| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CHCl₃ δ 7.27 and 77.2 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
|---|---|
| ¹H NMR (400 MHz, CDCl₃) | δ 7.63 (dd, J = 2.1, 2.1 Hz, 1H), 7.59 (dd, J = 8.1, 2.6 Hz, 1H), 7.30 (dd, J = 7.9, 7.9 Hz, 1H), 7.11 (dd, J = 8.1, 2.6 Hz, 1H), 6.48 (s, 1H), 3.92 (s, 3H) |
| ¹³C NMR (101 MHz, CDCl₃) | δ 168.04, 156.33, 131.30, 129.98, 121.98, 120.79, 116.65, 52.71 |
Nirob K. Saha, William S. Salvia, Dominik Konkolewicz, C. Scott Hartley. “Exchange in transient covalent assembly.” ChemRxiv (). https://doi.org/10.26434/chemrxiv.15007684/v1
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CHCl₃ δ 7.27 and 77.2 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
|---|---|
| ¹H NMR (500 MHz, CDCl₃) | δ 7.60 (dd, J = 7.7, 1.0 Hz, 1H), 7.53 (dd, J = 2.7, 1.5 Hz, 1H), 7.30 (dd, J = 7.9, 7.9 Hz, 1H), 7.09 (dd, J = 8.3, 1.0 Hz, 1H), 4.14 (dd, J = 5.7, 3.9 Hz, 2H), 3.88 (dd, J = 28.1, 0.6 Hz, 3H), 3.84 (dd, J = 5.7, 4.0 Hz, 3H), 3.77 – 3.55 (m, 82H), 3.52 (dd, J = 5.8, 3.6 Hz, 3H), 3.35 (s, 3H) |
| ¹³C NMR (101 MHz, CDCl₃) | δ 166.92, 158.79, 131.41, 129.42, 122.17, 120.11, 114.78, 72.55, 71.96, 70.89, 70.71, 70.66, 70.64, 70.60, 70.55, 70.39, 69.66, 67.67, 61.75, 59.06, 52.19 |
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
|---|---|
| ¹H NMR (400 MHz, Acetone-d₆) | δ 7.64 (d, J = 7.6 Hz, 1H), 7.59 (s, 1H), 7.44 (dd, J = 7.9, 2.7 Hz, 1H), 7.23 (dd, J = 8.3, 2.7 Hz, 1H), 4.22 (dd, J = 4.7, 4.7 Hz, 2H), 3.87 (dd, J = 4.8, 4.8 Hz, 2H), 3.71 – 3.45 (m, 64H), 3.30 (s, 3H) |
| ¹³C NMR (101 MHz, Acetone-d₆) | δ 205.87, 167.09, 159.68, 132.47, 130.12, 122.45, 120.06, 115.63, 72.33, 71.12, 70.97, 70.92, 70.74, 69.93, 68.32, 58.47, 30.11, 29.92, 29.72, 29.53, 29.34, 29.15, 28.95 |
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
|---|---|
| ¹H and ¹³C NMR monitoring, sample | mAc (102 mM), pyridine-d₅ (62 mM), ethylene carbonate (104 mM), and one equiv. EDC (105 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹³C NMR calibration factors | mAc: 0.509 for the signal at 124.4 ppm; mAn: 0.544 for the signal at 118.2 ppm |
| ¹H and ¹³C NMR monitoring, 57 min | mAn: 39.2 mM; mAc: 0 mM |
| ¹H and ¹³C NMR monitoring, 1532 min | mAn: 22.4 mM; mAc: 24.7 mM |
| ¹H and ¹³C NMR monitoring, 2744 min | mAn: 16.9 mM; mAc: 47.2 mM |
| ¹H and ¹³C NMR monitoring, 4265 min | mAn: 9.46 mM; mAc: 50.8 mM |
| ¹H and ¹³C NMR monitoring, 5609 min | mAn: 9.57 mM; mAc: 69.0 mM |
| ¹H and ¹³C NMR monitoring, 7061 min | mAn: 5.21 mM; mAc: 69.8 mM |
| ¹H and ¹³C NMR monitoring, 8468 min | mAn: 2.57 mM; mAc: 74.5 mM |
| ¹H and ¹³C NMR monitoring, 10004 min | mAn: 1.47 mM; mAc: 75.3 mM |
| ¹H and ¹³C NMR monitoring, 12898 min | mAn: 1.29 mM; mAc: 76.6 mM |
| ¹H and ¹³C NMR monitoring, 15562 min | mAn: 1.14 mM; mAc: 80.5 mM |
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
|---|---|
| ¹H and ¹³C NMR monitoring, sample | pAc (101 mM), pyridine-d₅ (59 mM), ethylene carbonate (106 mM), and one equiv. EDC (104 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹³C NMR calibration factors | pAc: 0.230 for the signal at 134.2 ppm; pAn: 0.240 for the signal at 135.2 ppm |
| ¹H and ¹³C NMR monitoring, 61 min | pAn: 46.8 mM; pAc: 0 mM |
| ¹H and ¹³C NMR monitoring, 1407 min | pAn: 45.6 mM; pAc: 0 mM |
| ¹H and ¹³C NMR monitoring, 2937 min | pAn: 37.9 mM; pAc: 0 mM |
| ¹H and ¹³C NMR monitoring, 4273 min | pAn: 40.3 mM; pAc: 0 mM |
| ¹H and ¹³C NMR monitoring, 5819 min | pAn: 38.8 mM; pAc: 1.32 mM |
| ¹H and ¹³C NMR monitoring, 7196 min | pAn: 34.8 mM; pAc: 4.35 mM |
| ¹H and ¹³C NMR monitoring, 8510 min | pAn: 38.0 mM; pAc: 7.75 mM |
| ¹H and ¹³C NMR monitoring, 11554 min | pAn: 32.2 mM; pAc: 10.9 mM |
| ¹H and ¹³C NMR monitoring, 14269 min | pAn: 32.4 mM; pAc: 11.7 mM |
| ¹H and ¹³C NMR monitoring, 18980 min | pAn: 33.0 mM; pAc: 17.5 mM |
| ¹H and ¹³C NMR monitoring, 21813 min | pAn: 29.6 mM; pAc: 17.8 mM |
| ¹H and ¹³C NMR monitoring, 26174 min | pAn: 29.4 mM; pAc: 22.3 mM |
| ¹H and ¹³C NMR monitoring, 28972 min | pAn: 25.9 mM; pAc: 24.7 mM |
| ¹H and ¹³C NMR monitoring, 34716 min | pAn: 24.6 mM; pAc: 30.0 mM |
| ¹H and ¹³C NMR monitoring, 44549 min | pAn: 24.5 mM; pAc: 40.2 mM |
| NMR concentration definition | For the polymers, apparent concentrations of the anhydride functional groups were monitored, not polymer chains |
|---|---|
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
| ¹H and ¹³C NMR monitoring, sample | pDAc (102 mM), pyridine-d₅ (61 mM), ethylene carbonate (104 mM), and one equiv. EDC (104 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹³C NMR calibration factors | pDAc: 0.093 for the signal at 134.2 ppm; pP: 0.434 for the signal at 166.7 ppm |
| ¹H and ¹³C NMR monitoring, 59 min | pP: 45.9 mM; pDAc: 13.8 mM |
