This readme.txt file was generated on 2025-11-09 by Daniel M. Krajovic. Recommended citation for the data: Biswas, A.; Krajovic, D. M; MacIver, R.; Hillmyer, M. A. Supporting data for Plastically Deformable, Mechanically Strong, and Degradable Polymeric Airway Stents from Sustainable Aliphatic Polyester Block Polymers. ACS Biomater Sci Eng 2025, 11 (10), 6282-6291. Retrieved from the Data Repository for the University of Minnesota (DRUM). https://doi.org/10.13020/779z-mf12 ------------------- GENERAL INFORMATION ------------------- 1. Title of Dataset: Supporting data for Plastically Deformable, Mechanically Strong, and Degradable Polymeric Airway Stents from Sustainable Aliphatic Polyester Block Polymers. 2. Author Information Author Contact: Marc A. Hillmyer (hillmyer@umn.edu) Principal Investigator Contact Information Name: Marc A. Hillmyer Institution: University of Minnesota, Twin Cities Address: 225 Pleasant St SE, Minneapolis, MN 55455, USA Email: hillmyer@umn.edu ORCID: 0000-0001-8255-3853 Associate or Co-investigator Contact Information Name: Arpan Biswas Institution: University of Minnesota, Twin Cities Address: 225 Pleasant St SE, Minneapolis, MN 55455, USA Email: biswasa@umn.edu ORCID: 0000-0002-7028-6388 Associate or Co-investigator Contact Information Name: Daniel M. Krajovic Institution during this work: University of Minnesota, Twin Cities Address during this work: 421 Washington Ave SE, Minneapolis, MN 55455, USA Current institution: Massachusetts Institute of Technology Current address: 25 Ames St, Cambridge, MA 02139, USA Email: dkrajovi@mit.edu ORCID: 0000-0001-5311-1941 Associate or Co-investigator Contact Information Name: Robroy MacIver Institution: Children s Minnesota Specialty Center - The Children s Heart Clinic Address: 2525 Chicago Ave, Minneapolis, MN 55404, USA Email: maci0035@umn.edu ORCID: N/A 3. Date published or finalized for release: 2025-09-24 4. Date of data collection: 2022-09-01 to 2025-06-01 5. Geographic location of data collection (where was data collected?): X-ray scattering: Brookhaven National Laboratory, Upton, NY, USA In vivo cadaver studies: Children's Minnesota Specialty Center - The Children's Heart Clinic, Minneapolis, MN, USA All other data: University of Minnesota, Minneapolis, MN, USA 6. Information about funding sources that supported the collection of the data: We thank the Office of Discovery and Translation (ODAT) and the NSF Center for Sustainable Polymers, CHE-1901635, for the financial support. Synchrotron-source X-ray scattering was conducted at the National Synchrotron Light Source-II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory, under Contract No. DE-SC0012704. D.M.K. acknowledges funding from a University of Minnesota College of Science and Engineering Fellowship and a National Science Foundation (NSF) Graduate Research Fellowship (grant no. 2237827). 7. Overview of the data (abstract): This work investigated the use of poly(L-lactide)-poly(4-methylcaprolactone) block polymers as 3D printable, degradable airway stents for treating tracheomalacia. -------------------------- SHARING/ACCESS INFORMATION -------------------------- 1. Licenses/restrictions placed on the data: CC0 1.0 Universal http://creativecommons.org/publicdomain/zero/1.0/ 2. Links to publications that cite or use the data: Biswas, A.; Krajovic, D. M; MacIver, R.; Hillmyer, M. A. Supporting data for Plastically Deformable, Mechanically Strong, and Degradable Polymeric Airway Stents from Sustainable Aliphatic Polyester Block Polymers. ACS Biomater Sci Eng 2025, 11 (10), 6282-6291. https://doi.org/10.1021/acsbiomaterials.5c01235 3. Was data derived from another source? No If yes, list source(s): 4. Terms of Use: Data Repository for the U of Minnesota (DRUM) By using these files, users agree to the Terms of Use. https://conservancy.umn.edu/pages/policies/#drum-terms-of-use --------------------- DATA & FILE OVERVIEW --------------------- 1. File List A. Filename: README.txt Short description: Readme document with dataset information B. Filename: Fig. 4 Short description: