This file was updated on 2024-12-31 by Shuquan Cui Recommended citation for the data: Cui, Shuquan; Murphy, Elizabeth A; Zhang, Wei; Zografos, Aristotelis; Shen, Liyang; Bates, Frank S; Lodge, Timothy P. (2025). Supporting Data for Cylinders-in-Undulating-Lamellae Morphology from ABC Bottlebrush Block Terpolymers. Retrieved from the Data Repository for the University of Minnesota (DRUM), https://doi.org/10.13020/134v-8d32 ------------------- GENERAL INFORMATION ------------------- Title of Dataset: Supporting Data for Cylinders-in-Undulating-Lamellae Morphology from ABC Bottlebrush Block Terpolymers Author Information: Principal Investigator Contact Information Name: Prof. Timothy P. Lodge Institution: University of Minnesota Address: Department of Chemistry, 207 Pleasant St SE, Minneapolis, Minnesota 55455 Email: lodge@umn.edu ORCID: 0000-0001-5916-8834 Principal Investigator Contact Information Name: Prof. Frank S. Bates Institution: University of Minnesota Address: Department of Chemical Engineering and Materials Science, 421 Washington Ave SE, Minneapolis, Minnesota 55455 Email: bates001@umn.edu ORCID: 0000-0003-3977-1278 Associate or Co-investigator Contact information Name: Shuquan Cui Institution: University of Minnesota Address: Department of Chemistry, 207 Pleasant St SE, Minneapolis, Minnesota 55455 Email: cui00123@umn.edu ORCID: 0000-0002-8764-0718 Associate or Co-investigator Contact Information Name: Elizabeth A. Murphy Institution: University of California, Santa Barbara Address: Materials Research Laboratory and Department of Chemistry & Biochemistry, University of California, Santa Barbara, CA 93106, USA Email: emurphy@ucsb.edu ORCID: 0000-0003-0846-7943 Associate or Co-investigator Contact Information Name: Wei Zhang Institution: University of Minnesota Address: Department of Diagnostic and Biological Sciences, School of Dentistry, and Institute for Molecular Virology, Characterization Facility, College of Science and Engineering, University of Minnesota, Minneapolis, MN 55455, USA Email: zhangwei@umn.edu ORCID: 0000-0002-9888-3889 Associate or Co-investigator Contact Information Name: Aristotelis Zografos Institution: University of Minnesota Address: Department of Chemical Engineering and Materials Science, 421 Washington Ave SE, Minneapolis, Minnesota 55455 Email: zogra005@umn.edu ORCID: 0000-0001-9612-091X Associate or Co-investigator Contact Information Name: Liyang Shen Institution: University of Minnesota Address: Department of Chemical Engineering and Materials Science, 421 Washington Ave SE, Minneapolis, Minnesota 55455 Email: shen0481@umn.edu ORCID: 0000-0001-9928-2877 Date of data collection (20221129 - 20230824) Geographic location of data collection (where was data collected?): University of Minnesota and University of California, Santa Barbara Information about funding sources that supported the collection of the data: This work was supported by the National Science Foundation (NSF) through the University of Minnesota MRSEC under Award DMR-2011401. Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from NSF through the MRSEC program. The research reported here was partially supported by the BioPACIFIC Materials Innovation Platform of the National Science Foundation under Award No. DMR-1933487 (equipment and characterization). Synchrotron SAXS experiments were performed at the 5-ID-D beamlines of the Advanced Photon Source (APS). This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract no. DE-AC02-06CH11357. -------------------------- 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: Cui S. Q., Murphy E. A., Zhang W., Zografos A., Shen L. Y., Bates F. S., Lodge T. P., Cylinders-in-undulating-lamellae morphology from ABC bottlebrush block terpolymers, Journal of the American Chemical Society 2024 (146): 6796-6805. https://doi.org/10.1021/jacs.3c13543 3. Links to other publicly accessible locations of the data: NA 4. Links/relationships to ancillary data sets: NA 5. Was data derived from another source? No. --------------------- DATA & FILE OVERVIEW --------------------- Purpose Statement: This document describes all data associated with Cui et al. "Cylinders-in-Undulating-Lamellae Morphology from ABC Bottlebrush Block Terpolymers", classifies data based on different Figures in the paper. Several Figures with just schemes are not included. The sample's ID is provided in a word file. Files Contained: 1. Data for Figure 1. SAXS and TEM data for sample 4-3 TXT file of small-angle X-ray scattering (SAXS) data from sample 4-3, and TIF file of transmission electron microscopy (TEM) image of sample 4-3 2. Data for Figure 2. 