On the use of high-pressure to study the speciation, solvation, and excited state energetics of luminescent lanthanide complexes

Muller, Gilles; Muller, Françoise C.; Riehl, James P.

doi:10.1016/j.jallcom.2004.03.011

Cited by 7 publications

(6 citation statements)

References 13 publications

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“…[17][18][19] So the preparation and properties of metal ion dipicolinic acid complexes become more and more attractive for the researchers. [20][21][22][23] The relevant rare earth complex materials especially have been widely used in cathodoluminescent display screens, lasers, and lamps because their photoluminescence exhibits high quantum efficiencies and very sharp spectral bands. [24] In recent years, the fabrication of luminescent complex materials based on lanthanide pyridine dicarboxylates has been reported in several works.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Spectroscopic Study of a Terbium(III) 2,6-Pyridinedicarboxylate Complex

Zhou

Wang

Tang

et al. 2010

Spectroscopy Letters

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The terbium(III) 2,6-pyridinedicarboxylate complex Na 3 Tb(PDA) 3 Á 8H 2 O with intense green luminescence was synthesized by liquid phase reaction and characterized by means of infrared (IR), ultraviolet (UV), 1 H nuclear magnetic resonance ( 1 HNMR), 13 C nuclear magnetic resonance ( 13 CNMR), and fluorescence spectra. In this complex, the coordination function of each PDA 2À group with terbium(III) center is tridentate chelate from two carboxyl oxygen and one heterocyclic nitrogen atoms while carboxylate group in a monodentate fashion. Terbium(III) is in nine-coordination configuration. Due to the high paramagnetic character and strong electron attraction ability of Tb 3þ ion, the chemical shifts of 1 HNMR and 13 CNMR spectra on the complex heterocycle to lower field compared with free H 2 PDA, while that of C 7 and C 8 of the complex move to higher fields probably due to shielding effects of the carboxyl group as well as conjugation system of two five-membered chelate cycles. Moreover, the 1 HNMR and 13 CNMR spectra of the complex have broader peak width than that of free H 2 PDA. The excitation and emission spectra of the complex show that the energy of the p(n)-p Ã excited state of C 5 H 3 NðCOOÞ 2À 2 can be effectively transferred to Tb 3þ ion, resulting in emission from the 5 D 4 ! 7 F j (j ¼ 3-6) electronic transitions of Tb 3þ ion. Because of the low symmetric center and strong coordination field that were affected, 5 D 4 and 7 F j (j ¼ 6,5,4) energy levels of Tb 3þ have split. In addition, the complex exhibits thermal stability below 460 C in air.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Spectroscopic Study of a Terbium(III) 2,6-Pyridinedicarboxylate Complex

Zhou

Wang

Tang

et al. 2010

Spectroscopy Letters

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“…The pH was also maintained within a range that was equivalent to physiological pH (6–7). This was also the pH range at which the amino acid l -serine is in its zwitterionic form, and the D 3 -[Tb(DPA) 3 ] 3− complex equilibrium is established [23–33,35]. The Eu(III)-based complex ([Eu(DPA) 3 ] 3− ) was also used with the same parameters, as mentioned for the [Tb(DPA) 3 ] 3− experiments; however, only the formamide solvents were used with this system (see explanation later).…”

Section: Resultsmentioning

confidence: 99%

The Importance of Solvent Effects on the Mechanism of the Pfeiffer Effect

et al. 2018

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The Pfeiffer effect is observed when an optically active compound such as an amino acid is introduced to a solution containing a labile racemic metal complex, and an equilibrium shift is obtained. The “perturbation” results in an excess of one enantiomer over the other. The shift is a result of a preferential outer sphere interaction between the introduced chiral species and one enantiomeric form (Λ or ∆) of a labile metal complex. Speculations regarding the mechanism of the Pfeiffer effect have attributed observations to a singular factor such as pH, solvent polarity, or numerous other intermolecular interactions. Through the use of the lanthanide(III) complexes [Tb(DPA)3]3− and [Eu(DPA)3]3− (where DPA = 2,6-pyridinedicarboxylate) and the amino acids l-serine and l-proline; it is becoming clear that the mechanism is not so simply described as per the preliminary findings that are discussed in this study. It appears that the true mechanism is far more complicated than the attribute just a singular factor. This work attempts to shine light on the fact that understanding the behavior of the solvent environment may hypothetically be the key to offering a more detailed description of the mechanism.