Data presented in Figure 4 plots C. Filename: Fig. 5 Short description: Data presented in Figure 5 plots D. Filename: Fig. 6 Short description: Data presented in Figure 6 plots E. Filename: Fig. S1 Short description: Data presented in Figure S1 plots F. Filename: Fig. S2 Short description: Data presented in Figure S2 plots G. Filename: Fig. S3 Short description: Data presented in Figure S3 plots H. Filename: Fig. S4 Short description: Data presented in Figure S4 plots I. Filename: Fig. S5 Short description: Data presented in Figure S5 plots J. Filename: Fig. S7 Short description: Data presented in Figure S7 plots K. Filename: Fig. S8 Short description: Data presented in Figure S8 plots L. Filename: Fig. S9 Short description: Data presented in Figure S9 plots M. Filename: Fig. S12 Short description: Data presented in Figure S12 plots N. Filename: Fig. S13 Short description: Data presented in Figure S13 plots O. Filename: Fig. S15 Short description: Data presented in Figure S15 plots P. Filename: Fig. S16 Short description: Data presented in Figure S16 plots Q. Filename: Fig. S17 Short description: Data presented in Figure S17 plots R. Filename: Fig. S21 Short description: Data presented in Figure S21 plots 2. Relationship between files: see data tree below 3. Abbreviations PLLA - poly(L-lactide) P?MCL - poly(4-methylcaprolactone) LML - poly(L-lactide)-b-poly(4-methylcaprolactone)-b-poly(L-lactide) triblock polymer NMR - nuclear magnetic resonance FT-IR - Fourier transform infrared TGA - thermogravimetric analysis DSC - differential scanning calorimetry SEC - size exclusion chromatography DMTA - dynamic mechanical thermal analysis SAXS - small-angle X-ray scattering WAXS - wide-angle X-ray scattering 4. Software requirements: NMR - .fid files can be opened using standard NMR software, such as MestreNova and Topspin * All other files are .txt, .csv, .xls, .xlsx, and can be opened using Microsoft Excel -------------------------- METHODOLOGICAL INFORMATION -------------------------- Materials. L-lactide was generously provided by NatureWorks, LLC, recrystallized three times from anhydrous ethyl acetate and three times from anhydrous toluene, and finally sublimed (60 C, 50 mTorr). ?-methyl-e-caprolactone (P?MCL) was purchased from Renewable Solutions, LLC, and purified through fractional distillation. 1,4-benzenedimethanol (BDM) was purchased from Alfa Aesar and recrystallized three times from anhydrous toluene. Tin (II) 2-ethylhexanoate (Sn (Oct)2) was purchased from Sigma-Aldrich and purified through fractional distillation. Deuterium-labeled chloroform (CDCl3, 99.8% with 0.05% v/v tetramethylsilane (TMS) as reference standard), was purchased from Sigma-Aldrich and used as received. Anhydrous toluene was obtained from a solvent drying system (JC Meyer), cannulated into a round bottom flask, and stored over activated 4 molecular sieves under an argon atmosphere. Anhydrous ethyl acetate was purchased from Sigma-Aldrich, cannulated into a round bottom flask, and stored over activated 4 molecular sieves under an argon atmosphere. Dichloromethane, chloroform, methanol, and hexane were purchased from Sigma-Aldrich and used as received. Synthesis. The lactide-rich triblock copolymers of PLLA and P?MCL were synthesized in two steps using ring-opening polymerization following the protocol reported by Krajovic et al.20 In the first step, P?MCL homopolymers with different molar masses were synthesized, followed by chain extension of P?MCL with L-lactide. Initially, purified ?MCL and BDM were added to an oven-dried, Schlenk-adapted round bottom flask with a Teflon-coated magnetic stir bar under a nitrogen atmosphere inside a glove box. The flask was sealed with a septum and placed on a hot plate with a pie-block solid heating mantle inside the glove box. The reaction was performed at 105 C, with the temperature equilibrated for 5 minutes before catalyst injection. To initiate the reaction, a 1.014 M solution of Sn(Oct)2 in anhydrous toluene was injected into the mixture to supply 0.02 mol % Sn(Oct)2 with respect to ?MCL monomer. Aliquots were periodically extracted to monitor the monomer conversion, and fitting these points to a first-order kinetics model provided the predicted required reaction times for chosen conversions. The reaction was halted at 80% conversion by removing the flask from the glovebox and submerging it in an ice-water bath. The crude product was dissolved in chloroform and precipitated twice into liquid nitrogen-cooled methanol and once into liquid nitrogen-cooled hexane. The final viscous precipitate was decanted from the cold hexene and dried under nitrogen flow for 30 min, followed by drying at 50 C under reduced pressure for at least 48 h. The polymer was then stored in a jar within a vacuum desiccator under reduced pressure. 1H-NMR (400 MHz, CDCl3) d = 7.35 (s, 4H), 5.11 (s, 4H), 4.40-3.80 (m, 244 H), 3.79-3.54 (m, 4 H), 2.55-2.03 (m, 248 H), 1.77-1.62 (m, 244 H), 1.62-1.53 (m, 145 H), 1.53-1.35 (m, 257 H), 0.97-0.87 (d, 365 H). In the next step, the dried P?MCL macroinitiator was dissolved in anhydrous toluene overnight inside the glove box, with a Teflon-coated magnetic stir bar aiding the process. Approximately 15% w/v of 4 molecular sieves were added to the solution, which was then stored without disturbing the stir bar to prevent contamination from sieve fragments. After at least a day, the macroinitiator solution and L-lactide were placed into an oven-dried 100-mL round-bottom flask. Additional anhydrous toluene was added to achieve an initial L-lactide concentration of 1 M. The flask was stoppered and heated to 105 C in a glove box using a hot plate with a pie-block heating mantle. As in the first step, a 1.014 M Sn(Oct)2 solution in toluene was added to the mixture to initiate the reaction, this time supplying 0.06 mol % Sn(Oct)2 with respect to L-lactide monomer. Aliquots were taken at specific time intervals to monitor the reaction's progress. To halt the reaction at approximately 80% conversion, the vessel was removed from the glove box and placed in an ice-water bath. The crude triblock was then dissolved in chloroform and precipitated twice into ice-cooled methanol and once into ice-cooled hexanes. Purified triblocks were dried at 80 C under reduced pressure for a week. 1H-NMR (400 MHz, CDCl3) d = 7.35 (s, 4.0 H), 5.50-4.86 (q, 395 H), 4.35 (quintet, 2 H), 4.25-3.95 (m, 217 H), 2.65 (d, 2 H), 2.5-2.0 (m, 219 H), 1.80-1.32 (m, 1930 H), 1.00-0.82 (d, 326 H). Characterization 1H-NMR spectroscopy. The synthesized polymers' 1H-NMR spectra were recorded on a Bruker 400 MHz Spectrometer. Chemical shifts are reported in d units, expressed in parts-per-million (ppm), using the TMS signal (0.00 ppm) as an internal standard for CDCl3. Differential Scanning Calorimetry (DSC). A TA Instruments Discovery DSC was used to investigate the LMLs thermal properties. Melt-pressed and 3D-printed samples were scanned in the temperature range of 90 to 200 oC. The temperature ramp rate was maintained at 10 C / min during heating-cooling cycles. The degree of crystallization (?c) was determined from fusion enthalpy using the following equation. X_c=((?H)_m-(?H)_pmc-(?H)_cc)/(w_PLLA ?H_m^o ) 100% Where (??)m is the melting enthalpy, (?H)pmc is the pre-melting crystallization enthalpy, (?H)cc is the cold crystallization enthalpy, ?Hm0 (93 J/g) is the melting enthalpy of a PLLA crystallite of infinite dimension, and wPLLA is the total weight fraction of PLLA in the material. Thermogravimetric analysis. Thermal stability was characterized using TA instruments Q500 under a nitrogen atmosphere with a heating rate of 10 C/min. Size exclusion chromatography (SEC). HFIP (1,1,1,3,3,3-hexafluroroisopropanol) SEC was performed using an EcoSEC SEC system HLC-8240GPC series liquid chromatograph (0.35 mL/min, 40 oC) fitted with a refractive index detector and two Tosoh TSKgel SuperAMW-H columns. Samples were prepared by dissolving synthesized block copolymers in 0.05 M potassium trifluoroacetate in HFIP overnight, maintaining the concentration of 0.5 mg/mL, and filtered through a 0.2 ?m syringe filter (Whatman) before