Excited-state chiral discrimination observed by time-resolved circularly polarized luminescence measurements

Metcalf, David; Snyder, Seth W.; Wu, Shao-Yi; Hilmes, Gary L.; Riehl, James P.; Demas, J. N.; Richardson, F. S.

doi:10.1021/ja00190a062

Cited by 54 publications

(36 citation statements)

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“…10 This is achieved through the use of a pulsed excitation light source. Combination of the aforementioned methodologies has facilitated the study of the kinetics of excited state racemisation processes.…”

Section: Cpl Spectroscopy -Instrumentationmentioning

confidence: 99%

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence

2012

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The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source• a link is made to the metadata record in Durham E-Theses• the full-text is not changed in any wayThe full-text must not be sold in any format or medium without the formal permission of the copyright holders. Statement of CopyrightThe copyright of this thesis rests with the author. No quotations should be published without prior consent and information derived from it must be acknowledged. ABSTRACT -ii - ABSTRACTA series of studies has been undertaken to facilitate the identification and development of chiral lanthanide complexes that are able to report on changes in their local environment through modulation of the circular polarization of their emission. Reports of such systems remain relatively rare in the literature, notwithstanding the prevalence and importance of chirality in biological systems.The work described herein is separated into five chapters, the first of which comprises a discussion of relevant background information, along with a comprehensive review of responsive lanthanide-based CPL probes reported to date. A classification of these probes is built up, which informs the content of the following three chapters.Chapter 2 describes work undertaken in the pursuit of a novel lanthanide-based system for use as a CPL probe for the detection of proteins. The synthesis of an enantiopure lanthanide complex was undertaken and characterisation of this system carried out with reference to a structurally related racemic complex. A series of comparative investigations designed to probe the relative protein binding capability of these complexes was subsequently performed, which revealed that the observation of induced CPL from racemic lanthanide systems may be brought about by a change in complex constitution. This is the first example of such an effect from a well-defined racemic lanthanide complex in solution. Chapter 3 goes on to detail studies undertaken to demonstrate the utility of this racemic lanthanide system as a probe for chiral detection.Chapter 4 describes investigations carried out in an attempt to identify new systems exhibiting chiral quenching effects in solution. Initially, two pairs of enantiomeric electron-rich quenching species were assessed for their ability to quench the emission from an enantiopure DOTA-derived lanthanide complex differentially. Subsequently, investigations were focussed on examining the quenching of emission from novel enantiopure lanthanide complexes based on a 1,4,7-triazacyclononane framework, using cobalt complexes as the quenching species.Finally, Chapter 5 contains experimental procedures for each compound synthesised, as well as general experimental procedures.

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Section: Cpl Spectroscopy -Instrumentationmentioning

confidence: 99%

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence

2012

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“…52,53 Recently, they have been employed by Muller and colleagues 54 as probes for amino acids. Tb 3+ tris 2,6-pyridinedicarboxylate (L 18 ) and chelidamic acid (L 19 ) (Scheme 5) D 3 racemic complexes can interact with nonracemic compounds, giving rise to CPL.…”

Section: Lanthanide Cpl and Organic Moleculesmentioning

confidence: 99%

“…Tb 3+ tris 2,6-pyridinedicarboxylate (L 18 ) and chelidamic acid (L 19 ) (Scheme 5) D 3 racemic complexes can interact with nonracemic compounds, giving rise to CPL. 52,53 Recently, they have been employed by Muller and colleagues 54 as probes for amino acids. These are in fact chiral D 3 complexes, but Λ and Δ enantiomers undergo a rapid equilibrium in solution and cannot be resolved.…”

Section: Lanthanide Cpl and Organic Moleculesmentioning

confidence: 99%

Lanthanide Circularly Polarized Luminescence: Bases and Applications

2014

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Lanthanide (III) luminescence is very characteristic: it is characterized by narrow emission bands, large Stokes shift, and a long excited state lifetime. Moreover, chiral lanthanide complexes can emit strongly circularly polarized light in a way that is almost precluded to purely organic molecules. Thanks to the sensitivity and specificity of the Ln circularly polarized luminescence (CPL) signal, CPL-active complexes are therefore employed as bioanalytical tools and other uses can be envisaged in many other fields. Here we present a brief overview of the most recently developed CPL-active lanthanide complexes and a selected few examples of their applications. We briefly discuss the main mechanisms that can rationalize the observed outstanding CPL properties of these systems, and some practical suggestions on how to measure and report data.

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“…). Of special importance is that the studies by the research groups of Meskers and Dekkers,73–75 Richardson,70,72,77 and Riehl78 showed that the effectiveness of the enantioselective quenching processes is dependent on the strength of the intermolecular interactions between the racemic donor and chiral acceptor molecules and, therefore, responsible for the chiral recognition/discrimination abilities. In other words, the degree and sense of enantiomeric preference in these quenching processes are governed by the electronic and stereochemical properties of the optically active quenchers.…”

Section: Survey Of Luminescent Chiral Ln(iii) Complexes As Potentiamentioning

confidence: 99%

Luminescent chiral lanthanide(iii) complexes as potential molecular probes

2009

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This perspective gives an introduction into the design of luminescent lanthanide(III)-containing complexes possessing chiral properties and used to probe biological materials. The first part briefly describes general principles, focusing on the optical aspect (i.e. lanthanide luminescence, sensitization processes) of the most emissive trivalent lanthanide ions, europium and terbium, incorporated into molecular luminescent edifices. This is followed by a short discussion on the importance of chirality in the biological and pharmaceutical fields. The second part is devoted to the assessment of the chiroptical spectroscopic tools available (typically circular dichroism and circularly polarized luminescence) and the strategies used to introduce a chiral feature into luminescent lanthanide(III) complexes (chiral structure resulting from a chiral arrangement of the ligand molecules surrounding the luminescent center or presence of chiral centers in the ligand molecules). Finally, the last part illustrates these fundamental principles with recent selected examples of such chiral luminescent lanthanide-based compounds used as potential probes of biomolecular substrates.

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Excited-state chiral discrimination observed by time-resolved circularly polarized luminescence measurements

Cited by 54 publications

References 1 publication

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence

Lanthanide complexes as chiral probes exploiting circularly polarized luminescence

Lanthanide Circularly Polarized Luminescence: Bases and Applications

Luminescent chiral lanthanide(iii) complexes as potential molecular probes

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