Tuning Hydrophobicity to Program Block Copolymer Assemblies from the Inside Out

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1 Electronic Supplementary Information for Tuning Hydrophobicity to Program Block Copolymer Assemblies from the Inside Out C. Adrian Figg, R. Nicholas Carmean, Kyle C. Bentz, Soma Mukherjee, Daniel A. Savin, and Brent S. Sumerlin* George & Josephine Butler Polymer Research Laboratory, Center for Macromolecular Science & Engineering, Department of Chemistry, University of Florida, PO Box , Gainesville, FL Table of Contents Experimental Materials Characterization Kinetics Reactivity Ratios Nanoparticle Syntheses Light Scattering Data and Discussion Dynamic Light Scattering (Zetasizer Nano ZS) SEC-MALS Discussion Complete Nanoparticle Profiles (SEC-MALS) Dynamic Light Scattering (ALV/CGS-3) Worm Length Worm Length Determination Worm Length Measurements Analyzed Images for Worm Length References S2 S2 S4 S8 S9 S12 S13 S16 S17 S20 S21 S22 S29 S1

2 Experimental Materials 4,4 -Azobiscyanovaleric acid (ACVA, 98%, Alfa-Aesar), trioxane (> 99.5%, Acros Organics), deionized water ASTM Type II (DI water, Aqua Solutions, Inc.) were used as received. S-Ethyl-S -(α,α dimethyl-α -acetic acid)-trithiocarbonate chain transfer agent (CTA) was synthesized according to a previously published report. 1 Diacetone acrylamide (DAAm, > 98%, TCI Chemicals) was recrystallized 2 from ethyl acetate and once from hexanes prior to use. N,N-Dimethylacrylamide (DMA, 99%, Sigma- Aldrich) was filtered through basic alumina prior to use. O,O -1,3-Propanediylbishydroxyamine2HCl (crosslinker, > 99%, Sigma-Aldrich) was prepared as a 250 mg/ml deionized (DI) water solution immediately prior to use. Characterization 1 H NMR spectroscopy was conducted on an Inova 500 MHz, 2 RF channel instrument at 25 C. D 2 O (Cambridge Isotopes Laboratories, Inc, 99.9%) solvent was used as received. Size exclusion chromatography (SEC) was performed in N,N-dimethylacetamide (DMAc) with 50 mm LiCl at 50 C and a flow rate of 1.0 ml min -1 (Agilent isocratic pump, degasser, and autosampler, colums: Plgel 5 µm guard + two ViscoGel I-series G3078 mixed bed columns: molecular weight range and g mol -1 ). Detection consisted of a Wyatt Optilab T-rEX refractive index detector operating at 658 nm and a Wyatt minidawn Treos light scattering detector operating at 659 nm. Absolute molecular weights and polydispersities were calculated using the Wyatt ASTRA software and 100% mass recovery methods. Prior to absolute molecular weight determination, unimer samples were purified via dialysis against DI water for 3 days (Spectra/Por 3 Dialysis Membranes (3500 Molecular weight cut-off (MWCO) from Spectrum Laboratories), and nanoparticle samples were purified via dialysis against DI water for 3 days using Spectra/Por Float-A-Lyzer G2 100k MWCO 5 ml tubes from Spectrum Labs before being isolated by freeze-drying. S2

