“Click” access to multilayer functionalized Au surface: A terpyridine patterning example

• Published in: Materials Science & Engineering C Vol. 75; pp. 1343 - 1350
• Main Authors: Martin, Flavia A., Marconi, Daniel, Neamtu, Silvia, Radu, Teodora, Florescu, Monica, Turcu, Rodica, Lar, Claudia, Hădade, Niculina D., Grosu, Ion, Turcu, Ioan
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier B.V 01-06-2017; Elsevier BV
• Subjects: Azides (organic); Catalysts; Chemical bonds; Chemical compounds; Chemical reactions; Click Chemistry - methods; Coated Materials, Biocompatible - chemistry; Covalently bonded SAMs; DPN patterning; Fabrication; Fe(II) bis-terpyridine complex; Gold; Gold - chemistry; Iron; Iron - chemistry; Materials science; Microscopy, Atomic Force; Molecular interactions; Monolayers; Multilayered deposition; Patterning; Pyridines - chemistry; Self-assembled monolayers; SPAAC; Surface Properties; Topology; SPAAC; DPN patterning; Covalently bonded SAMs; Fe(II) bis-terpyridine complex; Multilayered deposition
• ISSN: 0928-4931; 1873-0191
• DOI: 10.1016/j.msec.2017.03.033

This work is focused on self-assembled monolayers (SAMs) fabrication, using two types of Au surfaces, by subsequent attachment of different layers in order to develop a stable platform consisting of covalent multilayer functionalized gold surfaces. The key step in the construction of SAMs is the covalent linkage to the gold surface, via an amino-thiol derivative, of a cyclooctyne unit exhibiting strained triple bonds which react fast (catalysts are not needed) and quantitatively with organic azides and enable the introduction of various chemical functionalized entities on the gold surface. The versatility of the system is demonstrated by the reaction of the cyclooctyne decorated gold surface with an azide functionalized terpyridine followed by step by step complexation with Fe(II) and another terpyridine unit resulting into a multilayer covered gold surface. The Au surfaces were characterized by XPS to determine the chemical composition of the resulting SAMs. SPR was applied for real-time monitoring of the molecular interactions that occurred on the Au surface for each deposited layer. DPN was used to direct pattern the terpyridine-ink on a pre-functionalized AuIDE electrode. The AFM topology resulted from DPN and PEIS demonstrated metal-coordinating ligand of Fe(II)-Terpy.
•construction of a stable platform consisting of covalent multilayer functionalized gold surfaces;•reaction of the cyclooctyne decorated gold surface with an azide functionalized terpyridine;•Dip-Pen Nanolithography direct patterning with terpyridine-ink on a prefunctionalized gold electrode.