Biofunctionalization on Alkylated Silicon Substrate Surfaces
A R T I C L E S
binding, the silicon substrates are commonly modified with
organosiloxane films presenting oligo- or poly(ethylene glycol)
(OEG or PEG) on the oxide surface of the substrates.14
However, the protein resistance and stability of these films are
not satisfactory, probably due to the relatively low packing
density of the films and the high density of defects resulting
from the interaction of silanols with the hydrophilic OEG
chains.14,15 We and others have developed monolayers present-
ing OEG, which are directly bound on nonoxidized silicon
substrates via Si-C bonds.7,9,16-19 Formation of the Si-C bonds
is via surface hydrosilylation on hydrogen-terminated silicon
surfaces20-22 using OEG-terminated alkenes, such as 1 in
Scheme 1.9,17–19,23 Our OEG-terminated monolayers are highly
protein resistant and stable in phosphate-buffered saline (PBS).19
Herein, we describe the development of a monolayer platform
presenting OEG-alkyne on silicon substrates that allows
efficient bioconjugation using copper-catalyzed azide-alkyne
1,3-dipolar cycloaddition (CuAAC, a “click” reaction).24-26
Among a variety of reactions for biofunctionalization on
surfaces,10,27 CuAAC reaction is specific and bioorthogonal and
can be performed under physiological conditions.25,26,28 It has
been used on a wide variety of substrates.4,29-32 To use CuAAC
reaction on alkylated silicon substrates, we need to incorporate
either azido or alkynyl groups on the surface. Azido-presenting
monolayers on silicon were prepared from H-Si surfaces
through two steps: chlorination33 or hydrosilylation with Br-
terminated alkenes34 followed by substitution with NaN3. Direct
attachment of N3-alkenes onto H-Si surfaces by hydrosilylation
has not been reported and failed in our attempts, likely because
the azido groups readily decompose during photo or thermally
activated hydrosilylation via a highly reactive nitrenen inter-
mediate.35
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