Formation and Stability of Alkylthiol Monolayers on Carbon Substrates

Lockett, Matthew R.; Smith, Lloyd M.

doi:10.1021/jp102821x

Cited by 13 publications

(22 citation statements)

References 23 publications

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“…The combination of these techniques is commonly used to gain a better understanding of surface processes 15a. 24, 25 X‐Ray photoelectron spectroscopy (XPS) is probably the most appropriate tool for determining the chemical composition of organic thin layers9b, 26 because it analyzes just the first 10 nm of the surface, and for this reason it is widely used for evaluating the percentage of atoms covalently bound to surfaces 17. 27…”

Section: Resultsmentioning

confidence: 99%

“…Halogenation with thionyl chloride (SOCl 2 ) or phosphorus tri/pentachloride (PCl 3/5 ) in organic solvents has recently been reported as ways of increasing the reactivity of H‐terminated surfaces. These brominated or chlorinated surfaces were then modified through the formation of CC bonds between the surface and different types of alkyl Grignard reagents15 or alkylthiols,9b and the formed monolayers were demonstrated to be extremely stable even at temperatures above 200 °C 9b. This chemical halogenation represents a straightforward approach compared with previously used methods such as atomic beams,16 and a new approach based on the use of carbon tetrachloride cold plasma has been reported for the extensive chlorination of carbon nanotubes 17.…”

Section: Introductionmentioning

confidence: 96%

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Facile Electrochemical Hydrogenation and Chlorination of Glassy Carbon to Produce Highly Reactive and Uniform Surfaces for Stable Anchoring of Thiolated Molecules

Debela

Ortiz

Beni

et al. 2014

Chemistry A European J

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Carbon is a highly adaptable family of materials and is one of the most chemically stable materials known, providing a remarkable platform for the development of tunable molecular interfaces. Herein, we report a two-step process for the electrochemical hydrogenation of glassy carbon followed by either chemical or electrochemical chlorination to provide a highly reactive surface for further functionalization. The carbon surface at each stage of the process is characterized by AFM, SEM, Raman, attenuated total reflectance (ATR) FTIR, X-ray photoelectron spectroscopy (XPS), and electroanalytical techniques. Electrochemical chlorination of hydrogen-terminated surfaces is achieved in just 5 min at room temperature with hydrochloric acid, and chemical chlorination is performed with phosphorus pentachloride at 50 °C over a three-hour period. A more controlled and uniform surface is obtained using the electrochemical approach, as chemical chlorination is observed to damage the glassy carbon surface. A ferrocene-labeled alkylthiol is used as a model system to demonstrate the genericity and potential application of the highly reactive chlorinated surface formed, and the methodology is optimized. This process is then applied to thiolated DNA, and the functionality of the immobilized DNA probe is demonstrated. XPS reveals the covalent bond formed to be a C-S bond. The thermal stability of the thiolated molecules anchored on the glassy carbon is evaluated, and is found to be far superior to that on gold surfaces. This is the first report on the electrochemical hydrogenation and electrochemical chlorination of a glassy carbon surface, and this facile process can be applied to the highly stable functionalization of carbon surfaces with a plethora of diverse molecules, finding widespread applications.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 96%

Facile Electrochemical Hydrogenation and Chlorination of Glassy Carbon to Produce Highly Reactive and Uniform Surfaces for Stable Anchoring of Thiolated Molecules

Debela

Ortiz

Beni

et al. 2014

Chemistry A European J

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“…It is difficult to introduce functional groups for attaching biomolecules with this chemistry because these organometallic reagents are highly reactive. A similar two-step approach formed monolayers of alkanethiols on chlorine-terminated amorphous carbon or glassy carbon substrates (70, 71). Although the alkanethiols do not result in a carbon-carbon bond with the surface, they do provide a means of modifying both the wettability and chemical reactivity of the surface.…”

Section: Carbon Substrates: Surface Chemistrymentioning

confidence: 99%

Carbon Substrates: A Stable Foundation for Biomolecular Arrays

Lockett

Smith²

2015

Annual Rev. Anal. Chem.

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Since their advent in the early 1990s, microarray technologies have developed into a powerful and ubiquitous platform for biomolecular analysis. Microarrays consist of three major elements: the substrate upon which they are constructed, the chemistry employed to attach biomolecules, and the biomolecules themselves. Although glass substrates and silane-based attachment chemistries are used for the vast majority of current microarray platforms, these materials suffer from severe limitations in stability, due to hydrolysis of both the substrate material itself and of the silyl ether linkages employed for attachment. These limitations in stability compromise assay performance and render impossible many potential microarray applications. We describe here a suite of alternative carbon-based substrates and associated attachment chemistries for microarray fabrication. The substrates themselves, as well as the carbon-carbon bond-based attachment chemistries, offer greatly increased chemical stability, enabling a myriad of novel applications.

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“…In the case of carbons urfaces, ab road spectrum of strategies to achieve covalentb onds between electrode and linkers, includingd iazonium salts, [6] alkenes, [7] and thiolated molecules, [8,9] have been reported. In the case of carbons urfaces, ab road spectrum of strategies to achieve covalentb onds between electrode and linkers, includingd iazonium salts, [6] alkenes, [7] and thiolated molecules, [8,9] have been reported.…”

Section: Introductionmentioning

confidence: 99%

“…R ct values obtainedf rom EIS [W]a nd static contact angles[8]o f the unmodified and modified surfaces. More details about XPS data are given inTable SI-1 in the Supporting Information.…”

mentioning

confidence: 99%

Stable Carboxylate‐Terminated Gold Surfaces Produced by Spontaneous Grafting of an Alkyltin Compound

Ortiz

Debela

Méthivier

et al. 2018

Chemistry A European J

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Self-assembled monolayers formed by chemisorption of thiolated molecules on gold surfaces are widely applied for biosensing. Moreover, and due to the low stability of thiol-gold chemistry, contributions to the functionalisation of gold substrates with linkers that provide a more stable platform for the immobilisation of electroactive or biological molecules are highly appreciated. Herein, it is demonstrated that a carboxylated organotin compound can be successfully grafted onto gold substrates to form a highly stable organic layer with reactivity for subsequent binding to an aminated molecule. A battery of techniques were used to characterise the surface chemistry. The grafted layer was used to anchor aminoferrocene and subjected to both thermostability tests and long-term stability studies over a period of one year, demonstrating thermostability up to 90 °C and storage stability for at least 12 months at 4 °C protected from light. The stable surface tethering of molecules on gold substrates can be exploited in a plethora of applications, including molecular techniques, such as solid-phase amplification and solid-phase melting curve analysis, that require elevated temperature stability, as well as biosensors, which require long-term storage stability.

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Formation and Stability of Alkylthiol Monolayers on Carbon Substrates

Cited by 13 publications

References 23 publications

Facile Electrochemical Hydrogenation and Chlorination of Glassy Carbon to Produce Highly Reactive and Uniform Surfaces for Stable Anchoring of Thiolated Molecules

Facile Electrochemical Hydrogenation and Chlorination of Glassy Carbon to Produce Highly Reactive and Uniform Surfaces for Stable Anchoring of Thiolated Molecules

Carbon Substrates: A Stable Foundation for Biomolecular Arrays

Stable Carboxylate‐Terminated Gold Surfaces Produced by Spontaneous Grafting of an Alkyltin Compound

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