Understanding Odd−Even Effects in Organic Self-Assembled Monolayers

Feng, Tao; Bernasek, Steven L.

doi:10.1021/cr050258d

Cited by 366 publications

(444 citation statements)

References 215 publications

(674 reference statements)

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“…3,37,40,43,48,67 PEGylated surfaces demonstrate some of the highest protein resistance; they are relatively durable; and chemically, PEGs are relatively easy to manipulate. 40,52,58 Utilizing self-assembled monolayers (SAMs) of alkylthiols on gold surfaces for engineering of bioactive interfaces has gained significant popularity due to the simplicity of the used chemistry 45,74 and to the availability of high-resolution structural information for such SAMs. 80 Furthermore, engineering of bioactive interfaces over thin metal films has been a driving force for the development of biosensing applications based on surface plasmon resonance techniques.…”

Section: Introductionmentioning

confidence: 99%

Surface-Bound Proteins with Preserved Functionality

et al. 2009

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Abstract-Biocompatibility of materials strongly depends on their surface properties. Therefore, surface derivatization in a controllable manner provides means for achieving interfaces essential for a broad range of chemical, biological, and medical applications. Bioactive interfaces, while manifesting the activity for which they are designed, should suppress all nonspecific interaction between the supporting substrates and the surrounding media. This article describes a procedure for chemical derivatization of glass and silicon surfaces with polyethylene glycol (PEG) layers covalently functionalized with proteins. While the proteins introduce the functionality to the surfaces, the PEGs provide resistance against nonspecific interactions. For formation of aldehyde-functionalized surfaces, we coated the substrates with acetals (i.e., protected aldehydes). To avoid deterioration of the surfaces, we did not use strong mineral acids for the deprotection of the aldehydes. Instead, we used a relatively weak Lewis acid for conversion of the acetals into aldehydes. Introduction of a,x-bifunctional polymers into the PEG layers, bound to the aldehydes, allowed us to covalently attach green fluorescent protein and bovine carbonic anhydrase to the surfaces. Spectroscopic studies indicated that the surface-bound proteins preserve their functionalities. The surface concentrations of the proteins, however, did not manifest linear proportionality to the molar fractions of the bifunctional PEGs used for the coatings. This finding suggests that surface-loading ratios cannot be directly predicted from the compositions of the solutions of competing reagents used for chemical derivatization.

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Section: Introductionmentioning

confidence: 99%

Surface-Bound Proteins with Preserved Functionality

et al. 2009

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“…On the other hand, the intermolecular steric repulsion at the atomic level possibly results in distinctly different self-assembled structures and even induces different chirality for the self-assembled monolayers [14,15]. The simplest example is the odd-even effect on structure and chirality of carboxylic acid self-assembled on graphite (Fig.…”

Section: Molecule-molecule Interactions-determined Packing Structure mentioning

confidence: 99%

Nanoscale surface chemistry in self- and directed-assembly of organic molecules on solid surfaces and synthesis of nanostructured organic architectures

Tao

2008

Pure and Applied Chemistry

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This article briefly reviews the interplay of weak noncovalent interactions involved in the formation of self-assembled monolayers of organic molecules and the strong chemical binding in directed-assembly of organic molecules on solid surfaces. For a self-assembled monolayer, each molecule involves at least three categories of weak interactions, including molecule-substrate interactions, molecule-molecule interactions in a lamella, and molecule-molecule interactions between two adjacent lamellae. Basically, molecule-substrate interactions play a major role in determining molecular configuration. Molecule-molecule interactions, particularly the interactions of molecular ending functional groups between two adjacent lamellae, such as hydrogen bonds, play a dominant role in determining the molecular packing pattern in a monolayer. These weak interactions may induce or influence molecular chirality. This understanding at the atomic scale allows us to design 2D nanostructured organic materials via precisely manipulating these weak noncovalent interactions. Compared to the self-assembled monolayer formed via weak noncovalent interactions, the structure of directed-assembled monolayer/multilayers formed through strong chemical bonds is significantly dependent on the geometric arrangement and reactivity of active sites on the solid surface. In contrast to the significant role of weak intermolecular interactions in determining molecular packing in a self-assembled monolayer, strong chemical binding between molecules and reactive sites of a substrate plays a major role in determining the molecular packing pattern in a directed-assembly monolayer. Controllable chemical attachment between organic functional groups and reactive sites of the solid surface is crucial for the formation of a highly oriented organic monolayer and the following multilayer.

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“…This phenomenon, called the odd-even effect, has been discussed in terms of the steric repulsion of terminal methyl groups. [1] There are many examples showing the odd-even effect, such as melting point, crystalline packing, chirality, optical property, and so on. [2][3][4][5][6][7] The melting point and the enthalpy of fusion of linear alkanes changed periodically, and these alternating changes were more remarkable for alkane-α,ω-diols.…”

Section: Introductionmentioning

confidence: 99%

“…[20] Such structural modulations due to the odd-even effect of alkyl chains have also been reported in an anthracene derivative, dicarbamate compounds, and so on. [1,[21][22][23][24][25] For the study of physisorbed monolayers, the typical substrate is highly oriented pyrolytic graphite (HOPG). Scanning tunneling microscopy (STM) enables the 2D structural analysis at the molecular level.…”

Section: Introductionmentioning

confidence: 99%

2D Structural Modulation by Odd-Even Effect of Alkyl Chains Revealed by Scanning Tunneling Microscopy at Solid/Liquid Interface

Kikkawa

2014

Trans. Mat. Res. Soc. Japan

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This review paper presents our recent progress on the formation of self-assembled two-dimensional (2D) structures, and their modulation by the odd-even effect of alkyl chains on porphyrin derivatives, isobutenyl compounds and bipyridine derivatives. The 2D structures were directly visualized by scanning tunneling microscopy (STM) at the highly oriented pyrolytic graphite (HOPG)/solvent interface. The alkyl tails in the compounds work as moleculemolecule and molecule-substrate interaction sites, and the nature of the 2D structures depended on the alkyl chain length. These STM observations revealed that, for each compound, an odd-even effect exists for a specific range of alkyl chain lengths.

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Understanding Odd−Even Effects in Organic Self-Assembled Monolayers

Cited by 366 publications

References 215 publications

Surface-Bound Proteins with Preserved Functionality

Surface-Bound Proteins with Preserved Functionality

Nanoscale surface chemistry in self- and directed-assembly of organic molecules on solid surfaces and synthesis of nanostructured organic architectures

2D Structural Modulation by Odd-Even Effect of Alkyl Chains Revealed by Scanning Tunneling Microscopy at Solid/Liquid Interface

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