| ¹H and ¹³C NMR monitoring, 1403 min | pP: 45.5 mM; pDAc: 15.0 mM |
| ¹H and ¹³C NMR monitoring, 2931 min | pP: 44.9 mM; pDAc: 16.3 mM |
| ¹H and ¹³C NMR monitoring, 4241 min | pP: 44.4 mM; pDAc: 17.3 mM |
| ¹H and ¹³C NMR monitoring, 5616 min | pP: 44.2 mM; pDAc: 17.8 mM |
| ¹H and ¹³C NMR monitoring, 7267 min | pP: 43.6 mM; pDAc: 18.3 mM |
| ¹H and ¹³C NMR monitoring, 8819 min | pP: 43.0 mM; pDAc: 19.4 mM |
| ¹H and ¹³C NMR monitoring, 11971 min | pP: 42.1 mM; pDAc: 21.3 mM |
| ¹H and ¹³C NMR monitoring, 14790 min | pP: 41.3 mM; pDAc: 23.0 mM |
| ¹H and ¹³C NMR monitoring, 19178 min | pP: 40.4 mM; pDAc: 25.4 mM |
| ¹H and ¹³C NMR monitoring, 20315 min | pP: 39.9 mM; pDAc: 26.2 mM |
| ¹H and ¹³C NMR monitoring, 21758 min | pP: 39.4 mM; pDAc: 26.8 mM |
| ¹H and ¹³C NMR monitoring, 26079 min | pP: 38.5 mM; pDAc: 29.1 mM |
| ¹H and ¹³C NMR monitoring, 29023 min | pP: 37.9 mM; pDAc: 30.7 mM |
| ¹H and ¹³C NMR monitoring, 34655 min | pP: 36.4 mM; pDAc: 33.6 mM |
| ¹H and ¹³C NMR monitoring, 72276 min | pP: 28.0 mM; pDAc: 49.8 mM |
| ¹H and ¹³C NMR monitoring, 93742 min | pP: 23.6 mM; pDAc: 58.0 mM |
| ¹H and ¹³C NMR monitoring, 103777 min | pP: 21.7 mM; pDAc: 61.6 mM |
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
|---|---|
| ¹H and ¹³C NMR monitoring, sample | pAc (101 mM), pyridine-d₅ (64 mM), ethylene carbonate (104 mM), one equiv. EDC (104 mM), and mAc (233 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹³C NMR quantitation signals and calibration factors | pAn: 135.25 ppm, c 0.24/2; pAc: 134.2 ppm, c 0.23; mAc: 124.42 ppm, c 0.544; pmAn: 135.4 ppm, c 0.24; mAn: 118.20 ppm, c 0.509/2 |
| ¹H and ¹³C NMR monitoring, 87 min | pAn: 42.2 mM; pAc: 0 mM; mAc: --; pmAn: --; mAn: -- |
| ¹H and ¹³C NMR monitoring, 5624 min | pAn: 42.2 mM; pAc: 0 mM; mAc: --; pmAn: --; mAn: -- |
| ¹H and ¹³C NMR monitoring, 5700 min; 69 min after mAc addition | pAn: 32.8 mM; pAc: 0 mM; mAc: 256 mM; pmAn: 0 mM; mAn: 0 mM |
| ¹H and ¹³C NMR monitoring, 7092 min; 1461 min after mAc addition | pAn: 18.4 mM; pAc: 18.2 mM; mAc: 212 mM; pmAn: 7.79 mM; mAn: 4.43 mM |
| ¹H and ¹³C NMR monitoring, 8641 min; 3010 min after mAc addition | pAn: 15.2 mM; pAc: 36.1 mM; mAc: 218 mM; pmAn: 10.1 mM; mAn: 10.3 mM |
| ¹H and ¹³C NMR monitoring, 10002 min; 4371 min after mAc addition | pAn: 10.3 mM; pAc: 44.7 mM; mAc: 235 mM; pmAn: 10.6 mM; mAn: 9.40 mM |
| ¹H and ¹³C NMR monitoring, 11457 min; 5826 min after mAc addition | pAn: 5.24 mM; pAc: 45.7 mM; mAc: 202 mM; pmAn: 9.42 mM; mAn: 7.68 mM |
| ¹H and ¹³C NMR monitoring, 13020 min; 7389 min after mAc addition | pAn: 4.61 mM; pAc: 48.5 mM; mAc: 200 mM; pmAn: 9.38 mM; mAn: 8.93 mM |
| ¹H and ¹³C NMR monitoring, 15782 min; 10151 min after mAc addition | pAn: 4.23 mM; pAc: 53.6 mM; mAc: 216 mM; pmAn: 8.79 mM; mAn: 8.10 mM |
| ¹H and ¹³C NMR monitoring, 17364 min; 11733 min after mAc addition | pAn: 4.06 mM; pAc: 63.7 mM; mAc: 238 mM; pmAn: 10.73 mM; mAn: 7.08 mM |
| ¹H and ¹³C NMR monitoring, 18663 min; 13032 min after mAc addition | pAn: 3.47 mM; pAc: 56.1 mM; mAc: 204 mM; pmAn: 7.42 mM; mAn: 8.00 mM |
| ¹H and ¹³C NMR monitoring, 21909 min; 16278 min after mAc addition | pAn: 1.86 mM; pAc: 50.5 mM; mAc: 204 mM; pmAn: 9.15 mM; mAn: 4.26 mM |
| ¹H and ¹³C NMR monitoring, 25854 min; 20223 min after mAc addition | pAn: 2.74 mM; pAc: 64.4 mM; mAc: 228 mM; pmAn: 6.56 mM; mAn: 4.10 mM |
| ¹H and ¹³C NMR monitoring, 30246 min; 24615 min after mAc addition | pAn: 1.27 mM; pAc: 66.3 mM; mAc: 232 mM; pmAn: 4.01 mM; mAn: 1.76 mM |
| ¹H and ¹³C NMR monitoring, 34658 min; 29027 min after mAc addition | pAn: 1.49 mM; pAc: 68.1 mM; mAc: 235 mM; pmAn: 3.89 mM; mAn: 0 mM |
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
|---|---|
| ¹H and ¹³C NMR monitoring, sample | pAc (102 mM), pyridine-d₅ (62 mM), ethylene carbonate (103 mM), one equiv. EDC (104 mM), and mAc (513 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹³C NMR quantitation signals and calibration factors | pAn: 135.25 ppm, c 0.24/2; pAc: 134.2 ppm, c 0.23; mAc: 124.42 ppm, c 0.544; pmAn: 135.4 ppm, c 0.24; mAn: 118.20 ppm, c 0.509/2 |
| ¹H and ¹³C NMR monitoring, 82 min | pAn: 38.9 mM; pAc: 0 mM; mAc: --; pmAn: --; mAn: -- |
| ¹H and ¹³C NMR monitoring, 5690 min | pAn: 36.2 mM; pAc: 0 mM; mAc: --; pmAn: --; mAn: -- |
| ¹H and ¹³C NMR monitoring, 5767 min; 71 min after mAc addition | pAn: 29.2 mM; pAc: 0 mM; mAc: 555 mM; pmAn: 0 mM; mAn: 0 mM |
| ¹H and ¹³C NMR monitoring, 7084 min; 1388 min after mAc addition | pAn: 22.3 mM; pAc: 16.5 mM; mAc: 562 mM; pmAn: 4.88 mM; mAn: 2.86 mM |
| ¹H and ¹³C NMR monitoring, 8666 min; 2970 min after mAc addition | pAn: 14.2 mM; pAc: 27.5 mM; mAc: 489 mM; pmAn: 8.91 mM; mAn: 9.56 mM |
