Carborane–β-cyclodextrin complexes as a supramolecular connector for bioactive surfaces

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Brunsveld et al. Supporting informations

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Carborane-beta-cyclodextrin interaction as an efficient strategy to create

supramolecular bioactive surface

P. Neirynck, a_{J. Schimer,}b_{P. Cigler,}b_{P. Jonkheijm,}c_{L.-G. Milroy,}a_{L. Brunsveld}a

a

Laboratory of Chemical Biology and Institute of Complex Molecular Systems (ICMS), Department of Biomedical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612 AZ, Eindhoven, The

Netherlands Fax: (+31) 40-247-8367; E-mail: l.brunsveld@tue.nl b

Institute of Organic Chemistry and Biochemistry AS CR, v.v.i., Flemingovo nam. 2, Prague 6, 166 10, Czech Republic, Tel.: +420-220-183-429, Fax: +420-224-310-090, E-mail: cigler@uochb.cas.cz c _{Molecular Nanofabrication Group, MESA}+ _{Institute for Nanotechnology, Department of Science and}

Technology, University of Twente, P.O. Box 217, 7500 AE, Enschede, The Netherlands E-mail: p.jonkheijm@utwente.nl

Telephone: int+31(0)40 247 3737 FAX: int+31(0)40 247 8367

SUPPORTING INFORMATIONS

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry B.

This journal is © The Royal Society of Chemistry 2014

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Synthesis of cRGD-maleimide 4 and cRAD-maleimide 5

Synthesis of NHS-maleimide linker 10 was carried out following previously described protocol, with a

final yield of 43 % after purification.1

Synthesis of cRGDfK 4’ and cRADfK 5’ was performed following previously described protocol.2

1 eq of 10 was dissolved together with 1 eq of DIPEA and 1 eq of 4’ or 5’ in DMF:PBS 1:1, pH was

adjusted to 7 and reaction was stirred at room temperature for 1 h. Solvents were evaporated and LCMS confirmed the product formation. Product was purified on reverse-phase HPLC equipped with UV detection with a gradient of 10 to 25 % in 20 min, yielding 4 and 5 in respectively 25 and 28 % yield.

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Figure S7. LCMS of carborane-cRGD 6 after purification.

fileD:\users\Pauline\PN101-run2-fc8 date9/25/2013 17:24:56

autosamplera:28 methodD:\methods\Wencke\peptides2-70_3min.meth inj. vol.2.000000

RT:0.00 - 4.28 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 Time (min) 0 10 20 30 40 50 60 70 80 90 100 R e la ti ve A b u n d a n ce 2.82 516.58 1.02 352.33 3.40 516.92 4.17 352.33 4.04 352.33 3.53 516.58 2.57 149.00 2.35 149.08 2.20 148.92 2.00 149.00 1.84 148.92 1.66 149.00 1.42 149.00 1.22 149.00 0.05 1468.33 0.31 148.92 0.47 148.92 0.71 516.92 NL: 8.85E5 TIC MS PN101-run2-fc8

PN101-run2-fc8 #126-134 RT:2.77-2.87 AV:9 NL:1.78E4 T:ITMS + p ESI Full ms [100.00-2000.00]

100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 m/z 0 10 20 30 40 50 60 70 80 90 100 R e la ti ve A b u n d a n ce 517.00 1032.67 120.08 227.08 312.42 410.58508.67 526.00 658.58 755.33 838.17 1004.83 1054.67 1216.751276.42 1460.83 1586.00 1697.67 1849.171928.08

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Figure S8. LCMS of carborane-cRAD 7 after purification.

fileD:\users\Pauline\PN102-run2-fc3 date9/25/2013 17:53:05

autosamplera:25 methodD:\methods\Wencke\peptides2-70_3min.meth inj. vol.2.000000

RT:0.00 - 4.28 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 Time (min) 0 10 20 30 40 50 60 70 80 90 100 R e la ti ve A b u n d a n ce 2.82 524.00 1.02 352.33 3.04 523.58 4.19 352.33 3.30 290.33 3.99 352.33 3.50 149.00 3.75 352.33 2.66 149.08 2.17 149.08 2.11 149.00 1.93 148.92 1.69 149.00 1.49 148.92 1.26 149.00 0.20 149.00 0.43 149.08 0.82 148.92 0.60 149.00 NL: 7.47E4 TIC MS PN102-run2-fc3

PN102-run2-fc3 #126-134 RT:2.77-2.89 AV:9 NL:1.27E3 T:ITMS + p ESI Full ms [100.00-2000.00]

100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 m/z 0 10 20 30 40 50 60 70 80 90 100 R e la ti ve A b u n d a n ce 523.92 1046.67 533.00 1067.67 149.00 227.17 361.83413.42 672.33 803.17863.33 981.33 1212.17 1306.001396.00 1521.171586.83 1676.67 1825.25 1948.58