Electronic Supplementary Information for: Photo-reversible surfaces to regulate cell adhesion

Transcription

1 Electronic Supplementary Information for: Photo-reversible surfaces to regulate cell adhesion Alexis Goulet-Hanssens, Karen Lai Wing Sun, Timothy E. Kennedy * and Christopher J. Barrett * Department of Chemistry, Program in euroengineering, McGill University, 8 Sherbrooke Street West, Montreal, Quebec, Canada HA B8 Department of eurology and eurosurgery, Program in euroengineering, Montreal eurological Institute, 8 University Street, Montreal, Quebec, Canada HA B General considerations H MR spectra were acquired on a Varian-Mercury MHz and C MR were acquired on a Varian-Mercury MHz MR at K. Chemical shifts are reported in ppm on the δ-scale using either the solvent signal for reference. ESI-MS was acquired on a Thermo-Finnigan LcQ- Duo with a spray voltage of.kv.

2 , -aminophenyl-azo-benzoic acid In a L round-bottom flask with stir bar, added ml milliq water and.g ah pellets to yield a % ah solution, stirred to dissolution and let cool to room temperature. Added g (.8 mol) p-phenylenediamine and.g (. mol) p-nitrobenzoic acid and set to stir in an oil bath equipped with a water-cooled condenser. The reaction which began as a black solution was set to heat at 9 C, within a few hours, the reaction flask began turning orange. After hours reaction time, the reaction was allowed to cool to room temperature and was then placed on ice to chill the suspension before filtration. nce cooled to ~ C, orange/gold crystals were filtered on a Buchner funnel and were generously rinsed with water before being placed in a vacuum oven to dry. The final yield of 8. grams (% yield) was used without further purification. AGH_-9.ESP DMS H ormalized Intensity..,,,, H, Water Figure s. Proton MR spectra of, -aminophenyl-azo-benzoic acid.

3 ormalized Intensity AGH_-9C.ESP.... H H Figure s. Carbon MR spectra of, -aminophenyl-azo-benzoic acid. -acryloyl--aminohexanoic acid In a ml round-bottom flask with stir bar added ml M KH solution (.g KH in ml milliq water), added in. g (. mol) of -aminobenzoic acid set to cool in an ice bath. nce cooled, began dropwise addition of ml (. mol) Acryloyl Chloride while keeping the reaction flask chilled. nce addition complete, the ice bath was removed and the reaction was left to stir for. hours. The reaction was transferred to a ml separatory funnel and washed twice with ml diethyl ether. The aqueous phase was acidified through dropwise addition of concentrated HCl until it reached ph - then extracted with portions of ml chloroform. The organic phases were collected and dried with magnesium sulfate then filtered and evaporated to a yellow oil. This product was recrystallized from a mixture of : diethyl ether:ethyl acetate solution and filtered to yield g (% yield) white crystals.

4 AGH_-8.ESP H 9 8 H.8 ormalized Intensity ,, Figure s. Proton MR spectra of -acryloyl--aminohexanoic acid. ormalized Intensity.... AGH_-8C.ESP.9 H 9 8. H Figure s. Carbon MR spectra of -acryloyl--aminohexanoic acid.

5 -acryloyl--aminohexanoic-(-aminophenyl)azo--benzoic acid In a ml round-bottom flask with stir bar added in ml dry DMF,.8 grams ( mmol) of -acryloyl--aminohexanoic acid,.9 g ( mmol) HATU and µl ( mmol),,- collidine. Left reaction to stir at room temperature to pre-activate the carboxylic acid, after which g ( mol) of, -aminophenyl azobenzoic acid was added. Solution changed from clear to deep red after addition and was left to react for hours. DMF solution was added to ml water in a ml separatory funnel and was extracted with three portions of ml ethyl acetate. The organic phases were collected and dried with magnesium sulfate, filtered and evaporated under reduced evaporation. The precipitated product was filtered from a pale orange oil and rinsed generously with water, which after drying yielded 88 g (% yield) of pure product as determined by MR. AGH_-.ESP DMS ormalized Intensity H H,,,,,, H ,, Figure s. Proton MR spectra of -acryloyl--aminohexanoic-(-aminophenyl)azo--benzoic acid

6 ormalized Intensity AGH_-C.ESP H H H Figure s. Carbon MR spectra of -acryloyl--aminohexanoic-(-aminophenyl)azo-- benzoic acid

7 Figure s. ESI-MS of -acryloyl--aminohexanoic-(-aminophenyl)azo--benzoic acid. Molecular weight: 8. amu.

8 -acryloyl--aminohexanoic-(-aminophenyl)azo--benzocarbonyl-rgd In a ml round-bottom flask with stir bar added in ml dry DMF, added in. mg (. mmol) -acryloyl--aminohexanoic-(-aminophenyl)azo--benzoic acid,. mg (. mmol) HATU and µl (. mmol),,-collidine. This pale red solution was left to react for hours, after which. g (. mmol) Arg-Gly-Asp was added. After hours of reaction time, the solution was washed with x ml portions of ethyl acetate and concentrated to ml under reduced pressure deemed pure enough to be used for polymerization without further purification. range solid weighing.g, 8% yield. Figure s8. ESI-MS of -acryloyl--aminohexanoic-(-aminophenyl)azo--benzocarbonyl-rgd. Molecular weight:. amu.

9 -acryloyl--aminohexanoic-(-aminophenyl)azo--benzocarbonyl-c(rgdfk) In a ml round-bottom flask with stir bar added in ml dry DMF, added in. mg (8. µmol) -acryloyl--aminohexanoic-(-aminophenyl)azo--benzoic acid,. mg (8. µmol) HATU and 8 µl (. mmol),,-collidine. This pale red solution was left to react for hours, after which mg (8. µmol) Arg-Gly-Asp was added. After hours of reaction time, the solution was concentrated to ml under reduced pressure and purified by HPLC on a Silicycle (Québec, Canada) C8, µm, Å, x mm semi-prep column using an acetonitrile:water with.% TFA:8 gradient changing to 8: over minutes. The product was collected between and minutes elution time, the appropriate fractions were evaporated under reduced pressure to yield an orange solid. Yield.g, 89% yield. Figure s9. ESI-MS of -acryloyl--aminohexanoic-(-aminophenyl)azo--benzocarbonylc(rgdfk), Molecular weight: 99. amu.