Combining Click Sulfur(VI)‐Fluoride Exchange with Photoiniferters: A Facile, Fast, and Efficient Strategy for Postpolymerization Modification

Wang, Peixi; Dong, Yishi; Lü, Xin; Wu, Zhaoqiang; Chen, Hong

doi:10.1002/marc.201700523

Cited by 18 publications

(13 citation statements)

References 38 publications

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“…The binary Y-photoinitiator is synthesized in two steps (Scheme ): first, ester condensation of S -(carboxypropyl)- N , N -diethyldithiocarbamic acid (CNDDA) with 2-(2-bromoisobutyrylamido) propane-1,3-diol (BPDL); second, condensation of 3,4-dihydroxyhydrocinnamic acid with the product of step 1. In Scheme , the green color highlights the visible-light initiator moiety, , the red, the photoiniferter moiety, , and the blue, the catechol moiety used to attach the initiator to the solid substrate. The molecular structure of Y-photoinitiator was confirmed using 1 H and 13 C NMR spectra, MS, and FT-IR spectrum.…”

Section: Resultsmentioning

confidence: 99%

Design, Synthesis, and Application of a Difunctional Y-Shaped Surface-Tethered Photoinitiator

et al. 2019

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Mixed homopolymer brushes have unique interfacial properties that can be exploited for both fundamental studies and applications in technology. Herein, the synthesis of a new catechol-based biomimetic Y-shaped binary photoinitiator (Y-photoinitiator) and its applications for surface modification with polymer brushes through both “grafting to” and “grafting from” strategies are reported. The “leg” of the Y consists of a catechol group as surface anchoring moiety. The arms are photoinitiator moieties that can be “addressed” independent of each other by radiation of different wavelengths. Using ultraviolet and visible light successively, each arm of the Y-photoinitiator was activated, thereby allowing the synthesis of Y-shaped block copolymer brushes with dissimilar polymer chains. The suitability of the Y-photoinitiator for surface modification was first investigated using N-vinylpyrrolidone and styrene as the model monomers for successive UV-photoiniferter-mediated polymerization and visible-light-induced polymerization, respectively. Switching of the wetting properties of the Y-shaped block copolymer brush poly(N-vinylpyrrolidone)-block-poly(styrene) (PVP-b-PS)-grafted surfaces by contact with different solvents was also investigated. To further exploit this novel Y-photoinitiator for the preparation of functional interfaces, Y-shaped block copolymer brushes poly(1-(2-methacryloyloxyhexyl)-3-methylimidazolium bromide)-block-poly(N-vinylpyrrolidone-co-glycidyl methacrylate) (PIL(Br)-b-P(NVP-co-GMA)) were also prepared and subsequently functionalized with the cell-adhesive arginine–glycine–aspartic acid (RGD) peptides by reaction with the glycidyl groups (PILPNG-RGD). The PILPNG-RGD grafted surfaces showed excellent cell-adhesive, bacteriostatic, and bactericidal properties. Thus, it can be concluded that further exploitation of this novel Y-photoinitiator for graft polymerization should allow the preparation of a wide range of functional interfaces with tailored properties.

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Section: Resultsmentioning

confidence: 99%

Design, Synthesis, and Application of a Difunctional Y-Shaped Surface-Tethered Photoinitiator

et al. 2019

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“…This reaction has already demonstrated its potential in polycondensation and side chain modification [ 85 , 86 , 87 , 88 ]. Only recently, the SuFEx chemistry was applied to block copolymer synthesis with the assistance of newly developed RAFT agents III and IV ( Figure 3 ) [ 89 , 90 ]. These RAFT agents are versatile to the polymerization of a number of monomers, e.g., methyl methacrylate, styrene, tert-butyl acrylate, and 4-acrylomorpholine.…”