3 Dynamic light scattering (DLS) analysis was performed with a Malvern Zetasizer Nano ZS (Model No. ZEN 3600, Malvern Instruments Ltd., Worcestershire UK) and multi-angle dynamic light scattering measurements were performed on an ALV/CGS-3 four-angle, compact goniometer system (Langen, Germany), which consisted of a 22 mw HeNe linear polarized laser operating at a wavelength of λ = nm and scattering angles from θ = Fluctuations in the scattering intensity were measured via a ALV/LSE-5004 multiple tau digital correlator, and analyzed via the intensity autocorrelation function (g (2) (τ)). Decay rates, Γ, were obtained from single-exponential fits using a second-order cumulant analysis, and the mutual diffusion coefficient, D m, was calculated through the relation Γ = q! D! where q 2 is the scalar magnitude of the scattering vector. The hydrodynamic radius (R h ) was calculated through the Stokes-Einstein equation D! D! = k!t 6πη! R! Where D m is approximately equal to the tracer diffusion coefficient, D o, k B is the Boltzmann constant, T is the absolute temperature, and η s is the solvent viscosity. Light scattering samples were performed at 25 C following polymerization and crosslinking. Polymerization samples were diluted to 5 mg/ml solutions in water or DMAC, passed through a 0.45 um Nylon syringe filter, and placed in a plastic cuvette for analysis (Malvern) and to 1.25 mg/ml, passed through 0.45 um Nylon syringe filter, and placed into a borosilicate, pre-cleaned cuvette for analysis (ALV). The appearance (and disappearance) of multimodal distributions suggested that the varying hydrophilicity of the copolymers had an effect on the final morphology attained during PISA. Transmission electron microscopy (TEM) was conducted on an H-700 from Hitachi High Technologies America, Inc., Schaumber, IL USA. Digital images were acquired with a Veleta 2k 2k camera and item software (Olympus Soft-Imaging Solutions Corp., Lakewood, CO). Electron Microscopy Sciences Formvar Carbon Film on 400 mesh nickel grids (FCF400-Ni) were used for all measurements. For unstained samples, 10 µl purified nanoparticle solution (0.1 mg/ml) was spotted on the grid for 15 s. The excess solvent was wicked off and the grid air-dried. For sodium phosphotungstinate (PTA) staining, a drop of 0.5% PTA in water was placed on the grid and allowed to sit for 15 s. The excess solvent was S3

4 wicked off and the grid was air-dried. For uranyl acetate (UA) staining, a drop of 2% UA in water was placed on the grid and allowed to sit for 45 s. The excess solvent was wicked off and the grid air-dried. Worm length was measuring using ImageJ software with measured TEMs in the Worm Characterization section. Procedures Kinetics Poly(N,N-dimethylacrylamide) (PDMA) macro chain transfer agent synthesis (macro-cta 1) DMA (3.85 g, 38.9 mmol), CTA (194 mg, mmol), and ACVA (12.1 mg, mmol) were placed in a Schlenk flask to yield a [DMA]:[CTA]:[I] ratio = [45]:[1]:[0.05]. DI water (15 ml) was added to make the monomer concentration 2.6 M. The flask was sealed with a glass stopper, and a rubber septum was placed over the arm joint. The reaction was purged with nitrogen for 45 min, and left to stir at 70 C for 3 h. Time points were taken every 30 min, and DMA conversion was monitored by 1 H NMR spectroscopy by comparing the vinyl monomer peaks to the 6 protons on the amide group (D 2 O, 500 MHz). Figure S1. Poly(N,N-dimethylacrylamide) macro chain transfer agent synthesis kinetics monitored by 1 H NMR spectroscopy and size exclusion chromatography. Weight-average molecular weight by SEC-MALS yielded an M w = 7830 g/mol and a Ð = The remaining initiator in solution was calculated using the half-life equation and assuming a 10 h half-life time of AVCA at 70 C: I = [I]! (0.5)!/!!/! S4

5 I = (0.807 mg/ml)(0.5)!/!" I = mg/ml The concentration of polymer (assuming > 95% monomer conversion as observed by 1 H NMR) was found by dividing the total solids added by the volume of water added, resulting in a macro-cta 1 concentration of 270 mg/ml. These concentrations were then used for all subsequent polymerizations. 90% DAAm, 10% DMA polymerization kinetics Macro-CTA 1 polymerization solution (635 mg, 135 mg macro-cta 1, mmol macro-cta 1, mg ACVA, mmol ACVA), DMA (40.9 ul, 39.4 mg, mmol), and DAAm (605 mg, 3.58 mmol) were added to give a [macro-cta 1]:[DMA]:[DAAm]:[initiator] ratio of [1]:[20]:[180]:[0.06]. The solution was diluted with DI water (4.70 g) to give a final solids concentration of 15 w/w%. The solution was then split into 6 vials containing ml each and left to stir at 70 C. Monomer conversion was monitored by 1 H NMR spectroscopy by comparing the vinyl peaks of DAAm and DMA to the backbone polymer peaks. SEC showed the evolution of molecular weight and efficient blocking efficiency, confirming the efficacy of the RAFT polymerization. Figure S2. Kinetics of a polymerization-induced thermal self-assembly polymerization using a monomer feed ratio of 90% diacetone acrylamide to 10% N,N-dimethylacrylamide, as monitored by 1 H NMR spectroscopy and size exclusion chromatography. 85% DAAm, 15% DMA polymerization kinetics Macro-CTA 1 polymerization solution (635 mg, 135 mg macro-cta 1, mmol macro-cta 1, mg ACVA, mmol ACVA), DMA (61.5 ul, 59.1 mg, mmol), and DAAm (572 mg, S5