injection. Rheology. Rheological properties were assessed using a strain-controlled ARES-G2 rotational rheometer (TA Instruments). The experiments were performed by placing a block polymer disk samples punched from a melt-pressed film using a 25 mm parallel plate geometry. Viscoelastic functions such as elastic (G') and loss (G") moduli and complex viscosity (??) were recorded by sweeping the angular frequency from 0.1 to 100 rad/s at different temperatures above the block copolymers' melting temperatures. The time-temperature superposition (TTS) principle was used to shift the frequency data into a single master curve at a reference temperature corresponding to the 3D printing temperature, using a horizontal shift factor that depends on temperature following a William-Landel-Ferry (WLF) equation.43 Steady flow sweeps were conducted at the 3D printing temperature to study the viscosity dependency on the shear rate. Film processing. For film preparation, block copolymers were melt pressed using a Carver press (Wabash, IN) between Teflon sheets (American Durafilm Co., Inc.) sandwiched between stainless steel plates at 190 C (above the melting temperature of the polymers) and 287 kPa pressure. All polymers were dried overnight at 70 C under reduced pressure before melt pressing. The melt-pressed samples were rapidly quenched (<2 min) by transferring them to a secondary press circulated with cooling water. Quenched films were cold crystallized by holding them on the melt press isothermally at 100 C under minimal pressure for 5 min. Tensile testing. Tensile properties of the block copolymers were investigated using a tensile tester (Shimadzu Autograph AGS-X) operated at 1 mm/min crosshead speed following ASTM D1708 . . For tensile testing, dumbbell shape tensile bars were prepared from melt-pressed film using a specimen cutter (Dumbbell Co., Ltd. SDL 200, equipped with an SDMK-1000 dumbbell cutter) following ASTM D1708. Young s modulus, tensile strength, elongation at break and tensile toughness were calculated from stress-strain curve. All samples were aged for 12 days at room temperature before tensile testing. Reported properties are mean results from at least five tensile specimens for each polymer. 3D printing. Various solid and engineered stent structures were fabricated using the RegenHU R-GEN 200 3D printer. LMLs were dried overnight in a vacuum oven at 70 oC before 3D printing. Dried polymers were extruded above their melting temperature (Tm) and under sufficient pneumatic pressure to maintain continuous extrusion of the molten polymer from the nozzle during 3D printing. The desired 3D geometries were designed using Fusion 360 CAD software, and slicing was done using Shaper software provided by the RegenHU 3D printer. Compression testing. The ability of the stents to withstand the radial compression force was investigated using a TA Instruments RSA-G2 dynamic mechanical analyzer with a setup to measure the uniaxial compression force . . To measure the radial compression force, stents with a 3 mm outer diameter, 10 mm length, and 100 m wall thickness were fabricated and dilated using a balloon of 8 mm diameter after dilation. All stents were cold crystallized in an oven at 120 oC before use. Reported properties are mean results from at least five specimens for each polymer. X-ray scattering. Synchrotron X-ray scattering data were acquired from the 11-BM Complex Materials Scattering end station at the National Synchrotron Light Source-III (NSLS-III; Brookhaven, NY) using a photon wavelength of ? = 0.7293 (17 keV beam energy) and DECTRIS Pilatus area detectors (2M for SAXS, 800K for WAXS). Fragments of 3D printed LML stents were cut from the stents with a razor blade, mounted upright on Kapton tape at RT, and exposed for 3 seconds. In-situ tensile X-ray scattering data were collected for cold crystallized dog-bone films (~0.3 mm thickness). The specimens were mounted onto a Linkam MFS tensile stage with 60-grit sandpaper and subjected to the following protocol: (1) Elongate at 1 mm/min to a crosshead