A Modular Approach Towards Fluorescent pH and Ascorbic Acid Probes Based on Ring‐Opening Metathesis Polymerization

Abstract

Copolymerization represents a modular synthetic strategy toward optochemical sensors by disassembling small molecule probes and recombining them to screen various fluorophore‐quencher combinations, instead of synthesizing individual sensor molecules. To demonstrate this, a polymerizable, fluorescent 1,6,7,12‐tetrachloroperylene‐3,4:9,10‐bis(dicarboximide) derivative with a norbornene ester side chain is prepared and copolymerized with a tertiary‐amine‐bearing monomer, as well as an oligo‐glycol‐bearing monomer, via ring‐opening metathesis polymerization (ROMP). In this manner, water‐soluble optical pH sensor polymers (with apparent pka values of 6.4–7) are obtained. The effect of the macromolecular architecture on the sensing performance is evaluated, whereby a diblock copolymer structure made of an oligoglycol segment and a segment containing the secondary amine and the fluorescent moiety is identified as being most favorable for pH sensing. Similarly, profluorescent polymers are obtained by employing nitroxides instead of secondary amines, which allows detection of ascorbic acid (with a detection limit of 0.1 × 10−3m) in water.

Dye-functionalized polymers via ring opening metathesis polymerization: principal routes and applications

“…Adapted with permission from [29]. Copyright (2011) American Chemical Society molar ratios so that tailor-made block copolymers can be achieved easily [21,[40][41][42][43][44][45][46][47]. In addition to the tailored design of highly specific materials for bioimaging and visualization of tumor cells, even unspecifically labelled, self-assembled nanoparticles can be applied for e.g.…”

“…Furthermore, oligo(ethylenglycol)-functionalized norbornenes could be incorporated to render the resulting copolymers water-soluble. A key requirement is that the two functionalities are brought in proximity to each other, which was demonstrated by comparison of a blend system, random copolymers and block copolymers containing a perylene-based chromophore and trialkylamine and nitroxyl quenchers [21].…”

“…[2.2.1]Bicyclohept-5-enederivatives (norbornenes) are the most common monomers in ROMP, as a huge variety of different monomers can be [15][16][17], pentacene [18], tetracene [18] Anthracene [15,17], pyrene [19], benzothienobenzothiophene [20] --Anthracene [74] Fluorene [90] (Hetero)cycles Perylene bisimides [21][22][23][24], hexabenzocoronene [25][26][27], quinolone [26], pyrene [29] Phenanthroimidazole [30,31] perylene bisimides [21], quinizarine [32], phenoxynaphthacene [33] Perylene bisimides [21] Phenanthroimidazole [11], perylene bisimides [8], pyrene [9] Coumarin [79] Benzoxazole [81] Benzoxazole [76,90] a Triphenylmethane dyes (Dichloro)fluorescein [40], eosin [40] Eosin [41] Oregon Green 488 [42], rhodamin B [43], rhodamin [44], fluorescein [44], eosin [45][46][47] Fluorescein [10] Rhodamin, [10,…”

“…A wide range of suitable monomers has been copolymerized comprising (hetero)polyaromatic compounds [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33], and more sophisticated functionalities like conjugated oligomers [34][35][36][37][38][39], triphenylmethane [40][41][42][43][44][45][46][47], azo [48][49][50][51][52], or polymethine [53][54][55][56][57] dyes. Even transition metal coordination compounds of aluminum [58,59], iron [60], zinc [61][62][63], ruthenium [64, 65], europium …”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…67) [308], perfluoroalkyl chains [309], polyethylene chains [310], polypropylene chains [311], groups capable of initiating a free radical polymerization (e.g. 70) [312], radical scavenger groups [313], rhodamines and a peptide chain [314], a photoswitchable nucleus [315], a perylene nucleus [316], graphene oxide [317], and a cobalt diene complex (e.g. 74) [318]; (7) a tris(norbornenecarboxylate) connected to a carbon nanotube [319]; (8) bis(norbornenecarboxylate ester)s (e.g.…”