6 3.38 mmol) were added to give a [macro-cta 1]:[DMA]:[DAAm]:[initiator] ratio of [1]:[30]:[170]:[0.06]. The solution was diluted with DI water (4.61 g) to give a final solids concentration of 15 w/w%. The solution was then split into 6 vials containing ml each and left to stir at 70 C. Monomer conversion was monitored by 1 H NMR spectroscopy by comparing the vinyl peaks of DAAm and DMA to polymer backbone peaks. SEC showed the evolution of molecular weight and efficient blocking efficiency, confirming the efficacy of the RAFT polymerization. Figure S3. Kinetics of a polymerization-induced thermal self-assembly polymerization using a monomer feed ratio of 85% diacetone acrylamide to 15% N,N-dimethylacrylamide, as monitored by 1 H NMR spectroscopy and size exclusion chromatography. 80% DAAm, 20% DMA polymerization kinetics Macro-CTA 1 polymerization solution (635 mg, 135 mg macro-cta 1, mmol macro-cta 1, mg ACVA, mmol ACVA), DMA (82.0 ul, 78.8 mg, mmol), and DAAm (538 mg, 3.18 mmol) were added to give a [macro-cta 1]:[DMA]:[DAAm]:[initiator] ratio of [1]:[40]:[160]:[0.06]. The solution was diluted with DI water (4.52 g) to give a final solids concentration of 15 w/w%. The solution was then split into 6 vials containing ml each and left to stir at 70 C. Monomer conversion was monitored by 1 H NMR spectroscopy by comparing the vinyl peaks of DAAm and DMA to the polymer backbone peaks. SEC showed the evolution of molecular weight and efficient blocking efficiency, confirming the efficacy of the RAFT polymerization. S6

7 Figure S4. Kinetics of a polymerization-induced thermal self-assembly polymerization using a monomer feed ratio of 80% diacetone acrylamide to 20% N,N-dimethylacrylamide, as monitored by 1 H NMR spectroscopy and size exclusion chromatography. 75% DAAm, 25% DMA polymerization kinetics Macro-CTA 1 polymerization solution (635 mg, 135 mg macro-cta 1, mmol macro-cta 1, mg ACVA, mmol ACVA), DMA (82.0 ul, 78.8 mg, mmol), and DAAm (538 mg, 3.18 mmol) were added to give a [macro-cta 1]:[DMA]:[DAAm]:[initiator] ratio of [1]:[40]:[160]:[0.06]. The solution was diluted with DI water (4.52 g) to give a final solids concentration of 15 w/w%. The solution was then split into 6 vials containing ml each and left to stir at 70 C. Monomer conversion was monitored by 1 H NMR spectroscopy by comparing the vinyl peaks of DAAm and DMA to the polymer backbone peaks. SEC showed the evolution of molecular weight and efficient blocking efficiency, confirming the efficacy of the RAFT polymerization. Figure S5. Kinetics of a polymerization-induced thermal self-assembly polymerization using a monomer feed ratio of 75% diacetone acrylamide to 15% N,N-dimethylacrylamide, as monitored by 1 H NMR spectroscopy and size exclusion chromatography. S7

8 Monomer Conversions Across Different Compositions Figure S6. Overall monomer conversions across the four different monomer feed ratios of diacetone acrylamide (DAAm) to N,N-dimethylacrylamide (DMA); 75:25 DAAm:DMA = DAAm75, 80:20 DAAm:DMA = DAAm80, 85:15 DAAm:DMA = DAAm85, 90:10 DAAm:DMA = DAAm90. Reactivity Ratios Reactivity ratios were found to be r DAAm = and r DMA = using Finneman-Ross data fitting, f = moles of DAAm in the monomer feed, F = molar composition of DAAm in the polymer, and limiting monomer conversions between 8-10% by 1 H NMR spectroscopy. Figure S7. Finneman-Ross reactivity plot of the monomer reactivity ratios between diacetone acrylamide (DAAm) and N,N-dimethylacrylamide (DMA) where the slope is r DAAm and the y-intercept is r DMA. S8

