Star‐shaped fluorescent polypeptides

Abstract

Two series of novel, four-arm, star-shaped polypeptides were prepared via the ring-opening polymerization of ␥-benzyl-L-glutamate N-carboxyanhydride and ⑀-benzyloxycarbonyl-L-lysine N-carboxyanhydride with a tetra-amino-substituted perylene fluorophore as the initiator. The removal of the ␣-amino acid side-chainprotecting groups resulted in unprecedented water-soluble, perylene-functionalized, star-shaped polypeptides that showed strong fluorescence in aqueous solution. One of the features that distinguished these water-soluble star polypeptides from most other star polymers was that the conformation of the arms could be reversibly changed from a random coil into an ␣ helix by variations in the pH of the aqueous solution. These star polypeptides might be of interest for the development of novel fluorescent probes or as traceable, stimuli-sensitive molecular containers.

Polypeptide und 100 Jahre Chemie der α‐Aminosäure‐N‐carboxyanhydride

“…[177][178][179] Eine andere Klasse ungewöhnlicher Copolypeptide wurde durch Natrium-tert-butoxid-katalysierte Copolymerisation von N e -Z-Lys-NCA und O,O'-Bis-Z-l-Dopa realisiert (Dopa = 3,4-Dihydroxy-l-phenylalanin). [184][185][186] Die erstgenannte Synthesestrategie wurde von drei Arbeitsgruppen angewendet, [187][188][189][190] wobei b-Bzl-l-Asp-NCA und g-Bzl-l-Glu-NCA als Monomere eingesetzt wurden. So wurden neunarmige Sternpolymere aus dem mit NH 2 -Gruppen versehenen Sternzentrum 68 hergestellt.…”

Peptide-Based Polymer Therapeutics

“…For example, Klok et al [193] used perylene derivatives with four primary amine groups as initiators to lead 4-arm PBLG and PZLL and Inoue et al [194,195] used hexafunctional initiators for the synthesis of 6-arm PBLG star polymers both taking profit of the NCA polymerisation techniques. Other examples are provided from the work of Aliferis et al [196] who used 2-(aminomethyl)-2-methyl-1,3-propanediamine as a trifunctional initiator for the synthesis of P(BLL-b-BLG) 3 3-arm star-block co-polypeptides; or the studies of Karatzas et al [197] in the synthesis of 4-arm (PEO-b-PBLG)4 hybrid star block co-polymers using four-arm PEO stars end-functionalised with primary amines as initiators for the polymerisation of BLG-NCA among others.…”

Water soluble fluorescent-magnetic perylenediimide-containing maghemite-nanoparticles for bimodal MRI/OI imaging

“…PDI-1 was prepared as described elsewhere [23]. On the other hand, the synthesis of PDI-2 starts with the substitution on the N, N′-bis-(2,6-diisopropylphenyl)-1,6,7,12-tetrachloroperylene-3,4:9, 10-tetracarboxydiimide [27] with 4-prop-2-ynyloxyphenol to obtain the tetraalkynyl substituted 3. Click reaction of the latter with 6-azido-6-deoxy-1,2:3,4-di-o-isopropylidene-α-D-galactopyranose [28] yields compound 4, which after acetal deprotection with TFA affords PDI-2 in moderate yield (Scheme 1).…”