We report the crystallization-driven self-assembly of diblock copolymers bearing a poly(L-lactide) block into cylindrical micelles. Three different hydrophilic corona-forming blocks have been employed: poly(4-acryloyl morpholine) (P4AM), poly(ethylene oxide) (PEO) and poly(N,N-dimethylacrylamide) (PDMA). Optimization of the experimental conditions to improve the dispersities of the resultant cylinders through variation of the solvent ratio, the polymer concentration, and the addition speed of the selective solvent is reported. The last parameter has been shown to play a crucial role in the homogeneity of the initial solution, which leads to a pure cylindrical phase with a narrow distribution of length. The hydrophilic characters of the polymers have been shown to direct the length of the resultant cylinders, with the most hydrophilic corona block leading to the shortest cylinders

Albertsson

Anaïs Pitto-Barry

Andrew P. Dove

Blanazs

Dove

Elsabahy

Fujiwara

Fulmer

Gadt

Grob

Kline

Korczagin

Lazzari

Massey

Mihut

Mohd Yusoff

Nigel Kirby

Patra

Petzetakis

Portinha

Pratt

Rachel K. O'Reilly

Schmelz

Wang

Zhang

English

Pitto-Barry, Anaïs

Kirby, Nigel

Dove, Andrew P.

O'Reilly, Rachel K.

Warwick Research Archives Portal Repository

 1 Supporting Information For Expanding the scope of the crystallization-driven self-assembly of polylactide-containing polymers Anaïs Pitto-Barry, Nigel Kirby, Andrew P. Dove and Rachel K. O’Reilly Self-assembly procedure for the fast water addition: 50 mg of polymer were dissolved in THF in a 20 mL scintillation vial and the solution was stirred. Nanopure water was dropwise to the vial. The vial was closed and a needle was put through the cap to allow the slow evaporation of THF. The vial was then heated at 65 °C with stirring.  Self-assembly procedure for the slow water addition: 50 mg of polymer were dissolved in THF (0.5 mL) in a 20 mL scintillation vial and the solution was stirred. Nanopure water (2 mL) was added to the vial via a peristaltic pump so that the addition takes place over around 90 min. The vial was closed and a needle was put through the cap to allow the slow evaporation of THF. The vial was then heated at 65 °C with stirring.  Procedure for collect and analysis of the samples: Vial was removed from the heating system and opened. A sample was collected (up to 200 μL), allowed to cool down and then freeze-dried. The vial was closed again and the needle put through the cap. The powder resulting from the freeze-drying process was dissolved in nanopure water to a concentration of 0.5 mg × mL-1 and stirred overnight to obtain a homogeneous solution. DLS and TEM were performed on this dilute solution. Our group has previously demonstrated that this procedure allows for a view of the original sample in the vial.[1]  Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 2  Figure S1. 1H NMR spectrum of PLLA36 (1) (400 MHz, CDCl3).    Figure S2. 1H NMR spectrum of PLLA38 (2) (300 MHz, CDCl3).  Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 3  Figure S3. 1H NMR spectrum of PEO454-b-PLLA28 (3) (400 MHz, CDCl3).    Figure S4. 1H NMR spectrum of P4AM213-b-PLLA38 (4) (250 MHz, CDCl3).  Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 4  Figure S5. 1H NMR spectrum of P4AM166-b-PLLA36 (5) (400 MHz, CDCl3).    Figure S6. 1H NMR spectrum of PDMA248-b-PLLA36 (6) (400 MHz, CDCl3).  Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 5  Figure S7. Dynamic light scattering data for the self-assembly of P4AM213-b-PLLA38 (4) at different THF contents (10-30%) and heating times (27 hours: left, 51 hours: right).    Figure S8. Histograms of the spheres (top) and cylinders (bottom) length produced from the self-assembly of P4AM213-b-PLLA38 (4) at 20 mg × mL-1 in 10% THF with fast water addition after 27 hours (bottom left, Ln = 159 ± 58 nm) and 51 hours (bottom right, Ln = 173 ± 56 nm). A mixed phase was obtained.  Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 6  Figure S9. Histograms of the spheres (top) and cylinders (bottom) length produced from the self-assembly of P4AM213-b-PLLA38 (4) at 20 mg × mL-1 in 20% THF with fast water addition after 27 hours (bottom left, Ln = 224 ± 89 nm) and 51 hours (bottom right, Ln = 213 ± 114 nm). A mixed phase was obtained.  Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 7  Figure S10. Histograms of the spheres (top) and cylinders (bottom) length produced from the self-assembly of P4AM213-b-PLLA38 (4) at 20 mg × mL-1 in 30% THF after 27 hours (bottom left, Ln = 157 ± 62 nm) and 51 hours (bottom right, Ln = 212 ± 90 nm). A mixed phase was obtained.    Figure S11. Dynamic light scattering data for the self-assembly of P4AM166-b-PLLA36 (5) at different times (1-2 days) and polymer concentrations (10 mg × mL-1: left, 20 mg × mL-1: right).    Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 8  Figure S12. Histograms of the spheres (top) and cylinders (bottom) length produced from the self-assembly of P4AM166-b-PLLA36 (5) at 10 mg × mL-1 in 20% THF with fast water addition after 1 day (bottom left, Ln = 243 ± 112 nm) and 2 days (bottom right, Ln = 246 ± 92 nm). A mixed phase was obtained.    Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 9  Figure S13. Histograms of the spheres (top) and cylinders (bottom) length produced from the self-assembly of P4AM166-b-PLLA36 (5) at 20 mgmL-1 in 20% THF with fast water addition after 1 day (bottom left, Ln = 291 ± 155 nm) and 2 days (bottom right, Ln = 264 ± 124 nm). A mixed phase was obtained.    Figure S14. Dynamic light scattering data for the self-assembly of PDMA248-b-PLLA36 (6) at different times (1-2 days) and polymer concentrations (10 mg × mL-1: left, 20 mg × mL-1: right).    Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 10  Figure S15. Histograms of the spheres (top) and cylinders (bottom) length produced from the self-assembly of PDMA248-b-PLLA36 (6) at 10 mg × mL-1 in 20% THF with fast water addition after 1 day (bottom left, Ln = 236 ± 135 nm) and 2 days (bottom right, Ln = 216 ± 90 nm). A mixed phase was obtained.   Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 11  Figure S16. Histograms of the spheres (top) and cylinders (bottom) length produced from the self-assembly of PDMA248-b-PLLA36 (6) at 20 mg × mL-1 in 20% THF with fast water addition after 1 day (bottom left, Ln = 179 ± 88 nm) and 2 days (bottom right, Ln = 257 ± 103 nm). A mixed phase was obtained.     Figure S17. TEM images of the self-assembly of P4AM166-b-PLLA36 (5) with a slow water addition at 20 mg × mL-1 and 20% THF at different times (1-3 days).    Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 12  Figure S18. Dynamic light scattering data for the self-assembly of PEO454-b-PLLA28 (3) with a slow water addition at the initial starting point (left) and after 1 hour of heating (right).   Figure S19. Histogram of the cylinders length observed by TEM for the self-assembly of PEO454-b-PLLA28 (3) at 20 mg × mL-1 in 20% THF with a slow water addition at different times (1-3 days). Note that the size of the few spheres did not significantly change during assembly.   Figure S20. Dynamic light scattering data for the self-assembly of PDMA248-b-PLLA36 (6) with the slow addition of water at different times. Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 13  Figure S21. Histogram of the spheres (top) and cylinders (bottom) length observed by TEM for the self-assembly of PDMA248-b-PLLA36 (6) at 20 mg × mL-1 in 20% THF with slow water addition at different times (1-3 days).     Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013 14  Figure S22. SAXS profiles and fittings of the self-assembly process of diblocks PEO454-b-PLLA28 (3), P4AM166-b-PLLA36 (5) and PDMA248-b-PLLA36 (6) at 20 mg × mL-1 in 20% THF with slow addition of water at 3 days.    Figure S23. Hydrophilic character of the polymers PDMA, P4AM and PEO determined by prediction of logP according to the degree of polymerization.   References  [1] N. Petzetakis, A. P. Dove, R. K. O’Reilly, Soft Matter, 2012, 8, 7408-7414. Electronic Supplementary Material (ESI) for Polymer ChemistryThis journal is © The Royal Society of Chemistry 2013

