Enzymatic functionalization of HMLS-polyethylene

Transcription

1 Enzymatic functionalization of HMLS-polyethylene terephthalate fabrics improves the adhesion to rubber Sara Vecchiato, Jennifer Ahrens, Alessandro Pellis, Dennis Scaini, Bernhard Mueller *, Enrique Herrero Acero *, Georg M. Guebitz, Number of pages in the supporting information: 8 Number of figures in the supporting information: 4 Number of tables in the supporting information: 7 Number of videos in the supporting information: 2 S1

2 Figure S1: fpet samples after incubation with the toluidine blue O. The samples were before treated with different concentrations of NaOH (1M, 0.5M, 0.25M, 0.1M, 0.05M, 0.025M, from left to right) and phosphate buffer (blank sample, second row). The toluidine blue binds the new carboxylic groups created with the chemical treatment. (Toluidine Blue Method) Figure S2: fpet samples after incubation with the toluidine blue O and the washing step in SDS. The samples were before treated with different concentrations of NaOH (1M, 0.5M, 0.25M, 0.1M, 0.05M, 0.025M, from left to right) and phosphate buffer (blank sample, last well). The toluidine blue binds the new carboxylic groups created with the chemical treatment; SDS is then used to remove the dye bound that is measured at 625 nm. (Toluidine Blue Method) S2

3 Table S1: Parameters of RFL-dipping solution for PET cords 1440/2. ph Viscosity (cp) Solid Contant (%) PET Table S2: Conditions during the dipping step in tire s manufacturing. Oven N 1 Oven N 2 Oven N 3 C N # s Figure S3: Surface carboxylic groups detected after incubation with Thc_Cut2_DM (5.0 µm) for 24 h and 72 h. After and 72 h of Aging the DoC decreased due to the reorganization of the initially generated carboxylic groups. (Toluidine Blue O Method) S3

4 Figure S4: PET fabrics were incubated with 1M NaOH at 50 C for 72 h and Thc_Cut1 at 60 C for 72 h. The chemically treated fabric showed a structure considerably damaged. Table S3: Breaking strength (Bs) values of cpet detected after enzymatic incubation with Thc_Cut1 (5.0 µm, 24 h, 60 C) and chemical incubation with NaOH (0.5 M) for 2 and 4 h at 50 C. The elongation at break (E) is also reported for each sample. cpet showed a loss of mechanical properties of almost 10% after chemical treatment compared to the enzymatic one. Water NaOH- 2h NaOH-4h enzyme-24h Bs (N) E (%) Bs (N) E (%) Bs (N) E (%) Bs (N) E (%) average stdev S4

5 Table S4: Degradation of PET fabrics detected after enzymatic incubation with Thc_Cut1 (5.0 µm) and the Thc_Cut2_TM (5.0 µm) for 72 hours at 60 C, and chemical incubation with NaOH (1 M) for 2 and 24 hours at 50 C. The blank was incubated only with buffer, 72 h at 60 C. (Weight analysis) Conditions Name after cut (g) after washed and dry (g) after incubation (g) after washed and dry (g) after incubation (g) % % less 60 C, 72h Blank Blank Blank C, 72h Cut1_ Cut1_ Cut1_ C, 72h Cut2_TM_ Cut2_TM_ Cut2_TM_ C, 24h NaOH_ NaOH_ NaOH_ C, 2h NaOH_ NaOH_ NaOH_ Table S5: Crystallinity values detected after enzymatic incubation with Thc_Cut1 (0.5 µm, 5.0 µm) and the Thc_Cut2_TM (0.5 µm, 5.0 µm) for 24 and 72 hours at 60 C, and chemical incubation with NaOH (1 M) for 2 h at 50 C. The blank was incubated only with buffer, 24 h at 60 C. (DSC analysis) Blank NaOH Thc_Cut1 Thc_Cut2_TM Temperature 60 C 50 C 60 c Incubation Buffer 1 M 0.5µM 5.0µM 0.5µM 5.0µM Time 24 h 2 h 24 h 72 h 24 h 72 h 24 h 72 h 24 h 72 h Crystallinity 36.3 ± ± 36.0 ± ± 35.0 ± 35.3 ± 33.3 ± 35.0 ± 36.0 ± ± S5

6 Table S6: Crystallinity values detected after soxhlet extraction step. (DSC analysis) Blank NaOH Thc_Cut1 Thc_Cut2_TM Temperature 60 C 50 C 60 c Incubation Buffer 1 M 0.5µM 5.0µM 0.5µM 5.0µM Time 24 h 2 h 24 h 72 h 24 h 72 h 24 h 72 h 24 h 72 h Crystallinity 37.0 ± ± ± ± ± ± ± ± ± ± 0.2 Video S1 A-B: Water contact angle (WCA) was measured after the incubation with A) Thc_Cut1 (0.5 µm) and B) Thc_Cut2_TM (0.5 µm) for 72 h at 60 C. WCA was not detectable due to the super hydrophilic behavior of the samples. Video to confirm the hydrophilicity are reported. Table S7: Surface Free Energy (SFE) was measured after the incubation with Thc_Cut1 and Thc_Cut2_TM (5.0 µm) for 24 and 72 h at 60 C; the blank was incubated only with buffer, as control. The analysis was performed in triplicates. Conditions 60 C, 24h average Tot SFE (mn/m) stdev Tot SFE (mn/m) Name Tot SFE (mn/m) DispersePt PolarPt Blank Blank Cut1_ Cut1_ Cut1_ Cut2_TM_ Cut2_TM_ Cut2_TM_ Blank Blank Blank C, 72h Cut1_ Cut1_ Cut1_ Cut2_TM_ Cut2_TM_ Cut2_TM_ S6

7 LIST OF ABBREVIATIONS: HMLS-PET: high modulus-low shrinkage poly(ethylene-terephthalate) RFL: formaldehyde-resorcinol-latex fpet: PET fabrics Thc_Cut1: cutinase 1 from Thermobifida cellulosilytica Thc_Cut2: cutinase 2 from Thermobifida cellulosilytica Thc_Cut2_DM: cutinase 2 double mutant from Thermobifida cellulosilytica Thc_Cut2_TM: cutinase 2 triple mutant from Thermobifida cellulosilytica SoC: surface carboxylic groups TA: terephthalic acid MHET: mono-(2-hydroxyethyl) terephthalate BHET: bis-(2-hydroxyethyl) terephthalate HPLC-DAD: High-Performance Liquid Chromatography with Diode-Array Detection SC: Surface Carboxylic groups TBO: Toluidine Blue O TfCut2: cutinase from Thermobifida fusca KW3 SEM: Scanning Electron Microscope AFM: Atomic Force Microscope cpet: PET cord WCA: Water Contact Angle LB: Lysogeny Broth OD: Optical Density BSA: Bovin Serum Albumin SDS-PAGE: Sodium Dodecyl Sulphate - PolyAcrylamide Gel Electrophoresis S7

8 PNPB: p-nitrophenyl butyrate U: Unit HPLC: High Performance Liquid Chromatography RMS: root-mean-square DSC: Differential Scanning Calorimetry S8