pH-Responsive Intra- and Inter-Molecularly Micelle Formation of Anionic Diblock Copolymer in Water

Abstract

Poly(sodium2-(acrylamido)-2-methylpropanesulfonate)-block-poly(sodium11-(acrylamido) undecanoate) (PAMPS-PAaU) was synthesized via reversible addition-fragmentation chain transfer (RAFT)-controlled radical polymerization. The "living" polymerization of PAaU was evidenced by the fact that the molecular weight distribution was narrow (M w /M n = 1.23). The pH-induced association behavior of PAMPS-PAaU in 0.1 M NaCl aqueous solutions as a function of solution pH was investigated by 1 H NMR spin-spin relaxation time, dynamic light scattering (DLS), static light scattering (SLS), and fluorescence probe techniques. These results indicated that PAMPS-PAaU formed polymer micelles in 0.1 M NaCl aqueous solutions at pH < 9. At pH = 8-9, the polymer formed the micelles intramolecularly due to hydrophobic self-association of the PAaU block within the single polymer chain. On the other hand, at pH < 8, micellization occurred intermolecularly to form polymer micelles comprising hydrophobic PAaU cores and hydrophilic PAMPS shells.

Single-Chain Polymer Nanoparticles for Addressing Morphologies and Functions at the Nanoscale: A Review

“…The morphological control of the resulting nanostructures was investigated in depth in a follow-up work on PDMAEMA­(SCNP x % ) 51 - b -PMAAz n BCPs . Other systems capable of amphiphilic behavior were recently proposed in the literature, such as the so-called “photozymes”, − for efficient light harvesting as well as their immobilizations in the multilayer films.…”

Self-Organized Nanoparticles of Random and Block Copolymers of Sodium 2-(Acrylamido)-2-methyl-1-propanesulfonate and Sodium 11-(Acrylamido)undecanoate as Safe and Effective Zika Virus Inhibitors

“…PAMPS homopolymers and diblock copolymers (Figure 1) composed of poly(sodium 2-acrylamido-2-methyl-1-propanesulfonate) (PAMPS) and poly(sodium 11acrylamido undecanoate) (PAaU) were synthesized via reversible addition-fragmentation chain transfer (RAFT) radical polymerization following the procedure described earlier [26]. A typical synthesis of PAMPS75-b-PAaUn is given in Supplementary Materials.…”

“…Such a strategy was applied in the current work. A series of amphiphilic copolymers of sodium 2-acrylamido-2-methylpropanesulfonate (AMPS) and sodium 11-acrylamido undecanoate (AaU), both block (PAMPS75-b-PAaUn) and random (P(AMPS50-co-AaU50), undergoing self-organization in aqueous media with the formation of spherical, highly charged core-shell micelles were synthesized and tested for their ability to hamper ZIKV replication cycle in vitro [26]. Their antiviral activity was compared with poly(2acrylamido-2-methyl-1-propanesulfonic acid) (PAMPS) polyanions, including one with the same number of charged sulfonic units.…”

Reversible rearrangement of the cellular cytoskeleton: A key to the broad-spectrum antiviral activity of novel amphiphilic polymers

“…PAMPS homopolymers and diblock copolymers of poly (sodium 2-acrylamido-2-methyl-1-propanesulfonate) (PAMPS) with poly (sodium 11-acrylamido undecanoate) (PAaU) were synthesized via reversible addition-fragmentation chain transfer (RAFT) radical polymerization following the procedure described before [ 25 ]. Their characteristics are provided in our previous paper [ 19 ].…”

“…In our recent study, we documented the potent antiviral properties of a diblock copolymer, PAMPS-b-PAaU, comprising poly (sodium 2-(acrylamido)-2-methylpropanesulfonate) (PAMPS) and poly (sodium 11-(acrylamido) undecanoate) (PAaU), against the Zika virus [ 24 ]. This diblock copolymer demonstrates pH-induced self-association, leading to the formation of core-shell-type, negatively charged nanoparticles (with a zeta potential of −25 mV and hydrodynamic radius of 4–12 nm) [ 25 ]. Our investigations revealed that the copolymers impeded infection by exerting a protective influence on host cells; however, the precise molecular mechanism remains to be elucidated [ 24 ].…”