displacement giving 100% strain (calculated from measurement of initial gap); (2) Hold at constant strain for 10 minutes; (3) Retract crosshead to unload sample back to zero stress; (4) Elongate at 1 mm/min until sample fracture. Two-second exposures were taken every 2 s during elongation (4 s shutter period). All images and patterns were corrected by subtracting the intensities from the appropriate blank patterns. Reduction of 2D images to 1D patterns was performed using the Nika software package.44 Cell culture. Human primary tracheal epithelial cells (normal) and the airway epithelial cell growth kit were purchased from ATCC. The cells were cultured following the ATCC protocol. Briefly, the airway epithelial total media was prepared by adding 1.25 ml HLL Supplement, 15 ml L-glutamine, 2.0 ml Extract P (Final concentration 0.4%), 5.0 ml airway epithelial cell supplement, 0.5 ml Penicillin-Streptomycin-Amphotericin B solution, and 0.5 ml Phenol Red to 485 ml of airway epithelial cell basal medium. After receiving the epithelial cells, cells were mixed with total media and seeded in T-70 flasks, keeping the cell density at 5000/cm2. The T-70 flasks with seeded cells were kept in an incubator at 37 C and 5% CO2 atmosphere, and their growth was regularly monitored under a microscope. On 80% confluence, cells were lifted from the surface by treating them using a trypsin-EDTA solution. After the detachment, the cells were treated with a trypsin-neutralizing solution. The dissociated cells were transferred into a conical flask and centrifuged to make a pallet. After removing the supernatant, the cells were washed with D-PBS and homogeneously dispersed into the total culture media for further use. Cell proliferation and cell viability. The proliferation of cells on the triblocks' surface was examined by seeding dispersed epithelial cells onto the triblocks' surface and subsequently measuring the metabolic activity of these seeded cells at predetermined intervals, utilizing an alamarBlue assay. A 10% (v/v) solution of the alamarBlue reagent in the epithelial cell culture media was prepared and added to 48-well plates, ensuring coverage of the cells on the 3D-printed samples. Following a 90-minute incubation period in a CO2 incubator with gentle agitation to achieve uniform distribution, the medium containing reduced alamarBlue was removed and stored under dark and icy conditions. Subsequently, 100 L aliquots were transferred into 96-well plates, and fluorescence intensity was measured at 600 nm after excitation at 535 nm using a plate reader. The negative and positive controls consisted of non-reduced alamarBlue and 100% reduced alamarBlue without cells, respectively. AlamarBlue reduction (%)= (Flurescence value(LML with cells-negetive control))/(Flurescence value (positive control-negetive control)) 100 Furthermore, a live-dead assay was conducted to assess the viability of epithelial cells on the surface of the 3D-printed samples over time. In the live-dead assay, cells were stained at regular intervals (e.g., at 1, 7, and 14 days) with a solution of calcein AM and BOBO-3 Iodide after the culture media was removed from the 48-well plates. The well plates were then incubated under dark conditions for 30 minutes at room temperature. Finally, fluorescence images were captured using a Nikon Ti2 microscope. In-vitro degradation. For the in-vitro degradation study, stents with a 3 mm outer diameter and 10mm length were fabricated and cold crystalized at 120 C for 24 h. Then, the cold crystalized stents were dilated using a balloon of 8mm outer diameter (after dilation). The dilated stents were immersed in 20 ml of Dulbecco's Phosphate-Buffered Saline (D-PBS) and placed in a 37 oC water bath equipped with an orbital shaker. After a predetermined time interval, 20 ?l of solution was collected and diluted with 780 mL DI water to measure the total carbon in the solution using a TOC instrument. Polyethylene oxide (PEO) was dissolved in deionized (DI) water at various concentrations, and the total carbon content of the