“Clicking” Functionality onto Electrode Surfaces

Collman, James P.; Devaraj, Neal K.; Chidsey, Christopher E. D.

doi:10.1021/la0362977

Cited by 471 publications

(421 citation statements)

References 30 publications

Supporting

Mentioning

390

Contrasting

Unclassified

Order By: Relevance

“…Note also that the area under the voltammetric peaks and thus the redox charge to completely oxidize the two different redox species are very similar. Indeed, integration of the peaks and normalization by the scan rates 30 shows that the redox charges are 3.9 ± 0.01 and 4.0 ± 0.1 μC/cm 2 for the ferrocene and porphyrin modified monolayers, respectively. This constancy of redox charge is as expected if the coverage of the redox species on the surface after the coupling reaction is equal to the coverage of reactive azide on the surface before the coupling reaction.…”

Section: Resultsmentioning

confidence: 99%

“…The procedure relies on the recently discovered Cu(I)-catalyzed variant 27,28 of the Huisgen 1,3-dipolar cycloaddition 29 between an azide group and a terminal acetylene group where one of these groups is incorporated at the surface of the monolayer and the other is appended to the species to be coupled to the monolayer. [30][31][32] The resulting linkage is a five-member aromatic heterocycle (specifically a 1,4-disubstituted 1,2,3-triazole), which is thermally and hydrolytically very stable. Sharpless has dubbed this Cu(I)-catalyzed reaction a "click" reaction 27 by virtue of its chemoselectivity, high yield, and overall convenience.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Rate of Interfacial Electron Transfer through the 1,2,3-Triazole Linkage

et al. 2006

Self Cite

View full text Add to dashboard Cite

The rate of electron transfer is measured to two ferrocene and one iron tetraphenylporphyrin redox species coupled through terminal acetylenes to azide-terminated thiol monolayers by the Cu(I)-catalyzed azide-alkyne cycloaddition (a Sharpless "click" reaction) to form the 1,2,3-triazole linkage. The high yield, chemoselectivity, convenience, and broad applicability of this triazole formation reaction make such a modular assembly strategy very attractive. Electron-transfer rate constants from greater than 60,000 to 1 s −1 are obtained by varying the length and conjugation of the electron-transfer bridge and by varying the surrounding diluent thiols in the monolayer. Triazole and the triazole carbonyl linkages provide similar electronic coupling for electron transfer as esters. The ability to vary the rate of electron transfer to many different redox species over many orders of magnitude by using modular coupling chemistry provides a convenient way to study and control the delivery of electrons to multielectron redox catalysts and similar interfacial systems that require controlled delivery of electrons.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Rate of Interfacial Electron Transfer through the 1,2,3-Triazole Linkage

et al. 2006

Self Cite

View full text Add to dashboard Cite

show abstract

“…The excitement generated by this class of chemistry for surface modification may be traced back to a report from Chidsey and co-workers in which was claimed quantitative (for coverages lower than the steric limit) coupling between a surface azide and a solution alkyne species. 149,150 Remarkably, when an alkyne-tagged ferrocene derivative was ''clicked'' onto an azide-modified gold electrode, cyclic voltammograms with DE fwhm values close to 90.6/n were observed. That is, as referred to in case study 1 (Section 3.1), this chemistry allowed the stepwise fabrication of a redox interface with nearly ideal electrochemical behaviour.…”

Section: ''Click'' Reactions Between Azides and Alkynesmentioning

confidence: 99%

The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assemblies

2011

View full text Add to dashboard Cite

The modification of surfaces with self-assembled monolayers (SAMs) containing multiple different molecules, or containing molecules with multiple different functional components, or both, has become increasingly popular over the last two decades. This explosion of interest is primarily related to the ability to control the modification of interfaces with something approaching molecular level control and to the ability to characterise the molecular constructs by which the surface is modified. Over this time the level of sophistication of molecular constructs, and the level of knowledge related to how to fabricate molecular constructs on surfaces have advanced enormously. This critical review aims to guide researchers interested in modifying surfaces with a high degree of control to the use of organic layers. Highlighted are some of the issues to consider when working with SAMs, as well as some of the lessons learnt (169 references). 2011 The Royal Society of Chemistry. The modification of surfaces with self-assembled monolayers (SAMs) containing multiple different molecules, or containing molecules with multiple different functional components, or both, has become increasingly popular over the last two decades. This explosion of interest is primarily related to the ability to control the modification of interfaces with something approaching molecular level control and to the ability to characterise the molecular constructs by which the surface is modified. Over this time the level of sophistication of molecular constructs, and the level of knowledge related to how to fabricate molecular constructs on surfaces have advanced enormously. This critical review aims to guide researchers interested in modifying surfaces with a high degree of control to the use of organic layers. Highlighted are some of the issues to consider when working with SAMs, as well as some of the lessons learnt (169 references).

