Supporting Information

Transcription

1 Supporting Information Microcapsules with three orthogonal reactive sites Brian P. Mason, Steven M. Hira, Geoffrey F. Strouse, D. Tyler McQuade*, Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY and Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL

2 Figure. Shell Formation of Microcapsules Figure. Presence of Isocyanate Groups after Formation of Microcapsules Removal of Residual Isocyanates from Microcapsules. Microcapsules (100 mg) were swelled in a 9:1 THF:water solution (2 ml) with N,N-dimethylaminopyridine (10 mg, mmol) and placed on a rocker or stirred overnight. The resulting microcapsules were iteratively washed with THF and centrifuged (4x), then dried under vacuum. Complete loss of isocyanates was verified by ATR-IR. 2

3 Functionalization of Microcapsules with Trifluoroacetic anhydride. Polystyrenecontaining polyurea microcapsules (100 mg) were added to a solution of trifluoroacetic anydride (100 ml, 0.72 mmol) in methanol (3 ml) and allowed to react overnight. The capsules were then iteratively washed in methanol, THF, water, methanol, and diethyl ether, then dried under vacuum. Elemental analysis for fluorine. Found: 0.215% F which translates into 0.04 mmol/g amine loading 3

4 Synthesis of Acetylene-Containing Fluorescein Thiourea Derivative. Fluorescein isothiocyanate (FITC) (50 mg, 0.13 mmol) was combined with an excess of propargyl amine (50 μl, 0.73 mmol) in THF (2 ml) and allowed to react at room temperature until starting FITC isomers were exhausted, as determined by thin-layer chromatography and loss of isothiocyanate by ATR-IR (2013 cm -1 ). The solvent and unreacted propargyl amine were removed under vacuum to yield a red-orange solid. 1 H NMR (300 MHz, 0.5 mm, DMSO-d6, 35 C): d = 9.94 (s, 1H), 8.38 (s, 1H), 7.73 (s, 1H), 7.12 (d, J = 8.4 Hz, 1H, ArH), (m, 6H, ArH), 5.30 (s, 1H, ArH), 5.25 (s, 1H, ArH), 4.88 (s, 2H, CH2), 3.17 (s, 1H, C CH); 13 C NMR (75 MHz, 0.5 mm, DMSO-d6, 25 C): 169, 160, 152, 147, 145, 142, 129, 125, 124, 112.6, 112, 109, 103, 102, 83, 79, 72, 68, 56; IR (thin film): 3059, 1734, 1636, 1588, 1495, 1460, 1385, 1315, 1269, 1207, 1179, 1109, 1042, 994, 913, 849. See also: Ikeda, M.; Minari, J.; Shimada,N.; Numata,M. Sakurai,K.; and Shinkai, S. OBC, 2007, 5, HO O O HO O O H 2 N COOH THF COOH NCS HN S FITC HN FITC - Acetylene Shell Functionalization of Microcapsules with rhodamine B. Polyurea microcapsules (30 mg) were exposed to excess rhodamine B sulfonyl chloride (0.5 mg, 0.87 μmol) in 4

5 THF (3 ml) and were rocked overnight at room temperature. The capsules were then iteratively washed and centrifuged in DMF (until supernatant did not fluoresce), water, methanol, THF, and diethyl ether, then dried under vacuum. Final shell loading of the fluorophore was challenging to characterize. Though we added excess rhodamine, covalent attachment was assumed to have occurred because we observe uniform shell coverage even after repeated washings. We offer the fluorescence data as proof that the shells are labeled with dye having the spectra properties as rhodamine. Functionalization of Microcapsules with FITC-alkyne. Polyurea microcapsules containing poly(azidomethylstyrene-co-styrene) (30 mg) were exposed to FITC-alkyne (2 mg, 4.5 μmol) and copper (I) iodide (1 mg, 5.2 μmol) in THF (3 ml) and were rocked overnight at room temperature. The capsules were then iteratively washed and centrifuged in DMF (until supernatant did not fluoresce), water, methanol, THF, and diethyl ether, then dried under vacuum. Functionalization of Microcapsules with cascade blue hydrazide. Polyurea microcapsules (30 mg) were exposed to cascade blue hydrazide (0.5 mg, 0.78 μmol) in THF (3 ml) and were rocked overnight at room temperature. The capsules were then iteratively washed and centrifuged in DMF (until supernatant did not fluoresce), water, methanol, THF, and diethyl ether, then dried under vacuum. Triple Functionalization of Microcapsules with rhodamine B, FITC-alkyne, and cascascade blue hydrazide. Polyurea microcapsules containing both 5

6 poly(azidomethylstyrene-co-styrene) and poly(chloromethylstyrene-co-styrene) were triply functionalized by adding all rhodamine B, FITC-alkyne, and cascade blue hydrazide simultaneously in a 1:1:1 ratio in DMF:methanol (1 ml). The capsules were then iteratively washed and centrifuged in DMF (until supernatant did not fluoresce), water, methanol, THF, and diethyl ether, then dried under vacuum. NMR Data for FITC Acetylene HO O O COOH HN S HN FITC - Acetylene 1 D 1H and 13 C as well as a cosy are provided. The terminal acetylene peak was difficult to observe at room temperature prompting the use of 35oC to shift the solvent peak. 6

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