“Clicking” on/with polymers: a rapidly expanding field for the straightforward preparation of novel macromolecular architectures

Abstract

The combination of controlled polymerization techniques and "click" reactions form an efficient platform for the preparation of polymers in various architectures. In this critical review, an update of our 2007 review in Chem. Soc. Rev., we focus on the "click" reactions that have been used widely in the last four years to create new polymer architectures. Not only block copolymers and star-shaped polymers but also cyclic and dendritic macromolecules could be synthesized using these robust "click" reactions (205 references).

Self-assembling amphiphilic Janus dendrimers: mesomorphic properties and aggregation in water

“…G 2 (C17) 4 -G 2 (OH) 4 , and G 2 (C17) 4 -G 3 (OH) 8 presented several endothermic peaks before the formation of the mesophase that corresponded to transitions between different crystalline forms. Moreover, they showed small peaks with low enthalpy values 10 (0.6 kJ/mol) that correspond to the transition between the SmA phase and the isotropic liquid. This peak was not observed for the mesogenic compound G 1 (C17) 8 -G 3 (OH) 8 , the clearing temperature of which was deduced from POM observations.…”

“…However, the definite nature of these aggregates is not fully clear as it is difficult to establish if the roll-up of the bilayer formed an empty vesicle or a solid packed structure. According to the formation of aggregates of different 10 morphologies in water, we considered of interest to undertake preliminary studies on the possibilities of these amphiphilic Janus dendrimers to encapsulate hydrophobic molecules, which could set the basis for future studies of these systems as potential drug carriers. The encapsulation ability of the 15 amphiphiles was tested employing Plitidepsin, a lipophilic anticancer drug supplied by PharmaMar.…”

“…[1][2][3] The combination of conventional synthetic approaches, 25 divergent 4,5 or convergent strategies, 6,7 and new synthetic procedures, eg. chemoselective methods (click chemistry), [8][9][10][11][12][13][14] allows the realization of ad-hoc tailored dendrimers possessing specific and desired features. For instance, the possibility to synthesize separately dendrons with different characteristics 30 and to couple them in the last synthetic step allows the easy production of dendrimers with two different functionalities in two precise areas.…”

Synthesis and temperature gradient interaction chromatography of model asymmetric star polymers by the “macromonomer” approach

“…The ether linkage formed in this reaction is stable and its formation requires functionalities that can be easily introduced on the polymer chain-ends during living anionic polymerization and by deprotection and conversion reactions. The 'click' coupling reaction has been used widely in polymer synthesis and has proved an efficient reaction for the synthesis of a variety of polymeric architectures and the synthesis of block copolymers, cyclic polymers, star-shaped polymers, hyperbranched and dendritic polymers has been recently reviewed [78].…”

Synthesis and Solution Properties of Double Hydrophilic Poly(ethylene oxide)-block-poly(2-ethyl-2-oxazoline) (PEO-b-PEtOx) Star Block Copolymers

“…For the synthesis of star-shaped block copolymers, mainly two approaches have been employed, the divergent ("core-first") and the convergent ("arm-first") method [20,[23][24][25][26][27]. The divergent approach uses a multifunctional initiator, but typically not all initiation sites are easily accessible, which drastically influences the number of arms and the overall degree of polymerization.…”