3D TEM reconstruction TIF file from 3D TEM reconstruction (sample 4-4) 3. Data for Figure 4. SAXS data for triblock phase portrait TXT files of SAXS data. 4. Data for Figure 5. SAXS and TEM for a gyroid sample TXT file of SAXS data from sample 1-2, and TIF file of TEM image of sample 1-2 5. Data for Figure 6. SAXS and TEM for a PEP-PS-PEO sample TXT file of SAXS data from sample 9-2, and TIF file of TEM image of sample 9-2 6. Data for Figure 7. SAXS data for polymer fractions TXT files of SAXS data. 7. Data for Figure 8. SAXS and TEM for a polymer fraction TXT file of SAXS data from polymer fraction F3, and TIF file of TEM image of polymer fraction F3 8. Data for Figure S1. NMR for PLA macromonomer Excel workbook 9. Data for Figure S2. SEC for PLA macromonomer TXT file 10. Data for Figure S3. NMR for bottlebrushes Excel workbook 11. Data for Figure S4. SEC for the diblock bottlebrush Excel workbook 12. Data for Figure S5. SEC for examing degradation TXT file 13. Data for Figure S6. DSC for PEP-PS and PEP-PS-PLA TXT file 14. Data for Figure S7. DSC for PEP-PS-PEO Txt file 15. Data for Figure S8. 2D SAXS Jpg file 16. Data for Figure S9. SAXS and TEM for sample 4-4 TXT file of SAXS data from sample 4-4, and TIF file of TEM image of sample 4-4 17. Data for Figure S10. SAXS data for CUL Txt file 18. Data for Figure S11. SAXS data of a sample annealing using different methods Txt file 19. Data for Figure S12. Temperature-dependent SAXS Txt file 20. Data for Figure S13. 2D TEM slice Tiff file 21. Data for Figure S14. SAXS and TEM for sample 1-3 TXT file of SAXS data from sample 1-3, and TIF file of TEM image of sample 1-3 22. Data for Figure S15. SAXS and TEM for sample 2-3 TXT file of SAXS data from sample 2-3, and TIF file of TEM image of sample 2-3 23. Data for Figure S16. SAXS data for triblock phase portrait TXT file. 24. Data for Figure S17. Thin-layer chromatography data Jpg file. 25. Data for Figure S18. Fractionation curve (PDF report) PDF file. 26. Data for Figure S19. NMR data for polymer fractions Excel workbook 27. Data for Figure S20. SEC data for polymer fractions Excel workbook 28. Data for Figure S21. SAXS data for polymer fractions from sample 6-2 TXT file 29. Data for Figure S22. SAXS data for polymer fractions from sample 7-2 TXT file 30. Data for Figure S23. SAXS data for polymer fractions from sample 5-2 TXT file 31. Chemical Structures and Synthesis Route Jpg files from Chemdraw Additional related data collected that was not included in the current data package: None. Are there multiple versions of the dataset? N -------------------------- METHODOLOGICAL INFORMATION -------------------------- Description of methods used for collection, generation, and processing of data: Details of polymer synthesis were provided in paper "Cylinders-in-Undulating-Lamellae Morphology from ABC Bottlebrush Block Terpolymers". Fractionation of partial ABC bottlebrush block terpolymers was carried out by automated liquid chromatography, performed on a Biotage Isolera unit installed with an external evaporative light scattering detector at the BioPacific MIP, University of California, Santa Barbara. The number-average molecular weight (Mn) of macromonomers and the volume fraction of each block in bottlebrushes were characterized using proton nuclear magnetic resonance (1H NMR) spectroscopy with CDCl3 as the solvent on a Bruker Avance III HD nanobay AX-400 spectrometer (400 MHz) with a 60-slot SampleXpress autosampler. The molar-mass dispersity Ð of all polymers was measured by size exclusion chromatography (SEC) with a refractive index (RI) detector and tetrahydrofuran (THF) mobile phase (room temperature, 1.0 mL/min). The Mn of each ABC triblock was calculated based on the Mn of its parent diblock, which was measured by SEC using a