An efficient metal‐free homodifunctional bimolecular ring‐closure method is developed for the formation of cyclic polymers by combining reversible addition‐fragmentation chain transfer (RAFT) polymerization and self‐accelerating click reaction. In this approach, α,ω‐homodifunctional linear polymers with azide terminals are prepared by RAFT polymerization and postmodification of polymer chain end groups. By virtue of sym‐dibenzo‐1,5‐cyclooctadiene‐3,7‐diyne (DBA) as small linkers, well‐defined cyclic polymers are then prepared using the self‐accelerating double strain‐promoted azide–alkyne click (DSPAAC) reaction to ring‐close the azide end‐functionalized homodifunctional linear polymer precursors. Due to the self‐accelerating property of DSPAAC ring‐closing reaction, this novel method eliminates the requirement of equimolar amounts of telechelic polymers and small linkers in traditional bimolecular ring‐closure methods. It facilitates this method to efficiently and conveniently produce varied pure cyclic polymers by employing an excess molar amount of DBA small linkers.
The transition‐metal catalyzed and metal‐free click polymerizations have been developed as powerful tools for the construction of functional polymers with linear and hyperbranched structures. The latter provides a thorough solution for the completely removing metallic residues from the products encountered in the former. Compared to the activated alkyne–azide metal‐free click polymerization, the activated azide–alkyne one is rarely studied. In this Communication, a perfluorophenyl‐activated azide of hexane‐1,6‐diyl‐bis(4‐azido‐2,3,5,6‐tetrafluorobenzoate) is rationally designed and facilely prepared. Through systematical optimization of the reaction conditions, an efficient metal‐free perfluorophenylazide–alkyne polycycloaddition is established, and polytriazoles with high molecular weights (up to 166 000) and excellent solubility are obtained in excellent yields (up to 93%) under mild reaction conditions. Interestingly, the regioselectivity of the reaction could be fine‐tuned by the solvents and diyne monomers. Therefore, this work provides not only a powerful tool for the preparation of functional polytriazoles, but also an attractive method for fine‐tuning their regioregularity.
An alkyne‐functionalized ruthenium(II) bis‐terpyridine complex is directly copolymerized with phenylacetylene by alkyne polymerization. The polymer is characterized by size‐exclusion chromatography (SEC), 1H NMR spectroscopy, cyclic voltammetry (CV) measurements, and thermal analysis. The photophysical properties of the polymer are studied by UV–vis absorption spectroscopy. In addition, spectro‐electrochemical measurements are carried out. Time‐resolved luminescence lifetime decay curves show an enhanced lifetime of the metal complex attached to the conjugated polymer backbone compared with the Ru(tpy)22+ model complex.
A novel route for the synthesis of poly(ethylene glycol)‐b‐polystyrene copolymer, starting from commercially available poly(ethylene glycol) methyl ether and azido terminated polystyrene prepared by atom transfer radical polymerization and subsequent nucleophilic substitution, is applied with simplicity and high efficiency. The combination of photoinduced copper (I)‐catalyzed alkyne‐azide cycloaddition (CuAAC) and ketene chemistry reactions proceeds either simultaneously or sequentially in a one‐pot procedure under near‐visible light irradiation. In both cases, excellent block copolymer formations are achieved, with an average molecular weight of around 7000 g mo1−1 and a polydispersity index of 1.20.
An ultraviolet (UV)‐cleavable bottlebrush polymer is synthesized using the “grafting‐onto” strategy by combining living radical polymerization and copper‐catalyzed azide‐alkyne cycloaddition (CuAAC). In this approach, reversible addition‐fragmentation chain transfer polymerization is used to prepare a poly(methylacrylate) backbone with azide side groups, while atom transfer radical polymerization is employed to prepare polystyrene (PS) side chains end‐functionalized with o‐nitrobenzyl (UV‐cleavable) propargyl groups. CuAAC is then used to graft PS side chains onto the polymer backbone, producing the corresponding bottlebrush polymers with UV‐cleavable PS side chains. The formation of the bottlebrush polymer is characterized by 1H nuclear magnetic resonance spectroscopy, gel permeation chromatography (GPC), and Fourier transform infrared spectroscopy. The cleavage behavior of the bottlebrush polymer is monitored in tetrahydrofuran solution under UV irradiation by GPC and viscosity measurements.
The functionalization of zinc oxide (ZnO) nanoparticles by poly(3‐hexylthiophene) (P3HT) brush is completed by the combination of a mussel inspired biomimetic anchoring group and Huisgen cyclo‐addition “click chemistry.” Herein, the direct coupling of an azide modified catechol derivative with an alkyne end‐functionalized P3HT is described. This macromolecular binding agent is used to access core@corona ZnO@P3HT with a stable and homogeneous conjugated organic corona. Preliminary photoluminescence measurement proves an efficient electron transfer from the donor P3HT to the acceptor ZnO nanoparticles upon grafting, thus demonstrating the potential of such a combination in organic electronics.
