Nitro-functionality, with a large deficit of negative
charge, embraces
biological importance and has proven its therapeutic essence even
in chemotherapy. Functionally, with its strong electron-withdrawing
capability, nitro can manipulate the electron density of organic moieties
and regulates cellular-biochemical reactions. However, the chemistry
of nitro-functionality to introduce physiologically relevant macroscopic
properties from the molecular skeleton is unknown. Therefore, herein,
a neurotransmitter moiety, dopamine, was chemically modified with
a nitro-group to explore its influence on synthesizing a multifunctional
biomaterial for therapeutic applications. Chemically, while the nitro-group
perturbed the aromatic electron density of nitrocatecholic domain,
it facilitated the suturing of nitrocatechol moieties to regain its
aromaticity through a radical transfer mechanism, forming a novel
macromolecular structure. Incorporation of the sutured-nitrocatecholic
strand (S-nCAT) in a gelatin-based hydrogel introduced an electroconductive
microenvironment through the delocalization of Ï-electrons in
S-nCAT, while maintaining its catechol-mediated adhesive property
for tissue repairing/sealing. Meanwhile, the engineered hydrogel enriched
with noncovalent interactions, demonstrated excellent mechano-physical
properties to support tissue functions. Cytocompatibility of the bioadhesive
was assessed with in vitro and in vivo studies, confirming its potential usage for biomedical applications.
In conclusion, this novel chemical approach enabled designing a multifunctional
biomaterial by manipulating the electronic properties of small bioactive
molecules for various biomedical applications.