Surface layer orientation

Quantification at surfaces is more difficult, because the Raman intensities depend not only on the surface concentration but also on the orientation of the Raman scat-terers and the, usually unknown, refractive index of the surface layer. If noticeable changes of orientation and refractive index can be excluded, the Raman intensities are roughly proportional to the surface concentration, and intensity ratios with a reference substance at the surface give quite accurate concentration data. 

Figure 2. Segregation energy in layer Sp (p = 0 surface layer...) of a transition metal impurity of atomic number Z + 1 (d band-filling (Nj + l.l)e /atom, full curves (Nj + l)e /atom, dashed curve) in a BCC transition metal matrix of atomic number Z (d band-filling Nje" /atom) for various crystallographic orientations of the surface...

Based on this analysis it is evident that materials which are biaxially oriented will have good puncture resistance. Highly polar polymers would be resistant to puncture failure because of their tendency to increase in strength when stretched. The addition of randomly dispersed fibrous filler will also add resistance to puncture loads. From some examples such as oriented polyethylene glycol terephthalate (Mylar), vulcanized fiber, and oriented nylon, it is evident that these materials meet one or more of the conditions reviewed. Products and plastics that meet with puncture loading conditions in applications can be reinforced against this type of stress by use of a surface layer of plastic with good puncture resistance. Resistance of the surface layer to puncture will protect the product from puncture loads. An example of this type of application is the addition of an oriented PS layer to foam cups to improve their performance. 

Two-dimensional protein layer orientation could be also effected by metal-ion coordination Monolayer of iminodiacetate-Cu(II) lipid was successfully employed as substrate for oriented immobilization of proteins naturally displaying histidine residues on their surface [37]. Affmity-resin-displaying Ni(II) complexes could also be successfully employed for oriented protein immobilization [38]. 

The nonpolar lipid core consists of mainly triacylglycerol and cholesteryl ester and is surrounded by a single surface layer of amphipathic phospholipid and cholesterol molecules (Figure 25-1). These are oriented so that their polar groups face outward to the aqueous medium, as in the cell membrane (Chapter 14). The protein moiety of a lipoprotein is known as an apo-lipoprotein or apoprotein, constituting nearly 70% of some HDL and as litde as 1% of chylomicrons. Some apolipoproteins are integral and cannot be removed, whereas others are free to transfer to other hpoproteins. 

The surface potential of a solution can be calculated, according to Eq. (10.18), from the dilference between the experimental real energy of solvation of one of the ions and the chemical energy of solvation of the same ion calculated from the theory of ion-dipole interaction. Such calculations lead to a value of -1-0.13 V for the surface potential of water. The positive sign indicates that in the surface layer, the water molecules are oriented with their negative ends away from the bulk. 

Two types of EDL are distinguished superficial and interfacial. Superficial EDLs are located wholly within the surface layer of a single phase (e.g., an EDL caused by a nonuniform distribution of electrons in the metal, an EDL caused by orientation of the bipolar solvent molecules in the electrolyte solution, an EDL caused by specific adsorption of ions). Tfie potential drops developing in tfiese cases (the potential inside the phase relative to a point just outside) is called the surface potential of the given phase k. Interfacial EDLs have their two parts in dilferent phases the inner layer with the charge density in the metal (because of an excess or deficit of electrons in the surface layer), and the outer layer of counterions with the charge density = -Qs m in the solution (an excess of cations or anions) the potential drop caused by this double layer is called the interfacial potential... 

Some of the components of the EDL, such as a nonuniform electron distribution in the metal s surface layer and the layer of oriented dipolar solvent molecules in the solution surface layer adjacent to the electrode, depend on external parameters (potential, electrolyte concentration, etc.) to only a minor extent. Usually, the contribution of these layers is regarded as constant, and it is only in individual cases that we must take into account any change in these surface potentials, and which occurs as a result of changes in the experimental conditions. 