| ¹H and ¹³C NMR monitoring, 10003 min; 4307 min after mAc addition | pAn: 9.47 mM; pAc: 34.6 mM; mAc: 461 mM; pmAn: 6.40 mM; mAn: 8.36 mM |
| ¹H and ¹³C NMR monitoring, 11451 min; 5755 min after mAc addition | pAn: 7.47 mM; pAc: 43.3 mM; mAc: 509 mM; pmAn: 7.10 mM; mAn: 10.9 mM |
| ¹H and ¹³C NMR monitoring, 13008 min; 7312 min after mAc addition | pAn: 7.73 mM; pAc: 61.7 mM; mAc: 590 mM; pmAn: 7.56 mM; mAn: 12.4 mM |
| ¹H and ¹³C NMR monitoring, 15774 min; 10078 min after mAc addition | pAn: 2.93 mM; pAc: 57.0 mM; mAc: 496 mM; pmAn: 4.70 mM; mAn: 10.9 mM |
| ¹H and ¹³C NMR monitoring, 17352 min; 11656 min after mAc addition | pAn: 3.12 mM; pAc: 63.7 mM; mAc: 543 mM; pmAn: 5.82 mM; mAn: 9.35 mM |
| ¹H and ¹³C NMR monitoring, 18660 min; 12964 min after mAc addition | pAn: 2.08 mM; pAc: 65.9 mM; mAc: 548 mM; pmAn: 4.15 mM; mAn: 9.49 mM |
| ¹H and ¹³C NMR monitoring, 21923 min; 16227 min after mAc addition | pAn: 1.62 mM; pAc: 75.8 mM; mAc: 622 mM; pmAn: 3.81 mM; mAn: 9.91 mM |
| ¹H and ¹³C NMR monitoring, 25899 min; 20203 min after mAc addition | pAn: 0.956 mM; pAc: 61.9 mM; mAc: 487 mM; pmAn: 1.17 mM; mAn: 5.65 mM |
| ¹H and ¹³C NMR monitoring, 30256 min; 24560 min after mAc addition | pAn: 0 mM; pAc: 71.3 mM; mAc: 544 mM; pmAn: 0 mM; mAn: 4.27 mM |
| ¹H and ¹³C NMR monitoring, 34646 min; 28950 min after mAc addition | pAn: 0 mM; pAc: 78.0 mM; mAc: 584 mM; pmAn: 0 mM; mAn: 4.89 mM |
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
|---|---|
| ¹H and ¹³C NMR monitoring, sample | pAc (102 mM), pyridine-d₅ (62 mM), ethylene carbonate (103 mM), one equiv. EDC (104 mM), and mAc (1005 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹³C NMR quantitation signals and calibration factors | pAn: 135.25 ppm, c 0.24/2; pAc: 134.2 ppm, c 0.23; mAc: 124.42 ppm, c 0.544; pmAn: 135.4 ppm, c 0.24; mAn: 118.20 ppm, c 0.509/2 |
| ¹H and ¹³C NMR monitoring, 94 min | pAn: 46.5 mM; pAc: 0 mM; mAc: --; pmAn: --; mAn: -- |
| ¹H and ¹³C NMR monitoring, 5768 min | pAn: 34.4 mM; pAc: 0 mM; mAc: --; pmAn: --; mAn: -- |
| ¹H and ¹³C NMR monitoring, 5846 min; 75 min after mAc addition | pAn: 30.4 mM; pAc: 0 mM; mAc: 785 mM; pmAn: 0 mM; mAn: 0 mM |
| ¹H and ¹³C NMR monitoring, 7089 min; 1318 min after mAc addition | pAn: 22.4 mM; pAc: 12.0 mM; mAc: 852 mM; pmAn: 0 mM; mAn: 0 mM |
| ¹H and ¹³C NMR monitoring, 8672 min; 2901 min after mAc addition | pAn: 18.4 mM; pAc: 19.7 mM; mAc: 747 mM; pmAn: 5.85 mM; mAn: 5.48 mM |
| ¹H and ¹³C NMR monitoring, 10002 min; 4231 min after mAc addition | pAn: 12.2 mM; pAc: 26.1 mM; mAc: 693 mM; pmAn: 7.78 mM; mAn: 8.85 mM |
| ¹H and ¹³C NMR monitoring, 11448 min; 5677 min after mAc addition | pAn: 10.9 mM; pAc: 35.8 mM; mAc: 703 mM; pmAn: 5.45 mM; mAn: 7.97 mM |
| ¹H and ¹³C NMR monitoring, 13016 min; 7245 min after mAc addition | pAn: 8.12 mM; pAc: 41.6 mM; mAc: 753 mM; pmAn: 3.28 mM; mAn: 11.1 mM |
| ¹H and ¹³C NMR monitoring, 15784 min; 10013 min after mAc addition | pAn: 5.20 mM; pAc: 46.0 mM; mAc: 723 mM; pmAn: 9.12 mM; mAn: 13.5 mM |
| ¹H and ¹³C NMR monitoring, 17356 min; 11585 min after mAc addition | pAn: 3.31 mM; pAc: 51.3 mM; mAc: 774 mM; pmAn: 4.74 mM; mAn: 15.3 mM |
| ¹H and ¹³C NMR monitoring, 18658 min; 12887 min after mAc addition | pAn: 3.81 mM; pAc: 52.9 mM; mAc: 725 mM; pmAn: 5.68 mM; mAn: 12.1 mM |
| ¹H and ¹³C NMR monitoring, 21936 min; 16165 min after mAc addition | pAn: 2.46 mM; pAc: 60.6 mM; mAc: 756 mM; pmAn: 5.78 mM; mAn: 10.2 mM |
| ¹H and ¹³C NMR monitoring, 25896 min; 20125 min after mAc addition | pAn: 0.454 mM; pAc: 65.3 mM; mAc: 769 mM; pmAn: 5.91 mM; mAn: 13.1 mM |
| ¹H and ¹³C NMR monitoring, 30277 min; 24506 min after mAc addition | pAn: 1.38 mM; pAc: 62.7 mM; mAc: 729 mM; pmAn: 3.44 mM; mAn: 8.31 mM |
| ¹H and ¹³C NMR monitoring, 34730 min; 28959 min after mAc addition | pAn: 0 mM; pAc: 61.2 mM; mAc: 686 mM; pmAn: 0 mM; mAn: 5.00 mM |
| NMR concentration definition | For the polymers, apparent concentrations of the anhydride functional groups were monitored, not polymer chains |
|---|---|
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
| ¹H and ¹³C NMR monitoring, sample | pAc (101 mM), pyridine-d₅ (62 mM), ethylene carbonate (102 mM), one equiv. EDC (102 mM), and mAc (516 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹³C NMR quantitation signals and calibration factors | pP: 166.74 ppm, c 0.434/2; pDAc: 134.2 ppm, c 0.093; mAc: 124.64 ppm, c 0.544; pPmAn: 167 ppm, c 0.434; mAn: 124.20 ppm, c 0.6/2 |
| ¹H and ¹³C NMR monitoring, 62 min | pP: 46.1 mM; pDAc: 19.9 mM; mAc: --; pPmAn: --; mAn: -- |
| ¹H and ¹³C NMR monitoring, 5593 min | pP: 48.3 mM; pDAc: 22.3 mM; mAc: --; pPmAn: --; mAn: -- |
| ¹H and ¹³C NMR monitoring, 5672 min; 68 min after mAc addition | pP: 45.0 mM; pDAc: 18.2 mM; mAc: 577 mM; pPmAn: 0 mM; mAn: 0 mM |