9 Nanoparticle Syntheses PDMA macro chain transfer agent synthesis (macro-cta 2) DMA (3.85 g, 38.9 mmol), CTA (174 mg, mmol), and ACVA (10.9 mg, mmol) were placed in a Schlenk flask to yield a [DMA]:[CTA]:[I] ratio = [50]:[1]:[0.05]. DI water (15 ml) was added to make the monomer concentration 2.6 M. The flask was sealed with a glass stopper, and a rubber septum was placed over the arm joint. The reaction was purged with nitrogen for 45 min, and left to stir at 70 C for 3 h. Weight-average molecular weight by SEC-MALS of a purified sample yielded an M w = 8040 g/mol and a Ð = The remaining initiator in solution was calculated using the half-life equation and the 10 h half-life time of AVCA at 70 C: I = [I]! (0.5)!/!!/! I = (0.727 mg/ml)(0.5)!/!" I = mg/ml The concentration of polymer (assuming > 95% monomer conversion as observed by 1 H NMR) was found by dividing the total solids added by the volume of water added, resulting in a macro-cta 2 concentration of 269 mg/ml. These concentrations were then used for all subsequent polymerizations and numberaverage molecular weight (M n = 6870 g/mol) was used to calculate monomer feed ratios. 90% DAAm, 10% DMA DP 2 = 54 polymerization Macro-CTA 2 polymerization solution (317 mg, 67.2 mg macro-cta 2, mmol macro- CTA 2, mg ACVA, mmol ACVA), DMA (5.45 ul, 5.25 mg, mmol), and DAAm (80.6 mg, mmol) were added to give a [macro-cta 2]:[DMA]:[DAAm]:[initiator] ratio of [1]:[5.4]:[48.6][0.05]. The solution was diluted with DI water (0.771 g) to give a final solids concentration of 15 w/w% and purged with N 2 for 15 min. The solution was then left to stir at 70 C for 16 h. Following polymerization, a 0.2 ml aliquot was taken for unimer characterization. The remaining monomer unit concentration of DAAm was then calculated as follows: Total DAAm before polymerization: 80.6 mg Concentration of DAAm monomer units in solution: 78.9 mg/ml S9

10 DAAm removed with 0.2 ml aliquot: 15.8 mg Remaining DAAm monomer units in solution: 64.8 mg (0.383 mmol) Crosslinker solution (27.4 ul, 6.86 mg, mmol) was added via micro syringe. The solution was stirred at 70 C for approximately 1 min, then removed from the oil bath and allowed to cool to room temperature. 90% DAAm, 10% DMA DP 2 = 87 polymerization Macro-CTA 2 polymerization solution (317 mg, 67.2 mg macro-cta 2, mmol macro- CTA 2, mg ACVA, mmol ACVA), DMA (8.70 ul, 8.40 mg, mmol), and DAAm (129 mg, mmol) were added to give a [macro-cta 2]:[DMA]:[DAAm]:[initiator] ratio of [1]:[9]:[78][0.05]. The solution was diluted with DI water (1.12 g) to give a final solids concentration of 15 w/w% and purged with N 2 for 15 min. The solution was then left to stir at 70 C for 16 h. Following polymerization, a 0.2 ml aliquot was taken for unimer characterization. The remaining monomer unit concentration of DAAm was then calculated as follows: Total DAAm before polymerization: 129 mg Concentration of DAAm monomer units in solution: 94.5 mg/ml DAAm removed with 0.2 ml aliquot: 18.9 mg Remaining DAAm monomer units in solution: 110 mg (0.651 mmol) Crosslinker solution (46.6 ul, 11.7 mg, mmol) was added via micro syringe. The solution was stirred at 70 C for approximately 1 min then, removed from the oil bath and allowed to cool to room temperature. 90% DAAm, 10% DMA DP 2 = 141 polymerization Macro-CTA 2 polymerization solution (317 mg, 67.2 mg macro-cta 2, mmol macro- CTA 2, mg ACVA, mmol ACVA), DMA (14.2 ul, 13.6 mg, mmol), and DAAm (210 mg, 1.24 mmol) were added to give a [macro-cta 2]:[DMA]:[DAAm]:[initiator] ratio of [1]:[14]:[127][0.05]. The solution was diluted with DI water (1.69 g) to give a final solids concentration of 15 w/w% and purged with N 2 for 15 min. The solution was then left to stir at 70 C for 16 h. Following polymerization, a 0.2 ml S10