The results of the above-mentioned Langmuir analysis of the SHG responses may be interpreted in terms of a tightly packed monolayer of the SHG active cation complexes at the membrane surface. The tight layer may, however, also be a layer thicker than a monolayer in which the potential aligns the complexes to the electric field. As a consequence of the increase of the potential near the surface, the oriented complexes would on the average be nearer to the surface than the average of all complexes. 

It may be noted that the statement made above—that the surface potential in the electrolyte phase does not depend on the orientation of the crystal face—is necessarily an assumption, as is the neglect of S s1- It is another example of separation of metal and electrolyte contributions to a property of the interface, which can only be done theoretically. In fact, a recent article29 has discussed the influence of the atomic structure of the metal surface for solid metals on the water dipoles of the compact layer. Different crystal faces can allow different degrees of interpenetration of species of the electrolyte and the metal surface layer. Nonuniformities in the directions parallel to the surface may be reflected in the results of capacitance measurements, as well as optical measurements. 

Kornyshev et al.76 proposed several models of the interface, including both orienting solvent dipoles and polarizable metal electrons, to calculate the position of the capacitance hump. Although it had been shown32,79 101 that this was one of the features of the interfacial capacity curves that should depend on the nature of the metal, available calculations did not give the proper position of the hump. The solvent molecules in the surface layer were modeled as charged layers, associated with the protons and the oxygen atoms of molecules oriented either toward or away from the surface. These layers also carried Harrison-type pseudopoten-... 

In reality, as the barrier becomes narrower, it deviates from the square shape. One often used model is the parabolic barrier (dashed line in Fig. 1). When the barrier is composed of molecules, not only is the barrier shape difficult to predict, but the effective mass of the electron can deviate significantly from the free-electron mass. In order to take these differences into account, a more sophisticated treatment of the tunneling problem, based on the WKB method, can be used [21, 29-31]. Even if the metals are the same, differences in deposition methods, surface crystallographic orientation, and interaction with the active layer generally result in slightly different work functions on either side of the barrier. 

In order to verify that the adsorbed lipid membrane indeed forms a bilayer film, another experiment is conducted with an aim to detect the formation of a monolayer lipid. It starts with a piranha-cleaned micro-tube treated with silane to render its inner surface hydrophobic. POPC liposome is then injected into the microtube. It is known that POPC lipid will form a monolayer to such a surface by orienting their hydrophobic tails toward the hydrophobic wall. The experimental results using a mode with similar sensitivity as the previous experiment are shown in Fig. 8.39. The resonance shift in this case is 22 pm, which is about half of that observed for the adsorption of a lipid bilayer. These two experiments suggest that the microtube resonator is capable of accurately determining an adsorbed biomolecular layer down to a few nm thicknesses. 

The platinum single crystals treated in this May are small spherical platinum beads Hith a diameter ranging from l.S to 1.9 am obtained by melting of a Mire. They are oriented, cut and polished according to the technique described in (10.) Mith an accuracy uithin 3 minutes of the nominal orientation. After polishing, the samples are annealed at 1300°-1500 C to eliminate the perturbed surface layer. 

We could not conclude at the moment whether the solvent dependent surface properties are to be explained only by the difference in the depth of graft layer. Another possibility is the change in polar group orientation in graft layer as suggested by Hoffman(18). This arguement will be settled by direct determination of the thickness of graft layer prepared under various conditions. Clarification of the surface layer thickness - sur-... 

Water colloid solutions of fullerenes C60 (10 4 M) were prepared as described in Scharff et al. (2004). Fullerene-aminopropylaerosyl (fullerene C60-composite-l) was synthesized (Golub et al., 2003) by the introduction of aminopropyl chains oriented ad extra by amine groups (0.9 mM/g), to the surface layer of sihcon dioxide nanoparticles that were bound to fullerene C60 (0.12 mM/g) (Fig. 6.1). Fullerene-anthracenaliminopropylaerosyl (fullerene C60-composite-2) was composed also from anthraccnaliminc (0.2mM/g) that was introduced via azomethine condensation of aldehyde group of anthracenal with surface amino group. 

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