PEO solutions was measured to create the standard curve. Cadaver experiment. A cadaver porcine respiratory system was obtained from the experimental surgery services of the University of Minnesota and kept under frozen conditions. A portion of the respiratory system, with a diameter of 6 mm, was used to demonstrate the deployability and post-deployment stability of the stent. The stent, with an outer diameter of 4 mm and a thickness of 0.3 mm, was fabricated by rolling and heat sealing the two ends of a flat sheet of the LML triblock polymer. The stent was deployed inside the lumen of the respiratory system using a catheter-guided balloon of a diameter of 7 mm (after dilation), and the stent was dilated by applying a pressure of 33 atm using a pressure gauge. -------------------------- DATA TREE -------------------------- | README.txt | +---Fig. 4.zip | \---Fig. 4 | +---Fig. 4c | | L14M16L14 prestretched.xlsx | | L14M16L14 pristine.xlsx | | | \---Fig. 4g | L14M16L14_AD.xlsx | L14M16L14_BD.xlsx | +---Fig. 5.zip | \---Fig. 5 | +---Fig. 5b | | Alamar blue Assay Day-1.xlsx | | Alamar blue Assay Day-14.xlsx | | Alamar blue Assay Day-3.xlsx | | Alamar blue Assay Day-7.xlsx | | | \---Fig. 5c | Live-dead assay.xlsx | +---Fig. 6.zip | \---Fig. 6 | +---Fig. 6a | | TOC data degradation.xlsx | | | +---Fig. 6c | | Compression test after degradation.xlsx | | | \---Fig.6b | Degradation-Stent1 .xlsx | +---Fig. S1.zip | \---Fig. S1 | +---Fig S1b | | \---1H-NMR | | \---10 | | | acqu | | | acqus | | | audita.txt | | | fid | | | format.temp | | | fq1list | | | precom.output | | | prosol_History | | | pulseprogram | | | scon2 | | | shimvalues | | | specpar | | | stanprogram10231 | | | uxnmr.info | | | uxnmr.par | | | vtc_pid_settings | | | | | \---pdata | | \---1 | | outd | | proc | | procs | | title | | | +---Fig S1c | | L14M16L14.xlsx | | P4MCL.xlsx | | | +---Fig. S1a | | \---1H-NMR | | \---10 | | | acqu | | | acqus | | | audita.txt | | | fid | | | format.temp | | | fq1list | | | precom.output | | | prosol_History | | | pulseprogram | | | scon2 | | | shimvalues | | | specpar | | | stanprogram16000 | | | uxnmr.info | | | uxnmr.par | | | vtc_pid_settings | | | | | \---pdata | | \---1 | | outd | | proc | | procs | | title | | | \---Fig.S1d | L11M11L11.xlsx | L14M16L14.xlsx | L16M15L16.xlsx | L21M22L21.xlsx | +---Fig. S2.zip | \---Fig. S2 | L11M11L11.xls | L14M16L14xls.xls | L16M15L16.xls | L21M22L21.xls | +---Fig. S3.zip | \---Fig. S3 | L14M16L14.xlsx | +---Fig. S4.zip | \---Fig. S4 | L11M11L11.xlsx | L16M15L16.tri.xlsx | L21M222L21.xlsx | +---Fig. S5.zip | \---Fig. S5 | \---Figure S5a and S5b | L11M11L11.xlsx | L14M16L14.xlsx | L16M15L16.xlsx | L21M22L21.xlsx | +---Fig. S7.zip | \---Fig. S7 | Shear thinng.xlsx | +---Fig. S8.zip | \---Fig. S8 | L14M16L14.xlsx | L21M22L21.xlsx | \---Fig. S9.zip | \---Fig. S9 | L14M16L14.xlsx | | +|---Fig. S12.zip | \---Fig. S12 | +---L11M11L11 | | AP.xlsx | | BP.xlsx | | | +---L16M15L16 | | AP.xlsx | | BP.xlsx | | | \---L21M22L21 | AP.xlsx | BP.xlsx | +---Fig. S13.zip | \---Fig. S13 | +---Fig. S13a | | SAXS_ L14M16L14.xlsx | | WAXS_ L14M16L14.xlsx | | | \---Fig. S13b | L14M16L14-3d printed.xls | L14M16L14_hot pressed and quenched.xls | +---Fig. S15.zip | \---Fig. S15 | \---Fig. S15a | L11M11L11 .xlsx | L14M16L14.xlsx | L21M22L21.xlsx | +---Fig. S16.zip | \---Fig. S16 | +---Fig. S16b | | SAXS-Tensile.xlsx | | | \---Fig. S16c | WAXS_Tensile.xlsx | +---Fig. S17.zip | \---Fig. S17 | +---Fig. S17b | | SAXS_Tensile.xlsx | | | \---Fig. S17c | WAXS_Tensile.xlsx | | +---Fig. S21.zip | \---Fig. S21 | +---Fig S21a | | Standard carve.xlsx | | | +---Fig. S21b | | \---1H-NMR after degradation | | \---11 | | | acqu | | | acqus | | | audita.txt | | | fid | | | format.temp | | | fq1list | | | precom.output | | | prosol_History | | | pulseprogram | | | scon2 | | | shimvalues | | | specpar | | | stanprogram17257 | | | topshimreport | | | uxnmr.info | | | uxnmr.par | | | vtc_pid_settings | | | | | \---pdata | | \---1 | | outd | | proc | | procs | | title | | | \---Fig. S21c | DSC after degradation-1st heating.xlsx