Final published version
Research output: Contribution to Journal/Magazine › Journal article › peer-review
Research output: Contribution to Journal/Magazine › Journal article › peer-review
}
TY - JOUR
T1 - One-Step Covalent Immobilization of β-Cyclodextrin on sp2 Carbon Surfaces for Selective Trace Amount Probing of Guests
AU - Li, Z.
AU - Van Guyse, J.F.R.
AU - R. de la Rosa, V.
AU - Van Gorp, H.
AU - Walke, P.
AU - González, M.C.R.
AU - Uji-i, H.
AU - Hoogenboom, R.
AU - De Feyter, S.
AU - Mertens, S.F.L.
PY - 2019/9/3
Y1 - 2019/9/3
N2 - The modification of solid surfaces with supramolecular hosts is a powerful method to tailor interfacial properties and confer chemical selectivity, but often involves multistep protocols that hinder facile upscaling. Here, the one-step covalent modification of highly oriented pyrolytic graphite (HOPG) with a β-cyclodextrin (β-CD) derivative, which efficiently forms inclusion complexes with hydrophobic guests of suitable size, is demonstrated. The grafted β-CD-HOPG surface is investigated toward electrochemical detection of ferrocene and dopamine. The enrichment of the analytes at the electrode surface, through inclusion in β-CD, leads to an enhanced electrochemical response and an improved detection limit. Furthermore, the modified β-CD-HOPG electrode discriminates analytes that form host–guest complexes with β-CD against a 100-fold higher background of electroactive substances that do not. Atomic force microscopy, scanning tunneling microscopy, and Raman spectroscopy confirm the covalent nature of the modification and reveal high stability toward solvent rinsing, ultrasonication, and temperatures up to 140 °C. The one-step covalent modification therefore holds substantial promise for the routine production of inexpensive, yet robust and highly performant electrochemical sensors. Beyond electrochemical sensor development, our strategy is valuable to prepare materials where accurate spatial positioning of functional units and efficient current collection are crucial, e.g. in photoelectrodes or electrocatalysts.
AB - The modification of solid surfaces with supramolecular hosts is a powerful method to tailor interfacial properties and confer chemical selectivity, but often involves multistep protocols that hinder facile upscaling. Here, the one-step covalent modification of highly oriented pyrolytic graphite (HOPG) with a β-cyclodextrin (β-CD) derivative, which efficiently forms inclusion complexes with hydrophobic guests of suitable size, is demonstrated. The grafted β-CD-HOPG surface is investigated toward electrochemical detection of ferrocene and dopamine. The enrichment of the analytes at the electrode surface, through inclusion in β-CD, leads to an enhanced electrochemical response and an improved detection limit. Furthermore, the modified β-CD-HOPG electrode discriminates analytes that form host–guest complexes with β-CD against a 100-fold higher background of electroactive substances that do not. Atomic force microscopy, scanning tunneling microscopy, and Raman spectroscopy confirm the covalent nature of the modification and reveal high stability toward solvent rinsing, ultrasonication, and temperatures up to 140 °C. The one-step covalent modification therefore holds substantial promise for the routine production of inexpensive, yet robust and highly performant electrochemical sensors. Beyond electrochemical sensor development, our strategy is valuable to prepare materials where accurate spatial positioning of functional units and efficient current collection are crucial, e.g. in photoelectrodes or electrocatalysts.
KW - carbonaceous materials
KW - cyclodextrins
KW - electrodes
KW - grafting
KW - surface modification
KW - van der Waals solids
KW - Amines
KW - Atomic force microscopy
KW - Carbon
KW - Chemical detection
KW - Chemical modification
KW - Cyclodextrins
KW - Electrocatalysts
KW - Electrochemical electrodes
KW - Electrodes
KW - Grafting (chemical)
KW - Iron compounds
KW - Organometallics
KW - Scanning tunneling microscopy
KW - Surface treatment
KW - Van der Waals forces
KW - Carbonaceous materials
KW - Covalent immobilization
KW - Covalent modifications
KW - ELectrochemical detection
KW - Electrochemical response
KW - Highly oriented pyrolytic graphite
KW - Interfacial property
KW - Van der waals
KW - Electrochemical sensors
U2 - 10.1002/adfm.201901488
DO - 10.1002/adfm.201901488
M3 - Journal article
VL - 29
JO - Advanced Functional Materials
JF - Advanced Functional Materials
SN - 1616-301X
IS - 36
M1 - 1901488
ER -