| ¹H and ¹³C NMR monitoring, 5730 min; 126 min after mAc addition | pP: 39.0 mM; pDAc: 19.3 mM; mAc: 575 mM; pPmAn: 0 mM; mAn: 0 mM |
| ¹H and ¹³C NMR monitoring, 5794 min; 190 min after mAc addition | pP: 39.2 mM; pDAc: 19.4 mM; mAc: 572 mM; pPmAn: 0 mM; mAn: 0 mM |
| ¹H and ¹³C NMR monitoring, 5852 min; 248 min after mAc addition | pP: 35.6 mM; pDAc: 18.5 mM; mAc: 526 mM; pPmAn: 0 mM; mAn: 0 mM |
| ¹H and ¹³C NMR monitoring, 7052 min; 1448 min after mAc addition | pP: 29.9 mM; pDAc: 29.0 mM; mAc: 551 mM; pPmAn: 6.02 mM; mAn: 0 mM |
| ¹H and ¹³C NMR monitoring, 8483 min; 2879 min after mAc addition | pP: 22.5 mM; pDAc: 37.6 mM; mAc: 512 mM; pPmAn: 8.67 mM; mAn: 8.66 mM |
| ¹H and ¹³C NMR monitoring, 9954 min; 4350 min after mAc addition | pP: 17.8 mM; pDAc: 47.4 mM; mAc: 498 mM; pPmAn: 10.5 mM; mAn: 12.8 mM |
| ¹H and ¹³C NMR monitoring, 11489 min; 5885 min after mAc addition | pP: 14.2 mM; pDAc: 50.5 mM; mAc: 495 mM; pPmAn: 12.9 mM; mAn: 17.6 mM |
| ¹H and ¹³C NMR monitoring, 13064 min; 7460 min after mAc addition | pP: 9.55 mM; pDAc: 43.5 mM; mAc: 444 mM; pPmAn: 15.0 mM; mAn: 16.2 mM |
| ¹H and ¹³C NMR monitoring, 14303 min; 8699 min after mAc addition | pP: 8.46 mM; pDAc: 62.2 mM; mAc: 504 mM; pPmAn: 14.0 mM; mAn: 17.5 mM |
| ¹H and ¹³C NMR monitoring, 15536 min; 9932 min after mAc addition | pP: 7.39 mM; pDAc: 59.7 mM; mAc: 481 mM; pPmAn: 12.0 mM; mAn: 13.3 mM |
| ¹H and ¹³C NMR monitoring, 17151 min; 11547 min after mAc addition | pP: 5.61 mM; pDAc: 57.4 mM; mAc: 454 mM; pPmAn: 9.91 mM; mAn: 14.1 mM |
| ¹H and ¹³C NMR monitoring, 18569 min; 12965 min after mAc addition | pP: 7.14 mM; pDAc: 61.0 mM; mAc: 468 mM; pPmAn: 11.2 mM; mAn: 13.0 mM |
| ¹H and ¹³C NMR monitoring, 20045 min; 14441 min after mAc addition | pP: 5.61 mM; pDAc: 67.0 mM; mAc: 500 mM; pPmAn: 10.2 mM; mAn: 12.0 mM |
| ¹H and ¹³C NMR monitoring, 23040 min; 17436 min after mAc addition | pP: 4.81 mM; pDAc: 71.5 mM; mAc: 531 mM; pPmAn: 11.6 mM; mAn: 9.42 mM |
| ¹H and ¹³C NMR monitoring, 24437 min; 18833 min after mAc addition | pP: 2.99 mM; pDAc: 73.1 mM; mAc: 532 mM; pPmAn: 9.86 mM; mAn: 9.24 mM |
| ¹H and ¹³C NMR monitoring, 25910 min; 20306 min after mAc addition | pP: 4.07 mM; pDAc: 83.3 mM; mAc: 596 mM; pPmAn: 12.3 mM; mAn: 8.81 mM |
| ¹H and ¹³C NMR monitoring, 27308 min; 21704 min after mAc addition | pP: 4.11 mM; pDAc: 80.3 mM; mAc: 584 mM; pPmAn: 11.5 mM; mAn: 8.87 mM |
| ¹H and ¹³C NMR monitoring, 34599 min; 28995 min after mAc addition | pP: 4.89 mM; pDAc: 81.4 mM; mAc: 539 mM; pPmAn: 6.16 mM; mAn: 5.01 mM |
| NMR concentration definition | For the polymers, apparent concentrations of the anhydride functional groups were monitored, not polymer chains |
|---|---|
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
| ¹H and ¹³C NMR monitoring, sample | pAc (102 mM), pyridine-d₅ (62 mM), ethylene carbonate (105 mM), one equiv. EDC (104 mM), and mAc (1028 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹³C NMR quantitation signals and calibration factors | pP: 166.74 ppm, c 0.434/2; pDAc: 134.2 ppm, c 0.093; mAc: 124.64 ppm, c 0.544; pPmAn: 167 ppm, c 0.434; mAn: 124.20 ppm, c 0.6/2 |
| ¹H and ¹³C NMR monitoring, 62 min | pP: 46.4 mM; pDAc: 14.0 mM; mAc: --; pPmAn: --; mAn: -- |
| ¹H and ¹³C NMR monitoring, 5619 min | pP: 43.8 mM; pDAc: 17.4 mM; mAc: --; pPmAn: --; mAn: -- |
| ¹H and ¹³C NMR monitoring, 5682 min; 78 min after mAc addition | pP: 35.1 mM; pDAc: 12.8 mM; mAc: 924 mM; pPmAn: 0 mM; mAn: 0 mM |
| ¹H and ¹³C NMR monitoring, 7126 min; 1522 min after mAc addition | pP: 27.6 mM; pDAc: 18.4 mM; mAc: 925 mM; pPmAn: 0 mM; mAn: 0 mM |
| ¹H and ¹³C NMR monitoring, 8517 min; 2913 min after mAc addition | pP: 24.1 mM; pDAc: 25.6 mM; mAc: 900 mM; pPmAn: 34.9 mM; mAn: 10.5 mM |
| ¹H and ¹³C NMR monitoring, 10002 min; 4398 min after mAc addition | pP: 18.0 mM; pDAc: 31.2 mM; mAc: 808 mM; pPmAn: 34.6 mM; mAn: 10.4 mM |
| ¹H and ¹³C NMR monitoring, 11558 min; 5954 min after mAc addition | pP: 12.9 mM; pDAc: 33.9 mM; mAc: 753 mM; pPmAn: 46.8 mM; mAn: 14.1 mM |
| ¹H and ¹³C NMR monitoring, 13388 min; 7784 min after mAc addition | pP: 11.3 mM; pDAc: 40.6 mM; mAc: 783 mM; pPmAn: 52.1 mM; mAn: 15.6 mM |
| ¹H and ¹³C NMR monitoring, 14546 min; 8942 min after mAc addition | pP: 11.0 mM; pDAc: 41.4 mM; mAc: 742 mM; pPmAn: 64.1 mM; mAn: 19.2 mM |
| ¹H and ¹³C NMR monitoring, 16162 min; 10558 min after mAc addition | pP: 8.66 mM; pDAc: 43.7 mM; mAc: 757 mM; pPmAn: 67.5 mM; mAn: 20.3 mM |
| ¹H and ¹³C NMR monitoring, 17390 min; 11786 min after mAc addition | pP: 8.88 mM; pDAc: 54.9 mM; mAc: 907 mM; pPmAn: 81.0 mM; mAn: 24.3 mM |
| ¹H and ¹³C NMR monitoring, 18971 min; 13367 min after mAc addition | pP: 7.10 mM; pDAc: 53.2 mM; mAc: 831 mM; pPmAn: 65.7 mM; mAn: 19.7 mM |
