Table 1.
Comparative Self-Assembled Meso-Scale Morphologies of PEO-b-PCL Diblock Copolymers (PEO: 0.75 – 5.8K) Prepared via Thin-Film Hydration and their Corresponding Nanoscale Morphologies Observed in Aqueous Suspension
| PEO-b-PCL Copolymersa | fPEOb | µm-Morphologyc | nm-Morphologyd |
|---|---|---|---|
| PEO(0.75K)-b-PCL(2.9K) | 0.21 | MS,IP | V,S |
| PEO(0.75K)-b-PCL(5.8K) | 0.11 | IP | S |
| PEO(0.75K)-b-PCL(9K) | 0.07 | IP | P |
| PEO(1.1K)-b-PCL(2.9K) | 0.27 | MS, IP | V,S |
| PEO(1.1K)-b-PCL(3.7K) | 0.23 | MS, IP | V,S |
| PEO(1.1K)-b-PCL(6.3K) | 0.15 | MS, IP | V,S |
| PEO(1.1K)-b-PCL(7.0K) | 0.14 | IP,MS | V,S |
| PEO(1.1K)-b-PCL(7.7K) | 0.12 | IP | S,V |
| PEO(1.1K)-b-PCL(9.5K) | 0.1 | IP | S |
| PEO(1.1K)-b-PCL(13.0K) | 0.08 | IP | P |
| PEO(1.5K)-b-PCL(6.3K) | 0.19 | MS, IP | V,S |
| PEO(1.5K)-b-PCL(10.4K) | 0.13 | IP | S,V |
| PEO(1.5K)-b-PCL(12.4K) | 0.11 | IP | S |
| PEO(1.5K)-b-PCL(13.7K) | 0.1 | IP | S |
| PEO(2K)-b-PCL(7.4K) | 0.21 | IP,MS | V,S |
| PEO(2K)-b-PCL(9.5K) | 0.17 | V,IP | V,S |
| PEO(2K)-b-PCL(12K) | 0.14 | V,IP | V,S |
| PEO(2K)-b-PCL(15K) | 0.12 | IP,V | S,V |
| PEO(2k)-b-PCL(18k) | 0.1 | IP | S,V |
| PEO(2K)-b-PCL(22K) | 0.08 | IP | P |
| PEO(2.6K)-b-PCL(11.2K) | 0.19 | V, IP | V,S |
| PEO(2.6K)-b-PCL(12.3K) | 0.17 | IP,V | V,S |
| PEO(2.6K)-b-PCL(13.9K) | 0.16 | IP,V | V,S |
| PEO(2.6K)-b-PCL(15.5K) | 0.14 | IP,V | S,V |
| PEO(3K)-b-PCL(16.5K) | 0.15 | IP,V | V,S |
| PEO(3K)-b-PCL(19K) | 0.14 | IP,V | S,V |
| PEO(3K)-b-PCL(20.5K) | 0.13 | IP,V | S,V |
| PEO(3K)-b-PCL(24.7K) | 0.11 | IP | S,P |
| PEO(3K)-b-PCL(25.8K) | 0.1 | IP | S,P |
| PEO(3.8K)-b-PCL(17K) | 0.18 | IP,V | V,S |
| PEO(3.8K)-b-PCL(17.7K) | 0.17 | IP,V | V,S |
| PEO(3.8K)-b-PCL(20K) | 0.16 | IP,V | S,V |
| PEO(3.8K)-b-PCL(22.2K) | 0.15 | IP,V | S,V |
| PEO(5K)-b-PCL(10K) | 0.33 | MS,IP | S |
| PEO(5K)-b-PCL(16K) | 0.24 | MS,IP | S |
| PEO(5K)-b-PCL(22K) | 0.18 | IP | S |
| PEO(5K)-b-PCL(26K) | 0.16 | IP | S |
| PEO(5K)-b-PCL(32K) | 0.14 | IP | S,P |
| PEO(5K)-b-PCL(52K) | 0.09 | IP | P |
| PEO(5.8K)-b-PCL(23.8K) | 0.2 | MS,IP | S |
| PEO(5.8K)-b-PCL(24K) | 0.19 | MS,IP | S |
| PEO(5.8K)-b-PCL(30.2K) | 0.16 | IP | S |
| PEO(5.8K)-b-PCL(33.6K) | 0.15 | IP | S |
| PEO(5.8K)-b-PCL(37.7K) | 0.13 | IP | S,P |
| PEO(5.8K)-b-PCL(41.2K) | 0.12 | IP | S,P |
Number-average molecular weight of PEO-b-PCL diblock copolymers as determined by 1H NMR spectroscopy.
Weight fraction of the PEO block as determined by 1H NMR data.
Morphology of particles determined qualitatively from fluorescence confocal microscopic studies of the self-assembled structures formed from thin-film rehydration of 50:1 molar ratios of copolymer: Nile Red. Observed polymersome and irregularly shaped particle (IP) diameters ranged from less than 1 µm to greater than 30 µm; microsphere (MS) diameters ranged from ~5 – 30 µm; vesicle (V) diameters spanned ~5 – 50 µm. In the cases of mixed morphologies, the major component is reported first.
Morphologies of particles determined qualitatively from cryogenic transmission electron microscopic studies of the self-assembled structures formed from thin-film rehydration of 50:1 molar ratios of copolymer: Nile Red followed by extrusion through a 400 nm porous membrane (S = spherical micelles, V = vesicle, P = precipitate; for systems exhibiting mixed morphologies, the majority component is reported first). See Tables S3–4.