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Watching RAFT PISA grow spheres, worms, vesicles

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In situ SAXS shows PGMA45-PHPMA200 aqueous RAFT PISA nucleating in 9–10 min and finishing as ~227 nm vesicles.

Source

<i>In situ</i> SAXS studies of a prototypical RAFT aqueous dispersion polymerization formulation: monitoring the evolution in copolymer morphology during polymerization-induced self-assembly

Czajka A, Armes SP · Chemical science · 2020

doi.org/10.1039/d0sc03411hRead the full paper ↗40 citationscc by

Study at a glance

Design
Other — In situ SAXS of aqueous RAFT HPMA polymerization from a PGMA45 macro-CTA
N
~2 mL SAXS cell polymerization tracking — no sample N
Population
Aqueous RAFT polymerization forming micelles, worms, and vesicles
Outcome
Time-resolved nucleation and morphological transitions during polymerization

Structured fields used in claim comparison tables when every cited study has a complete layer.

What they did

Authors polymerized HPMA from a PGMA45 macro-CTA at 70 °C in a ~2 mL SAXS cell and tracked scattering while checking conversion, GPC, DLS, and TEM after the run.

What they found

Micelles nucleate at 9–10 min; worms appear near PHPMA DP 134 after 28–29 min; vesicles reach Dv = 227 ± 16 nm. HPMA conversion exceeds 99% within 80 min; GPC Mn is 51 200 g mol−1 with Đ = 1.25.

The limits

What it doesn't show

The SAXS nucleation clock is faster than the lab 1H NMR rate jump; other PISA monomers and concentrations are not mapped at the same time resolution.

Key terms

PISA
Polymerization-induced self-assembly: a growing insoluble block triggers in situ nanoparticle formation.
RAFT
Reversible addition–fragmentation chain-transfer living radical polymerization.
PGMA-PHPMA
Glycerol monomethacrylate stabilizer with a 2-hydroxypropyl methacrylate core-forming block.
SAXS
Small-angle X-ray scattering used here in situ to assign spheres, worms, and vesicles.
Jellyfish intermediate
Transient branched-worm structure en route from worms to vesicles.

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Quiz yourself

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SAXS nucleation of micelles occurs at:

Common questions

When do micelles nucleate?

Within 9–10 minutes by SAXS intensity upturn.

When do worms start?

Near PHPMA DP 134, around 28–29 min.

Final vesicle size?

227 ± 16 nm by SAXS.

How complete is HPMA conversion?

More than 99% within 80 min at 70 °C.

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