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Supplementary material Enzyme-catalyzed simultaneous hydrolysis-glycolysis reactions reveals tunability on PET depolymerization products Aline M. de Castro a* , Adriano Carniel b , Lys Sirelli c , Marcos L. Dias c , Sonia Maria Cabral de Menezes d , Luiz Silvino Chinelatto Junior d , Hercílio de Angeli Honorato d a Biotechnology Division, Research and Development Center (Cenpes), PETROBRAS, Av. Horácio Macedo, 950, 21941-915. Rio de Janeiro, Brazil. b Falcão Bauer. R. Aquinos, 111. Água Branca, São Paulo, 05036-070, Brazil. c Institute of Macromolecules Professor Eloisa Mano (IMA), Federal University of Rio de Janeiro (UFRJ). Av. Horácio Macedo, 2030, 21941-598. Rio de Janeiro, Brazil. 1

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Page 1: ars.els-cdn.com€¦ · Web viewEloisa Mano (IMA), Federal University of Rio de Janeiro (UFRJ). Av. Horácio Macedo, 2030, 21941-598. Rio de Janeiro, Brazil. d Chemistry Division,

Supplementary material

Enzyme-catalyzed simultaneous hydrolysis-glycolysis reactions reveals

tunability on PET depolymerization products

Aline M. de Castroa*, Adriano Carnielb, Lys Sirelli c, Marcos L. Dias c, Sonia Maria Cabral de

Menezes d, Luiz Silvino Chinelatto Junior d, Hercílio de Angeli Honorato d

a Biotechnology Division, Research and Development Center (Cenpes), PETROBRAS,

Av. Horácio Macedo, 950, 21941-915. Rio de Janeiro, Brazil.

b Falcão Bauer. R. Aquinos, 111. Água Branca, São Paulo, 05036-070, Brazil.

c Institute of Macromolecules Professor Eloisa Mano (IMA), Federal University of Rio

de Janeiro (UFRJ). Av. Horácio Macedo, 2030, 21941-598. Rio de Janeiro, Brazil.

d Chemistry Division, Research and Development Center (Cenpes), PETROBRAS,

Av. Horácio Macedo, 950, 21941-915. Rio de Janeiro, Brazil.

* Corresponding author. E-mail: [email protected]

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Page 2: ars.els-cdn.com€¦ · Web viewEloisa Mano (IMA), Federal University of Rio de Janeiro (UFRJ). Av. Horácio Macedo, 2030, 21941-598. Rio de Janeiro, Brazil. d Chemistry Division,

Fig. 1S. DSC curves of PC-PET and oligomers O1, O2 and O3 (First heating run).

Fig. 2S. DSC curves of PC-PET and oligomers O1, O2 and O3 (Second heating run).

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Page 3: ars.els-cdn.com€¦ · Web viewEloisa Mano (IMA), Federal University of Rio de Janeiro (UFRJ). Av. Horácio Macedo, 2030, 21941-598. Rio de Janeiro, Brazil. d Chemistry Division,

Fig. 3S. DSC curves of PC-PET and oligomers O1, O2 and O3 (Second cooling run).

Fig. 4S. TG curves of PC-PET and oligomers O1, O2 and O3.

3

Page 4: ars.els-cdn.com€¦ · Web viewEloisa Mano (IMA), Federal University of Rio de Janeiro (UFRJ). Av. Horácio Macedo, 2030, 21941-598. Rio de Janeiro, Brazil. d Chemistry Division,

Fig. 5S. SEM images of (a) O1, (b) O2 and (c) O3 particles before the reactions. Scale bars

correspond to 20 µm.

4

(c)

(b)(a)

Page 5: ars.els-cdn.com€¦ · Web viewEloisa Mano (IMA), Federal University of Rio de Janeiro (UFRJ). Av. Horácio Macedo, 2030, 21941-598. Rio de Janeiro, Brazil. d Chemistry Division,

Figure 6S. T2 relaxation curves obtained by CPMG sequence of oligomers O1, O2 and O3,

and PC-PET.

5

Normalized intensity

Time (ms)

Page 6: ars.els-cdn.com€¦ · Web viewEloisa Mano (IMA), Federal University of Rio de Janeiro (UFRJ). Av. Horácio Macedo, 2030, 21941-598. Rio de Janeiro, Brazil. d Chemistry Division,

Fig. 7S. Time course of TPA (a), MHET (b) and BHET (c) concentrations during

simultaneous hydrolysis-glycolysis reactions of PC-PET catalyzed by HiC. Reactions were

carried out at 62 °C and 0.02 gprotein/gPET. Different added EG contents were investigated: 0%

(closed squares), 20% (closed circles), 40% (closed triangles), 60% (open squares), 80%

(open circles) and 100% (open triangles).

6

0

10

20

30

40

50

60

70

80

90

100

0 2 4 6 8 10 12 14 16

TPA

Con

cent

ratio

n (m

M)

Reaction time (days)

A

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0 2 4 6 8 10 12 14 16

BH

ET C

once

ntra

tion

(mM

)

Reaction time (days)

C

0

5

10

15

20

25

30

35

40

45

0 2 4 6 8 10 12 14 16

MH

ET C

once

ntra

tion

(mM

)

Reaction time (days)

B

0

10

20

30

40

50

60

70

80

90

100

0 2 4 6 8 10 12 14 16

TPA

Con

cent

ratio

n (m

M)

Reaction time (days)

A

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0 2 4 6 8 10 12 14 16

BH

ET C

once

ntra

tion

(mM

)

Reaction time (days)

C

0

5

10

15

20

25

30

35

40

45

0 2 4 6 8 10 12 14 16

MH

ET C

once

ntra

tion

(mM

)

Reaction time (days)

Bba

c

Page 7: ars.els-cdn.com€¦ · Web viewEloisa Mano (IMA), Federal University of Rio de Janeiro (UFRJ). Av. Horácio Macedo, 2030, 21941-598. Rio de Janeiro, Brazil. d Chemistry Division,

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

0 2 4 6 8 10 12 14 16

ED

Reaction time (days)

Fig. 8S. Esterification degree (ED) of the reaction products mixture during simultaneous

hydrolysis-glycolysis reactions. Different added EG contents were investigated: 0% (closed

squares), 20% (closed circles), 40% (closed triangles), 60% (open squares), 80% (open

circles) and 100% (open triangles).

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Page 8: ars.els-cdn.com€¦ · Web viewEloisa Mano (IMA), Federal University of Rio de Janeiro (UFRJ). Av. Horácio Macedo, 2030, 21941-598. Rio de Janeiro, Brazil. d Chemistry Division,

Fig. 9S. DSC curves of PC-PET and residual PET samples depolymerized with added EG

percentages from 0 to 100% (First heating run).

Fig. 10S. DSC curves of PC-PET and residual PET samples depolymerized with added EG

percentages from 0 to 100% (Second heating run).

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Page 9: ars.els-cdn.com€¦ · Web viewEloisa Mano (IMA), Federal University of Rio de Janeiro (UFRJ). Av. Horácio Macedo, 2030, 21941-598. Rio de Janeiro, Brazil. d Chemistry Division,

Fig. 11S. DSC curves of PC-PET and residual PET samples depolymerized with added EG

percentages from 0 to 100% (Second cooling run).

Fig. 12S. TG curves of PC-PET and residual PET samples depolymerized with EG

percentages from 0 to 100%.

9