Dilute monolayers

Curve 5, Fig. 3.119 illustrates another case where s < 0, but H°b/a > 0 and a polymolecular spreading does not occur. Only the thin diluted monolayers can be stable. In such a case the isotherm differs from curve 4, Fig. 3.118 only by the value of the positive K... 

Unimolecular rectifiers are a reality. They have been made and they have been measured. However, there is still substantial room for improvement in the experimental techniques used to study the molecules and in the molecules used to give improved thermal stability. Current experiments need to be modified so that noble metal electrodes may be used to study a dilute monolayer, ideally at low temperature where molecular orbital signatures will be observable. This already has been achieved with robust molecules such as phthalocyanines, which suggests that the technological step to be made is not too great. 

At very low molecular densities, i.e. at very low Interfacial pressures, the mono-layer exhibits gaseous behaviour. The molecules are far apart, but, unlike in a three-dimensional gas, they are not completely disordered. Because of their amphi-polar nature, the molecules exhibit a preferential orientation relative to the surface-normal. As stated in sec. 3.1, the interfacial pressure exerted by an ideally dilute monolayer is equivalent to the osmotic pressure of an ideal three-dimensional solution. Ideal gaseous monolayer behaviour means obe3dng relation [3.1.1]. 

Scaled particle theory has not yet been discussed. Equation 13.4.39] is taken from Baumer and Findenegg but originally dates back to Helfand et al. The equation is rigorous for hard disk-like molecules it is combined with a mean field lateral Lennard-Jones pair interaction. In this equation their = na lA if a is the diameter of the disk, is the depth of the Lennard-Jones pair interactions (i.e. the minimum in fig. 1.4.1.a). In this case 6 = a F its maximum in a close-packed monolayer corresponds to (max) = 0.906. The accent emphasizes this different scaling. Baumer and Findenegg applied [3.4.39] to dilute monolayers of 1-chlorobutane, perfluorohexane and fluorobenzene, adsorbed on water from the gas phase. 

As our first case study, dealing with pol)miers, we consider Langmuir mono-layers of poly(methacrylic ester), PMA, at the water-air interface. Data for these layers can be used to illustrate some trends and principles, laid down in sec. 3.41. In that section we discussed how the surface pressure of physisorbed polymers depends on surface concentration. In a dilute monolayer of pancakes, the surface pressure was found to be given by the ideal term plus an excluded-area contribution. We rewrite [3.4.56] in terms of the adsorbed amount r = n°/A = N°/ N A) in moles of chains per unit area... 

Tn his classic book (I) N. K. Adam discussed the behavior of very dilute - monolayers at the air/water (A/W) interface and using measurements published ear her by Jessop and himself (2, 3, 4), he showed that surface pressure (n)-area (A) isotherms for insoluble uncharged species, when plotted on a nA vs. n basis, suggested a limit of IkT at zero II. The same limit was also suggested by Schofield and Rideal s plot (5) of Frumkin s surface tension data (6) using the Gibbs adsorption isotherm to calculate A. Adam (I) stressed that n should be measured to the second decimal place to establish this limit unequivocally Adam and Jessop (4) provide one of the few sound extrapolations to this limit with their data on the esters of some dicarboxylic acids. 

This example emphasizes the danger of using the ideal Langmuir-Szyszkowski equation of state in converting surface tension-time data into adsorption—time data even for very dilute monolayers. Also it clearly shows that any conclusion about the existence or non-existence of an... 

For dilute monolayers, the intermolecular potential between two surfactant molecules was not needed to construct the kinetic formulas. Obviously there are solvent-surfactant interactions since the entire system is a liquid. However, it was possible to incorporate such interactions into a friction coefficient that can be computed in principle or left as a parameter details are given by Cooper and Mann (7). The extension to dense gas monolayers requires a potential function and a radial distribution function for the surfactant molecules. The formulation based on the Rice-Allnatt approach was developed by Cooper and Mann (7). 

We have been searching for experimental methods that can measure surface viscosities as low as 10 10 g/sec or measure the collisional dynamics that should correspond to the Mann-Cooper model. To qualify, the experimental method must respond to dilute monolayers having densities less than 1014 mojecules/cm2. From our experience with the ESR spin label technique for measuring bulk viscosity effects in ultrathin films (8),... 

