Supramolecular Organic Hosts for Benzo[a]pyrene Binding and Detection
(CDCl3, 300 MHz): δ = 8.26 (d, J = 7.8 Hz, 2 H), 7.95 (t, J =
7.5 Hz, 1 H), 7.65 (s, 2 H), 7.52 (d, J = 6.0 Hz, 5 H), 7.46 (m, 4 [1]
H), 7.40 (d, J = 7.2 Hz, 3 H), 7.33 (s, 6 H), 5.50 (s, 4 H), 4.58 (s,
8 H) ppm. 13C NMR (CDCl3, 75 MHz): δ = 164.58, 148.63, 141.76,
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128.13, 127.96, 127.82, 127.57, 127.09, 126.67, 72.03, 67.91 ppm.
HRMS (ESI): calcd. for [C43H36NO6]+ [M + H]+ 662.2543, found
662.2550.
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Synthesis of BODIPY Fluorophore 12: The synthesis of fluorophore
12 occurred according to literature-reported procedures.[17]
Fluorescence Experimental Procedures
Binding Experiments: The following stock solutions were prepared:
(a) 3 mg/mL of each macrocycle in THF; (b) 1 mg/mL of each PAH
analyte in THF. Dilutions of the macrocycle stock solution were
prepared to obtain solutions of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8,
0.9, 1.0, 2.0 and 3.0 mg/mL solutions of each macrocycle. 20 μL of
the PAH stock solution was added to 2.5 mL of phosphate-buffered
saline (PBS) at pH 7.4. 200 μL of each macrocycle solution was
added, and the fluorescence of the solution was recorded with
360 nm excitation (scanned emission 370–710 nm). The fluores-
cence of the analyte was integrated with respect to wavenumber on
the x-axis. The resulting data was plotted using a Benesi–Hilde-
brand plot, with 1/[macrocycle] (in m–1) on the x-axis and 1/inte-
grated analyte emission on the y-axis. Linear fits were obtained
using macrocycles 2, 5, and 9 as hosts and benzo[a]pyrene (11) as
a guest. The binding constants were calculated by dividing the y-
intercept of the linear equation by the slope of the line.
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Energy Transfer Experiments: A 0.1 mg/mL stock solution of
BODIPY 12 in THF was prepared. 200 μL of the macrocycle host,
20 μL of the PAH analyte, and 20 μL of the BODIPY 12 fluoro-
phore were added to 2.5 mL of PBS. The solution was excited at
360 nm and 460 nm (scanned emission 370–710 nm and 470–
800 nm, respectively). The fluorescence emission of benzo[a]pyrene
(11) and of BODIPY 12 were integrated with respect to wave
number, and the efficiency of energy transfer was determined by
measuring the percentage of BODIPY emission from analyte exci-
tation compared to direct excitation [Equation (1)].
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1
1H NMR Titration Experiments: All H NMR titrations were car-
ried out by adding aliquots of benzo[a]pyrene in CDCl3 to the host
macrocycle already dissolved in CDCl3 in an NMR tube. After
each addition, the spectrum was recorded by using a Bruker
300 MHz instrument. For the titration of macrocycle 9 with
benzo[a]pyrene (11): A CDCl3 solution of macrocycle 9 (5.35 mg,
14.8 mm, 0.5 mL) was titrated by adding increasing amounts of
benzo[a]pyrene (11) (0.5, 1.0, 1.5, 2.0 and 4.0 equiv.) from a CDCl3
stock solution (18.70 mg, 29.6 mm, 2.5 mL) and showed a 1:1 ratio
of binding in macrocycle 9.
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Acknowledgments
Support is acknowledged from the University of Rhode Island
Chemistry Department start-up funds. Lindsey Prignano is
thanked for her assistance with the fluorescence experiments.
Eur. J. Org. Chem. 2015, 6194–6204
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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