Section: R/z Group Approachmentioning

confidence: 99%

RAFT-Based Polymers for Click Reactions

Черникова

Kudryavtsev

2022

Polymers

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The parallel development of reversible deactivation radical polymerization and click reaction concepts significantly enriches the toolbox of synthetic polymer chemistry. The synergistic effect of combining these approaches manifests itself in a growth of interest to the design of well-defined functional polymers and their controlled conjugation with biomolecules, drugs, and inorganic surfaces. In this review, we discuss the results obtained with reversible addition–fragmentation chain transfer (RAFT) polymerization and different types of click reactions on low- and high-molar-mass reactants. Our classification of literature sources is based on the typical structure of macromolecules produced by the RAFT technique. The review addresses click reactions, immediate or preceded by a modification of another type, on the leaving and stabilizing groups inherited by a growing macromolecule from the chain transfer agent, as well as on the side groups coming from monomers entering the polymerization process. Architecture and self-assembling properties of the resulting polymers are briefly discussed with regard to their potential functional applications, which include drug delivery, protein recognition, anti-fouling and anti-corrosion coatings, the compatibilization of polymer blends, the modification of fillers to increase their dispersibility in polymer matrices, etc.

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“…SuFEx is a "click" reaction between a sulfonyl fluoride (-SO 2 F) or fluorosulfate (-OSO 2 F) group and a silyl ether. [29,38,39] Since PEG has been widely used in a range of biological applications, such as drug delivery [40] and surface modification of biological materials, [41] the postpolymerization modification ability was investigated by attaching PEG to the chain ends of the prepared polymers. Then, the SuFEx click reaction between TBDMS-PEG (M n = 2000 g mol −1 ) and PDMA (M n = 8200 g mol −1 ) as a model sulfonyl fluoride end-functionalized polymer was conducted.…”

Section: Sufex Click Reaction For Postpolymerization Modificationmentioning

confidence: 99%

Oxygen‐Demanding Photocontrolled RAFT Polymerization Under Ambient Conditions

Peng

Liu

Wang

et al. 2022

Macromol. Rapid Commun.

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A photocontrolled reversible addition−fragmentation chain transfer (RAFT) process is developed by initiating polymerization through a 1,3‐diaminopropane‐triethylborane (DAPTB)−diphenyl iodonium salt (Ph2I+) complex (DAPTB/Ph2I+) under ambient temperature and atmospheric conditions. Upon demand, this air‐stable DAPTB/Ph2I+ complex is photolyzed to liberate a reactive triethylborane that consumes atmospheric oxygen and generates ethyl radicals, which initiate and mediate RAFT polymerization. Controlled RAFT polymerization is thus achieved without any prior deoxygenation using a novel RAFT chain transfer agent, BP‐FSBC, which contains both benzophenone and sulfonyl fluoride moieties. Furthermore, the kinetics of polymerization reveal that the reaction process is rapid, and well‐defined polymers are produced by a 61% conversion of 2‐hydroxyethyl acrylate (HEA) within 7 min and 77% conversion of N,N‐dimethylacrylamide (DMA) within 10.5 min. The temporal and spatial control of this photopolymerization is also demonstrated by an “on/off” switch of UV irradiation and a painting‐on‐a‐surface approach, respectively. In addition, active chain ends are demonstrated by preparing block copolymers by chain extension and click sulfur(VI)‐fluoride exchange postreaction using RAFT‐derived macrochain transfer agents.

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Combining Click Sulfur(VI)‐Fluoride Exchange with Photoiniferters: A Facile, Fast, and Efficient Strategy for Postpolymerization Modification

Cited by 18 publications

References 38 publications

Design, Synthesis, and Application of a Difunctional Y-Shaped Surface-Tethered Photoinitiator

Design, Synthesis, and Application of a Difunctional Y-Shaped Surface-Tethered Photoinitiator

RAFT-Based Polymers for Click Reactions

Oxygen‐Demanding Photocontrolled RAFT Polymerization Under Ambient Conditions

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