Table 1.
entry # | sample compositiona | [M1]0:[M2]0:[M3]0:[I]0b | Mn(theor.) (kDa)c | Mn(NMR) (kDa)d | Mn(SEC) (kDa)e | PDIe | f1f | f2f | f3f | Tgel (°C)g | G″ (Pa)h | G′ (Pa)h | E (Pa)i |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1 | A98M98D18 | 100:100:20 | 20.8 | 20.0 | 36.7 | 1.04 | 0.47 | 0.35 | 0.18 | 26.2 ± 1.2 | 36 ± 4 | 251 ± 23 | 762 ± 68 |
2 | A92M94D12 | 100:100:10 | 18.9 | 18.1 | 36.4 | 1.09 | 0.50 | 0.36 | 0.14 | 26.6 ± 0.6 | 58 ± 8 | 780 ± 46 | 2346 ± 139 |
3 | A94M158D16 | 100:150:20 | 26.0 | 23.6 | 41.4 | 1.09 | 0.39 | 0.48 | 0.13 | 30.7 ± 1.0 | 32 ± 1 | 189 ± 8 | 573 ± 22 |
4 | A43M92D9 | 50:100:10 | 14.0 | 12.6 | 29.8 | 1.08 | 0.33 | 0.52 | 0.14 | 40.9 ± 1.3 | j | j | j |
5 | A45M45D10 | 50:50:10 | 10.5 | 9.64 | 24.1 | 1.03 | 0.46 | 0.34 | 0.21 | 31.0 ± 0.3 | 11 ± 1 | 125 ± 8 | 378 ± 23 |
6 | A23M25D5 | 25:25:5 | 5.29 | 5.10 | 10.3 | 1.15 | 0.45 | 0.36 | 0.20 | > 60.0 | j | j | j |
7 | A45M47O10 | 50:50:10 | 10.2 | 9.50 | 26.5 | 1.06 | 0.46 | 0.35 | 0.18 | 31.4 ± 0.4 | 4 ± 1 | 25 ± 9 | 76 ± 27 |
8 | A41M47B11 | 50:50:10 | 9.64 | 8.66 | 28.2 | 1.06 | 0.47 | 0.39 | 0.14 | 32.7 ± 0.7 | 0.07 ± 0.01 | 0.2 ± 0.04 | 0.5 ± 0.1 |
9 | A50m55D11 | 50:50:10 | 12.7 | 13.5 | 26.5 | 1.07 | 0.31 | 0.54 | 0.15 | 30.6 ± 0.6 | 8 ± 1 | 60 ± 8 | 182 ± 25 |
10 | A46d42D9 | 50:50:10 | 14.9 | 13.0 | 26.8 | 1.07 | 0.36 | 0.51 | 0.14 | 42.6 ± 1.1 | j | j | j |
The numbers in subscripts correspond to the DPn of individual block determined by end-group analysis using 1H NMR spectroscopy in CD2Cl2.
Initial monomer to initiator ratio.
Theoretical molecular weights were calculated from the initial monomer to initiator ratio.
Determined by 1H NMR analysis.
determinde by the SEC-DRI method using polystyrene standards (0.1 M LiBr/DMF, room temperature).
f1, f2, and f3 refer to the weight fraction of the thermoresponsive A end block, the hydrophilic middle block, and the hydrophobic end block, respectively.
Tgel is the crossover point of G′ and G″ in the plot of G′ and G″ versus temperature: average of two measurements.
G′ and G″ in the gel state at physiological temperature (37 °C): average of two measurements.
Young’s modulus is calculated using E = 2G(1 + ν), where G = (G′2+G″2)1/2, ν = 0.5, and ν is the Poisson’s ratio.61
The polymer solution did not form a gel at 37 °C.