Supplementary information - Royal Society of Chemistry

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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: schramm@csulb.edu
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
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
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
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
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
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
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
Controls:
Cavitand 2 + HPC
HPC + n-propyltrimethylammonium iodide (expanded and magnified upfield region
inset).
S8
2, HPC, n-propyltrimethylammonium iodide.
+ 10 uL, 4 % NaOD
S9
2 + n-propyltrimethylammonium iodide
+ 10 uL, 4 % NaOD
+ HPC
S10
2, HPC, propargyltrimethyl ammonium iodide
+ 10 uL, 4 % NaOD
S11
2, HPC, n-butyltrimethylammonium iodide
+ 10 uL, 4 % NaOD
S12
2, HPC, n-amyltrimethylammonium iodide
+ 10 uL, 4 % NaOD
+ 10 uL, 4 % NaOD
S13
2, HPC, isoamyltrimethylammonium iodide
+ 10 uL, 4 % NaOD
S14
2, HPC, n-hexyltrimethylammonium iodide
+ 10 uL, 4 % NaOD
S15
2, HPC, n-octyltrimethylammonium iodide
+ 10 uL, 4 % NaOD
S16
2, HPC, n-decyltrimethylammonium iodide
+ 10 uL, 4 % NaOD
S17
2, HPC, cyclopentyltrimethylammonium iodide
+ 10 uL, 4 % NaOD
S18
2, HPC, cyclohexyltrimethylammonium iodide
+ 10 uL, 4 % NaOD
S19
2, HPC, cycloheptyltrimethylammonium iodide
+ 10 uL, 4 % NaOD
S20
2, HPC, adamanyltrimethylammonium iodide (bottom), + 10 uL, 4 % NaOD (top)
S21
2, HPC, 4-toluene trimethylammonium iodide
+ 10 uL, 4 % NaOD
S22
2, HPC, 4-ethylbenzene trimethylammonium iodide
+ 10 uL, 4 % NaOD
S23
2, HPC, 4-t-butylbenzene trimethylammonium iodide 3
+ 5 uL, 4 % NaOD
+ 10 uL, 4 % NaOD
S24
Controls
HPC + p-t-butylbenzene trimethylammonium iodide 3
2, HPC, 4-t-Butylaniline
+ 5 uL, 4 % NaOD
S25
1, HPC, p-t-butyl trimethylammonium iodide 3
+ 5 uL, 4 % NaOD
+ 10 uL, 4 % NaOD
S26
1, p-t-butyl trimethylammonium iodide 3 in 50:50 DMSO-d6:D2O
+ 5 uL, 4 % NaOD
+ 10 uL, 4 % NaOD
S27

Supplementary information - Royal Society of Chemistry

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