/pdf/self-assembled-monolayers-of-thiolates-on-metals-as-a-form-1neb0hj3k4.pdf

Self-assembled monolayers of thiolates on metals as a form of nanotechnology.

The field of self-assembled monolayers (SAMs) has witnessed tremendous growth in synthetic sophistication and depth of characterization over the past 15 years.1 However, it is interesting to comment on the modest beginning and on important milestones. The field really began much earlier than is now recognized. In 1946 Zisman published the preparation of a monomolecular layer by adsorption (self-assembly) of a surfactant onto a clean metal surface.2 At that time, the potential of self-assembly was not recognized, and this publication initiated only a limited level of interest. Early work initiated in Kuhn’s laboratory at Gottingen, applying many years of experience in using chlorosilane derivative to hydrophobize glass, was followed by the more recent discovery, when Nuzzo and Allara showed that SAMs of alkanethiolates on gold can be prepared by adsorption of di-n-alkyl disulfides from dilute solutions.3 Getting away from the moisture-sensitive alkyl trichlorosilanes, as well as working with crystalline gold surfaces, were two important reasons for the success of these SAMs. Many self-assembly systems have since been investigated, but monolayers of alkanethiolates on gold are probably the most studied SAMs to date. The formation of monolayers by self-assembly of surfactant molecules at surfaces is one example of the general phenomena of self-assembly. In nature, self-assembly results in supermolecular hierarchical organizations of interlocking components that provides very complex systems.4 SAMs offer unique opportunities to increase fundamental understanding of self-organization, structure-property relationships, and interfacial phenomena. The ability to tailor both head and tail groups of the constituent molecules makes SAMs excellent systems for a more fundamental understanding of phenomena affected by competing intermolecular, molecular-substrates and molecule-solvent interactions like ordering and growth, wetting, adhesion, lubrication, and corrosion. That SAMs are well-defined and accessible makes them good model systems for studies of physical chemistry and statistical physics in two dimensions, and the crossover to three dimensions. SAMs provide the needed design flexibility, both at the individual molecular and at the material levels, and offer a vehicle for investigation of specific interactions at interfaces, and of the effect of increasing molecular complexity on the structure and stability of two-dimensional assemblies. These studies may eventually produce the design capabilities needed for assemblies of three-dimensional structures.5 However, this will require studies of more complex systems and the combination of what has been learned from SAMs with macromolecular science. The exponential growth in SAM research is a demonstration of the changes chemistry as a disciAbraham Ulman was born in Haifa, Israel, in 1946. He studied chemistry in the Bar-Ilan University in Ramat-Gan, Israel, and received his B.Sc. in 1969. He received his M.Sc. in phosphorus chemistry from Bar-Ilan University in 1971. After a brief period in industry, he moved to the Weizmann Institute in Rehovot, Israel, and received his Ph.D. in 1978 for work on heterosubstituted porphyrins. He then spent two years at Northwestern University in Evanston, IL, where his main interest was onedimensional organic conductors. In 1985 he joined the Corporate Research Laboratories of Eastman Kodak Company, in Rochester, NY, where his research interests were molecular design of materials for nonlinear optics and self-assembled monolayers. In 1994 he moved to Polytechnic University where he is the Alstadt-Lord-Mark Professor of Chemistry. His interests encompass self-assembled monolayers, surface engineering, polymers at interface, and surfaces phenomena. 1533 Chem. Rev. 1996, 96, 1533−1554

/pdf/formation-and-structure-of-self-assembled-monolayers-5eorfomxfu.pdf

Formation and Structure of Self-Assembled Monolayers.

Using two-phase (water–toluene) reduction of AuCl4– by sodium borohydride in the presence of an alkanethiol, solutions of 1–3 nm gold particles bearing a surface coating of thiol have been prepared and characterised; this novel material can be handled as a simple chemical compound.

Synthesis of thiol-derivatised gold nanoparticles in a two-phase liquid-liquid system

▪ Abstract Soft lithography, a set of techniques for microfabrication, is based on printing and molding using elastomeric stamps with the patterns of interest in bas-relief. As a technique for fabricating microstructures for biological applications, soft lithography overcomes many of the shortcomings of photolithography. In particular, soft lithography offers the ability to control the molecular structure of surfaces and to pattern the complex molecules relevant to biology, to fabricate channel structures appropriate for microfluidics, and to pattern and manipulate cells. For the relatively large feature sizes used in biology (≥50 μm), production of prototype patterns and structures is convenient, inexpensive, and rapid. Self-assembled monolayers of alkanethiolates on gold are particularly easy to pattern by soft lithography, and they provide exquisite control over surface biochemistry.

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Soft Lithography in Biology and Biochemistry

https://is.muni.cz/el/1431/podzim2006/C7780/um/Read/2711172/SAM_str_grwth_ProgSurfSci00_151.pdf

Structure and growth of self-assembling monolayers

Spontaneously organized molecular assemblies. 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared spectroscopy, and electrochemistry

Adsorption of bifunctional organic disulfides on gold surfaces

This paper shows that stable, oriented, polyfunctional organic monolayers can be prepared by the spontaneous organization of structurally complex organic disulfides on polycrystalline gold substrates. Chemisorption proceeds to very high coverages, approaching that equivalent to the bulk-phase densities of the adsorbate molecules. The bonding to the surface is also highly specific, inasmuch as the chemisorption of the disulfide moiety is favored greatly over a wide range of other functionality. This latter feature allows the ready preparation of a broad variety of organic surfaces with well-defined microscopic and macroscopic characteristics. Several representative examples of monolayer films are described, their chemical and thermal properties explored, and their structures characterized by several techniques including infrared and photoelectron spectroscopies.

Spontaneously organized molecular assemblies. 3. Preparation and properties of solution adsorbed monolayers of organic disulfides on gold surfaces

On montre qu'il peut y avoir formation de couches monomoleculaires, orientees, a empilement compact, lors de l'adsorption d'acides n-alcanoiques sur des supports d'aluminium oxyde, a partir de solutions diluees

Spontaneously organized molecular assemblies. 1. Formation, dynamics, and physical properties of n-alkanoic acids adsorbed from solution on an oxidized aluminum surface

Determination de la structure des couches monomoleculaires des acides alcanoiques, a 16-22 atomes de carbone, termines par des groupes methyle, vinyle ou propargyle, formees lors de l'adsorption sur de l'oxyde d'Al, a partir d'une solution dans l'hexadecane

Spontaneously organized molecular assemblies. 2. Quantitative infrared spectroscopic determination of equilibrium structures of solution-adsorbed n-alkanoic acids on an oxidized aluminum surface

David L. Allara

Papers

Spontaneously organized molecular assemblies. 4. Structural characterization of n-alkyl thiol monolayers on gold by optical ellipsometry, infrared spectroscopy, and electrochemistry

Adsorption of bifunctional organic disulfides on gold surfaces

Spontaneously organized molecular assemblies. 3. Preparation and properties of solution adsorbed monolayers of organic disulfides on gold surfaces

Spontaneously organized molecular assemblies. 1. Formation, dynamics, and physical properties of n-alkanoic acids adsorbed from solution on an oxidized aluminum surface

Spontaneously organized molecular assemblies. 2. Quantitative infrared spectroscopic determination of equilibrium structures of solution-adsorbed n-alkanoic acids on an oxidized aluminum surface