11 aliquot was taken for unimer characterization. The remaining monomer unit concentration of DAAm was then calculated as follows: Total DAAm before polymerization: 210 mg Concentration of DAAm monomer units in solution: 108 mg/ml DAAm removed with 0.2 ml aliquot: 21.7 mg Remaining DAAm monomer units in solution: 188 mg (1.11 mmol) Crosslinker solution (79.6 ul, 19.9 mg, mmol) was added via micro syringe. The solution was stirred at 70 C for approximately 1 min, then removed from the oil bath and allowed to cool to room temperature. 90% DAAm, 10% DMA DP 2 = 217 polymerization Macro-CTA 2 polymerization solution (317 mg, 67.2 mg macro-cta 2, mmol macro- CTA 2, mg ACVA, mmol ACVA), DMA (21.7 ul, 20.9 mg, mmol), and DAAm (323 mg, 1.91 mmol) were added to give a [macro-cta 2]:[DMA]:[DAAm]:[initiator] ratio of [1]:[22]:[195][0.05]. The solution was diluted with DI water (2.49 g) to give a final solids concentration of 15 w/w% and purged with N 2 for 15 min. The solution was then left to stir at 70 C for 16 h. Following polymerization, a 0.2 ml aliquot was taken for unimer characterization. The remaining monomer unit concentration of DAAm was then calculated as follows: Total DAAm before polymerization: 323 mg Concentration of DAAm monomer units in solution: 118 mg/ml DAAm removed with 0.2 ml aliquot: 23.6 mg Remaining DAAm monomer units in solution: 299 mg (1.77 mmol) Crosslinker solution (127 ul, 31.7 mg, mmol) was added via micro syringe. The solution was stirred at 70 C for approximately 1 min, then removed from the oil bath and allowed to cool to room temperature. S11

12 Light Scattering Data and Discussion Dynamic light scattering using the Malvern Zetasizer Nano ZS directly following polymerization and crosslinking Figure S8. Diacetone acrylamide:n,n-dimethylacrylamide monomer feed ratio of 90:10 with varying second block degrees of polymerization (DP 2 ). Figure S9. Diacetone acrylamide:n,n-dimethylacrylamide monomer feed ratio of 85:15 with varying second block degrees of polymerization (DP 2 ). S12

13 Figure S10. Diacetone acrylamide:n,n-dimethylacrylamide monomer feed ratio of 80:20 with varying second block degrees of polymerization (DP 2 ). Figure S11. Diacetone acrylamide:n,n-dimethylacrylamide monomer feed ratio of 75:25 with varying second block degrees of polymerization (DP 2 ). SEC-MALS Discussion Nanoparticle weight-average molecular weight (M w,np ), nanoparticle aggregation number (N agg ), and nanoparticle radius of gyration (R g ) (Table 1) were compared to further study how unimer composition affected PISA where N agg was calculated by dividing the M w,np of the aggregates by M w,unimer. The M w,np increased for all monomer feed ratios with increasing unimer molecular weight. Assuming a constant or increasing N agg, an increase in nanoparticle molecular weight is expected during PISA, as the S13

