Mussel-inspired thermoresponsive polymers with a tunable LCST by Cu(0)-LRP for the construction of smart TiO₂ nanocomposites

Abstract

Thermoresponsive polymers with different microstructures, a tunable LCST and terminal catechol anchors were synthesized by Cu(0)-LRP for the surface functionalization of TiO2 nanoparticles.

Programming Self-Assembly and Stimuli-Triggered Response of Hydrophilic Telechelic Polymers with Sequence-Encoded Hydrophobic Initiators

“…Such a kinetic behavior is consistent with a constant concentration of active species throughout the entire reaction, the absence of major side reactions, and consequently a well-controlled radical polymerization. Based on the successful synthesis of telechelic homopolymers, a random copolymerization of both monomers ([DEGA] 0 /[OEGA] 0 /[DI A/L ] 0 /[Me 6 -TREN] 0 = 40/7/1/0.2) was performed under similar conditions, aiming at building up a nontoxic thermoresponsive copolymer ATP3 with LCST close to body temperature. − The random copolymerization reached 90% after 2 h, as proven by 1 H NMR spectroscopy, and GPC analysis confirmed the presence of a monomodal copolymer distribution with M n GPC = 12.1 kDa and M w / M n = 1.23 (Table ). As expected, the 1 H NMR spectrum of ATP3 in CDCl 3 (Figure S3, lower spectrum), a good solvent for both the core unit and copolymer chains, showed characteristic peaks associated with the repeating unit structure, i.e., δ 13,18 = 4.2 ppm, and middle-chain initiator residue, i.e., δ 9,7 = 6.7 and 5.4 ppm.…”

Coating Titania Nanoparticles with Epoxy-Containing Catechol Polymers via Cu(0)-Living Radical Polymerization as Intelligent Enzyme Carriers

“…Herein Cu(0)-LRP was utilized for the synthesis of thermoresponsive polymer with terminal catechol anchor, which has shown well control over the molecular weight (MW) and MW distribution during the polymerization from unprotected dopamine-functionalized initiator (2bromo-N-(3,4-dihydro-xyphenethy)-2-methylpropanamide, DOPA-Br). 44,45 As shown in Scheme 1, GA was used as a co-monomer for the DOPA-Br-initiated copolymerization with NIPAM.…”

“…In the previous report, a "one-pot" strategy has been used for simultaneous polymerization and post modification in order to avoid the multi-step purification procedures. 45 It is hypothesized that this strategy may help to reduce the side reactions between the epoxy ring and catechol groups, mostly due to the high reactivity of catechol groups toward TiO2. Thus TiO2 nanoparticles were directly added into the system at the beginning of the reaction for one polymerization conducted showed that a conversion of 93% could be obtained after two hours.…”

“…[39][40][41][42][43] By using RAFT or Cu(0)-LRP to incorporate functional anchor groups such as phosphine or dopamine groups etc., well-defined polymers could be immobilized to the surface of iron oxide and titanium dioxide (TiO2) nanoparticles via "grafting to" strategy for specific properties including glycomimetic surface, tuned LCST and antimicrobial properties. [44][45][46][47] It is of great interest for scientists to merge the enzyme with inorganic catalysts and multiresponsive polymers to form an intelligent "multi-catalyst" system, which could be able to catalyze different reactions in "one-pot" or treat different challenges in complex practical application. [48][49][50][51][52] TiO2 is an important photocatalytic material and has been used for efficient water disinfection and degradation of certain organic pollutants.…”

Copolymerization of a Catechol and a Diamine as a Versatile Polydopamine-Like Platform for Surface Functionalization: The Case of a Hydrophobic Coating

“…Nonetheless, stable SAMs can only be obtained on certain substrates where the interaction between catechol and surface is strong enough for achieving a proper stabilization of the molecular monolayer. This is the case of some metal oxides, where a coordination bond is established [32,33,34]. If only weak interactions come into play, such as hydrogen bonding, electrostatic forces or π–π stacking, cooperativity between catechol moieties is essential for generating a stable thin film on the surface.…”