Supporting Information for Chapter 2 - Polyglyoxylates: a new class of triggerable self-immolat

Figure A2. 11_{H NMR spectrum of poly(ethyl glyoxylate) without end-cap (Polymer}

2.1) (CDCl3, 400 MHz).

Figure A2. 2 13_{C NMR spectrum of poly(ethyl glyoxylate) without end-cap (Polymer}

Figure A2. 31_{H NMR spectrum of poly(ethyl glyoxylate) end-capped by phenyl}

isocyanate (Polymer 2.2) (CDCl3, 400 MHz).

Figure A2. 413_{C NMR spectrum of poly(ethyl glyoxylate) end-capped by phenyl}

Figure A2. 5 1_{H NMR spectrum of poly(ethyl glyoxylate) end-capped by benzyl}

chloroformate (Polymer 2.3) (CDCl3, 400 MHz).

Figure A2. 6 13_{C NMR spectrum of poly(ethyl glyoxylate) end-capped by benzyl}

Figure A2. 7 1_{H NMR spectrum of poly(ethyl glyoxylate) end-capped by NVOC-Cl}

(Polymer 2.4) (CDCl3, 400 MHz).

Figure A2. 813_{C NMR spectrum of poly(ethyl glyoxylate) end-capped by NVOC-Cl}

Figure A2. 91_{H NMR spectrum of methyl glyoxylate compound 2.8 (CDCl} 3, 400

Figure A2. 101_{H NMR spectrum of ethyl glyoxylate (CDCl}

3, 400 MHz).

Figure A2. 111_{H NMR spectrum of}_n_{-butyl glyoxylate compound 2.9 (CDCl} 3, 400

Figure A2. 12 13_{C NMR spectrum of}_n_{-butyl glyoxylate compound 2.9 (CDCl} 3, 150

MHz).

Figure A2. 131_{H NMR spectrum of benzyl glyoxylate compound 2.10 (CDCl} 3, 400

Figure A2. 141_{H NMR spectrum of poly(methyl glyoxylate) end-capped by NVOC-}

Figure A2. 15 13_{C NMR spectrum of poly(methyl glyoxylate) end-capped by NVOC-}

Cl (Polymer 2.11) (CDCl3, 150 MHz).

Figure A2. 161_{H NMR spectrum of poly(butyl glyoxylate) end-capped by NVOC-Cl}

Figure A2. 1713_{C NMR spectrum of poly(butyl glyoxylate) end-capped by NVOC-Cl}

(Polymer 2.12) (CDCl3, 150 MHz).

Figure A2. 18 1_{H NMR spectrum of poly(benzyl glyoxylate) end-capped by NVOC-}

Figure A2. 19 13_{C NMR spectrum of poly(benzyl glyoxylate) end-capped by NVOC-}

Cl (Polymer 2.13) (CDCl3, 150 MHz).

Figure A2. 20 1_{H NMR spectrum of poly(ethyl glyoxylate)-}_co_{-(methyl glyoxylate)}

end-capped by NVOC-Cl (Polymer 2.14) (CDCl3, 400 MHz).

Figure A2. 2113_{C NMR spectrum of poly(ethyl glyoxylate)-}_co_{-(methyl glyoxylate)}

Figure A2. 22 1_{H NMR spectrum of poly(ethyl glyoxylate)-}_co_{-(butyl glyoxylate) end-}

capped by NVOC-Cl (Polymer 2.15) (CDCl3, 400 MHz).

Figure A2. 2313_{C NMR spectrum of poly(ethyl glyoxylate)-}_co_{-(butyl glyoxylate)}

Figure A2. 241_{H NMR spectrum of compound 2.17}_(DMSO-_d6_{, 400 MHz).}

Figure A2. 261_{H NMR spectrum of compound 2.18 (CDCl}

3, 400 MHz).

Figure A2. 2713_{C NMR spectrum of compound 2.18 (CDCl}

Figure A2. 281_{H NMR spectrum of poly(ethyl glyoxylate) end-capped by compound}

2.18 (Polymer 2.19) (CDCl3, 400 MHz).

Figure A2. 29 13_{C NMR spectrum of poly(ethyl glyoxylate) end-capped by}

Figure A2. 30 1_{H NMR spectrum of block polymer (Polymer 2.21) (CDCl}

3, 400MHz).

Figure A2. 31 13_{C NMR spectrum of block polymer (Polymer 2.21) (CDCl}₃_{, 150}

Figure A2. 32SEC trace for Polymer 2.4

Figure A2. 34SEC curve of Polymer 2.14

Figure A2. 36TGA curves for: (a) polyglyoxylates 2.11-2.15 compared with PEtG 2.4; (b) triblock copolymer 2.21.

Figure A2. 37UV-visible spectroscopy of polymer 2.4 and its end-cap cleavage following different irradiation time with UV light.

Degradation studies on polymer 2.3.

To demonstrate that UV light was selective for cleaving the end-cap to initiate

depolymerization rather than the polymer backbone, polymer 2.3 was treated as described in the manuscript for the study of PEtG 2.4 degradation in solution.