Wyatt Technology DAWN Heleos II multiangle laser light scattering (MALS) detector with 658 nm wavelength and a Wyatt OPTILAB T-rEX RI detector (THF, 1.0 mL/min, 25 °C). The refractive index increment (dn/dc) for the diblock bottlebrushes was determined by SEC assuming 100% mass recovery. Differential scanning calorimetry (DSC) DSC measurements were conducted on a TA Instrument Q1000. Approximately 5-8 mg of sample was loaded into hermetically sealed aluminum Tzero DSC pans (DSC Consumables, Austin, MN). Samples were first cooled to –120 °C and then heated to 150 °C to erase any thermal history. Then the sample was cooled to –120 °C again and reheated to 150 °C. The temperature ramp rate was either 10 °C/min (for PEP-PS and PEP-PS-PLA) or 5 °C/min (for PEP-PS-PEO). Data collected on the second cooling and the second heating were used for analysis. Small-angle X-ray scattering (SAXS) SAXS data were collected either at the Advanced Photon Source (APS) at Argonne National Laboratory, Sector 5-ID-D beamline or at the Characterization Facility, University of Minnesota, using a Xenocs Ganesha instrument (Ganesha) equipped with a four-position INSTEC heating stage. At APS, samples were sealed in DSC pans, while using Ganesha, the samples were sandwiched between two Kapton films, a Viton o-ring, and two Teflon washers, and were sealed in a stainless-steel sandwich cell. Unless noted, bulk samples were annealed under vacuum at 150 °C for 24 h before measurement. During the measurements, each sample was first equilibrated at a target temperature for 10 min. The exposure time was 1 s for APS and 10 min for Ganesha to obtain high-resolution patterns. Transmission electron microscopy (TEM) TEM images were obtained on an FEI Tecnai Spirit Bio-Twin TEM with an accelerating voltage of 120 kV. Polymer samples were first loaded in a DSC pan and initially annealed at 150 °C under vacuum for 24 h before cooling to 140 °C or 80 °C for additional annealing for 2 h. Then, samples were cryo-sectioned using Leica EM UC6 ultramicrotome with a Diatome diamond knife and then placed on 400-mesh copper grids. Ultrathin sections (~ 70 nm) were stained with freshly prepared RuO4 solutions for 3-5 minutes. In PEP-PS-PLA samples, the PS domain is preferentially stained; in PEP-PS-PEO samples, PEP, PS, and PEO are unstained, slightly stained, and strongly stained, respectively. Electron tomography (ET) In sample preparation, gold nanoparticles as fiducial markers were first deposited onto the 200-mesh copper grids coated with carbon film. Then, annealed polymer samples were cryo-sectioned to 100 nm thick sections, which were transferred to the above copper grids, and then stained by RuO4 for 3 min. To mitigate the electron damage, a cryo-holder filled with liquid nitrogen was employed. Electron tomography tilt series were collected on an FEI TF30 field emission gun transmission electron microscope (FEI Company, Hillsboro, OR), from -40 to 40 degrees tilt angles at an incremental angle of 2 degrees using SerielEM.3 The 3D reconstruction was carried out using IMOD, followed by a subtomogram averaging procedure using Dynamo. Briefly, an initial sampling of 797 data points was generated at the ordered lattice regions of the specimen. Subtomograms with a box size of 128 pixels (equivalent to 98.3 nm) were cropped on the sampling positions in the tomogram. The boxed local maps were assigned with initial orientations along the normal direction to the section of the specimen with randomized azimuthal angles. An initial averaged map was used as the starting model for the first cycle of refinement. The resulting map was then shifted so that the center of one cylinder was aligned with the z-axis of the model. The new map was then used as the second model for further refinement. Next, for each sampling point, a new set of 7 sampling positions was generated according to the positions of the neighboring cylinders in the lattice. The subtomogram data set was expanded to 3296 subtomograms after removing duplicated positions. Further refinement resulted in a converged map computed from 1302 subtomograms. People involved with sample collection, processing, analysis and/or submission: Shuquan Cui - collection, processing and analysis of all data Elizabeth A. Murphy - polymer fractionation Wei Zhang - 3D TEM reconstruction Liyang Shen - collection of partial TEM data Frank S. Bates - analysis of data Timothy P. Lodge - analysis of data -------------------------------- DATA TREE -------------------------------- \---Data_Cui2024 | README.txt | Sample's ID.docx | +---Chemical Structures and Synthesis Route | Macromonomer PLA.jpg | Ring-opening metathesis polymerization.jpg | +---Data for Figure 1. SAXS and TEM data for sample 4-3 | SAXS.txt | TEM.tif | +---Data for Figure 2. 