Aggregation-induced emission polymers via reversible-deactivation radical polymerization Special Collection:Distinguished Australian Researchers

Aggregation-induced emission(AIE)is a unique phenomenon whereby aggregation of molecules induces fluorescence emission as opposed to the more commonly known aggregation-caused quenching(ACQ).AIE has the potential to be utilized in the large-scale production of AIE-active polymeric materials because of their wide range of practical applications such as stimuli-responsive sensors,biological imaging agents,and drug delivery systems.This is evident from the increasing number of publications over the years since AIE was first discovered.In addition,the evergrowing interest in this field has led many researchers around the world to develop new and creative methods in the design of monomers,initiators and crosslinkers,with the goal of broadening the scope and utility of AIE polymers.One of the most promising approaches to the design and synthesis of AIE polymers is the use of the reversible-deactivation radical polymerization(RDRP)techniques,which enabled the production of well-controlled AIE materials that are often difficult to achieve by other methods.In this review,a summary of some recent works that utilize RDRP for AIE polymer design and synthesis is presented,including(i)the design of AIE-related monomers,initiators/crosslinkers;the achievements in preparation of AIE polymers using(ii)reversible addition–fragmentation chain transfer(RAFT)technique;(iii)atom transfer radical polymerization(ATRP)technique;(iv)other techniques such as Cu(0)-RDRP technique and nitroxide-mediated polymerization(NMP)technique;(v)the possible applications of these AIE polymers,and finally(vi)a summary/perspective and the future direction of AIE polymers.

Recent Advances of CuAAC Click Reaction in Building Cyclic Polymer

Cyclic polymers have attracted more and more attentions in recent years because of their unique topological structures and characteristic properties in both solution and bulk state. There are relatively few reports on cyclic polymers, partly because of the more demanding synthetic procedures. In recent years, 'click' reaction, especially Cu(I)-catalyzed azide-alkyne cycloaddition(CuAAC), has been widely utilized in the synthesis of cyclic polymer materials because of its high efficiency and low susceptibility to side reactions. In this review, we will focus on three aspects:(1) Constructions of monocyclic polymer using CuAAC 'click' chemistry;(2) Formation of complex cyclic polymer topologies through CuAAC reactions;(3) Using CuAAC 'click' reaction in the precise synthesis of molecularly defined macrocycles. We believe that the CuAAC click reaction is playing an important role in the design and synthesis of functional cyclic polymers.

Facile synthesis of silicapolymer hybrids via simultaneous RAFT process and hydroxyl-alkoxysilane coupling reaction

This study aimed at the synthesis of silica particles grafted with better-defined homopolymers and block copolymers by tandem approach.Z-functionalized Sbenzyl S’-(3-trimethoxysilyl)propyltrithiocarbonate(BTPT)was used as a couplable RAFT agent to synthesize the target inorganic-organic hybrids.Simultaneous coupling reaction and RAFT process using silica particles and BTPT as raw materials efficiently afforded homopolymers grafted silica,and RAFTsynthesized macro chain transfer agents withω-terminal trimethoxysilane moiety were utilized to mediate graft reaction to prepare silica particles grafted with di-,tri-and tetrablock copolymers comprised of polymer segments such as polystyrene,polyacrylamides and polyacrylates.When the grafted chains had molecular weights ranging between 3920 and 24800 g/mol,the molar grafting ratios,which were dependent on reaction conditions and types and compositions of grafted chains,were estimated to be in the range of 15.2–101μmol/g,and grafted polymers usually had polydispersity indices lower than 1.3,revealing that the grafting process was almost controllable.To the best of our knowledge,this versatile tandem approach is one of the most facile techniques to prepare silica particles grafted with polymeric chains with controlled molecular weight,low polydispersity and precise composition due to its minimal reaction steps,mild conditions,straightforward synthesis and satisfactory controllability.