Self-Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology

Love, J. Christopher; Estroff, Lara A.; Kriebel, Jennah K.; Nuzzo, Ralph G.; Whitesides, George M.

doi:10.1021/cr0300789

Cited by 7,668 publications

(6,828 citation statements)

References 762 publications

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“…SAMs based on chemical Au-S bonds were first reported in 1983 9 and immediately attracted enormous attention. Systematic studies of their surface structures, properties and functions [10][11][12][13][14][15][16][17][18] have been achieved for a number of molecular systems, driven by a wide range of potential applications. 19,20 Besides Au-S bonding, metallic substrates can also be other transition metals such as silver and platinum.…”

Section: Qijin Chimentioning

confidence: 99%

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Zhang

Welinder

Chi

et al. 2011

Phys. Chem. Chem. Phys.

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Self-assembled organization of functional molecules on solid surfaces has developed into a powerful and sophisticated tool for surface chemistry and nanotechnology. A number of reviews on the topic have been available since the mid 1990s. This perspective article aims to focus on recent development in the investigations of electronic structures and assembling dynamics of electrochemically controlled self-assembled monolayers (SAMs) of thiol containing molecules on gold surfaces. A brief introduction is first given and particularly illustrated by a Table summarizing the molecules studied, the surface lattice structures and the experimental operating conditions. This is followed by discussion of two major high-resolution experimental methods, scanning tunnelling microscopy (STM) and single-crystal electrochemistry. In Section 3, we briefly address choice of supporting electrolytes and substrate surfaces, and their effects on the SAM structures. Section 4 constitutes the major body of the article by offering some details of recent studies for the selected cases, including in situ monitoring of assembling dynamics, molecular electronic structures, and the key external factors determining the SAM packing. In Section 5, we give examples of what can be offered by theoretical computations for the detailed understanding of the SAM electronic structures revealed by STM images. A brief summary of the current applications of SAMs in wiring metalloproteins, design and fabrication of sensors, and single-molecule electronics is described in Section 6. In the final two sections (7 and 8), we discuss the current status in understanding of electronic structures and properties of SAMs in electrochemical environments and what could be expected for future perspectives.

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Section: Qijin Chimentioning

confidence: 99%

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Zhang

Welinder

Chi

et al. 2011

Phys. Chem. Chem. Phys.

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“…Tuning the morphology is actually tuning the facets, edges and corners. There are many reviews concerning the facets of nanoparticles as key points for properties,5, 6, 7 however, the edges are less discussed.…”

Section: Introductionmentioning

confidence: 99%

Face the Edges: Catalytic Active Sites of Nanomaterials

Wang

2015

Advanced Science

158

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Edges are special sites in nanomaterials. The atoms residing on the edges have different environments compared to those in other parts of a nanomaterial and, therefore, they may have different properties. Here, recent progress in nanomaterial fields is summarized from the viewpoint of the edges. Typically, edge sites in MoS2 or metals, other than surface atoms, can perform as active centers for catalytic reactions, so the method to enhance performance lies in the optimization of the edge structures. The edges of multicomponent interfaces present even more possibilities to enhance the activities of nanomaterials. Nanoframes and ultrathin nanowires have similarities to conventional edges of nanoparticles, the application of which as catalysts can help to reduce the use of costly materials. Looking beyond this, the edge structures of graphene are also essential for their properties. In short, the edge structure can influence many properties of materials.

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“…Ligand 1 bears an N ‐aroyl hydrazone unit, connected through an aliphatic linker to a thiolate functionality for binding to AuNP surfaces (Figure 2 a). 13 The alkyl linker encourages the formation of a well‐ordered surface monolayer, maximizing van der Waals interactions between neighboring chains,2a whereas the outer tetraethylene glycol unit confers compatibility with polar solvents and conformational flexibility at the dynamic covalent reactive site 14…”

mentioning

confidence: 99%

Reversible Control of Nanoparticle Functionalization and Physicochemical Properties by Dynamic Covalent Exchange

Sala

Kay

2015

Angewandte Chemie

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Existing methods for the covalent functionalization of nanoparticles rely on kinetically controlled reactions, and largely lack the sophistication of the preeminent oligonucleotide‐based noncovalent strategies. Here we report the application of dynamic covalent chemistry for the reversible modification of nanoparticle (NP) surface functionality, combining the benefits of non‐biomolecular covalent chemistry with the favorable features of equilibrium processes. A homogeneous monolayer of nanoparticle‐bound hydrazones can undergo quantitative dynamic covalent exchange. The pseudomolecular nature of the NP system allows for the in situ characterization of surface‐bound species, and real‐time tracking of the exchange reactions. Furthermore, dynamic covalent exchange offers a simple approach for reversibly switching—and subtly tuning—NP properties such as solvophilicity.

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Self-Assembled Monolayers of Thiolates on Metals as a Form of Nanotechnology

Cited by 7,668 publications

References 762 publications

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Electrochemically controlled self-assembled monolayers characterized with molecular and sub-molecular resolution

Face the Edges: Catalytic Active Sites of Nanomaterials

Reversible Control of Nanoparticle Functionalization and Physicochemical Properties by Dynamic Covalent Exchange

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