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“…Among ions used to replace Ca(II), lanthanide ions are especially advantageous: First, they share with Ca(II) similar ionic radii, coordination geometries (six to eight ligands), water exchange rates and a strong preference for oxygen ligands (7,(13)(14)(15). Second, lanthanides are luminescent, providing useful spectroscopic tools for understanding metal ion environments in metal complexes and macromolecules (22,23,42,43). These properties have led to extensive use of lanthanides and lanthanide spectroscopy in the study of Ca(II) binding proteins.…”

Section: Discussionmentioning

confidence: 99%

Lanthanide Spectroscopic Studies of the Dinuclear and Mg(II)-Dependent PvuII Restriction Endonuclease

et al. 2004

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Type II restriction enzymes are homodimeric systems that bind four to eight base pair palindromic recognition sequences of DNA and catalyze metal ion-dependent phosphodiester cleavage. While Mg(II) is required for cleavage in these enzymes, in some systems Ca(II) promotes avid substrate binding and sequence discrimination. These properties make them useful model systems for understanding the roles of alkaline earth metal ions in nucleic acid processing. We have previously shown that two Ca(II) ions stimulate DNA binding by PvuII endonuclease and that the trivalent lanthanide ions Tb(III) and Eu(III) support subnanomolar DNA binding in this system. Here we capitalize on this behavior, employing a unique combination of luminescence spectroscopy and DNA binding assays to characterize Ln(III) binding behavior by this enzyme. Upon excitation of tyrosine residues, the emissions of both Tb(III) and Eu(III) are enhanced severalfold. This enhancement is reduced by the addition of a large excess of Ca(II), indicating that these ions bind in the active site. Poor enhancements and affinities in the presence of the active site variant E68A indicate that Glu68 is an important Ln(III) ligand, similar to that observed with Ca(II), Mg(II), and Mn(II). At low micromolar Eu(III) concentrations in the presence of enzyme (10-20 microM), Eu(III) excitation (7)F(0) --> (5)D(0) spectra yield one dominant peak at 579.2 nm. A second, smaller peak at 579.4 nm is apparent at high Eu(III) concentrations (150 microM). Titration data for both Tb(III) and Eu(III) fit well to a two-site model featuring a strong site (K(d) = 1-3 microM) and a much weaker site (K(d) approximately 100-200 microM). Experiments with the E68A variant indicate that the Glu68 side chain is not required for the binding of this second Ln(III) equivalent; however, the dramatic increase in DNA binding affinity around 100 microM Ln(III) for the wild-type enzyme and metal-enhanced substrate affinity for E68A are consistent with functional relevance for this weaker site. This discrimination of sites should make it possible to use lanthanide substitution and lanthanide spectroscopy to probe individual metal ion binding sites, thus adding an important tool to the study of restriction enzyme structure and function.

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On the use of high-pressure to study the speciation, solvation, and excited state energetics of luminescent lanthanide complexes

Cited by 7 publications

References 13 publications

Synthesis and Spectroscopic Study of a Terbium(III) 2,6-Pyridinedicarboxylate Complex

Synthesis and Spectroscopic Study of a Terbium(III) 2,6-Pyridinedicarboxylate Complex

The Importance of Solvent Effects on the Mechanism of the Pfeiffer Effect

Lanthanide Spectroscopic Studies of the Dinuclear and Mg(II)-Dependent PvuII Restriction Endonuclease

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