show abstract

“…5,6 The surface reaction is quantitative and regioselective, exclusively yielding a single product at a single orientation. The chemistry is orthogonal to most typical organic transformations and thus is chemoselective.…”

mentioning

confidence: 99%

“…6 The azideterminated thiol SAMs were exposed to a coupling solution of the 13mer (50 μM) and Cu(I) (400 μM) complexed by TBTA in aqueous dimethyl sulfoxide for 30 min at room temperature, after which the surfaces were rinsed thoroughly with both aqueous and organic solvents. This procedure is both simple and fast in comparison to many previously reported modifications that covalently attach oligonucleotides to surfaces.…”

mentioning

confidence: 99%

Chemoselective Covalent Coupling of Oligonucleotide Probes to Self-Assembled Monolayers

et al. 2005

Self Cite

View full text Add to dashboard Cite

Surface arrays of single-stranded DNA are at the center of some of the most active areas in biological research. These include conventional applications in genome sequencing and disease diagnostics, as well as more novel emerging examples, such as combinatorial drug and reaction discovery. 1 Most methods of oligonucleotide immobilization rely on traditional nucleophilicelectrophilic reactions to achieve coupling of the oligonucleotide to the surface. 2 Unfortunately, this strategy is susceptible to side reactions, for instance, with amino groups on the nucleotides or the small molecule contaminants inherent to oligonucleotide synthesis. 3 Additionally, popular reactive electrophiles, such as N-hydroxysuccinimide esters, are prone to hydrolysis before and during the coupling reaction, which both reduce coupling yields and can make the yields irreproducible. 4 Accurate and reproducible detection of target oligonucleotides depends on the accuracy and reproducibility with which the surface can be functionalized. In this paper, we report a chemoselective approach to the formation of oligonucleotide probe surfaces using copper(I) tris(benzyltriazolylmethyl)amine (TBTA)-catalyzed triazole formation between a controlled density of azide groups on densely packed selfassembled monolayers (SAMs) and acetylene groups on the oligonucleotide probe to be immobilized. We have found this strategy to be highly predictable, very fast, and resistant to side reactions, unaffected even by the presence of excess nucleophilic or electrophilic impurities.Recently, we have demonstrated that Sharpless "click" chemistry can be used to covalently attach acetylene-bearing molecules to azide-terminated SAMs. 5,6 The surface reaction is quantitative and regioselective, exclusively yielding a single product at a single orientation. The chemistry is orthogonal to most typical organic transformations and thus is chemoselective. 7 Recent studies have demonstrated that the chemistry is well suited for the coupling of biomolecules to surfaces. 8 Although application of this chemistry to the attachment of oligonucleotides may appear straightforward, the majority of past work used free Cu(I), typically generated and maintained in aqueous solution by an excess of reducing agent. Unfortunately, in the presence of dioxygen, Cu(I) rapidly damages DNA via the generation of reactive oxygen species. 9 In order for a surface array of oligonucleotides to be useful as a sensor, the structure of the oligonucleotides must be preserved. Recently, the Sharpless group has introduced a triazolylamine copper ligand, tris-(benzyltriazolylmethyl)amine, that can accelerate the cycloaddition reaction. 10 At the same time, this ligand was found to significantly deter the redox chemistry of Cu(I) with oxygen, which is essential for preventing damage to the oligonucleotides. Encouraged by the highly desirable features of the Cu(I)TBTA-catalyzed azide-alkyne cycloaddition, we studied its applicability to the attachment of oligonucleotide probes onto well-defined SAMs.Oligode...

show abstract

“Clicking” Functionality onto Electrode Surfaces

Cited by 471 publications

References 30 publications

Rate of Interfacial Electron Transfer through the 1,2,3-Triazole Linkage

Rate of Interfacial Electron Transfer through the 1,2,3-Triazole Linkage

The molecular level modification of surfaces: from self-assembled monolayers to complex molecular assemblies

Chemoselective Covalent Coupling of Oligonucleotide Probes to Self-Assembled Monolayers

Contact Info

Product

Resources

About