Photochemically Initiated Single Polymer Immobilization

Abstract

This Concept article surveys methods for attaching single polymer molecules on solid substrates. A general approach to single polymer immobilization based on the photochemistry of perfluorophenylazides is elaborated.

A comparison of charge transport behavior in functionalized and non-functionalized poly 3,4-(ethylenedioxythiophene) films

“…Quantum chemical calculations on aryl azide compounds by the same authors showed that upon irradiation, in the excited state, the N-N 2 bond strength is weakened which causes the elimination of the nitrogen from azide groups to form nitrene. In yet another report by Yan [25], it was shown that in perfluorophenyl azides, the fluorine substituents increase the lifetime of the singlet nitrenes and thus the pathway for covalent adduct formation is favored and insertion reaction yields are greatly enhanced. Thus previous reports on photochemical nitrene insertion [24][25][26][27] demonstrate that use of aryl nitrenes to produce secondary amines (as in FNAB with PEDOT here) is a direct and a convenient process, with large yields, as the only pre-requisite, the polymer must fulfill is the presence of unencumbered -CH groups, which PEDOT easily satisfies.…”

Engineering Nanomaterial Surfaces for Biomedical Applications

“…We have developed a photochemically initiated coupling chemistry that employs functionalized perfluorophenyl azides (PFPAs) to attach molecules and materials to solid substrate surfaces (86–88). Upon light activation, the azide moiety converts to a highly reactive nitrene that, notably, inserts into CH and NH bonds, creating highly robust covalent linkages.…”

Perfluorophenyl Azide Immobilization Chemistry for Single Molecule Force Spectroscopy of the Concanavalin A/Mannose Interaction

“…This PFPA photochemical method has indeed been popular for surface modification and introducing functional groups into fullerenes, proteins, polymers, as well as carbohydrates. 20 Following this approach, mannose and galactose immobilization on glass surfaces was achieved using PFPA-modified carbohydrates. Due to the high reactivity of PFPAs under UV irradiation, the surface modification chemistry described in this study is an effective alternative to other surface functionalization strategies (Figure 1).…”