are amphiphilic, both surface complexation and hydrophobic interactions may be involved in the adsorption of humic substances on oxide surfaces. 

Fig. 4 (a) The reactive-ester analogue of a carboxy-terminated monochloro-silane derivative self-assembles onto a glass substrate to result in a reactive monolayer, (b) Onto this, an ethyleneimine-containing polymer coil, obtained by the partial conversion of a polyoxazoline precursor polymer binds covalently after adsorption from solution to give a stable polymer cushion for the binding of a monolayer of a reactive amphiphile, a reactive ester derivative of a fatty acid in the example given in (c)... 

Fig. 5 Surface-plasmon resonance curves, i.e., reflectivity-vs-incident angle scans of the bare substrate, a Ag coated glass slide with a thin SiC>2 layer evaporated on top (A), after the self-assembly of a reactive monochlorosilane derivative (cf. Fig. 4a) (B), after the adsorption (from solution), covalent binding, and soxhlet extraction of the polymer cushion (C), and after the deposition of a model lipid monolayer (a layer of reactive ester derivatives of a fatty acid) (D)...

Surfactants. Some compounds, like short-chain fatty acids, are amphiphilic or amphipathic that is, they have one part that has an affinity for the nonpolar media (the nonpolar hydrocarbon chain), and one part that has an affinity for polar media, that is, water (the polar group). The most energetically favorable orientation for these molecules is at surfaces or interfaces so that each part of the molecule can reside in the fluid for which it has the greatest affinity (Figure 4). These molecules that form oriented monolayers at interfaces show surface activity and are termed surfactants. As there will be a balance between adsorption and desorption (due to thermal motions), the interfacial condition requires some time to establish. Because of this time requirement, surface activity should be considered a dynamic phenomenon. This condition can be seen by measuring surface tension versus time for a freshly formed surface. 

The fact that some fatty acids and inorganic salts in solution follow the approximate Langmuir adsorption isotherm does not prove, to be sure, that the mechanism of adsorption is the same as that of a gas, but it is part of the broad evidence that organic corrosion inhibitors as w ell as inorganic passivators function through the formation of one or more monolayers on the metal surface. The existence of a double layer does not alter the situation very much, for dilute solutions at least, such as characterize inhibitor solution concentrations, because most of the measurable effect derives from the fixed chemisorbed layer (1). 

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