Pethica, B. A. Phospholipid monolayers at the -heptane/water interface. Part 2. Dilute monolayers of saturated 1,2-diacyl-lecithins and -cephahns. J. Chem. Soc. Faraday Trans. 1 1976, 72, 2694-2702. (d) Yue, B. Y. T., Jackson, C. M., Taylor, J. A. G., Mingins, J., Pethica, B. A. Phospholipid monolayers at non-polar oU/water interfaces. Part 1. Phase transitions in distearoyl-lecithin films at the -heptane aqueous sodium chloride interface. J. Chem. Soc. Faraday Trans. 1 1976, 72, 2685-2693. 

The polystyrene latex particles carry a charge in aqueous solution resulting from the surface sulfate groups, and as mentioned the particle dispersions are stable. Particle monolayers can be formed at air/solution surfaces as well as at oil/solution interfaces. There is obviously an electrical double layer formed around the parts of the particle surface in contact with the aqueous phase. Lateral repulsions in the monolayer due to double-layer interactions can be screened by addition of inert electrolyte to the aqueous phase. Images of relatively dilute monolayers on 10 mM aqueous NaCl are depicted in Fig. 18. Monolayers at the air/0.01 M NaCl solution surface are much less ordered than those at the octane/solution interface, although there is very little particle aggregation. Monolayers at the octane/solution interface retain... 

It is not uncommon for this situation to apply, that is, for a Gibbs mono-layer to be in only slow equilibrium with bulk liquid—see, for example. Figs. 11-15 and 11-21. This situation also holds, of course, for spread monolayers of insoluble substances, discussed in Chapter IV. The experimental procedure is illustrated in Fig. Ill-19, which shows that a portion of the surface is bounded by bars or floats, an opposing pair of which can be moved in and out in an oscillatory manner. The concomitant change in surface tension is followed by means of a Wilhelmy slide. Thus for dilute aqueous solutions of a methylcellu-... 

A logical division is made for the adsorption of nonelectrolytes according to whether they are in dilute or concentrated solution. In dilute solutions, the treatment is very similar to that for gas adsorption, whereas in concentrated binary mixtures the role of the solvent becomes more explicit. An important class of adsorbed materials, self-assembling monolayers, are briefly reviewed along with an overview of the essential features of polymer adsorption. The adsorption of electrolytes is treated briefly, mainly in terms of the exchange of components in an electrical double layer. 

As discussed in Chapter III, the progression in adsoiptivities along a homologous series can be understood in terms of a constant increment of work of adsorption with each additional CH2 group. This is seen in self-assembling monolayers discussed in Section XI-IB. The film pressure r may be calculated from the adsorption isotherm by means of Eq. XI-7 as modified for adsorption from dilute solution ... 

A drop of a dilute solution (1%) of an amphiphile in a solvent is typically placed on tlie water surface. The solvent evaporates, leaving behind a monolayer of molecules, which can be described as a two-dimensional gas, due to tlie large separation between tlie molecules (figure C2.4.3). The movable barrier pushes tlie molecules at tlie surface closer together, while pressure and area per molecule are recorded. The pressure-area isotlienn yields infonnation about tlie stability of monolayers at tlie water surface, a possible reorientation of tlie molecules in tlie two-dimensional system, phase transitions and changes in tlie confonnation. Wliile being pushed togetlier, tlie layer at... 

Self-assembled monolayers (SAMs) are molecular layers tliat fonn spontaneously upon adsorjDtion by immersing a substrate into a dilute solution of tire surface-active material in an organic solvent [115]. This is probably tire most comprehensive definition and includes compounds tliat adsorb spontaneously but are neither specifically bonded to tire substrate nor have intennolecular interactions which force tire molecules to organize tliemselves in tire sense tliat a defined orientation is adopted. Some polymers, for example, belong to tliis class. They might be attached to tire substrate via weak van der Waals interactions only. 

Methods to Detect and Quantitate Viral Agents in Fluids. In order to assess the effectiveness of membrane filtration the abihty to quantitate the amount of vims present pre- and post-filtration is critical. There are a number of techniques used. The method of choice for filter challenge studies is the plaque assay which utilizes the formation of plaques, localized areas in the cell monolayer where cell death caused by viral infection in the cell has occurred on the cell monolayer. Each plaque represents the presence of a single infectious vims. Vims quantity in a sample can be determined by serial dilution until the number of plaques can be accurately counted. The effectiveness of viral removal may be determined, as in the case of bacterial removal, by comparing the vims concentration in the input suspension to the concentration of vims in the effluent. 

