Table 1. DLS z-Average Diameter (Dz) and Polydispersity Index (PDI) and Various SAXS Structural Parameters Obtained by Analysis of a Series of G55-Hx Copolymer Vesiclesa.
| DLS |
SAXS |
CD-MS |
|||||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| PHPMA DP (x) | Dz, nm | PDI | Dv, nm | Vm, nm3 | RmSAXS, nm | σRm, nm | TmSAXS, nm | σTm, nm | Rg, nm | xsol | NaggSAXS/103 | MnCD-MS, MDa | MwCD-MS/Mn | NaggCD-MS /103 | ⟨z⟩ / e | D, nm | TmCD-MS, nm |
| 200 | 239 | 0.28 | 244(5) | 40(4) | 111(3) | 45(2) | 12.8(1) | 1.3(1) | 2.2(1) | 0.38(1) | 31.0 ± 5.3 | – | – | – | – | – | – |
| 233(7) | 105(3) | 50(2) | 12.6(1) | 1.1(1) | 2.5(3) | 0.51(1) | 22.0 ± 3.9 | ||||||||||
| 300 | 219 | 0.14 | 236(6) | 59(6) | 105(3) | 45(1) | 17.8(1) | 2.1(1) | 2.1(1) | 0.38(1) | 25.7 ± 4.7 | 800 | 1.19 | 15.3 | 1952 | 177 | 12.6 |
| 228(6) | 101(4) | 51(2) | 17.8(1) | 2.1(1) | 2.4(1) | 0.52(1) | 18.2 ± 3.8 | ||||||||||
| 400 | 201 | 0.12 | 208(4) | 79(9) | 89(2) | 39(1) | 20.2(1) | 2.2(1) | 2.2(1) | 0.45(1) | 14.2 ± 2.5 | 1307 | 1.18 | 13.5 | 2076 | 184 | 20.8 |
| 213(3) | 91(1) | 45(1) | 20.3(1) | 2.3(1) | 2.4(1) | 0.56(1) | 11.8 ± 1.9 | ||||||||||
| 500 | 208 | 0.02 | 197(2) | 99(11) | 82(1) | 34(1) | 24.7(1) | 2.3(1) | 2.3(1) | 0.38(2) | 13.0 ± 2.0 | 1023 | 1.09 | 12.6 | 1838 | 170 | 19.2 |
| 197 (2) | 81(1) | 36(1) | 25.1(1) | 2.6(1) | 2.4(1) | 0.52(2) | 10.2 ± 1.8 | ||||||||||
| 600 | 204 | 0.04 | 205(2) | 119(13) | 83(1) | 38(1) | 29.7(1) | 2.7(1) | 2.3(1) | 0.51(2) | 10.8 ± 1.8 | 1366 | 1.12 | 14.3 | 2060 | 184 | 22.6 |
| 206(1) | 83(1) | 40(1) | 30.4(1) | 3.0(1) | 2.3(1) | 0.58(2) | 9.5 ± 1.8 | ||||||||||
| 700 | 204 | 0.04 | 205(2) | 139(15) | 82(1) | 34(1) | 34.1(1) | 3.0(1) | 1.7(1) | 0.63(1) | 7.9 ± 1.3 | 1421 | 1.08 | 12.9 | 2181 | 190 | 21.4 |
| 205(2) | 82(2) | 40(1) | 34.5(1) | 3.0(1) | 1.8(1) | 0.63(1) | 7.9 ± 1.3 | ||||||||||
| 800(A) | 205 | 0.02 | 204(3) | 158(17) | 79(1) | 32(1) | 37.7(1) | 2.9(1) | 2.0(1) | 0.62(1) | 7.3 ± 1.2 | 1282 | 1.11 | 10.3 | 2046 | 183 | 21.1 |
| 206(3) | 80(2) | 35(1) | 38.9(1) | 3.1(1) | 1.9(1) | 0.61(2) | 7.9 ± 1.5 | ||||||||||
| 800(B) | 201 | 0.03 | 197(1) | 158(17) | 75(1) | 30(1) | 37.1(1) | 4.8(1) | 2.3(4) | 0.57(1) | 7.4 ± 1.1 | 1220 | 1.11 | 9.8 | 2000 | 180 | 20.7 |
| 194(1) | 73(4) | 32(1) | 39.1(1) | 5.3(1) | 2.3(1) | 0.62(1) | 6.4 ± 0.8 | ||||||||||
| 1000 | 229 | 0.02 | 243(3) | 198(21) | 95(2) | 41 (1) | 45.7(1) | 3.8(1) | 1.7(1) | 0.68(1) | 8.4 ± 1.6 | 2003 | 1.15 | 17.9 | 2413 | 204 | 27.8 |
| 247(3) | 97(2) | 52 (1) | 46.9(1) | 3.9(1) | 1.6(1) | 0.66(1) | 9.7 ± 1.6 | ||||||||||
| 1500 | 455 | 0.23 | – | – | – | – | – | – | – | – | – | 4027 | 1.21 | 19.1 | 3070 | 240 | 45.6 |
| 2000 | 752 | 0.14 | – | – | – | – | – | – | – | – | – | 97/35700b | n/a | 0.362/125.2 | – | – | – |
Dv is the mean vesicle diameter, RmSAXS is the radius from the center of the vesicle to the center of the membrane and σRm is the associated standard deviation, Tm is the membrane thickness, and σTm is the associated standard deviation, Rg is the radius of gyration of the coronal stabilizer (PGMA) chains, xsol is the average water content of the hydrophobic PHPMA membrane, and NaggSAXS is the mean vesicle aggregation number. Numbers in brackets represent the error in the last significant digit of the SAXS fitting parameters. The volume of a PGMA55 block (Vvc) was calculated to be 11.2 ± 0.12 nm3 and Vm is the volume of the hydrophobic PHPMAx block. Two sets of SAXS fitting parameters are given for each sample: the first line corresponds to a ‘simple’ model fit, and the second line corresponds to a ‘complex’ model fit that accounts for the vesicle corona scattering length density profile. CD-MS results obtained for the same series of copolymer vesicles are also summarized, including the number-average particle mass of the vesicles (Mn), weight-average particle mass of the vesicles (MwCD-MS), polydispersity index (Mw/MnCD-MS), mean vesicle aggregation number (Nagg), average number of charges per vesicle (⟨z⟩; as calculated from the charge distribution), equivalent vesicle diameter (D) and vesicle membrane thickness (TmCD-MS); see main text for details.
A bimodal mass distribution was observed for this particular sample.