(Bio)Functionalisation of gold surfaces based on CS2 – amine reaction

Inês Almeida 1António C. Cascalheira 2Ana S. Viana 1

1. Centro (CQB), Campo Grande Bloco C-8, Lisboa 1749-016, Portugal
2. Lumisense, Lda, Campo Grande, Lisbon 1749-016, Portugal

Abstract

Several strategies have been employed to immobilise biological compounds onto surfaces for the development of biosensing interfaces. The Self-Assembly method for the anchoring of enzymes or other bio-compounds displays several advantages relative to other approaches, namely, high reproducibility, molecular level control, vicinity from the surface allowing direct electron transfer [1]. In more recent studies [2,3], it has been shown that a variety of secondary amines condense with carbon disulfide (CS2) onto gold surfaces at room temperature, forming dithiocarbamate monolayers that have been regarded as a versatile chemical alternative for thiols in self-assembled systems [4]. The major structural aspect distinguishing dithiocarbamates from thiolates is the resonance structure among the sulphur atoms, carbon and nitrogen, providing distinct binding properties, namely higher sulphur densities with possible overlapping of molecular and metal states.

The purpose of this work is to use the reaction between CS2 and amines for direct biomolecule immobilisation onto gold surfaces. To achieve this goal the chemical coupling between carbon disulphide and distinct compounds containing primary (e.g. dopamine) or secondary amines (e.g. tryptophan, hexylmethylamine, epinephrine) have been primarily investigated. Three different approaches were used for the formation of dithiocarbamates on gold (111) electrodes: (i) one pot chemical reaction: gold in contact with a mixture of CS2 and amines; (ii) self-assembling of a CS2 monolayer and post-reaction with the amines, and (iii) dithiocarbamate formation through reaction of CS2 with amines following exposure to the gold surface. The amount of sulphur attached to gold as well as the stability and packing of the monolayers were evaluated by electrochemical reductive desorption studies. In addition, the use of electrochemically active amine compounds (dopamine and epinephrine) enabled to infer on the amount of amines present on the electrode surface, as a result of the successful reaction. Evidence for dithiocarbamate formation has been obtained using the three methodologies, and the modified electrodes were characterised by scanning tunnelling microscopy. Biofunctionalisation of gold surfaces has been also attempted through the reaction of CS2 with amines present in Glucose Oxidase. Enzyme immobilisation was confirmed through its electrocatlytic response towards glucose.

Acknowledgements

The authors acknowledge Fundação para a Ciência e a Tecnologia for financial support, project (PTDC/QUI/66612/2006).

References

[1] J. F. Cabrita, L. M. Abrantes, A. S. Viana, Electrochimica Acta, 50 (2005) 2117.

[2] Y. Zhao, P.-S. Waleska, Q. Shi, A. Wei, J. Am. Chem. Soc., 127 (2005) 7328.

[3] H. Zhu, D. M. Coleman, C. J. Dehen I. M. Geisler, D. Zemlyanov, J. Chmielewski, G. J. Simpson, Alexander Wei, Langmuir, 24 (2008) 8660.

[4] P. Morf, F. Raimondi, H.-G. Nothofer, B. Schnyder, A. Yasuda, J. M. wessels, T. A. Jung, Langmuir 22 (2006) 658.

 

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Presentation: Poster at SMCBS'2009 International Workshop, by Ana S. Viana
See On-line Journal of SMCBS'2009 International Workshop

Submitted: 2009-08-31 23:46
Revised:   2009-10-27 18:13