The simplest mode of IGC is the infinite dilution mode , effected when the adsorbing species is present at very low concentration in a non-adsorbing carrier gas. Under such conditions, the adsorption may be assumed to be sub-monolayer, and if one assumes in addition that the surface is energetically homogeneous with respect to the adsorption (often an acceptable assumption for dispersion-force-only adsorbates), the isotherm will be linear (Henry s Law), i.e. the amount adsorbed will be linearly dependent on the partial saturation of the gas. The proportionality factor is the adsorption equilibrium constant, which is the ratio of the volume of gas adsorbed per unit area of solid to its relative saturation in the carrier. The quantity measured experimentally is the relative retention volume, Vn, for a gas sample injected into the column. It is the volume of carrier gas required to completely elute the sample, relative to the amount required to elute a non-adsorbing probe, i.e. 

Another interesting class of phase transitions is that of internal transitions within amphiphilic monolayers or bilayers. In particular, monolayers of amphiphiles at the air/water interface (Langmuir monolayers) have been intensively studied in the past as experimentally fairly accessible model systems [16,17]. A schematic phase diagram for long chain fatty acids, alcohols, or lipids is shown in Fig. 4. On increasing the area per molecule, one observes two distinct coexistence regions between fluid phases a transition from a highly diluted, gas -like phase into a more condensed liquid expanded phase, and a second transition into an even denser... 

Calf kidneys, dog kidneys and rhesus monkey kidneys were treated with trypsin to give suspensions of cells. The suspensions were centrifuged and the packed cells diluted with 400 volumes (calf cells) or 200 volumes (dog cells and rhesus monkey cells) of a growth medium consisting of 5% horse serum and 0.5% lactalbumen hydrolysate in Earle s saline, with 100 units/ml each of penicillin and streptomycin. These media were used separately to produce Semliki Forest/calf interferon, Semliki Forest/dog interferon and Semliki Forest/rhesus monkey interferon. The cell-containing growth medium was dispensed into 500 ml medical flat bottles (70 ml in each). The cultures were incubated at 36°C. Confluent sheets of cells (monolayers) were formed in 5 to 6 days. The growth medium was then removed and the monolayers were washed with isotonic phosphate-buffered saline, pH 7.5. 

Figure 1. The magnetic interlayer coupling in Fe/Cu/Fe bcc (001) trilayers. The squares denote the coupling energies for the pure trilayer and the circles the coupling energies for the dilute trilayers with 50% of intermixing in a single monolayer at each Fe/Cu interface. One example of an averaged interlayer coupling is indicated by the diamonds.

The terminology of L-B films originates from the names of two scientists who invented the technique of film preparation, which transfers the monolayer or multilayers from the water-air interface onto a solid substrate. The key of the L-B technique is to use the amphiphih molecule insoluble in water, with one end hydrophilic and the other hydrophobic. When a drop of a dilute solution containing the amphiphilic molecules is spread on the water-air interface, the hydrophilic end of the amphiphile is preferentially immersed in the water and the hydrophobic end remains in the air. After the evaporation of solvent, the solution leaves a monolayer of amphiphilic molecules in the form of two-dimensional gas due to relatively large spacing between the molecules (see Fig. 15 (a)). At this stage, a barrier moves and compresses the molecules on the water-air interface, and as a result the intermolecular distance decreases and the surface pressure increases. As the compression from the barrier proceeds, two successive phase transitions of the monolayer can be observed. First a transition from the gas" to the liquid state. 

The first step in the preparation of an LB film is the successful spreading of a monolayer of the material of interest, which may be molecular, polymeric, or particulate and need not be amphiphilic in the traditional sense. This is accomplished by depositing drops of a dilute solution of the material in an appropriate spreading solvent onto the water surface. The concentration is generally millimolar or less, and the solvent selected should be one that will spread across the surface rapidly and evaporate without remaining at the surface or dissolving into the subphase. Common spreading solvents include chloroform, benzene,... 

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