| ¹H and ¹³C NMR monitoring, 20324 min; 14720 min after mAc addition | pP: 5.34 mM; pDAc: 58.8 mM; mAc: 863 mM; pPmAn: 76.7 mM; mAn: 23.0 mM |
| ¹H and ¹³C NMR monitoring, 21769 min; 16165 min after mAc addition | pP: 3.94 mM; pDAc: 47.8 mM; mAc: 703 mM; pPmAn: 55.4 mM; mAn: 16.6 mM |
| ¹H and ¹³C NMR monitoring, 23382 min; 17778 min after mAc addition | pP: 5.03 mM; pDAc: 60.5 mM; mAc: 842 mM; pPmAn: 67.3 mM; mAn: 20.2 mM |
| ¹H and ¹³C NMR monitoring, 26089 min; 20485 min after mAc addition | pP: 5.54 mM; pDAc: 65.2 mM; mAc: 932 mM; pPmAn: 70.7 mM; mAn: 21.2 mM |
| ¹H and ¹³C NMR monitoring, 27667 min; 22063 min after mAc addition | pP: 4.84 mM; pDAc: 56.5 mM; mAc: 808 mM; pPmAn: 61.2 mM; mAn: 18.3 mM |
| ¹H and ¹³C NMR monitoring, 28959 min; 23355 min after mAc addition | pP: 4.11 mM; pDAc: 54.2 mM; mAc: 755 mM; pPmAn: 55.2 mM; mAn: 16.5 mM |
| ¹H and ¹³C NMR monitoring, 32122 min; 26518 min after mAc addition | pP: 1.04 mM; pDAc: 57.8 mM; mAc: 787 mM; pPmAn: 52.6 mM; mAn: 15.8 mM |
| ¹H and ¹³C NMR monitoring, 34595 min; 28991 min after mAc addition | pP: 2.38 mM; pDAc: 63.2 mM; mAc: 822 mM; pPmAn: 55.8 mM; mAn: 16.7 mM |
| ¹H and ¹³C NMR monitoring, 40663 min; 35059 min after mAc addition | pP: 0 mM; pDAc: 68.4 mM; mAc: 893 mM; pPmAn: 49.7 mM; mAn: 14.9 mM |
| NMR concentration definition | For the polymers, apparent concentrations of the anhydride functional groups were monitored, not polymer chains |
|---|---|
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
| ¹H NMR monitoring, sample | pDAc (101 mM), pyridine-d₅ (61 mM), ethylene carbonate (103 mM), one equiv. EDC (102 mM), and AcOH (10 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹H NMR quantitation signals | pP: 8.18 ppm; pDAc: 8.07 ppm; AcOH: 2.08 ppm |
| ¹H NMR monitoring, 107 min | pP: 44.3 mM; pDAc: 19.4 mM; AcOH: --; pPAcAn: --; Ac₂O: -- |
| ¹H NMR monitoring, 5856 min | pP: 42.5 mM; pDAc: 22.8 mM; AcOH: --; pPAcAn: --; Ac₂O: -- |
| ¹H NMR monitoring, 5947 min; 61 min after AcOH addition | pP: 42.0 mM; pDAc: 24.1 mM; AcOH: 8.29 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 7238 min; 1352 min after AcOH addition | pP: 40.4 mM; pDAc: 27.4 mM; AcOH: 9.00 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 8693 min; 2807 min after AcOH addition | pP: 38.4 mM; pDAc: 30.4 mM; AcOH: 8.32 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 10058 min; 4172 min after AcOH addition | pP: 37.3 mM; pDAc: 33.5 mM; AcOH: 9.16 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 11548 min; 5662 min after AcOH addition | pP: 35.4 mM; pDAc: 36.4 mM; AcOH: 7.97 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 13014 min; 7128 min after AcOH addition | pP: 34.2 mM; pDAc: 38.5 mM; AcOH: 8.51 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 14467 min; 8581 min after AcOH addition | pP: 33.0 mM; pDAc: 41.3 mM; AcOH: 8.53 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 17412 min; 11526 min after AcOH addition | pP: 31.5 mM; pDAc: 45.1 mM; AcOH: 9.20 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 20365 min; 14479 min after AcOH addition | pP: 29.4 mM; pDAc: 48.6 mM; AcOH: 9.21 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 27551 min; 21665 min after AcOH addition | pP: 27.5 mM; pDAc: 53.2 mM; AcOH: 9.01 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 31608 min; 25722 min after AcOH addition | pP: 23.0 mM; pDAc: 60.6 mM; AcOH: 8.57 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 35899 min; 30013 min after AcOH addition | pP: 21.2 mM; pDAc: 63.5 mM; AcOH: 7.85 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 48928 min; 43042 min after AcOH addition | pP: 15.8 mM; pDAc: 71.6 mM; AcOH: 5.63 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 53097 min; 47211 min after AcOH addition | pP: 14.1 mM; pDAc: 75.1 mM; AcOH: 4.76 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 57852 min; 51966 min after AcOH addition | pP: 10.6 mM; pDAc: 81.2 mM; AcOH: 5.37 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| NMR concentration definition | For the polymers, apparent concentrations of the anhydride functional groups were monitored, not polymer chains |
|---|---|
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
| ¹H NMR monitoring, sample | pDAc (101 mM), pyridine-d₅ (61 mM), ethylene carbonate (103 mM), one equiv. EDC (102 mM), and AcOH (32 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹H NMR quantitation signals | pP: 8.18 ppm; pDAc: 8.07 ppm; AcOH: 2.08 ppm |
| ¹H NMR monitoring, 107 min | pP: 44.3 mM; pDAc: 19.4 mM; AcOH: --; pPAcAn: --; Ac₂O: -- |
| ¹H NMR monitoring, 5856 min | pP: 42.5 mM; pDAc: 22.8 mM; AcOH: --; pPAcAn: --; Ac₂O: -- |