3D TEM reconstruction | Reconstruction.tif | +---Data for Figure 4. SAXS data for triblock phase portrait | 1-1-140C.txt | 1-2-140C.txt | 1-3-140C.txt | 2-1-140C.txt | 2-2-140C.txt | 2-3-140C.txt | 2-4-140C.txt | 2-5-140C.txt | 3-1-140C.txt | 3-2-140C.txt | 3-3-140C.txt | 3-4-140C.txt | 4-1-140C.txt | 4-2-140C.txt | 4-3-140C.txt | 4-4-140C.txt | 4-5-140C.txt | 4-6-140C.txt | 4-7-140C.txt | 5-1-140C.txt | 5-2-140C.txt | 6-1-80C.txt | 6-2-80C.txt | 7-1-140C.txt | 7-2-140C.txt | 8-1-140C.txt | 8-2-140C.txt | 8-3-140C.txt | 8-4-140C.txt | 9-1-140C.txt | 9-2-140C.txt | +---Data for Figure 5. SAXS and TEM for a gyroid sample | 1-2-140C.txt | TEM.tif | +---Data for Figure 6. SAXS and TEM for a PEP-PS-PEO sample | 9-2-140C.txt | TEM.tif | +---Data for Figure 7. SAXS data for polymer fractions | 6-2-80C.txt | F16-34-80C.txt | F2-80C-1.txt | F3-80C.txt | F71-116-80C.txt | +---Data for Figure 8. SAXS and TEM for a polymer fraction | F3-80C.txt | TEM.tif | +---Data for Figure S1. NMR for PLA macromonomer | PLA-MM NMR.csv | +---Data for Figure S10. SAXS data for CUL | 8-2-140C.txt | 8-3-140C.txt | 8-4-140C.txt | +---Data for Figure S11. SAXS data of a sample annealing using different methods | 5-2-solvent casting + thermo-annealing.txt | 5-2-thermo-annealing.txt | +---Data for Figure S12. Temperature-dependent SAXS | 3-3-190C.txt | 3-3-80C-cooling.txt | 3-3-80C.txt | +---Data for Figure S13. 2D TEM slice | 2D TEM slice.tif | +---Data for Figure S14. SAXS and TEM for sample 1-3 | 1-3-140C.txt | TEM.tif | +---Data for Figure S15. SAXS and TEM for sample 2-3 | 2-3-140C.txt | TEM.tif | +---Data for Figure S16. SAXS data for triblock phase portrait | 1-1-140C.txt | 1-2-140C.txt | 1-3-140C.txt | 2-1-140C.txt | 2-2-140C.txt | 2-3-140C.txt | 2-4-140C.txt | 2-5-140C.txt | 3-1-140C.txt | 3-2-140C.txt | 3-3-140C.txt | 3-4-140C.txt | 4-1-140C.txt | 4-2-140C.txt | 4-3-140C.txt | 4-4-140C.txt | 4-5-140C.txt | 4-6-140C.txt | 4-7-140C.txt | 5-1-140C.txt | 5-2-140C.txt | 6-1-80C.txt | 6-2-80C.txt | 7-1-140C.txt | 7-2-140C.txt | 8-1-140C.txt | 8-2-140C.txt | 8-3-140C.txt | 8-4-140C.txt | 9-1-140C.txt | 9-2-140C.txt | +---Data for Figure S17. Thin-layer chromatography data | TLC.jpg | +---Data for Figure S18. Fractionation curve (PDF report) | Fractionation curve.pdf | +---Data for Figure S19. NMR data for polymer fractions | 6-2.xlsx | F16-34.xlsx | F2.xlsx | F3.xlsx | F71-116.xlsx | +---Data for Figure S2. SEC for PLA macromonomer | PLA-NB.txt | +---Data for Figure S20. SEC data for polymer fractions | 6-1.xlsx | 6-2.xlsx | F-2.xlsx | F-3.xlsx | F16-34.xlsx | F71-116.xlsx | +---Data for Figure S21. SAXS data for polymer fractions from sample 6-2 | 6-2-80C.txt | F16-34-80C.txt | F2-80C-1.txt | F3-80C.txt | F71-116-80C.txt | +---Data for Figure S22. SAXS data for polymer fractions from sample 7-2 | 7-2.txt | F2-7.txt | F24-58.txt | F28-44.txt | F96-140.txt | +---Data for Figure S23. SAXS data for polymer fractions from sample 5-2 | 5-2.txt | F16-21.txt | F2.txt | F22-30.txt | F3-4.txt | F3.txt | F36-66.txt | F74-140.txt | +---Data for Figure S3. NMR for bottlebrushes | diblock.csv | triblock.csv | +---Data for Figure S4. SEC for the diblock bottlebrush | Diblock.csv | +---Data for Figure S5. SEC for examing degradation | 2-2-after annealing.txt | 2-2-before annealing.txt | 9-2-after annealing.txt | 9-2-before annealing.txt | +---Data for Figure S6. DSC for PEP-PS and PEP-PS-PLA | PEP-PS-PLA.txt | PEP-PS.txt | +---Data for Figure S7. DSC for PEP-PS-PEO | Bottlebrush PEP-PS-PEO.txt | +---Data for Figure S8. 2D SAXS | 2D SAXS.jpg | \---Data for Figure S9. SAXS and TEM for sample 4-4 4-4-140C.txt TEM.tif