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Life in extreme environments : lanthanide-based detection of bacterial spores and other sensor design pursuits

Citation

Cable, Morgan Leigh (2010) Life in extreme environments : lanthanide-based detection of bacterial spores and other sensor design pursuits. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:05102010-145436548

Abstract

Bacterial spores, or endospores, are produced by certain genera of bacteria under stress and are considered to be one of the most resilient forms of life on Earth. Detection of endospores is vital in areas ranging from bioburden reduction to homeland security. Rapid bacterial spore detection is achieved by targeting dipicolinic acid (DPA), a chemical marker unique to endospores. An improvement on the current bacterial spore detection assay based on sensitized lanthanide luminescence is presented through the implementation of a dipicolinate-specific Tb^(3+) receptor site. The use of a chelating ligand such as DO2A (1,4,7,10-tetraazacyclododecane-1,7-bisacetate) can increase both the sensitivity and selectivity of the assay. The luminescent series of Ln(DO2A)(DPA)- complexes (Ln = Sm, Eu, Tb and Dy) is fully characterized in terms of structure, photophysics and stability, and the Tb(DO2A)^+ binary complex in particular is investigated as a sensing complex for bacterial spores. The ‘ligand enhancement’ observed in all cases improves dipicolinate binding affinity by approximately one order of magnitude over the lanthanide ion alone. Binding of the DO2A ligand also appears to generate a ‘gadolinium break’ effect, creating a discrepancy in binding affinity in the lanthanide series and rendering the terbium complex the most effective dipicolinate receptor site of all investigated. We have also extended the application of this receptor site design technology to the targeted detection of other aromatic analytes of biological relevance, such as salicylates and catecholamines. Our work indicates that construction of effective receptor site complexes is not governed by net electrostatic considerations, and that local charge variations from the ligand-induced perturbation of lanthanide electron density may play a significant role. This work sets the stage for the development of the next-generation terbium(macrocycle) complex for bacterial spore detection, with the aim of constructing a solid-state endospore microsensor for applications ranging from sterilization validation to life detection in extreme environments.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:lanthanide luminescence; sensitized lanthanide luminescence; bacterial spore; endospore; anthrax; salicylate; salicylurate; aspirin metabolite; receptor site design; dipicolinate; macrocycle; DO2A; sensor design; terbium; europium; dysprosium; samarium; gadolinium; ternary complex
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Awards:The Herbert Newby McCoy Award, 2010
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Ponce, Adrian (co-advisor)
  • Gray, Harry B. (co-advisor)
Thesis Committee:
  • Lewis, Nathan Saul (chair)
  • Goddard, William A., III
  • Okumura, Mitchio
Defense Date:3 May 2010
Funders:
Funding AgencyGrant Number
National Defense Science and Engineering Graduate Fellowship ProgramUNSPECIFIED
NASA Graduate Student Research ProgramUNSPECIFIED
NASA Astrobiology and Planetary Protection ProgramUNSPECIFIED
Department of Homeland Security's Chemical and Biological Research & Development ProgramUNSPECIFIED
Arnold and Mabel Beckman FoundationUNSPECIFIED
National Science FoundationCHE-518164
NASAJPL-0098901
National Science FoundationCHE-0639094
Record Number:CaltechTHESIS:05102010-145436548
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:05102010-145436548
Related URLs:
URLURL TypeDescription
http://ponce.caltech.edu/Morgan.htmlAuthorUNSPECIFIED
http://ponce.caltech.edu/Curriculum%20vitae/Morgan%20L%20Cable%20CV.pdfCurriculum VitaeUNSPECIFIED
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:5791
Collection:CaltechTHESIS
Deposited By: Morgan Cable
Deposited On:21 May 2010 17:44
Last Modified:26 Dec 2012 03:25

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PDF (Chapter 1 - Introduction) - Final Version
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PDF (Chapter 2 - Ternary Complex Characterization) - Final Version
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PDF (Chapter 3 - A First-Generation Receptor Site) - Final Version
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PDF (Chapter 4 - Towards a Second-Generation Receptor Site) - Final Version
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PDF (Chapter 5 - Other Analytes) - Final Version
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PDF (Appendix A - Model for Ln(DPA) Binding Affinity) - Final Version
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PDF (Appendix B - Model for Ln(DO2A)(DPA) Binding Affinity) - Final Version
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PDF (Appendix E - Crystallography Files, Eu Temp Dep) - Final Version
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PDF (Appendix F - Crystallography File of F-DPA Complex) - Final Version
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PDF (Appendix G - Characterization of DOAAM Ligand) - Final Version
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[img] Crystallographic Info File (CIF) (Tb(DO2A)(DPA) complex) - Supplemental Material
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[img] Crystallographic Info File (CIF) (Eu(DO2A)(DPA) complex) - Supplemental Material
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[img] Crystallographic Info File (CIF) (Dy(DO2A)(DPA) complex) - Supplemental Material
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[img] Crystallographic Info File (CIF) (Sm(DO2A)(DPA) complex) - Supplemental Material
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[img] Crystallographic Info File (CIF) (Tb(DO2A)(DPA) complex, 300 K) - Supplemental Material
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[img] Crystallographic Info File (CIF) (Eu(DO2A)(DPA) complex, 100 K) - Supplemental Material
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[img] Crystallographic Info File (CIF) (Eu(DO2A)(DPA) complex, 300 K) - Supplemental Material
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[img] Crystallographic Info File (CIF) (Gd(DO2A)(DPA) complex) - Supplemental Material
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[img] Crystallographic Info File (CIF) (Tb(DO2A)(F-DPA) complex) - Supplemental Material
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