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Journal Name
study the influence of the nitro group on the binding affinity to
FPBA at pH 6.5 and pH 7.4, exhibiting similar EnF with small
molecules. The concentrations of diol moieties in polymer
chains were used to calculate binding constants. At pH 7.4 and
Ulman, A. Dyal, X. Yan, N.-L. Yang, C.DEOstI:o1u0r.1n0è3s9,/CL9. CFCo0u4r4n2e5sF,
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o
20 C, KP(NDMA-co-NIPAM)-FPBA (2830 M-1) is about 5 times higher
2
o
than KP(DMA-co-NIPAM)-FPBA (550 M-1). At pH 6.5 and 15 C below
LCST, KP(DMA-co-NIPAM)-FPBA (90 M-1) and KP(NDMA-co-NIPAM)-FPBA (2120
M-1) reflect a more than 20 times higher binding ability to
FPBA of P(NDMA-co-NIPAM)-5% (Table S4, ESI†). The lower
binding ability of polymers to FPBA, compared to catechol and
4-nitrocatechol, might be due to the steric hindrance and
lower accessibility to the diol functionalities.1i
In conclusion, we have successfully demonstrated a
strategy to prepare nitrocatecholic random copolymers using
radical polymerization of vinyl monomer with protected
catechol moieties, followed by nitration, thus circumventing
the adverse side reactions, including chain transfer, inhibition
and crosslink. The enhancement of the binding affinity toward
Fe3O4 NPs due to the incorporation of the nitro group was
assessed through competitive binding by two copolymers
originating from the same parent copolymer with only the
nitro group difference. Upon the introduction of the nitro
group to the copolymers, a remarkable enhancement of
binding affinity was obtained: a factor of 40 and 20 toward
Fe3O4 NPs and a small boronic acid, FPBA. This versatile
strategy can contribute to the synthesis of ultra-strong
nitrocatecholic adhesives containing a broad range of counits
stable toward nitration procedure.
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8
We thank CUNY research foundation (RF 68464-0046 and
66617-0044) for financial support and the access to TEM of
Advanced Imaging Facility at CSI.
9
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Notes and references
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