In this article, well‐defined cyclic amphiphilic random copolymers bearing azobenzene side chains and pendent carboxyl moieties, cyclic‐P(BHMEm‐co‐AAn)s, are synthesized by combining atom transfer radical polymerization (ATRP) with Cu(I)‐catalyzed azide/alkyne cycloaddition (CuAAC) “click” reaction and selective hydrolysis of tert‐butyl ester. Successful synthesis of the cyclic‐P(BHMEm‐co‐AAn)s is fully characterized and verified via conventional gel permeation chromatography, triple detection gel permeation chromatography, nuclear magnetic resonance, Fourier transform infrared, and matrix‐assisted laser desorption ionization–time‐of‐flight mass spectrometry. The cyclic topology induces profound effects on the glass transition temperatures, self‐assembly behavior, and photoresponsive performance of the copolymers compared with their linear counterparts.
Binary polystyrene and poly(4‐vinylpyridine) mixed grafted silica nanoparticles (PSt/P4VP‐g‐SNPs) are fabricated using CuI‐catalyzed azide‐alkyne Huisgen cycloaddition (CuAAC) via grafting‐to method. Azide‐terminated PSt and P4VP are synthesized via post‐ and pre‐atom transfer radical polymerization modification, respectively. Then, the polymers are simultaneously anchored onto alkyne‐modified SNPs by CuAAC yielding mixed brushes as shown by Raman spectroscopy, dynamic light scattering, and thermogravimetric analysis. To the best of our knowledge, this is the first report of simultaneously grafting two distinct polymer chains to synthesize mixed grafted silica nanoparticles using CuAAC technique via grafting‐to method.
The successful chain‐growth copper(I)‐catalyzed azide–alkyne cycloaddition (CuAAC) polymerization employing Cu(0)/pentamethyldiethylenetriamine (PMDETA) and alkyl halide as catalyst is first investigated by a combination of nuclear magnetic resonance, gel‐permeation chromatography, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. In addition, the electron transfer mediated “click‐radical” concurrent polymerization utilizing Cu(0)/PMDETA as catalyst is successfully employed to generate well‐defined copolymers, where controlled CuAAC polymerization of clickable ester monomer is progressed in the main chain acting as the polymer backbone, the controlled radical polymerization (CRP) of acrylic monomer is carried out in the side chain. Furthermore, it is found that there is strong collaborative effect and compatibility between CRP and CuAAC polymerization to improve the controllability.
A range of amphiphilic polymers with diverse macromolecular architectures has been developed and incorporated into films and coatings with potential for marine antibiofouling applications, without resorting to addition of currently used biocidal, toxic agents. Novel “green” chemical technologies employ different building blocks to endow the polymer film with surface activity, functionality, structure, and reconstruction according to the outer environment as a result of a tailored amphiphilic character of the polymer platform. We emphasise how these features can interplay and add synergistically to affect antifouling and fouling‐release against common, widespread marine micro‐ and macro‐fouling organisms.
Recently, polymer drug conjugates (PDCs) have attracted considerable attention in the treatment of cancer. In this work, a simple strategy has been developed to make PDCs of an antitumor alkylating agent, chlorambucil, using a biocompatible disulphide linker. Chlorambucil‐based chain transfer agent was used to prepare various homopolymers and block copolymers in a controlled fashion via reversible addition–fragmentation chain transfer polymerization. Chlorambucil conjugated block copolymer, poly(polyethylene glycol monomethyl ether methacrylate)‐b‐poly(methyl methacrylate), formed nanoaggregates in aqueous solutions, which are characterized by dynamic light scattering and field emission‐scanning electron microscopy. Finally, the simplicity of the design is exemplified by performing a release study of chlorambucil under reducing condition by using D,L‐dithiothreitol.
The controlled folding of a single polymer chain is for the first time realized by metal‐ complexation. α,ω‐Bromine functional linear polymers are prepared via activators regenerated by electron transfer (ARGET) ATRP (,SEC = 5900 g mol−1, Đ = 1.07 and 12 000 g mol−1, Đ = 1.06) and the end groups of the polymers are subsequently converted to azide functionalities. A copper‐catalyzed azide–alkyne cycloaddition (CuAAC) reaction is carried out in the presence of a novel triphenylphosphine ligand and the polymers to afford homotelechelic bis‐triphenylphosphine polymeric‐macroligands (MLs) (,SEC = 6600 g mol−1, Đ = 1.07, and 12 800 g mol−1, Đ = 1.06). Single‐chain metal complexes (SCMCs) are formed in the presence of Pd(II) ions in highly diluted solution at ambient temperature. The results derived via 1H and 31P{1H} NMR experiments, SEC, and DLS unambiguously evidence the efficient formation of SCMCs via metal ligand complexation.
