Supplementary information - Royal Society of Chemistry
Transcription
Supplementary information - Royal Society of Chemistry
Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 pH Influenced Molecular Switching with Micelle Bound Cavitands Supporting Information Yeon Joo Kim,a Mark Leka and Michael P. Schramm*a California State University Long Beach, Department of Chemistry and Biochemistry, 1250 Bellflower Blvd., Long Beach, CA, 90840, USA. Fax: +1 562-985-8557; Tel: +1 562-985-1866; E-mail: [email protected] 1. Synthesis of New Compounds General Procedure for Preparation of Trimethylammonium Iodide Salts. A 100 mL round bottom flash was charged with amine (5 mmoles, >95 %) and ethyl acetate (25 mL, ACS grade). Iodomethane (1.55 mL, 25 mmoles, 97 %) and potassium carbonate (3.45g, 25 mmoles, Anhydrous powder) were added and the mixture was stirred vigorously for 18 hours. The reaction mixture was filtered by vacuum using a course sintered funnel and washed with ethyl acetate (2 X 25 mL). The solid was dissolved in ethanol (200 proof) and gravity filtered to separate excess potassium carbonate, and the solvent was evaporated. The solid was again dissolved in ethanol, filtered and the ethanol was removed by rotary evaporation (1.5 mm Hg, 50 °C) to give analytically pure trimethylammonium iodide salts as white fluffy powders in greater than 70% yield. S1 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2. 1H NMR spectra of trimethylammonium iodide salts N n-propyltrimethylammonium iodide 1 H NMR (300 MHz, D2O) δ 0.98 (t, 3H); 1.80 (m, 2H); 3.11 (s, 9H); 3.28 (m, 2H). N Propargyltrimethylammonium iodide 1 H NMR (300 MHz, D2O) δ 3.23 (s, 10H); 4.27 (s, 2H) S2 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 N n-butyltrimethylammonium iodide 1 H NMR (300 MHz, D2O) δ 0.98 (t, 3H); 1.42 (sextet, 2H); 1.80 (m, 2H); 3.14 (s, 9H); 3.35 (m, 2H) N n-pentyltrimethylammonium iodide 1 H NMR (300 MHz, D2O) δ 0.90 (t, 3H); 1.36 (m, 4H); 1.80 (m, 2H); 3.11 (s, 9H) 3.32 (m, 2H). S3 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 N Isoamyltrimethylammonium iodide 1 H NMR (300 MHz, D2O) δ 0.93 (m, 6H); 1.66 (t, 3H); 3.09 (s, 9H); 3.34 (d, 2H). N n-hexyltrimethylammonium iodide 1 H NMR (300 MHz, D2O) δ 1.00 (t, 3H); 1.46 (m, 6H); 1.905 (pentet, 2H); 3.25 (s, 9H); 3.47 (m, 6H). S4 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 N cyclopentyltrimethylammonium iodide 1 H NMR (300 MHz, D2O) δ 1.74 (m, 6H); 2.06 (m, 2H); 3.07 (s, 9H); 3.89 (pentet, 1H). N p-trimethylammonium toluene iodide 1 H NMR (300 MHz, D2O) δ 2.40 (s, 3H); 3.63 (s, 9H); 7.47 (d, 2H); 7.71 (d, 2H). S5 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 N p-ethylbenzene trimethylammonium iodide 1 H NMR (300 MHz, D2O) δ 1.21 (t, 3H); 2.71 (quartet, 2H); 3.63 (s, 9H); 7.49 (d, 2H); 7.74 (d, 2H). N p-t-butylbenzene trimethylammonium iodide 1 H NMR (300 MHz, D2O) δ 1.31 (s, 9H); 3.64 (s, 9H); 7.76 (m, 4H). S6 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 3. NMR Binding Studies General Procedure To a 20 mL scintillation vial was added alkyl trimethylammonium iodide (10 mg), nhexadecylphosphocholine (10 mg, >99 %, Avanti Polar Lipids), cavitand 1 or 2 (2 mg), and D2O (0.550 mL, 99.9 % D, Cambridge Isotope Laboratories). The mixture was sonicated for 10 minutes to aid in dissolution. 1H NMR was acquired on a Varian Gemini 300 MHz instrument at 298 K. Or a Bruker Apollo 400 MHz at 298 K. 512 scans were acquired and the data was then processed (iNMR 3.5.1) using a Fourier transform with exponential weighting (0.50 Hz). Next a 4 % solution of NaOD (Cambridge Isotope Laboratories) was titrated, the NMR tube was shaken, and 1H NMR was acquired. S7 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 Controls: Cavitand 2 + HPC HPC + n-propyltrimethylammonium iodide (expanded and magnified upfield region inset). S8 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, n-propyltrimethylammonium iodide. + 10 uL, 4 % NaOD S9 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2 + n-propyltrimethylammonium iodide + 10 uL, 4 % NaOD + HPC S10 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, propargyltrimethyl ammonium iodide + 10 uL, 4 % NaOD S11 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, n-butyltrimethylammonium iodide + 10 uL, 4 % NaOD S12 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, n-amyltrimethylammonium iodide + 10 uL, 4 % NaOD + 10 uL, 4 % NaOD S13 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, isoamyltrimethylammonium iodide + 10 uL, 4 % NaOD S14 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, n-hexyltrimethylammonium iodide + 10 uL, 4 % NaOD S15 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, n-octyltrimethylammonium iodide + 10 uL, 4 % NaOD S16 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, n-decyltrimethylammonium iodide + 10 uL, 4 % NaOD S17 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, cyclopentyltrimethylammonium iodide + 10 uL, 4 % NaOD S18 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, cyclohexyltrimethylammonium iodide + 10 uL, 4 % NaOD S19 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, cycloheptyltrimethylammonium iodide + 10 uL, 4 % NaOD S20 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, adamanyltrimethylammonium iodide (bottom), + 10 uL, 4 % NaOD (top) S21 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, 4-toluene trimethylammonium iodide + 10 uL, 4 % NaOD S22 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, 4-ethylbenzene trimethylammonium iodide + 10 uL, 4 % NaOD S23 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 2, HPC, 4-t-butylbenzene trimethylammonium iodide 3 + 5 uL, 4 % NaOD + 10 uL, 4 % NaOD S24 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 Controls HPC + p-t-butylbenzene trimethylammonium iodide 3 2, HPC, 4-t-Butylaniline + 5 uL, 4 % NaOD S25 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 1, HPC, p-t-butyl trimethylammonium iodide 3 + 5 uL, 4 % NaOD + 10 uL, 4 % NaOD S26 Electronic Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2011 1, p-t-butyl trimethylammonium iodide 3 in 50:50 DMSO-d6:D2O + 5 uL, 4 % NaOD + 10 uL, 4 % NaOD S27