Self assembled monolayers definition

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. 

As the analytical, synthetic, and physical characterization techniques of the chemical sciences have advanced, the scale of material control moves to smaller sizes. Nanoscience is the examination of objects—particles, liquid droplets, crystals, fibers—with sizes that are larger than molecules but smaller than structures commonly prepared by photolithographic microfabrication. The definition of nanomaterials is neither sharp nor easy, nor need it be. Single molecules can be considered components of nanosystems (and are considered as such in fields such as molecular electronics and molecular motors). So can objects that have dimensions of >100 nm, even though such objects can be fabricated—albeit with substantial technical difficulty—by photolithography. We will define (somewhat arbitrarily) nanoscience as the study of the preparation, characterization, and use of substances having dimensions in the range of 1 to 100 nm. Many types of chemical systems, such as self-assembled monolayers (with only one dimension small) or carbon nanotubes (buckytubes) (with two dimensions small), are considered nanosystems. 

In their experiments the authors worked with gold-coated silica spheres, with self-assembled monolayers of mixtures of undecanethiols and co-hydroxy undecane thiols, to vaiy the contact angle between 20 and 100°. The results were compared with sessile drop measurements on the same system. A systematic difference up to 20° for the receding angles) between the two sets of results was observed, but since these differences depend on the nature of the solid surface it was not possible to pinpoint the origin definitely. A remarkable feature was that in the AFM method, hysteresis was very small, if not absent. Anyhow, this appears to be a promising technique. 

By definition, mediated electron transfer of the type discussed in Section 14.4.2(c) cannot occur in blocking films. However for very thin films, e.g., self-assembled monolayers (SAM) of alkane thiols or oxide films, electrons can tunnel through the film and cause faradaic reactions. This phenomenon is important in electronic devices, in passivation of metal surfaces, and in fundamental studies of the distance dependence of the rate of electron transfer. 

With regard to its electronic properties, no studies are available that clearly demonstrate that electron transfer through such a supramolecular assembly is possible. Solid-state electrochemical studies on the crystalline material are not available at the present time. The closest to supramolecular electrochemistry are studies of ordered two-dimensional peptide arrays on gold. For some Fc-peptide cystamines, self-assembled monolayers of Fc-peptide cystamines were prepared that allow the quantification of the electron transfer kinetics by electrochemical techniques. Similar to the supramolecular assemblies, H-bonding plays an important role. At the present time (2003), only a few systems were studied and offer a rather complex picture of the ET properties. Additional experimental work is required to obtain definite results on the influence of the peptide primary and secondary structure on ET kinetics. In addition, tile issue of lateral interactions needs to be addressed by detailed dilution studies with alkylthiols. 

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