| ¹H NMR monitoring, 5954 min; 66 min after AcOH addition | pP: 42.2 mM; pDAc: 23.4 mM; AcOH: 76.8 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 7245 min; 1357 min after AcOH addition | pP: 37.7 mM; pDAc: 32.3 mM; AcOH: 76.4 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 8712 min; 2824 min after AcOH addition | pP: 34.0 mM; pDAc: 39.1 mM; AcOH: 76.5 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 10066 min; 4178 min after AcOH addition | pP: 31.2 mM; pDAc: 44.7 mM; AcOH: 76.5 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 11555 min; 5667 min after AcOH addition | pP: 28.7 mM; pDAc: 49.7 mM; AcOH: 76.5 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 13022 min; 7134 min after AcOH addition | pP: 26.3 mM; pDAc: 54.3 mM; AcOH: 76.7 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 14482 min; 8594 min after AcOH addition | pP: 24.7 mM; pDAc: 57.6 mM; AcOH: 77.4 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 17429 min; 11541 min after AcOH addition | pP: 22.0 mM; pDAc: 63.9 mM; AcOH: 76.8 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 20372 min; 14484 min after AcOH addition | pP: 19.3 mM; pDAc: 68.8 mM; AcOH: 76.5 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 27558 min; 21670 min after AcOH addition | pP: 14.0 mM; pDAc: 78.0 mM; AcOH: 76.0 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 31616 min; 25728 min after AcOH addition | pP: 11.9 mM; pDAc: 83.1 mM; AcOH: 76.5 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 35907 min; 30019 min after AcOH addition | pP: 9.66 mM; pDAc: 85.1 mM; AcOH: 74.6 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 53106 min; 47218 min after AcOH addition | pP: 4.91 mM; pDAc: 96.0 mM; AcOH: 75.9 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 57843 min; 51955 min after AcOH addition | pP: 3.19 mM; pDAc: 98.7 mM; AcOH: 75.0 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| NMR concentration definition | For the polymers, apparent concentrations of the anhydride functional groups were monitored, not polymer chains |
|---|---|
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
| ¹H NMR monitoring, sample | pDAc (101 mM), pyridine-d₅ (63 mM), ethylene carbonate (103 mM), one equiv. EDC (104 mM), and AcOH (118 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹H NMR quantitation signals | pP: 8.18 ppm; pDAc: 8.07 ppm; AcOH: 2.08 ppm |
| ¹H NMR monitoring, 70 min | pP: 45.2 mM; pDAc: 16.2 mM; AcOH: --; pPAcAn: --; Ac₂O: -- |
| ¹H NMR monitoring, 5492 min | pP: 43.0 mM; pDAc: 20.0 mM; AcOH: --; pPAcAn: --; Ac₂O: -- |
| ¹H NMR monitoring, 5604 min; 62 min after AcOH addition | pP: 42.2 mM; pDAc: 21.0 mM; AcOH: 102 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 7340 min; 1798 min after AcOH addition | pP: 30.8 mM; pDAc: 43.7 mM; AcOH: 101 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 8676 min; 3134 min after AcOH addition | pP: 25.0 mM; pDAc: 54.8 mM; AcOH: 103 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 10199 min; 4657 min after AcOH addition | pP: 20.1 mM; pDAc: 64.2 mM; AcOH: 100 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 11624 min; 6082 min after AcOH addition | pP: 17.0 mM; pDAc: 71.5 mM; AcOH: 102 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 14227 min; 8685 min after AcOH addition | pP: 12.3 mM; pDAc: 81.0 mM; AcOH: 104 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 16117 min; 10575 min after AcOH addition | pP: 9.7.0 mM; pDAc: 84.4 mM; AcOH: 101 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 17587 min; 12045 min after AcOH addition | pP: 8.30 mM; pDAc: 87.5 mM; AcOH: 103 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 19044 min; 13502 min after AcOH addition | pP: 7.15 mM; pDAc: 89.7 mM; AcOH: 101 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 20407 min; 14865 min after AcOH addition | pP: 6.13 mM; pDAc: 91.3 mM; AcOH: 102 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 21897 min; 16355 min after AcOH addition | pP: 5.14 mM; pDAc: 93.0 mM; AcOH: 101 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 23362 min; 17820 min after AcOH addition | pP: 4.38 mM; pDAc: 94.5 mM; AcOH: 101 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| NMR concentration definition | For the polymers, apparent concentrations of the anhydride functional groups were monitored, not polymer chains |
|---|---|
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
| ¹H NMR monitoring, sample | pDAc (102 mM), pyridine-d₅ (63 mM), ethylene carbonate (104 mM), one equiv. EDC (104 mM), and AcOH (242 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹H NMR quantitation signals | pP: 8.18 ppm; pDAc: 8.07 ppm; AcOH: 2.08 ppm |
| ¹H NMR monitoring, 72 min | pP: 44.4 mM; pDAc: 18.3 mM; AcOH: --; pPAcAn: --; Ac₂O: -- |
