Ambiguous Anti-Fouling Surfaces: Facile Synthesis by Light-Mediated Radical Polymerization | C.W. Pester, UCSB
Supplementary Information
Ambiguous Anti-Fouling Surfaces: Facile
Synthesis by Light-Mediated Radical
Polymerization
Christian W. Pester,†,‡,# Justin E. Poelma,†,‡ Benjaporn Narupai,†,‡ Shrayesh N. Patel,† Gregory
M. Su,†,# Thomas E. Mates,† Yingdong Luo,†,‖ Christopher K. Ober,§ Craig J. Hawker,†,‡,‖,*
Edward J. Kramer†,‡,#,*
†
#
Materials Department, ‡Materials Research Laboratory, ‖Department of Chemistry and Biochemistry, and
Department of Chemical Engineering, University of California, Santa Barbara, California 93106, United States
§
Department of Materials Science and Engineering, Cornell University, Ithaca, New York 14853, United States
Contents
1
Monomer Growth Kinetics ................................................................................................. 1
2
Diblock Polymerization Growth Kinetics ........................................................................... 2
3
Surface Composition of TFEMA-b-PEGMA Diblocks ...................................................... 3
4
NEXAFS Spectra of TFEMA/PEGMA Diblock Brushes .................................................. 4
5
STXM Micrographs of TFEMA/PEGMA Diblock Brushes .............................................. 5
1 Monomer Growth Kinetics
Figure SI 1 shows brush growth for various methacrylates: poly(ethylene glycol methacrylate)
(PEGMA) with two different number-average molecular weights of the –(CH2CH2O)–
sidechain: Mn = 300 g mol-1 (nPEG = 7), and Mn = 450 g mol-1 (nPEG = 10), sulfobetaine
methacrylate (SBMA), 2-methacryloyloxyethyl phosphorylcholine (PMPC), trifluoroethyl
1 of 5
Ambiguous Anti-Fouling Surfaces: Facile Synthesis by Light-Mediated Radical Polymerization | C.W. Pester, UCSB
methacrylate (TFEMA), hexafluoroisopropyl methacrylate (HFiPMA), heptafluorobutyl
methacrylate (HFBMA), and tridecafluorooctyl methacrylate (TDFOMA).
SI 1. Increase of brush height with time for various PEG-based, fluorinated, and zwitterionic methacrylates. We
refer the reader to the main text for full names. The solid lines serve as guides to the eye.
2 Diblock Polymerization Growth Kinetics
In the manuscript we discuss diblock copolymers of poly(ethylene glycol methacrylate)
(PEGMA) and trifluoroethyl methacrylate (TFEMA). Figure SI 2 shows the final thickness of
the resulting |-p(TFEMAn-b-PEGMAm) and |-p(PEGMAn-b-TFEMAm) diblock brushes.
Polymerization time for the second B-block was kept constant at 15 minutes.
SI 2. Thickness of surface-initiated ├p(TFEMAn-b-PEGMA15) and ├p(PEGMAn-b-TFEMA15) diblock brushes as
determined by optical thickness experiments.
2 of 5
Ambiguous Anti-Fouling Surfaces: Facile Synthesis by Light-Mediated Radical Polymerization | C.W. Pester, UCSB
3 Surface Composition of TFEMA-b-PEGMA Diblocks
In the main article we describe X-ray photoelectron spectroscopy (XPS) data for |p(PEGMAn-b-TFEMAm) diblock copolymer brushes. Figure SI 3 shows XPS data for the
inverse |-p(TFEMAn-b-PEGMAm) diblock brushes.
SI 3. (a) X-ray photoelectron spectroscopy (XPS) high-resolution C1s scan of ├p(TFEMAn-b-PEGMAm) diblock
copolymer brushes recorded at  = 0° emission angle, and corresponding Gaussian component fit for individual
Carbon atoms within the polymer brush. Subscripts n and m denote layer polymerization time in minutes.
Binding energy was normalized to the location of the CF3 peak at 292.72 eV. (b) Relative surface content of
individual Gaussian components and (c) relative content of PEGMA and TFEMA monomer-specific peaks,
determined through the integral ratio of BEPEG C-O = 285.79 eV and BECF3 = 292.72 eV.
3 of 5
Ambiguous Anti-Fouling Surfaces: Facile Synthesis by Light-Mediated Radical Polymerization | C.W. Pester, UCSB
4 NEXAFS Spectra of TFEMA/PEGMA Diblock Brushes
NEXAFS experiments were carried out on the U7A end station at the National Synchrotron
Light Source at Brookhaven National Laboratory. Figure SI 4 shows the NEXAFS spectra of
various ├p(PEGMAn-b-TFEMA15) and ├p(TFEMAn-b-PEGMA15) diblock brush films.
SI 4. Near Edge X-ray absorption fine spectra (NEXAFS) of ├p(PEGMAn-b-TFEMA15) and ├p(TFEMAn-b-PEGMA15)
diblock brushes. The subscript n refers to the initial homopolymer brush polymerization time in minutes.
4 of 5
Ambiguous Anti-Fouling Surfaces: Facile Synthesis by Light-Mediated Radical Polymerization | C.W. Pester, UCSB
5 STXM Micrographs of TFEMA/PEGMA Diblock Brushes
Scanning X-ray transmission microscopy was performed at beam line 5.3.2.2 of the Advanced
Light Source (ALS) at the Lawrence Berkeley National Laboratory. Patterned ├p(PEGMA30b-TFEMA15) copolymer brush samples were grown on silicon nitride window TEM grids.
Figure SI 5 shows corresponding STXM micrographs at X-ray absorption energies 288.6 eV
(a) and 532.0 eV (b), which correspond to the *(C=O) transition and the Oxygen edge,
respectively.
SI 5. STXM micrographs of a patterned ├p(PEGMA30-b-TFEMA15) diblock copolymer brush recorded at 288.6 eV
(*(C=O), a) and the Oxygen edge (532.0 eV, b). The subscripts refer to polymerization time in minutes.
5 of 5