Self-organization monolayer

These monolayers form themselves spontaneously by adsorption of suitable components from a diluted solution directly onto a surface. The formation of ordered and orientated monomolecular layers by spontaneous adsorption from a diluted solution is called self-assembling, the respective layers are called self-assembled monolayers (SAM) or self-organized monolayers. In the first part of this review, the coating of surfaces with functionalized SAMs will be examined. After that, some aspects of the attachment of the biomolecules onto these SAM-modified surfaces will be discussed. 

Fig, 10.1. Self-organized monolayer prepared by solution casting of octyl-decorated Frechet dendritic wedges functionalized by a methyl ester group (30 nm x 30 nm, bias voltage tJbias = 500 mV, tunnelling current /t = 70 pA 0.2 mM in hexane), C. Rohr, LMU... 

Webber, G. B. Wanless, E. J. Butun, V. Armes, S. P Biggs, S. Self-organized monolayer films of stimulus-responsive micelles. Nano Lett. 2002, 2,1307-1313. 

C2.4 Organics films (Langmuir-Blodgett films and self-assembled monolayers)... 

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. 

Sheen C W, Martensson J, Shi J, Parikh A N and Allara D L A 1992 New class of organized self-assembled monolayers—alkane thiols on GaAs(IOO) J. Am. Chem. Soc. 114 1514-5... 

Nuzzo R G, Dubois L FI and Allara D L 1990 Fundamental-studies of microscopic wetting on organic-surfaces. 1. formation and structural characterization of a self-consistent series of polyfunctional organic monolayers J. Am. Chem. Soc. 112 558-69... 

The monolayer resulting when amphiphilic molecules are introduced to the water—air interface was traditionally called a two-dimensional gas owing to what were the expected large distances between the molecules. However, it has become quite clear that amphiphiles self-organize at the air—water interface even at relatively low surface pressures (7—10). For example, x-ray diffraction data from a monolayer of heneicosanoic acid spread on a 0.5-mM CaCl2 solution at zero pressure (11) showed that once the barrier starts moving and compresses the molecules, the surface pressure, 7T, increases and the area per molecule, M, decreases. The surface pressure, ie, the force per unit length of the barrier (in N/m) is the difference between CJq, the surface tension of pure water, and O, that of the water covered with a monolayer. Where the total number of molecules and the total area that the monolayer occupies is known, the area per molecules can be calculated and a 7T-M isotherm constmcted. This isotherm (Fig. 2), which describes surface pressure as a function of the area per molecule (3,4), is rich in information on stabiUty of the monolayer at the water—air interface, the reorientation of molecules in the two-dimensional system, phase transitions, and conformational transformations. 

Patterns of ordered molecular islands surrounded by disordered molecules are common in Langmuir layers, where even in zero surface pressure molecules self-organize at the air—water interface. The difference between the two systems is that in SAMs of trichlorosilanes the island is comprised of polymerized surfactants, and therefore the mobihty of individual molecules is restricted. This lack of mobihty is probably the principal reason why SAMs of alkyltrichlorosilanes are less ordered than, for example, fatty acids on AgO, or thiols on gold. The coupling of polymerization and surface anchoring is a primary source of the reproducibihty problems. Small differences in water content and in surface Si—OH group concentration may result in a significant difference in monolayer quahty. Alkyl silanes remain, however, ideal materials for surface modification and functionalization apphcations, eg, as adhesion promoters (166—168) and boundary lubricants (169—171). 

The expectation of the structural dependence of lubrication motivated great numbers of investigations that intended to prepare and use highly ordered organic films, such as the Langmuir-Blodgett (L-B) hlms and Self-Assembled Monolayers (SAMs), as solid lubricant, which will be discussed more specihcally in Section 4. 

Self-assembled monolayers are formed spontaneously by the immersion of an appropriate substrate into a solution of active surfactant in an organic solvent. After the substrate is immersed for a time from minutes to hours, it is rinsed with ligroin, methanol, distilled water, and dried in a steam of nitrogen. An apparent effect of the monolayer coating is the drastic change in wettability of the surface so that the measurement of the contact angle can be considered as an effective way to detect the formation of the SAMs. 

This chapter introduces three kinds of surface organic modihcation hlms on a magnetic head that we have studied. These are polyfluoroalkylmethacrylate films, X-1P films, and self-assembled monolayers (SAMs). It also reviews the works of surface lube on a hard disk surface. In the last, the challenges on the development of a magnetic recording system are discussed. 

Most studies of ORR catalysis by metalloporphyrins have been carried out using water-insoluble catalysts absorbed on a graphite electrode in contact with aqueous solution. In a limited number of cases, four other approaches have been used catalysts imbedded in an inert film (i.e., Nafion or lipid) on the electrode surface self-assembled monolayers of catalysts catalysts in aqueous or mixed organic/aqueous solutions in contact with an electrode and catalysis in mixed aqueous/organic medium using... 

Luderer F, Walschus U (2005) Immobilization of Oligonucleotides for Biochemical Sensing by Self-Assembled Monolayers Thiol-Organic Bonding on Gold and Silanization on Silica Surfaces. 260 37-56... 

---