| ¹H NMR monitoring, 5496 min | pP: 42.6 mM; pDAc: 21.9 mM; AcOH: --; pPAcAn: --; Ac₂O: -- |
| ¹H NMR monitoring, 5615 min; 74 min after AcOH addition | pP: 41.1 mM; pDAc: 23.6 mM; AcOH: 246 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 7343 min; 1802 min after AcOH addition | pP: 25.9 mM; pDAc: 53.4 mM; AcOH: 244 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 8687 min; 3146 min after AcOH addition | pP: 19.2 mM; pDAc: 68.0 mM; AcOH: 249 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 10203 min; 4662 min after AcOH addition | pP: 13.9 mM; pDAc: 78.1 mM; AcOH: 249 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 11629 min; 6088 min after AcOH addition | pP: 10.4 mM; pDAc: 85.2 mM; AcOH: 249 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 14231 min; 8690 min after AcOH addition | pP: 6.10 mM; pDAc: 92.9 mM; AcOH: 245 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 16122 min; 10581 min after AcOH addition | pP: 4.28 mM; pDAc: 95.4 mM; AcOH: 244 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 17595 min; 12054 min after AcOH addition | pP: 3.06 mM; pDAc: 99.0 mM; AcOH: 250 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| NMR concentration definition | For the polymers, apparent concentrations of the anhydride functional groups were monitored, not polymer chains |
|---|---|
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
| ¹H NMR monitoring, sample | pAc (101 mM), pyridine-d₅ (59 mM), ethylene carbonate (102 mM), one equiv. EDC (104 mM), and AcOH (541 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹H NMR quantitation signals | pP: 8.18 ppm; pDAc: 8.07 ppm; AcOH: 2.08 ppm |
| ¹H NMR monitoring, 64 min | pP: 46.4 mM; pDAc: 19.4 mM; AcOH: --; pPAcAn: --; Ac₂O: -- |
| ¹H NMR monitoring, 5644 min | pP: 45.1 mM; pDAc: 21.7 mM; AcOH: --; pPAcAn: --; Ac₂O: -- |
| ¹H NMR monitoring, 5714 min; 58 min after AcOH addition | pP: 43.8 mM; pDAc: 22.6 mM; AcOH: 562 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 7023 min; 1367 min after AcOH addition | pP: 32.4 mM; pDAc: 43.5 mM; AcOH: 544 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 8617 min; 2961 min after AcOH addition | pP: 23.3 mM; pDAc: 62.6 mM; AcOH: 542 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 10056 min; 4400 min after AcOH addition | pP: 17.4 mM; pDAc: 74.4 mM; AcOH: 544 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 11374 min; 5718 min after AcOH addition | pP: 13.5 mM; pDAc: 82.0 mM; AcOH: 549 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 12916 min; 7260 min after AcOH addition | pP: 9.99 mM; pDAc: 87.7 mM; AcOH: 555 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 14406 min; 8750 min after AcOH addition | pP: 7.16 mM; pDAc: 93.6 mM; AcOH: 551 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 15722 min; 10066 min after AcOH addition | pP: 5.36 mM; pDAc: 99.0 mM; AcOH: 571 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 16966 min; 11310 min after AcOH addition | pP: 3.75 mM; pDAc: 100 mM; AcOH: 562 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 18716 min; 13060 min after AcOH addition | pP: 2.85 mM; pDAc: 101 mM; AcOH: 544 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 20135 min; 14479 min after AcOH addition | pP: 2.10 mM; pDAc: 101 mM; AcOH: 536 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 28916 min; 23260 min after AcOH addition | pP: 0 mM; pDAc: 103 mM; AcOH: 531 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| NMR concentration definition | For the polymers, apparent concentrations of the anhydride functional groups were monitored, not polymer chains |
|---|---|
| NMR reporting reference | Calibrated using residual undeuterated solvent as an internal reference (CD₃COCD₃ δ 2.09 and 30.60 ppm) and reported in parts per million relative to trimethylsilane (TMS, δ 0.00 ppm) |
| ¹H NMR monitoring, sample | pAc (101 mM), pyridine-d₅ (61 mM), ethylene carbonate (102 mM), one equiv. EDC (104 mM), and AcOH (1134 mM) in 80:20 acetone-d₆:D₂O at rt |
| ¹H NMR quantitation signals | pP: 8.18 ppm; pDAc: 8.07 ppm; AcOH: 2.08 ppm |
| ¹H NMR monitoring, 59 min | pP: 44.8 mM; pDAc: 14.1 mM; AcOH: --; pPAcAn: --; Ac₂O: -- |
| ¹H NMR monitoring, 5765 min | pP: 43.0 mM; pDAc: 17.7 mM; AcOH: --; pPAcAn: --; Ac₂O: -- |
