Supporting Information

Transcription

1 Supporting Information Surface Functionalization and Patterning by Multifunctional Resorcinarenes F. Behboodi-Sadabad,, V. Trouillet,, A. Welle,, Phillip B. Messersmith, # Pavel A. Levkin*, Institute of Organic Chemistry (IOC), Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany Institute of Toxicology and Genetics (ITG), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Germany Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Eggenstein- Leopoldshafen, Germany Karlsruhe Nano Micro Facility (KNMF), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Germany Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Germany # Departments of Materials Science and Engineering and Bioengineering, University of California Berkeley, 9472 Berkeley, USA KEYWORDS: surface functionalization, resorcinarene, phenolic compounds, thiol-ene photochemistry, wettability Corresponding Author * levkin@kit.edu. S-1

2 a b c d e HO f OH HO g OH i h j HO OH HO OH e j h i c a b g d f PPM Figure S1. Nuclear magnetic resonance ( 1 H NMR, 5 MHz, CDCl 3 ) spectrum of C-dec-9- enylresorcin[4]arene (3). S-2

3 Figure S2. Mass spectrometry (ESI-MS, positive mode) spectrum of C-dec-9-enylresorcin[4]arene (3). ESI-MS (positive mode, m/z): [M+Na] + theor.= , [M+Na] + exp. = S-3

4 (A) (B) Zn 2p Al 2p Al 2 O 3 Zn+3 Al at% Al Al() Normalized Intensity Zn Normalized Intensity Cu 3p Al 12.2 at% Al Binding Energy (ev) Binding Energy (ev) Figure S3. (A) Detailed Zn 2p and (B) Al 2p XPS spectra of Zinc copper alloy (Zn) and aluminum (Al) substrates before and after modification with C-dec-9-enylresorcin[4]arene (3). The signal intensities for Al 2p were normalized to the maximum of intensity. S-4

5 (A) (B) Bare Silicon nm Height (nm).6 nm Height (nm) (C) (D) nm nm Height (nm) Height (nm) Figure S4. AFM height image of the (A) bare, (B) 1-modified, (C) 2-modified, and (D) 3-modified silicon surface. Corresponding height profiles along the lines are shown in the graphs. S-5

6 (A) Apparent Water Contact Angle ( ) (B) Time (h) poly(hema)+1+sonication PE+1 PE+1+sonication Steel+1 Steel+1+sonication Apparent Water Contact Angle ( ) Time (h) poly(hema)+2+sonication PE+2 PE+2+sonication Steel+2 Steel+2+sonication Figure S5. Apparent water contact angle (WCA) of PE, steel, and amine-functionalized porous poly(hema) substrates modified with C-methylresorcin[4]arene (1) (A) or C- undecylresorcin[4]arene (2) (B) after immersing or sonication in ethanol:water 1:1 mixture for 24 h. S-6

7 (A) (B) (C) Apparent water contact angle ( ) Steel-pH 3 Steel-pH 7 Steel-pH 9 Apparent water contact angle ( ) PE-pH 3 PE-pH 7 PE-pH 9 Apparent water contact angle ( ) Glass-pH 3 Glass-pH 7 Glass-pH 9 Figure S6. Stability of the resorcinarene layer of 3 deposited on the surface of (A) steel, (B) PE, and (C) (amine-functionalized) glass substrates monitored by measuring the apparent water contact angle of the substrates after immersing for different time intervals at aqueous buffer solitons at 1 mm formate (ph 3), phosphate (ph 7), or carbonate-bicarbonate (ph 9) buffers. h 12 h 24 h 48 h S-7

8 PCA of F 1s Figure S7. Principal component analysis (PCA) of F 1s / XPS mapping of the 3-modified surface after post-functionalization with PFDT (borders) and ME (squares). S-8