Stepwise synthesis of Gly−Gly−His on gold surfaces modified with mixed self-assembled monolayers

Peptide-modified electrode surfaces have been shown to have excellent recognition properties for metal ions. An efficient method of screening a potential peptide for its selectivity for a given metal would involve the synthesis of the peptide directly on the electrode surface. This paper outlines a procedure in which the tripeptide Gly−Gly−His was synthesized one amino acid at a time on a gold surface modified with a self-assembled monolayer of the mixed alkanethiolates 3-mercaptopropionic acid (MPA) and 3-mercaptopropane (MP). Electrochemistry and high-resolution mass spectrometry were used to elucidate the structure of the adsorbed species and follow the synthesis. The amino acids can be attached only to MPA, but the presence of a diluting unreactive molecule of MP reduces steric crowding about the reaction center. The maximum coverage of synthesized tripeptide occurs at a ratio of MPA/MP of 1:1.

A digital watermarking scheme for Bezier surfaces

Owners and vendors are increasingly publishing their materials in digital form. Because such materials can be exactly copied, a mechanism is required that will protect the legitimate owners of these works, by providing proof of original ownership. Digital watermarking has now become one accepted method of establishing ownership of digital materials. The owner of a work embeds a pattern, called a digital watermark, in the content. This embedded watermark is normally undetectable, but its presence can be demonstrated by the owner of the work or his agent, thereby proving ownership. Digital watermarking has been used for many types of multimedia content, primarily audio, video and flat images. Recently, interest has been shown in applying digital watermarking schemes to 3D surfaces, in various formats. In this paper, we examine a method whereby a digital watermark can be embedded in a Bezier surface. A prototype watermarking method for such surfaces is presented, with some experimental results, and a discussion of directions for future research.

Graph matching with subdivision surfaces for texture synthesis on surfaces

Existing texture synthesis-from-example strategies for polygon meshes typically make use of three components: a multi-resolution mesh hierarchy that allows the overall nature of the pattern to be reproduced before filling in detail; a matching strategy that extends the synthesized texture using the best fit from a texture sample; and a transfer mechanism that copies the selected portion of the texture sample to the target surface. We introduce novel alternatives for each of these components. Use of p2-subdivision surfaces provides the mesh hierarchy and allows fine control over the surface complexity. Adaptive subdivision is used to create an even vertex distribution over the surface. Use of the graph defined by a surface region for matching, rather than a regular texture neighbourhood, provides for flexible control over the scale of the texture and allows simultaneous matching against multiple levels of an image pyramid created from the texture sample. We use graph cuts for texture transfer, adapting this scheme to the context of surface synthesis. The resulting surface textures are realistic, tolerant of local mesh detail and are comparable to results produced by texture neighbourhood sampling approaches.

The drainage of thin liquid films between solid surfaces

We present measurements of the thickness as a function of time of liquid films as they are squeezed between molecularly smooth mica surfaces. Three Newtonian, nonpolar liquids have been studied: octamethylcyclotetrasiloxane, n-tetradecane, and n-hexadecane. The film thicknesses are determined with an accuracy of 0.2 nm as they drain from ∼1 μm to a few molecular layers. Results are in excellent agreement with the Reynolds theory of lubrication for film thicknesses above 50 nm. For thinner films the drainage is slower than the theoretical prediction, which can be accounted for by assuming that the liquid within about two molecular layers of each solid surface does not undergo shear. In very thin films the continuum Reynolds theory breaks down, as drainage occurs in a series of abrupt steps whose size matches the thickness of molecular layers in the liquid. The presence of trace amounts of water has a dramatic effect on the drainage of a nonpolar liquid between hydrophilic surfaces, causing film rupture which is not observed in the dry liquids.

Structuring in liquid alkanes between solid surfaces : force measurements and mean-field theory

Measurements have been made of the solvation forces between mica surfaces in the even-numbered n-alkanes from hexane to hexadecane. In all cases the force law is qualitatively very similar, characterized by a decaying oscillatory function of distance, as occurs for simple isotropic liquids. The spacing between successive minima in the force does not increase with carbon number, and is comparable to the width of a linear alkane molecule rather than its length or any average diameter. This suggests that the alkanes have some tendency towards a parallel orientation near the mica surfaces. The measurements give no indication of any strong repulsive component expected from mean-field theories of higher alkanes or polymers. The results of one such theory are presented, and the reasons for its failure to match the experimental data are discussed.

Forces between mica surfaces in ethylene glycol

Measurements are presented of the force as a function of separation between two molecularly smooth mica surfaces immersed in ethylene glycol, and in solutions of lithium chloride and sulfuric acid in ethylene glycol. At surface separations greater than 3 nm the measured force is in very good agreement with double-layer theory, but at smaller separations there is an oscillatory solvation force which is superimposed on the double-layer repulsion. In contrast to the case in water, the adsorption of hydrogen ions at the mica surface does not markedly affect the short-range forces.

Measurement of aqueous film thickness between charged mercury and mica surfaces : a direct experimental probe of the Poisson-Boltzmann distribution

A stable aqueous electrolyte film is formed between a mercury drop and a flat mica surface due to electrical double-layer repulsion when a negative potential is applied to the mercury. Film thickness has been measured as a function of applied potential while keeping the film pressure constant. By making measurements in this way, it is possible to map the data directly according to the Poisson-Boltzmann equation. An excellent fit to the data is obtained, providing direct evidence for this classical equation and its use as the basis of the Gouy-Chapman model of the diffuse double layer in electrolyte solutions.

Molecular organization and viscosity of a thin film of molten polymer between two surfaces as probed by force measurements

Measurements are presented of the force between two molecularly smooth mica surfaces immersed in liquid poly(dimethylsiloxane) (Dow Corning 200 of nominal viscosity 50 cS) over a range of film thicknesses from 3 to 200 nm. There is a repulsion, attributed to conformational restrictions, when the polymer molecules are confined to a gap less than about 15 nm thick. In extremely thin films (<5 nm) the force is an oscillatory function of thickness with a repeat spacing corresponding to the width of the polymer molecule, which suggests that the polymer segments are arranged in layers near the solid surfaces. Dynamic force measurements show that the polymer has a viscosity equal to its bulk value even in very thin films, but a region next to each surface, only about one radius of gyration thick, does not flow. Saturation of the polymer with water destabilizes the film when it is very thin.

Attractive forces between surfaces : what can and cannot be learned from a jump-in study with the surface forces apparatus?

We study theoretically the dynamics of film thinning under the action of an attractive surface force near the point of a jump instability. Our approach is illustrated by modeling van der Waals and hydrophobic attractive forces. The main result is that with the hydrophobic force law reported previously it is often impossible to establish the jump separation with any certainty. The surfaces instead approach slowly from a distance which is much larger than the point where an actual jump is expected. We conclude that an attractive force measured by the static jump technique is overestimated, and we formulate principles of a new dynamic jump method. The use of this new technique would permit direct measurements of attractive forces at separations below the static jump distance down to contact of the surfaces.