New enzymatically polymerized copolymers from 4-tert-butylphenol and 4-ferrocenylphenol and their modification and inclusion complexes with β-cyclodextrin

Abstract

SummaryThe enzymatically catalyzed synthesis of a copolymer of 4-tert-butylphenol and 4-ferrocenylphenol by horse radish peroxidase (HRP) in the presence of H2O2 in a 1,4-dioxane/water system is described. Furthermore, polymer-analogous alkylation of the free hydroxy groups and subsequent click reaction with mono-6-azido-6-desoxy-β-cyclodextrin (N3-β-CD) was carried out. The formation of inter- and intramolecular inclusion complexes was investigated by DLS measurement.

Enzymes as Green Catalysts for Precision Macromolecular Synthesis

“…An urushiol analogue, an unsaturated higher alkyl group-containing phenolic monomer, was subjected to an oxidative polymerization by HRP or Fe-salen (a model complex of peroxidase) to produce a soluble prepolymer, which was further cured thermally or by a cobalt catalyst to yield the cross-linked film (artificial urushi, see also section ) with a high gloss surface . HRP-catalyzed copolymerization of 4- tert -butylphenol and 4-ferrocenylphenol in an aqueous 1,4-dioxane produced the corresponding copolymer, which was further modified for preparation of inclusion complexes with β-cyclodextrin …”

“…152 HRP-catalyzed copolymerization of 4-tert-butylphenol and 4-ferrocenylphenol in an aqueous 1,4-dioxane produced the corresponding copolymer, which was further modified for preparation of inclusion complexes with βcyclodextrin. 153 Schiff bases containing a phenol group, 4-(benzylideneamino)-phenol and 4-[(anthracen-9-ylmethylene)-amino]-phenol, were polymerized by HRP in a mixture of 1,4-dioxane and phosphate buffer. 154 Large red shift was observed for the polymer from the latter, suggesting the increase of the conjugation length.…”

Self-Assembly of Amphiphilic Homopolymers Bearing Ferrocene and Carboxyl Functionalities: Effect of Polymer Concentration, β-Cyclodextrin, and Length of Alkyl Linker

“…Winnik and Manner have prepared a variety of well-defined cylinder micelles and comicelles through the “crystalline-driven self-assembly” of polyferrocenylsilane-based copolymers, in which the excellent crystallization property of ferrocene-based repeating unit was a crucial parameter for micellar morphologies. − In addition, the ferrocene group can form a 1:1 stable adduct with β-CD in aqueous solution, which are oligosaccharides composed of seven d -glucopyranose residues attached by α-1,4-linkages in a cyclic array. , The fundamental driving force of inclusion complexation of β-CD with ferrocene group is the hydrophobic interaction, which pushes the hydrophobic ferrocene group into the hydrophobic internal cavity of β-CD. , Because the exterior of β-CD is highly polar due to the presence of hydroxyls, the complex of β-CD with ferrocene group is hydrophilic. Thus, the incorporation of β-CD into a ferrocene-containing polymer will significantly change the “water solubility” of the polymer, which could be employed to tune the solubility and self-assembly of ferrocene-containing polymers. − Given these aforementioned attractive properties of ferrocene group, the ferrocene group is chosen as a hydrophobic building block for constructing amphiphilic homopolymer in the current work. Moreover, carboxyl is chosen as the hydrophilic building block since it render the formed aggregates able to introduce biomacromolecules, fluorescent label molecules, drugs, or inorganic nanoparticles via electrostatic interaction or 1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC) chemistry. ,, …”

Oligomeric epoxide–amine adducts based on 2-amino-N-isopropylacetamide and α-amino-ε-caprolactam: Solubility in presence of cyclodextrin and curing properties

“…Explanation for this can be steric effects, since the isopropyl group in our system 9 is placed not so close at the backbone as in PNIPAM. For further confirmation of these findings, the solution of 9 with RAMEB-CD was treated with potassium 1-adamantylcarboxylate (AdCOO − K + ) in some excess, which should displace 9 from RAMEB-CD due to its high complexation properties [ 6 , 24 – 25 ]. As predicted, the cloud point shifted back to the initial temperature of about 27 °C.…”