Monolayer concept

A formal application of Eq. (51) leads to the conclusion that the time of adsorption appears to be dependent on the amount adsorbed and drops to zero for a fully occupied layer (200). This is caused by the assumption of the monolayer -conception, according to which molecules striking the occupied parts of that layer are supposed to reflect, without being adsorbed even for a moment. Equation (51), therefore, gives t as the average value for such an ideal monolayer. ... 

On the other hand, the difference will be accentuated in cases where there is a weak specific uptake of one component into the adsorbed phase because the contribution of n to n will be small and the second term, on the right-hand side of Equation (5), will contribute more to the amount adsorbed. Then approximation (6) cannot be used and Equation (5) must be utilized and therefore, a definition of the adsorbed phase, (n ), must be specified. This is commonly done by the acceptance of the monolayer concept of adsorption from liquid solutions. It is assumed that only one layer of molecules covering the solid surface is affected by the solid and hence only this monolayer differs from the bulk liquid phase. This concept allows the number of molecules present in the adsorbed phase to be calculated based on a known specific area of solids and known cross-sectional areas of molecules of the adsorbate and the solvent ... 

The most straightforward approach is to find the amount of additive that can just cover the surface of the inclusion, if it is spread one molecule thick. This gives rise to the monolayer concept. 

While the monolayer concept is easily understood, its relevance to final properties is less clear. With some coupling agents, property changes can start with the first fraction of a monolayer and increase up to and past the monolayer level. With others there is a sharp optimum at or near the monolayer level and excess additive is very undesirable. Durability, especially under humid conditions, can follow a different pattern and generally requires at least monolayer coverage. 

In very small pores the molecules never escape from the force field of the pore wall even at the center of the pore. In this situation the concepts of monolayer and multilayer sorption become blurred and it is more useful to consider adsorption simply as pore filling. The molecular volume in the adsorbed phase is similar to that of the saturated Hquid sorbate, so a rough estimate of the saturation capacity can be obtained simply from the quotient of the specific micropore volume and the molar volume of the saturated Hquid. 

From surfactant molecules it is known that the repeated vertical dipping of a substrate through a floating monolayer of these molecules leads to the formation of an LB multilayer on the substrate. In principle, the same procedure should also allow the preparation of multilayers of latex particles. In Figure 8b, the preparation of a particle bilayer is schematically indicated multiple repetition should result in the formation of an LB multilayer of particles. However, if one tries to realize this concept, one immediately gets into difficulties, because the contact of the particles with the underlying substrate is very poor, and the already deposited particle layer tends to detach from the surface when the substrate is dipped into... 

Here we shall consider a different concept, which has an interesting potential, particularly in liquid phase reactions used for the production of fine chemicals. The concept is schematically illustrated in Fig. 3. The modification of the metal catalysts is achieved by very small quantities (usually a sub-monolayer) of adsorbed auxiliaries (modifiers), which are either simply added to the reaction mixture (in-situ), or brought onto the catalyst surface in a... 

After complete formation of each successive monolayer of atoms, the next layer should start to form. This requires two-dimensional nucleation by the union of several adatoms in a position 1. Like three-dimensional nucleation, two-dimensional nucleation requires some excess energy (i.e., elevated electrode polarization). Introducing the concept of excess linear energy p of the one-dimensional face (of length L) of the nucleus, we can derive an expression for the work of formation of such a nucleus (analogous to that used in Section 14.2.2). When the step of two-dimensional nucleation is rate determining, the polarization equation becomes, instead of (14.39),... 

In addition to the self-spreading lipid bilayer, it was also found that a lipid mono-layer showed similar spreading behavior on a hydrophobic surface (Figure 13.6) [51]. By fabricating an appropriate hydrophobic surface pattern, the spreading area and direction can be easily controlled. For both the self-spreading bilayer and monolayer, non-biased molecular transportation is an important key concept for the next generation of microfiuidic devices. 

For a molecule characterised by a AH value of 40 k.I mol 1 and undergoing facile surface diffusion, i.e. a A/ dir value close to zero, then each molecule will visit, during its surface lifetime (10 r s), approximately 107 surface sites. Since the surface concentration a is given by a = NtSUIf, then for a AH value of 40 kJ mol-1 and zsurf= 10-6 s at 295 K, the value of a is 109 molecules cm-2. These model calculations are illustrative but it is obvious that no conventional spectroscopic method is available that could monitor molecules present at a concentration 10-6 monolayers. These molecules may, however, contribute, if highly reactive, to the mechanism of a heterogeneously catalysed reaction we shall return to this important concept in discussing the role of transient states in catalytic reactions. 

Gorter and Grendel in 1925 [527], drawing on the work of Langmuir, extracted lipids from RBC ghosts and formed monolayers. They discovered that the area of the monolayer was twice that of the calculated membrane surface of intact RBC, indicating the presence of a bilayer. This was the birth of the concept of a lipid bilayer as the fundamental structure of cell membranes (Fig. 7.1). 

Very few published data exist on the evaluation of automated systems, though one report has been made of an automated absorption assay using Caco-2 cells cultured on both sides of polycarbonate membranes [93], The concept of culturing cells on the lower sides of the membranes was investigated as a means of improving the opportunity to study transport in the secretory basolateral to apical direction. However, this approach resulted in increased variability and impaired active transport properties of the cell monolayers, and was therefore not recommended. 

More recently, a new method of assembling multilayers of PB on surfaces has been described.110 In contrast to the familiar process of self-assembly, which is spontaneous and leads to single monolayers, directed assembly is driven by the experimenter and leads to extended multilayers. In a proof-of-concept experiment, the generation of multilayers of Prussian blue (and the mixed Fein/Run analog ruthenium purple) on gold surfaces by exposing them alternately to positively charged ferric cations and [Fe(CN)6]4- or [Ru(CN)f,]4 anions has been demonstrated.110... 

Assuming that an efficient D-A type of molecule can be synthesized, it should be possible to deposit these molecules as a monolayer onto a glass slide coated with a metal such as aluminum or a wide bandgap semiconductor such as Sn(>2. With the acceptor end of the molecule near the conductor and with contact to the other side via an electrolyte solution it should be possible to stimulate electron transfer from D to A and then into the conductor, through an external circuit and finally back to D through the electrolyte. This would form the basis of a new type of solar cell in which the layer of D-A molecules would perform the same function as the p-n junction in a silicon solar cell (50). Only the future will tell whether or not this concept will be feasible but if nature can do it, why can t we ... 

A major advance in adsorption theory generalized the treatment of monolayer adsorption and incorporated the concept of multilayer adsorption. This is known as the BET theory after Brunauer, Emmett and Teller [32], The adsorption of a gas on a solid surface can be described by... 

Novel concepts of aggregation structure of fatty acid monolayers on the water surface... 

Concerning the mode of formation of ES, we prefer the concept that the substrate in a monolayer is chemisorbed to the active center of the enzyme protein, just as the experimental evidence pertaining to surface catalysis by inorganic catalysts indicates that in these reactions chemisorbed, not physically adsorbed, reactants are involved. Such a concept is supported by the demonstration of spectroscopically defined unstable intermediate compounds between enzyme and substrate in the decomposition by catalase of ethyl hydroperoxide,11 and in the interaction between peroxidase and hydrogen peroxide.18 Recently Chance18 determined by direct photoelectric measurements the dissociation con-... 

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