Circularly polarized luminescence (CPL)-active lanthanide(III) complexes present a new method for chiral distinction of biomolecules upon metal binding or structural arrangements. This study is envisaged to understand the significantly different photophysical and chiroptical properties of the europium(III)-tetracycline (Eu:TC) complex. It is worth noting that the TC class of antibiotics has achieved importance beyond their therapeutic use as broad-spectrum antibiotics because many metal complexes utilizing TC have been used as luminescent probes for the investigation of biomolecular interactions. The method involves understanding the (a) speciation of TC, (b) conformation and ternary complexes formed between the Eu:TC complexes in aqueous and/or organic solvents at varied pH values and (c) variation of this Eu:TC complex using various TC-like derivatives. By identifying the structural changes of the various Eu:TC complexes, this CPL-active luminescent molecular probe can be designed and studied in diverse solutions at targeted pH values to allow for the molecular and chiral recognition/sensing of biomolecules such as amino acids, sugar derivatives, proteins, etc. Using luminescence, 5D07F0 Eu(III) excitation, and CPL spectroscopy, will allow for the study of the Eu:TC complex to recognize and interact with different chiral compounds in solution. The results from this study will explicate information on the local microenvironment about the lanthanide(III) metal by understanding the interactions of added analytes, in reference to chiral biomolecules like L-malic acid, human serum albumin (HSA), and bovine serum albumin (BSA), on the Eu:TC probe. CPL spectroscopy is used as a """"""""fingerprint"""""""" to indicate the structural changes within the Eu:TC complex as a result in a chiral signal correlated to the molecular and chiral sensing of an added biomolecule. The use of molecular probing using luminescent lanthanide(III) metals will aid in understanding the structural and functional aspects of each essential metal ion within many biological systems. In addition, the development of a straightforward and sensitive CPL-based technique for chiral elucidation has the potential to become a standard technique in biology and biochemistry laboratories, so the broader impacts are significant.

Public Health Relevance

The purpose of this project is to demonstrate the application of molecular probes using luminescent lanthanide(III) ions as a means of determining fundamental principles of bioinorganic functions within biological systems;in particular, the structural composition of circularly polarized luminescence-active tetracycline-like lanthanide complexes and the chiral sensing/recognition of biomolecules.

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Continuance Award (SC3)
Project #
2SC3GM089589-05
Application #
8739976
Study Section
Special Emphasis Panel (ZGM1-TWD-3 (SC))
Program Officer
Rogers, Michael E
Project Start
2010-01-01
Project End
2018-05-31
Budget Start
2014-09-05
Budget End
2015-05-31
Support Year
5
Fiscal Year
2014
Total Cost
$107,550
Indirect Cost
$32,550
Name
San Jose State University
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
056820715
City
San Jose
State
CA
Country
United States
Zip Code
95112
Nguyen, Brian T; Ingram, Andrew J; Muller, Gilles (2016) Localizing Perturbations of the Racemic Equilibria Involving Dipicolinate-Derived Lanthanide(III) Complexes. Chirality 28:325-31
Ray, César; Sánchez-Carnerero, Esther M; Moreno, Florencio et al. (2016) Bis(haloBODIPYs) with Labile Helicity: Valuable Simple Organic Molecules That Enable Circularly Polarized Luminescence. Chemistry 22:8805-8
Isla, Helena; Srebro-Hooper, Monika; Jean, Marion et al. (2016) Conformational changes and chiroptical switching of enantiopure bis-helicenic terpyridine upon Zn(2+) binding. Chem Commun (Camb) 52:5932-5
Feuillastre, Sophie; Pauton, Mathilde; Gao, Longhui et al. (2016) Design and Synthesis of New Circularly Polarized Thermally Activated Delayed Fluorescence Emitters. J Am Chem Soc 138:3990-3
Saleh, Nidal; Srebro, Monika; Reynaldo, Thibault et al. (2015) enantio-Enriched CPL-active helicene-bipyridine-rhenium complexes. Chem Commun (Camb) 51:3754-7
Saleh, Nidal; Moore 2nd, Barry; Srebro, Monika et al. (2015) Acid/base-triggered switching of circularly polarized luminescence and electronic circular dichroism in organic and organometallic helicenes. Chemistry 21:1673-81
Sánchez-Carnerero, Esther M; Agarrabeitia, Antonia R; Moreno, Florencio et al. (2015) Circularly Polarized Luminescence from Simple Organic Molecules. Chemistry 21:13488-500
Zhang, Xiao-Peng; Chang, Victoria Y; Liu, Jian et al. (2015) Potential switchable circularly polarized luminescence from chiral cyclometalated platinum(II) complexes. Inorg Chem 54:143-52
Sánchez-Carnerero, Esther M; Moreno, Florencio; Maroto, Beatriz L et al. (2014) Circularly polarized luminescence by visible-light absorption in a chiral O-BODIPY dye: unprecedented design of CPL organic molecules from achiral chromophores. J Am Chem Soc 136:3346-9
Shen, Chengshuo; Anger, Emmanuel; Srebro, Monika et al. (2014) Straightforward access to mono- and bis-cycloplatinated helicenes that display circularly polarized phosphorescence using crystallization resolution methods. Chem Sci 5:1915-1927

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