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Abstract Header
Sensing of Enantiomeric Excess in Chiral Carboxylates
Author Info
Akdeniz, Ali
ORCID® Identifier
http://orcid.org/0000-0002-9734-3282
Permalink:
http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1465223828
Abstract Details
Year and Degree
2016, Doctor of Philosophy (Ph.D.), Bowling Green State University, Photochemical Sciences.
Abstract
Chirality of organic compounds plays a crucial role in human and veterinary medicine. More specifically, chiral carboxylates are extensively utilized in drug development processes, and a number of them are commercialized as drugs. Due to distinct pharmacological properties of enantiomers of chiral drugs, asymmetric synthesis became an essential tool to synthesize enantiopure compounds. While combinatorial libraries enable to screen catalysts, auxiliaries, and conditions rapidly, the enormous amount of resulting samples cannot be tested simultaneously. In this dissertation, we have reported two optical methods to determine the ee values of the chiral carboxylates in a high-throughput fashion. In the first method, we have employed cinchona alkaloids, known as Corey-Lygo catalysts, as chemosensors for ee analysis of chiral carboxylates. N-alkylated 9-chloromethylanthracenyl cinchona alkaloids form complexes with carboxylates by means of electrostatic interactions and hydrogen bonds. Using characteristic changes in fluorescence intensities of the chemosensors upon addition of analytes, we were able to perform the successful qualitative and quantitative ee analysis of enantiomers of chiral carboxylates in aqueous media. Using the sensor array comprising four N-alkylated cinchona alkaloids, we were able to achieve 100 % correct classification of chiral carboxylates, including several enantiomers of non-steroidal anti-inflammatory drugs (NSAIDs) successfully. Furthermore, quantitative ee analysis of (S)-Ibuprofen, (S)-Naproxen, and (S)-Ketoprofen shows prediction errors as low as 3%. The second method involves fluorescent macrocyclic sensors containing the chiral BINOL moiety, and H-bond donors in the pocket to form complexes with carboxylates. The intrinsic structure of the pocket of macrocycles displays an enantioselective behavior for chiral carboxylates, while the substituents at the 3,3’-positions of the BINOL moiety allow for tuning the shape and size of the cavity to enhance the recognition performance of the macrocycles. The resulting macrocycles show distinct responses for a number of carboxylates, including the enantiomers of ibuprofen, ketoprofen, 2-phenylpropanoate, mandelate, and phenylalanine. The fingerprint-like responses of the macrocycles, for structurally similar analytes, enabled to perform a qualitative analysis of 12 carboxylates with 100 % correct classification. Quantitative ee analysis of ibuprofen, ketoprofen, and phenylalanine shows that the sensors correctly identify the ee values of the unknown samples with an error of prediction < 3% even in the presence of impurities.
Committee
Pavel Anzenbacher, Jr., Ph.D. (Advisor)
Carol Heckman, Ph.D. (Committee Member)
H. Peter Lu, Ph.D. (Committee Member)
Andrew T. Torelli, Ph.D. (Committee Member)
Pages
216 p.
Subject Headings
Analytical Chemistry
;
Chemistry
;
Organic Chemistry
;
Physical Chemistry
Keywords
Chemosensors
;
Anion detection
;
Sensor Arrays
;
Pattern Recognition
;
Fluorescence
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Citations
Akdeniz, A. (2016).
Sensing of Enantiomeric Excess in Chiral Carboxylates
[Doctoral dissertation, Bowling Green State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1465223828
APA Style (7th edition)
Akdeniz, Ali.
Sensing of Enantiomeric Excess in Chiral Carboxylates.
2016. Bowling Green State University, Doctoral dissertation.
OhioLINK Electronic Theses and Dissertations Center
, http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1465223828.
MLA Style (8th edition)
Akdeniz, Ali. " Sensing of Enantiomeric Excess in Chiral Carboxylates." Doctoral dissertation, Bowling Green State University, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1465223828
Chicago Manual of Style (17th edition)
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Document number:
bgsu1465223828
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Copyright Info
© 2016, some rights reserved.
Sensing of Enantiomeric Excess in Chiral Carboxylates by Ali Akdeniz is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 3.0 Unported License. Based on a work at etd.ohiolink.edu.
This open access ETD is published by Bowling Green State University and OhioLINK.