Figure A2. 381_{H NMR spectrum of polymer 2.3 after UV irradiation following the}

same procedure described for the study of polymer 2.4 (following incubation in 9:1 CD3CN:D2O). No changes were observed, indicating that the polymer is stable

Figure A2. 39 Zoom of 1_{H NMR spectra corresponding to Figure 2.2a from chapter 2, showing} relative peak integrals that were used to calculate the % polymer remaining for Figure 2.4 of

chapter 2. The initial integral (t = 0) for the peak at 5.6 ppm was set to 100 to indicate 100% polymer and it decreased over time. Integration of the peak at 4.2 ppm remained constant as it

corresponds to the CH3CH2-O- in both the polymer and degradation product. Before UV

3 hours 1 day 7 days

Figure A2. 40 Zoom of 1_{H NMR spectra corresponding to Figure 2.2a from the manuscript,}

showing relative peak integrals that were used to calculate the % polymer remaining for Figure 2.4 of the manuscript. The initial integral (t = 0) for the peak at 5.6 ppm was set to 100 to indicate 100%

polymer and it decreased over time. Integration of the peak at 4.2 ppm remained constant as it corresponds to the CH3CH2-O- in both the polymer and degradation product.

0 hours 3 hours 1 day 7 days

Degradation studies on polymers 2.11 to 2.15 and 2.21.

As for polymer 2.4, before irradiation, the polymers showed broad peaks and several small peaks corresponding to the end-cap. However, following irradiation of a 9:1 CD3CN:D2O solution of the polymer with UV light and incubation at ambient

temperature (21 C), the broad peak at 5.5 ppm started decreasing, and a new singlet at 5.1 ppm (alkyl glyoxylate hydrate) began increasing (a in Figures A2.51 – 2.56). Peaks associated with the alkyl/benzyl chains became sharper. In each case the control group (b in Figures A2.51 – 2.56) did not show any signs of significant degradation.

Figure A2. 41(a) 1_{H NMR spectra of polymer 2.11 after irradiation; (b)}1_{H NMR}

spectra of polymer 2.11 without irradiation (following incubation in 9:1 CD3CN:D2O).

Figure A2. 42(a) 1_{H NMR spectra of polymer 2.12 after irradiation; (b)}1_{H NMR}

spectra of polymer 2.12 without irradiation (following incubation in 9:1 CD3CN:D2O).

Figure S52. (a) 1_{H NMR spectra of polymer 13 after irradiation; (b)}1_{H NMR spectra of polymer 13}

without irradiation (following incubation in 9:1 CD3CN:D2O). Note that in this case there was a small

amount of benzyl glyoxylate hydrate was observable from the control group (Figure b) as well, but it did not showed any signs of increasing, and even after 8 days less than 2 % of hydrate was observed.

Figure A2. 43 (a) 1_{H NMR spectra of polymer 2.13 after irradiation; (b)}1_{H NMR}

spectra of polymer 2.13 without irradiation (following incubation in 9:1 CD3CN:D2O)

Figure A2. 44(a) 1_{H NMR spectra of polymer 2.14 after irradiation; (b)}1_{H NMR}

spectra of polymer 2.14 without irradiation (following incubation in 9:1 CD3CN:D2O)

Figure A2. 45(a) 1_{H NMR spectra of polymer 2.15 after irradiation; (b)}1_{H NMR}

spectra of polymer 2.15 without irradiation (following incubation in 9:1 CD3CN:D2O).

Figure A2. 46 (a) 1_{H NMR spectra of polymer 2.21 after irradiation; (b)}1_{H NMR}

spectra of polymer 2.21 without irradiation (following incubation in 9:1 CD3CN:D2O).

Depolymerization profiles of individual polyglyoxylates

Figure A2. 47Depolymerization of polymer 2.4 following cleavage of the NVOC end-caps by UV irradiation in 9:1 CD3CN:D2O following by incubation at ambient

Figure A2. 48Depolymerization of polymer 2.11 following cleavage of the NVOC end-caps by UV irradiation in 9:1 CD3CN:D2O following by incubation at ambient

temperature (21C).

Figure A2. 49Depolymerization of polymer 2.12 following cleavage of the NVOC end-caps by UV irradiation in 9:1 CD3CN:D2O following by incubation at ambient

Figure A2. 50 Depolymerization of polymer 2.13 following cleavage of the NVOC end-caps by UV irradiation in 9:1 CD3CN:D2O following by incubation at ambient

temperature (21C).

Figure A2. 51Figure SX. Depolymerization of polymer 2.14 following cleavage of the NVOC end-caps by UV irradiation in 9:1 CD3CN:D2O following by incubation at

Figure A2. 52 Depolymerization of polymer 2.15 following cleavage of the NVOC end-caps by UV irradiation in 9:1 CD3CN:D2O following by incubation at ambient

Figure A2. 53Depolymerization of polymer 2.21 following cleavage of the NVOC end-caps by UV irradiation in 9:1 CD3CN:D2O following by incubation at ambient

In document Polyglyoxylates: a new class of triggerable self-immolative polymers (Page 140-170)