RAFT dispersion polymerization induced self-assembly (PISA) of boronic acid-substituted acrylamides

Reversible addition-fragmentation chain transfer (RAFT)-mediated dispersion polymerization induced self-assembly (PISA) of boronic acid (BA)-substituted acrylamides is established. The first PISA on unprotected BA-substituted monomer yields spherical nanoparticles (NPs) that undergo...

). 13 C NMR spectra confirmed the absence of impurities (Fig. S17). Volumetric flasks were used for serial dilutions and to make standardized solutions.

Instruments and Measurements
General. Melting points were measured on a Stuart Scientific melting point apparatus SMP1.
Nuclear Magnetic Resonance (NMR) Spectroscopy. NMR spectra were recorded using a Bruker Avance II 400 MHz spectrometer. The chemical shifts are in ppm relative to tetramethylsilane. 13 C NMR spectra at 100 MHz are with complete proton decoupling. NMR assignments are supported by distortionless enhancement by polarization transfer (DEPT).
Conversion was estimated using 1 H NMR spectroscopy by comparing the monomer content at 2 h to the monomer content before polymerization (Fig S18) >99.8%, 5.00 mL) and the polymerization sample (20 µl) were added to the activated MS, and stirred for 24 h, at room temperature. MS were removed using gravity filtration, and the solution evaporated to a residue, which was dissolved in 1 mL of the GPC eluent.

Transmission Electron Microscopy (TEM).
Micrographs were obtained at an accelerating voltage of 100 keV (JEOL-1400). Neat samples were deposited onto carbon-coated copper grids (Ted Pella, Redding CA). Excess solvent was drained using filter paper. The samples were subsequently stained with uranyl acetate for 2 min at room temperature. Images were recorded digitally using a Phurona CCD Camera (Emsis) and radius imaging software (Emsis).

Attempted preparation of the longer stabilizer block by single RAFT polymerization.
The initiator serial dilution used VA-044 (45 mg, 0.14 mmol) diluted 625 times with 20% aq.
Representative RAFT dispersion polymerizations.  Fig. 3. Conversion was by 1 H NMR and GPC are as described above.

Fig. S1
Additional TEM images for the dispersion polymerization in Fig. 1 (Run 3).