14 unimer chains are constantly growing. Interestingly, DAAm75 showed a nanoparticle molecular weight at DP 2 = 217 almost an order of magnitude larger than the other three compositions, even though elution times were similar, suggesting the presence of a different morphology. N agg of all the nanoparticles increased with increasing M w,unimer. This result suggests the nanoparticles formed are not kinetically trapped and are able to overcome unfavorable entropic and steric interactions to combine into more thermodynamically favorable morphologies. Armes and coworkers recently reported similar results for spherical morphologies, 2 therefore our results provide further evidence of the combinatorial nature of PISA throughout the assembly and reorganization process. The difference in relative hydrophobicity of aggregated blocks is expected to affect N agg, as more hydrophobic chains should be more collapsed and therefore require more chains per nanoparticle to lower the interfacial area per chain. 3 When comparing the nanoparticles formed when DP 2 = 217, the aggregation number decreases from DAAm90 (Table 1, entry 4) to DAAm85 (Table 1, entry 8) to DAAm80 (Table 1, entry 12). However, DAAm75 showed a significantly higher N agg when DP 2 = 217 (Table 1, entry 16) than the other three monomer feed ratios suggesting this monomer ratio contains a different morphology. Other conclusions from N agg are difficult to obtain due to the apparent distribution of nanoparticle morphologies present between different compositions. Fortunately, the average R g may provide some insight into distribution of nanoparticle morphologies present. The continuous, monotonic increase in R g exhibited by DAAm90 further suggests there are few anisotropic structures during PISA for this composition. When the DMA ratio is increased by only 5% in the monomer feed (DAAm85), the R g increases significantly at a low DP 2 (Table 1, entry 5) then remains approximately the same for higher DP 2 values. A more dramatic peak in R g was observed for DAAm80 (Table 1, entry 10) and DAAm75 (Table 1, entry 15) at an intermediate DP 2 accompanied by broad and multimodal SEC traces. This large increase then decrease in R g may be indicative of a sphereto-worm-to-sphere transition, as worms are known to exhibit large and disperse R g values due to the morphology s high aspect ratio. To confirm some of the results we observed during DLS analysis using the Zetasizer and SEC- MALS were accurate, we performed subsequent DLS measurements in DMAc using an ALV/CGS-3 fourangle, compact goniometer system. This analysis allows for more accurate determination of S14

15 hydrodynamic radii because angular dependence of the diffusion coefficient can be accounted for, which is particularly important for disperse samples. The ρ value obtained by dividing the R g (obtained by SEC- MALS) by the R h (obtained by diffusion coefficients given by the slope in Γ vs q 2 plots) agreed with the morphologies observed during TEM imaging and helped to check the accuracy of the data obtained by SEC-MALS (Table S2). Theoretically, ρ values for micelles and vesicles are and 1.0, respectively. As R g begins to exceed the value of R h the ρ value begins to exceed unity, which indicates the presence of elongated structures. For the samples analyzed using the multi-angle analysis technique, the ρ values observed are in agreement with the theoretical values for the morphologies determined by TEM analysis. Specifically, samples with micelle morphology DAAm90/DP 2 87 and DAAm90/DP were determined to have ρ values of 0.87 and 0.77, respectively, which are in excellent agreement with the theoretical value of Sample DAAm85/DP 2 141, which exhibited a mixed morphology of micelles and worms, gave a ρ value of 1.0, which may be expected due to the blend of morphologies. Finally, sample DAAm80/DP 2 87 which exhibited worm morphology, gave a ρ value of 2.2, which agrees with the extended, anisotropic morphology shown in TEM analysis. Detailed analysis of the remaining samples is outside the scope of the current manuscript, but will be pursued in future publications, specifically the interesting anisotropic, worm morphology systems. S15

16 Complete nanoparticle profiles obtained using SEC-MALS Table S1. Profile of nanoparticles synthesized using the various monomer feed ratios. %DAAm in Monomer Feed Second Block Degree of Polymerization, a DP 2 Unimer Molecular Weight, M w,unimer ( 10 3 g/mol) b Unimer dn/dc values (ml/g) b Nanoparticle Molecular Weight, M w,np ( 10 6 g/mol) b Nanoparticle Aggregation Number, N agg Radius of Gyration, R g (nm) b Observed Morphology c M M M M M W W + M W + M W + M M M M W W + M W + M W + M V + W + M V + M M M + W M + W W W V + W V a According to initial monomer feed ratio and >95% monomer conversion, b determined using a multi-angle laser light scattering, c observed during transmission electron microscopy imaging where M = micelle, W = worm, and V = vesicle. Figure S12. Nanoparticle molecular weight data according to polymer composition obtained using SEC- MALS a) nanoparticle absolute molecular weights; b) nanoparticle aggregation numbers; and c) nanoparticle radii of gyration determined by multi-angle laser light scattering. S16

