Core-crosslinked micelles with a poly-anionic poly(styrene sulfonate)-based outer shell made by RAFT polymerization

Phosphine-Functionalized Core-Crosslinked Micelles and Nanogels with an Anionic Poly(styrenesulfonate) Shell: Synthesis, Rhodium(I) Coordination and Aqueous Biphasic Hydrogenation Catalysis

“…The DLS measurements indicate the presence of micelles with average diameter in the 50-80 nm range, although distributions of larger agglomerates are also observed for the unfiltered dispersions. This behavior is quite similar to that observed for the equivalent diblock copolymers with a neat PSt block [34]. The NMR spectra of the self-assembled di/triblock copolymers in DMSO-d 6 (Figures S1 and S2 The final cross-linking step was carried out using either a 10:90 DEGDMA/St comonomer mixture or neat DEGDMA, using in all cases 15 DEGDMA units per macromolecular chain.…”

“…The NMR spectra of the self-assembled di/triblock copolymers in DMSO-d6 (Figures S1 and S2 The final cross-linking step was carried out using either a 10:90 DEGDMA/St comonomer mixture or neat DEGDMA, using in all cases 15 DEGDMA units per macromolecular chain. As detailed in our recent contribution [34], using this amount of neat DEGDMA is sufficient to ensure quantitative cross-linking of all diblock copolymers without Given previously encountered difficulties (precipitation of DPPS as a result of the faster incorporation of styrene, especially when using the higher DPPS fractions), a few CCMs were also initially developed by first extending the R 0 -(SS − Na + ) 140− SC(S)SnPr macromolecules with a short PSt block (50 monomer units), yielding an amphiphilic diblock copolymer, which self-assembles. Further chain extension of the R 0 -(SS − Na + ) 140 -b-St 50 -SC(S)SnPr macro-RAFT agent with the St/DPPS mixture then starts off directly as an emulsion polymerization, removing any potential DPPS precipitation issues and ensuring full incorporation of the DPPS monomer in the CCM core.…”

“…The RAFT agent 4-cyano-4-thiothiopropylsulfanyl pentanoic acid (CTPPA) or R 0 -SC(S)SnPr (R 0 = -C(CH 3 )-(CN)-CH 2 CH 2 COOH), was prepared according to the literature [33]. The R 0 -(SS − Na + ) 140 -SC(S)SnPr and R 0 -(SS − Na + ) 140 -b-St 50 -SC(S)SnPr macroRAFT agents were synthesized as described in our recent contribution [34]. The deionized water used for the syntheses and DLS analyses was obtained from a Purelab Classic UV system (Elga Lab-Water).…”

“…The α and ω chain ends of the macromolecule are provided by the RAFT chain transfer agent 4-cyano-4-thiothiopropylsulfanyl pentanoic acid (CTPPA) (R 0 = −C(CH 3 ) (CN) CH 2 CH 2 COOH). We have already optimized and recently published [34] the synthesis of unimolecular CCMs that are fully equivalent to those described here, except for the absence of ligand-functionalized monomer. As a short summary, the aqueous dispersions of the micelles formed by the intermediate R 0 -(SS − Na + ) x -b-St y -SC(S)SnPr diblock copolymer were found unstable, featuring equilibria with single chains and large agglomerates, especially for polymers with a short PSt block.…”

Amphiphilic Block Copolymers: Their Structures, and Self-Assembly to Polymeric Micelles and Polymersomes as Drug Delivery Vehicles

“…Janus micelles do form as result of self-assembly of ABC type triblock copolymers with the two incompatible and hydrophilic or hydrophobic blocks [ 60 , 61 , 62 , 63 ]. The crew-cut core shell micelles are obtained when the core forming block is much larger in size than the hydrophilic block [ 64 , 65 , 66 ]. Zhang and Eisenberg examined polystyrene-b-poly (acrylic acid) aggregates in water following the dissolution procedure and using good solvent to the solution to induce aggregation of the polystyrene segments and noticed that crew-cut aggregates can show multiple morphologies such as spheres, rods, vesicles, lamellae, large compound micelles and several other structures [ 66 ].…”