Tertiary Amine Methacrylate‐Based ABC Triblock Copolymers: Synthesis, Characterization, and Self‐Assembly in both Aqueous and Nonaqueous Media

Abstract

Water soluble poly[2‐(diisopropylamino)ethyl methacrylate]‐block‐poly[2‐(dimethylamino) ethyl methacrylate]‐block‐poly[2‐(N‐morpholino)ethyl methacrylate] triblock copolymers are synthesized via group transfer polymerization. They are molecularly soluble in acidic solution but give PDPA‐core three‐layer “onion‐like” micelles in alkaline solution. They also give two types of micelles in hexane depending on whether a cosolvent is used: i) PMEMA‐core “onion‐like” reverse micelles are formed with a cosolvent, or, ii) [PDMA‐b‐PMEMA]‐core core–shell micelles without. In addition, novel shell cross‐linked micelles and reverse SCL micelles are also synthesized by cross‐linking the inner PDMA shell of both PDPA‐core micelles in water and PMEMA‐core reverse micelles in hexane. magnified image

Aqueous Solutions of Poly[2‐(N‐morpholino)ethyl methacrylate]: Learning about Macromolecular Aggregation Processes from a Peculiar Three‐Step Thermoresponsive Behavior

“…Even though, knowledge of polymer's salt‐responsivity is essential for in vivo applications, concerning the significant concentration of salts in blood plasma (mainly the concentration of NaCl is ≈ 0.1 m ). PMEMA's multiple stimuli‐responsivity was indeed highlighted in a series of publications about the schizophrenic micellization behavior of PMEMA‐containing block copolymers and triblock terpolymers …”

Self-Assembly of Block and Graft Copolymers in Organic Solvents: An Overview of Recent Advances

“…These authors found that both the N agg and R h of spherical core-shell micelles, having a P2VP-core and a corona of PS and PMMA, depend on the DP n of the insoluble P2VP sequence. Core-shell micelles, based on amino (meth)acrylates, were also obtained by Bütün et al [ 92 ] for poly[2-(diisopropylamino)ethyl methacrylate]-poly[2-(dimethylamino)ethyl methacrylate]-poly[2-( N -morpholino)ethyl methacrylate] (PDPA-PDMA-PMEMA) triblock terpolymers in hexane. In this case, the PDMA and PMEMA sequences are in the core of the micelles, which have a R h of 46 nm, whereas the PDPA block formed the solvated corona.…”

“…The self-assembly of ABC terpolymers in organic solvent mixtures was performed essentially through the precipitation method starting from a homogeneous solution in a common solvent for all three blocks, followed by the addition of a non-solvent. As previously described, Bütün et al [ 92 ] studied the self-assembly of two PDPA-PDMA-PMEMA triblock terpolymers, not only in n -hexane, but also in a mixture of CHCl 3 / n -hexane, starting from a unimer’s solution in CHCl 3 . In this case, core-shell-corona micelles were obtained with a PMEMA core and a R h value of 15 nm.…”

Polymer Micelles

“…Especially o-nitrobenzyl chromophores are discussed as promising candidates for biological applications since even stimulation with NIR light is possible (see Section 3.3). Consequently, several block copolymers bearing o-nitrobenzyl ester groups in the side chain in combination with blocks of PEO/PEG or POEGMA [89][90][91][92][93][94][95][96][97], polystyrene [98][99][100], poly(methyl acrylate) [101], poly(2-ethyl-2-oxazoline) [102], or polydimethylacrylamide [103] have been synthesized and investigated towards their response upon irradiation with far UV light. Exemplarily, Liu and Dong showed the photo-controlled release of the anticancer drug doxorubicin from a biodegradable polypeptide-based poly(S-(o-nitrobenzyl)-L-cysteine)-block-poly(ethylene oxide) block copolymer.…”