17 Table S2. Light scattering studies of selected nanoparticles %DAAm in Monome r Feed Ratio Second Block Degree of Polymerization, a DP 2 Hydrodynamic Radius, b R h (water) Hydrodynamic Radius, b R h (DMAc) Radius of Gyratio n, c R g (DMAc) ρ, DMAc (R g /R h ) Observed Morphology d M M W + M W a According to initial monomer feed ratio and >95% monomer conversion, b determined using multi-angle DLS, c determined using SEC-MALS, d observed during transmission electron microscopy imaging where M = micelle and W = worm Dynamic light scattering in water using multi-angle DLS following nanoparticle purification via dialysis and lyophilization Figure S13. Diacetone acrylamide:n,n-dimethylacrylamide monomer feed ratio of 80:20 with a second block degrees of polymerization of 87. S17

18 Figure S14. Diacetone acrylamide:n,n-dimethylacrylamide monomer feed ratio of 90:10 with a second block degrees of polymerization of 217. Figure S15. Diacetone acrylamide:n,n-dimethylacrylamide monomer feed ratio of 85:15 with a second block degrees of polymerization of 141. S18

19 Dynamic light scattering in DMAc using the multi-angle DLS following nanoparticle purification via dialysis and lyophilization Figure S16. Diacetone acrylamide:n,n-dimethylacrylamide monomer feed ratio of 80:20 with a second block degrees of polymerization of 87. Figure S17. Diacetone acrylamide:n,n-dimethylacrylamide monomer feed ratio of 90:10 with a second block degrees of polymerization of 217. S19

20 Figure S18. Diacetone acrylamide:n,n-dimethylacrylamide monomer feed ratio of 90:10 with a second block degrees of polymerization of 87. Figure S19. Diacetone acrylamide:n,n-dimethylacrylamide monomer feed ratio of 85:15 with a second block degrees of polymerization of 141. Worm Length Determination Worm lengths were measured end-to-end of randomly selected worms across different TEM images from different regions of the TEM grids using ImageJ software. Measured worm length (L) and number of worms measured (n) were used to calculate average worm length (L n ), weighted worm length (L w ), and worm length polydispersity (PDI) according to the following equations: S20

21 L! = Σ L n L! = Σ L! L! n PDI = L! L! with the table represented in Table S3. Table S3. Worm length measurements from transmission electron microscopy images and calculated average worm length, worm length standard deviation, weighted worm length, and worm polydisersity (PDI). %DAAm in Monomer Feed Second Block Degree of Polymerization Sample Size Average Worm Length (L n, nm) Worm Length Standard Deviation Weighted Worm Length (L w, nm) Worm PDI S21

22 Analyzed TEM Images for Worm Lengths Measured worms are marked with a black or white dot. For longer worms, the path of the measurement is traced with a black or white line. 85% DAAm, 15% DMA DP 2 = 87 85% DAAm, 15% DMA DP 2 = 111 S22

23 85% DAAm, 15% DMA DP2 = % DAAm, 15% DMA DP2 = 141 S23

24 80% DAAm, 20% DMA DP2 = 87 80% DAAm, 20% DMA DP2 = 111 S24

25 80% DAAm, 20% DMA DP 2 = % DAAm, 20% DMA DP 2 = 141 S25

26 80% DAAm, 20% DMA DP2 = % DAAm, 25% DMA DP2 = 87 S26

27 75% DAAm, 25% DMA DP 2 = % DAAm, 25% DMA DP 2 = 127 S27

28 75% DAAm, 25% DMA DP2 = 141 S28

29 75% DAAm, 25% DMA DP 2 = 176 References (1) Li, H.; Bapat, A. P.; Li, M.; Sumerlin, B. S. Polym. Chem. 2011, 2 (2), (2) Jones, E. R.; Mykhaylyk, O. O.; Semsarilar, M.; Boerakker, M.; Wyman, P.; Armes, S. P. Macromolecules 2016, 49, (3) Jacquin, M.; Muller, P.; Cottet, H.; Théodoly, O. Langmuir 2010, 26 (24), S29