We have developed novel surface plasmon
resonance (SPR) sensor
chips whose surfaces bear newly synthesized functional self-assembled
monolayer (SAM) anchoring lignin through covalent chemical bonds.
The SPR sensor chips are remarkably robust and suitable for repetitive
and accurate measurement of noncovalent lignin–peptide interactions,
which is of significant interest in the chemical or biochemical conversion
of renewable woody biomass to valuable chemical feedstocks. The lignin-anchored
SAMs were prepared for the first time by click chemistry based on
an azide–alkyne Huisgen cycloaddition: mixed SAMs are fabricated
on gold thin film using a mixture of alkynyl and methyl thioalkyloligo(ethylene
oxide) disulfides and then reacted with azidated milled wood lignins
to furnish the functional SAMs anchoring lignins covalently. The resulting
SAMs were characterized using infrared reflection–absorption,
Raman, and X-ray photoelectron spectroscopies to confirm covalent
immobilization of the lignins to the SAMs via triazole linkages and
also to reveal that the SAM formation induces a helical conformation
of the ethylene oxide chains. Further, SPR measurements of the noncovalent
lignin–peptide interactions using lignin-binding peptides have
demonstrated high reproducibility and durability of the prepared lignin-anchored
sensor chips.