Polymers featuring photolabile groups are the subject of intense research because they allow the alteration of polymer properties simply by irradiation. In particular, the o-nitrobenzyl group (o-NB) is utilized frequently in polymer and materials science. This Perspective pays particular attention to the increasing utilization of this chemical group in polymer chemistry. It covers the use of (i) o-NB-based cross-linkers for photodegradable hydrogels, (ii) o-NB side chain functionalization in (block) copolymers, (iii) o-NB side chain functionalization for thin film patterning, (iv) o-NB for self-assembled monolayers, (v) photocleavable block copolymers, and (vi) photocleavable bioconjugates. We conclude with an outlook on new research directions in this rapidly expanding area.
Poly(styrene-block-ethylene oxide) with an o-nitrobenzyl ester photocleavable junction (PS-hν-PEO) was synthesized by a combined RAFT polymerization and “click chemistry“ approach and represents the first report utilizing this method for the synthesis of photocleavable block copolymers. After solvent annealing, highly ordered thin films were prepared from PS-hν-PEO. Following a very mild UV exposure and successive washing with water, PS-hν-PEO thin films were transformed into highly ordered nanoporous thin PS films with pore diameters of 15–20 nm and long range ordering (over 2 μm × 2 μm). Afterwards the pores were filled with PDMS by spin-coating in combination with capillary forces. After treatment with oxygen plasma to remove the PS templates, highly ordered arrays of silica nanodots were obtained. This represents the first template application example from highly ordered nanoporous thin films derived from block copolymers featuring a photocleavable junction.
A series of poly(pentafluorophenyl (methyl)acrylates)-block-poly-(ethylene oxide) with o-nitrobenzyl ester photocleavable junctions (PPFP(M)A-hv-PEO) were synthesized by RAFT polymerization. The block copolymers were used to fabricate thin films and fibers by spin-coating and electrospinning, respectively. After solvent annealing, UV exposure, and washing with methanol/water to remove the minor PEO block, nanoporous structures were obtained. Both the porous thin films and fibers remained reactive to amine substitution of the pentafluorophenyl esters under mild conditions, which was confirmed by XPS, fluorescence confocal microscopy, FT-IR, and contact angle measurements.
Two novel triptycene quinoxaline cavitands (DiTriptyQxCav and MonoTriptyQxCav) have been designed, synthesized, and applied in the supramolecular detection of benzene, toluene, ethylbenzene, and xylenes (BTEX) in air. The complexation properties of the two cavitands towards aromatics in the solid state are strengthened by the presence of the triptycene moieties at the upper rim of the tetraquinoxaline walls, promoting the confinement of the aromatic hydrocarbons within the cavity. The two cavitands were used as fiber coatings for solid-phase microextraction (SPME) BTEX monitoring in air. The best performances in terms of enrichment factors, selectivity, and LOD (limit of detection) values were obtained by using the DiTriptyQxCav coating. The corresponding SPME fiber was successfully tested under real urban monitoring conditions, outperforming the commercial divinylbenzene-Carboxen-polydimethylsiloxane (DVB-CAR-PDMS) fiber in BTEX adsorption.
An integrated cellulose polymer concentrator/single-walled carbon nanotube (SWCNT) sensing system is demonstrated to detect benzene, toluene, and xylenes (BTX) vapors. The sensing system consists of functionalized cellulose as a selective concentrator disposed directly on top of a conductive SWCNT sensing layer. Functionalized cellulose concentrator (top layer) selectively adsorbs the target analyte and delivers the concentrated analyte as near as possible to the SWCNT sensing layer (bottom layer), which enables the simultaneous concentrating and sensing within a few seconds. The selectivity can be achieved by functionalizing cellulose acetate with a pentafluorophenylacetyl selector that interacts strongly with the target BTX analytes. A new design of the integrated cellulose concentrator/SWCNT sensing system allows high sensitivity with limits of detection for benzene, toluene, and m-xylene vapors of 55 ppm, 19 ppm, and 14 ppm, respectively, selectivity, and fast responses (<10 s to reach equilibrium), exhibiting the potential ability for on-site, real-time sensing applications. The sensing mechanism involves the selective adsorption of analytes in the concentrator film, which in turn mediates changes in the electronic potentials at the polymer-SWCNT interface and potentially changes in the tunneling barriers between nanotubes.
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