1. Synthesis of BODIPY appended β-cyclodextrin sensors
for improved understanding of molecular interactions
Gordon Rix, Sauradip Chaudhuri, Mindy Levine*
Department of Chemistry, University of Rhode Island, Kingston, RI 02881
Background
Acknowledgements
-Dr. Mindy Levine and the Levine research group
-This material is based upon work supported in part by
the National Science Foundation EPSCoR Cooperative
Agreement #EPS-1004057
-Special thanks to the office of Governor Raimondo for
the Gov. Gina M. Raimondo’s Summer Undergraduate
Research Fellowship award
References
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11618
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561-572
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721
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6. Mako,T.; Marks, P.; Cook, N.; Levine, M. Supramol. Chem. 2012, 24, 743-747
7. Hamai, S. J. Inclusion Phenom. Macrocyclic Chem. 2010, 67, 471-481
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Dafonte, P.; Garcia-Rio, L. Org. Biomol. Chem. 2015, 13, 1213-1224
Fluorescence Applications
 Past work has produced sensing systems that rely on
independent fluorophores and cyclodextrins in solution
 Contingent upon formation of a ternary complex
between the analyte, fluorophore, and cyclodextrin
Emission
Analyte
Analyte
Reaction Scheme
β-CD
β-CD β-CD
β-CD β-CD
n = 2, 5, 10
Preliminary evidence suggests synthesis of both
βCD-BD5 and βCD-BD10 was successful, while
synthesis of βCD-BD2 is still in progress
Conclusions and Future Work
 Through attachment of fluorophore to the cyclodextrin,
efficient sensing requirements are reduced to a binary
complex between the analyte and the fluorophore-
appended cyclodextrin
 BODIPY chosen for high quantum yield and low stokes shift
 β-cyclodextrin chosen for ability to accommodate only one
guest molecule
 Synthesis of higher order cyclodextrin
architectures may also yield more effective
sensing systems
 Dimerization of cyclodextrin with fluorophore
attachment may allow for effective study of
molecular interactions including more than one
analyte
 Structures reported herein as well as future
cyclodextrin architectures could constitute
valuable components in highly sensitive
detection of aromatic compounds
 Statistical analysis is used
to achieve maximal
separation of aromatic
analytes based on energy
transfer
 Data can then be used to
identify unknown analyte

1
H NMR suggests attachment of BD5 and
BD10 to β-cyclodextrin proceeded as
expected, while attachment of BD2 may
have been unsuccessful
 BD2 attachment reaction will be run again
at a larger scale
 Concurrent work is exploring alternative
attachment sites
 While secondary rim functionalization
provides the fluorophore with improved
cavity access, primary rim functionalization
may improve sensitivity and selectivity for
some analytes
β-cyclodextrin
βCD-BD10
BODIPY Fluorophore
βCD-BD5
βCD-BD2
β-cyclodextrin with fluorophore attached
at varying covalent tether lengths
Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated
biphenyls (PCBs) are two types of carcinogenic aromatic pollutants
that can have profound impacts on marine environments, even at low
concentrations.
Our lab has worked on the development of detection methods that
depend on the transfer of energy from these compounds and other
analytes to fluorescent compounds, whose signal can then be
interpreted. However, this energy transfer can only occur efficiently
when both the fluorophore and the analyte are within close
proximity.This is accomplished with the use of a cavity-containing
cyclodextrin, which serves as a host for the two molecules.
By covalently attaching the fluorophore to the cyclodextrin, we hope
to reduce the requirements needed for efficient energy transfer, and
drastically improve the capabilities of toxicant sensing systems.
Depiction of a ternary complex between an
analyte, a fluorophore, and a cyclodextrin host
Analyte
Primary rim
Nonpolar cavity
Secondary rim