Expanding the scope of the crystallization-driven self-assembly of polylactide-containing polymers

Pitto-Barry, Anais

University of Birmingham Research Portal

Expanding the scope of the crystallization-driven self-assembly of polytactide-containing polymers

YesWe report the crystallization-driven self-assembly of diblock copolymers bearing a poly(L-lactide) block into cylindrical micelles. Three different hydrophilic corona-forming blocks have been employed: poly(4-acryloyl morpholine) (P4AM), poly(ethylene oxide) (PEO) and poly(N,N-dimethylacrylamide) (PDMA). Optimization of the experimental conditions to improve the dispersities of the resultant cylinders through variation of the solvent ratio, the polymer concentration, and the addition speed of the selective solvent is reported. The last parameter has been shown to play a crucial role in the homogeneity of the initial solution, which leads to a pure cylindrical phase with a narrow distribution of length. The hydrophilic characters of the polymers have been shown to direct the length of the resultant cylinders, with the most hydrophilic corona block leading to the shortest cylinders.EPSRC and the University of Warwick, the Swiss National Science Foundation - Early Postdoc Mobility fellowship (Grant no PBNEP2-142949 to A.P.B.). The Warwick Research Development Fund. Some items of equipment funded by Birmingham Science City: Innovative Uses for Advanced Materials in the Modern World (West Midlands Centre for Advanced Materials Project 2), with support from Advantage West Midlands (AWM) and part funded by the European Regional Development Fund (ERDF)

Expanding the scope of the crystallization-driven self-assembly of polylactide-containing polymers

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