Cyclic multiblock polymers with high‐order blocks are synthesized via the combination of single‐electron transfer living radical polymerization (SET‐LRP) and copper‐catalyzed azide‐alkyne cycloaddition (CuAAC). The linear α,ω‐telechelic multiblock copolymer is prepared via SET‐LRP by sequential addition of different monomers. The SET‐LRP approach allows well control of the block length and sequence as A‐B‐C‐D‐E, etc. The CuAAC is then performed to intramolecularly couple the azide and alkyne end groups of the linear copolymer and produce the corresponding cyclic copolymer. The block sequence and the cyclic topology of the resultant cyclic copolymer are confirmed by the characterization of 1H nuclear magnetic resonance spectroscopy, gel permeation chromatography, Fourier transform infrared spectroscopy, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry.
The phase behavior of block copolymer based supramolecular complexes polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) and amphiphilic pentadecylphenol (PDP) molecules resembles the phase behavior of conventional block copolymers. Several PS‐b‐P4VP(PDP) complexes are found to self‐assemble into gyroid nanostructures. Typically, the grains are randomly oriented with a maximal size of several micrometers. Here, the orientation of a gyroid PS‐b‐P4VP(PDP) complex upon shearing is reported. It is found that the (111) gyroid lattice direction orients parallel to the shear direction after only several seconds of large amplitude oscillatory shearing. Oriented gyroid complexes can be used as templates for the preparation of metal nanofoams with improved ordering with potentially superior properties.
Hierarchical self‐assembly of transient composite hydrogels is demonstrated through a two‐step, orthogonal strategy using nanoparticle tectons interconnected through metal–ligand coordination complexes. The resulting materials are highly tunable with moduli and viscosities spanning many orders of magnitude, and show promising self‐healing properties, while maintaining complete optical transparency.
Porous conjugated polymers are synthesized by metal‐catalyzed coupling reactions. The progress for porous polymers when planar or tetrahedral building blocks are connected by alkyne units into novel materials is highlighted. The most prominent reaction for the buildup of the microporous alkyne‐bridged polymers is the Sonogashira reaction, connecting alkynes to aromatic iodides or bromides. The availability of the building blocks and the potency of the Sonogashira reaction allow preparing a large variety of intrinsically porous polymeric materials, in which rigid struts connect multipronged centers. The microporous polymers are used as catalysts and as storage materials for gases and sensors. Postfunctionalization schemes, understanding of structure‐property relationships, and the quest for high porosity are pertinent.
A straightforward and expeditious monotopic approach for the preparation of 1,2,3‐triazolium‐based poly(ionic liquids) (TPILs) is reported. It is based on the solvent‐ and catalyst‐free polyaddition of an α‐azide‐ω‐alkyne monomer in the presence of methyl iodide or N‐methyl bis[(trifluoromethyl)sulfonyl]imide alkylating agents. Poly(1,2,3‐triazole)s generated in bulk or by thermal azide–alkyne cycloaddition (AAC) are quaternized in‐situ to afford TPILs composed of 1,3,4‐ and 1,3,5‐trisubstituted 1,2,3‐triazolium units. The physical and ion‐conducting properties of the prepared samples are compared with the TPILs composed solely of 1,3,4‐trisubstituted 1,2,3‐triazolium units obtained through a multistep approach involving copper(I)‐catalyzed AAC polyaddition, quaternization of the 1,2,3‐triazole groups, and anion metathesis. TPILs obtained through the monotopic approach display thermal stabilities and ionic conductivities comparable to their pure regioisomeric analogues.
A targeted micellar drug delivery system is developed from a biocompatible and biodegradable amphiphilic polyester, poly(Lac‐OCA)‐b‐(poly(Tyr(alkynyl)‐OCA)‐g‐mannose) (PLA‐b‐(PTA‐g‐mannose), that is synthesized via controlled ring‐opening polymerization of O‐carboxyanhydride (OCA) and highly efficient “Click” chemistry. Doxorubicin (DOX), a model lipophilic anticancer drug, can be effectively encapsulated into the micelles, and the mannose moiety allows active targeting of the micelles to cancer cells that specifically express mannose receptors, which thereafter enhances the anticancer efficiency of the drug. Comprised entirely of biodegradable and biocompatible polyesters, this micellar system demonstrates promising potentials for targeted drug delivery and cancer therapy.
The preparation of multifunctional polymers and block copolymers by a straightforward one‐pot reaction process that combines enzymatic transacylation with light‐controlled polymerization is described. Functional methacrylate monomers are synthesized by enzymatic transacylation and used in situ for light‐controlled polymerization, leading to multifunctional methacrylate‐based polymers with well‐defined microstructure.
The synthesis of propargyl‐functional poly(carbonate)s with different content of glycidyl propargyl ether (GPE) units is achieved via the copolymerization of propargyl glycidyl ether and carbon dioxide. A new type of functional poly(carbonate) synthesized directly from CO2 and the glycidyl ether is obtained. The resulting polymers show moderate polydispersities in the range of 1.6–2.5 and molecular weights in the range of 7000–10 500 g mol−1. The synthesized copolymers with varying number of alkyne functionalities and benzyl azide are used for the copper‐catalyzed Huisgen‐1,3‐dipolar addition. Moreover, the presence of vicinal alkyne groups opens a general pathway to produce functional aliphatic poly(carbonate)s from a single polymer scaffold.