| ¹H NMR monitoring, 5828 min; 75 min after AcOH addition | pP: 42.1 mM; pDAc: 21.7 mM; AcOH: 1240 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 7141 min; 1388 min after AcOH addition | pP: 28.1 mM; pDAc: 47.0 mM; AcOH: 1190 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 8843 min; 3090 min after AcOH addition | pP: 17.8 mM; pDAc: 68.5 mM; AcOH: 1220 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 10038 min; 4285 min after AcOH addition | pP: 12.9 mM; pDAc: 78.9 mM; AcOH: 1230 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 11557 min; 5804 min after AcOH addition | pP: 8.54 mM; pDAc: 86.8 mM; AcOH: 1210 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 12907 min; 7154 min after AcOH addition | pP: 6.08 mM; pDAc: 92.1 mM; AcOH: 1200 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 14461 min; 8708 min after AcOH addition | pP: 3.80 mM; pDAc: 96.8 mM; AcOH: 1220 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| ¹H NMR monitoring, 17458 min; 11705 min after AcOH addition | pP: 1.77 mM; pDAc: 100.5 mM; AcOH: 1210 mM; pPAcAn: 0 mM; Ac₂O: 0 mM |
| NMR reporting qualifier | ¹³C NMR signal intensities were calibrated against concentrations measured by ¹H NMR; calibration factors for pmAn were assumed identical to those of pAn or mAn depending on which side of pmAn was considered; [pAc] + 2[pAn] + [pmAn] was verified as constant; because of the assumption and ¹³C NMR signal-to-noise, the results should be treated as semi-quantitative and as broad estimates of rate constants |
|---|---|
| Experimental kinetic fit, basis | Four-parameter simultaneous fit using the steady-state approximation in pI and mI |
| Experimental kinetic fit, parameter definitions | k₁ and k₂ are the rates of attack by pyridine on pAn and mAn, respectively; α₁ = k₃/k₋₁ and α₂ = k₄/k₋₂ represent partitioning of the corresponding intermediates between hydrolysis and exchange |
| Experimental kinetic fit, residual weighting | kinmodel optionally weights residuals by 1/C, where C is the concentration of interest; lower bound on C: 5 mM |
| Experimental kinetic fit, k₁ | 2.4 (+0.3/−0.5) × 10⁻⁴ min⁻¹ |
| Experimental kinetic fit, k₂ | 3.9 (+0.6/−1.2) × 10⁻⁴ min⁻¹ |
| Experimental kinetic fit, α₁ | 0.7 (+0.3/−0.1) mM |
| Experimental kinetic fit, α₂ | 140 (+80/−20) mM |
| Experimental kinetic fit, uncertainty estimation | 95 % confidence interval from 10,000 non-parametric random-x bootstrap iterations, corresponding to the 2.5 % and 97.5 % entries in the ranked results |
| NMR concentration definition | For the polymers, apparent concentrations of the anhydride functional groups were monitored, not polymer chains |
|---|---|
| NMR reporting qualifier | Because of inherent challenges of monitoring kinetics by ¹³C NMR, including signal-to-noise, the results should be treated as semi-quantitative and as broad estimates of rate constants |
| Experimental kinetic fit, basis | Four-parameter simultaneous fit using the steady-state approximation |
| Experimental kinetic fit, parameter definitions | k₁ and k₂ are the rates of attack by pyridine on pP and mAn, respectively; α₁ = k₃/k₋₁ and α₂ = k₄/k₋₂ represent partitioning of the corresponding intermediates between hydrolysis and exchange |
| Experimental kinetic fit, residual weighting | kinmodel optionally weights residuals by 1/C, where C is the concentration of interest; lower bound on C: 5 mM |
| Experimental kinetic fit, k₁ | 1.3 (+0.2/−0.2) × 10⁻⁴ min⁻¹ |
| Experimental kinetic fit, k₂ | 1.3 (+0.5/−0.5) × 10⁻⁴ min⁻¹ |
| Experimental kinetic fit, α₁ | 1.2 (+0.3/−0.2) mM |
| Experimental kinetic fit, α₂ | 200 (+100/−100) mM |
| Experimental kinetic fit, uncertainty estimation | 95 % confidence interval from 10,000 non-parametric random-x bootstrap iterations, corresponding to the 2.5 % and 97.5 % entries in the ranked results |
| NMR concentration definition | For the polymers, apparent concentrations of the anhydride functional groups were monitored, not polymer chains |
|---|---|
| Experimental kinetic fit, basis | Four-parameter simultaneous fit using the steady-state approximation |
| Experimental kinetic fit, parameter definitions | k₁ and k₂ are the rates of attack by pyridine on pP and Ac₂O, respectively; α₁ = k₃/k₋₁ and α₂ = k₄/k₋₂ represent partitioning of the corresponding intermediates between hydrolysis and exchange |
| Experimental kinetic fit, residual weighting | kinmodel optionally weights residuals by 1/C, where C is the concentration of interest; lower bound on C: 5 mM |
| Experimental kinetic fit, k₁ | 2.3 (+0.1/−0.1) × 10⁻⁴ min⁻¹ |
| Experimental kinetic fit, k₂ | 500 (+500/−400) min⁻¹ |
| Experimental kinetic fit, α₁ | 0.6 (+0.1/−0.3) mM |
| Experimental kinetic fit, α₂ | 11 (+116/−7) mM |
| Experimental kinetic fit, reporting qualifier | Uncertainties in k₂ and α₂ are large because two of the anhydrides were not observed |
| Experimental kinetic fit, parameter-determination qualifier | k₂ and α₂ are not determined by the data |
| Experimental kinetic fit, uncertainty estimation | 95 % confidence interval from 10,000 non-parametric random-x bootstrap iterations, corresponding to the 2.5 % and 97.5 % entries in the ranked results |