Asymmetric monolayers

The other chapters then lead from the simple to the more complex molecular assemblies. Syntheses of simple synkinons are described at first. Micelles made of 10-100 molecules follow in chapter three. It is attempted to show how structurally ill-defined assemblies can be most useful to isolate single and pairs of molecules and that micelles may produce very dynamic reaction systems. A short introduction to covalent micelles, which actually are out of the scope of this book, as well as the discussion of rigid amphiphiles indicate where molecular assembly chemistry should aim at, namely the synkinesis of solid spherical assemblies. Chapter four dealing with vesicles concentrates on asymmetric monolayer membranes and the perforation of membranes with pores and transport systems. The regioselective dissolution of porphyrins and steroids, and some polymerization and photo reactions within vesicle membranes are also described in order to characterize dynamic assemblies. 

Figure 2.5.14 Asymmetrical monolayered vesicle membranes have been obtained from the two bolaamphiphiles shown, (a) All large headgroups are on the outer surface, all small headgroups at the inside of the vesicle. This phenomenon is by no means universal. It has to be tested for each individual asymmetrical bolaamphiphile. In most cases there is only a small difference in the localization of different headgroups. In (b) the metachromatic effect of polyanions on methylene blue aggregation on the sulfonated membrane outside is indicated (see text above).

Chemical properties of deposited monolayers have been studied in various ways. The degree of ionization of a substituted coumarin film deposited on quartz was determined as a function of the pH of a solution in contact with the film, from which comparison with Gouy-Chapman theory (see Section V-2) could be made [151]. Several studies have been made of the UV-induced polymerization of monolayers (as well as of multilayers) of diacetylene amphiphiles (see Refs. 168, 169). Excitation energy transfer has been observed in a mixed monolayer of donor and acceptor molecules in stearic acid [170]. Electrical properties have been of interest, particularly the possibility that a suitably asymmetric film might be a unidirectional conductor, that is, a rectifier (see Refs. 171, 172). Optical properties of interest include the ability to make planar optical waveguides of thick LB films [173, 174]. 

LB films of 1,4,8,11,15,18-hexaoctyl-22,25-bis-(carboxypropyl)-phthalocyanine (2), an asymmetrically substituted phthalocyanine, were stable monolayers formed at the water—air interface that could be transferred onto hydrophilic siUca substrates (32—34). When a monolayer film of the phthalocyanine derivative was heated, there was a remarkable change in the optical spectmm. This, by comparison to the spectmm of the bulk material, indicated a phase transition from the low temperature herringbone packing, to a high temperature hexagonal packing. 

Proteins that can flip phospholipids from one side of a bilayer to the other have also been identified in several tissues (Figure 9.11). Called flippases, these proteins reduce the half-time for phospholipid movement across a membrane from 10 days or more to a few minutes or less. Some of these systems may operate passively, with no required input of energy, but passive transport alone cannot establish or maintain asymmetric transverse lipid distributions. However, rapid phospholipid movement from one monolayer to the other occurs in an ATP-dependent manner in erythrocytes. Energy-dependent lipid flippase activity may be responsible for the creation and maintenance of transverse lipid asymmetries. 

From this discussion it is clear, that, independently of their redox properties, suitably modified electrodes offer themselves for the introduction of diastereo- or enantioselectivity into electrochemistry. Early reports of chiral inductions at modified electrodes include reactions at graphite and SnO surfaces derivatized with monolayers of (S)-(—)-phenylalanine. Asymmetric inductions at the chiral graphite electrode could, however, not be verified in other laboratories even after great efforts... 

Thus the formation of tilted analogues of the smectic A phases, i.e. monolayer Cl and bilayer C2, is possible for mesogens with relatively large electric quadrupoles. In the case of strongly sterically asymmetric molecules (e.g., zigzag shaped or dumbell shaped molecules, Fig. 3b) these quadrupolar interactions may be steric in origin. From this point of view observation of molecular tilt in the molecular dynamics simulations for a one-layer film of DOBAMBC in the absence of electrostatic interactions is not so surprising [106]. 

Microscopy methods based on nonlinear optical phenomena that provide chemical information are a recent development. Infrared snm-frequency microscopy has been demonstrated for LB films of arachidic acid, allowing for surface-specific imaging of the lateral distribution of a selected vibrational mode, the asymmetric methyl stretch [60]. The method is sensitive to the snrface distribntion of the functional gronp as well as to lateral variations in the gronp environmental and conformation. Second-harmonic generation (SHG) microscopy has also been demonstrated for both spread monolayers and LB films of dye molecules [61,62]. The method images the molecular density and orientation field with optical resolution, and local qnantitative information can be extracted. 

Figure 5. Integrated band areas vs. 1/T for 2 and 6 monolayers of cadmium arachidate on Ag. Comparison of asymmetric (1630 -1490 cm-1) and symmetric (1490 - 1380 cm-1) bands.

Figure 16.7 Schematic drawing of the asymmetric electrode pattern. The gold electrode was covered with a Fc-alkanethiol monolayer. The wetting of the gold electrode was switched from wetting to repulsive and vice versa by changing the electrochemical potential of the electrode.

A BLM can even be prepared from phospholipid monolayers at the water-air interface (Fig. 6.10B) and often does not then contain unfavourable organic solvent impurities. An asymmetric BLM can even be prepared containing different phospholipids on the two sides of the membrane. A method used for preparation of tiny segments of biological membranes (patch-clamp) is also applied to BLM preparation (Fig. 6.10C). 

The first process is due to Schottky barriers [30], which are electrical dipole moments that form at the metal I molecule interfaces, as discussed above [34,40]. The second process arises if the electrically-active portion of the molecule is placed asymmetrically within the metal I molecule I metal sandwich. This geometry is common, because a long alkyl tail is often needed to make the molecule amphiphilic so that it will form well-ordered Langmuir-Blodgett monolayers [76-78]. 

Between 1982 and 1997, one of us (Metzger) studied many D-cr-A molecules as potential rectifiers, but could not measure their IV properties reliably [11, 12, 100]. Due to difficulties in interpreting how electron transport occurs between adjacent layers in a multilayer, Metzger decided to focus on monolayers, and to avoid difficulties with asymmetric Schottky barriers, decided to use the same metal on both sides of the monolayer (first A1 for 36a, later Au). 

Geddes NJ, Sambles JR, Jarvis DJ, Parker WG, Sandman DJ (1990) Fabrication and investigation of asymmetric current-voltage characteristics of a metal/Langmuir-Blodgett monolayer/metal structure. Appl Phys Lett 56 1916-1918... 

Fig. 14. Surface area dependences of surface pressure and frequency maximum of the CH2 asymmetric band for (a) crystalline stearic acid monolayer and (b) amorphous myristic acid monolayer.

The transients given in Figure 3b are asymmetric. The area under the curves is almost two times higher than the product of imax and traax. In ttle initial segment of the curves, the current varies linearly with time. These features are consistent with the process controlled by the instantaneous nucleation and growth of a fixed number of oxide islands % in the CO monolayer. The transients are well described by the expression [16, 17] ... 

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