Luminescence Quantum Efficiency of Gd and Tb in Borate Glasses and the Mechanism of Energy Transfer between Them

Reisfeld, Renata; Greenberg, E.; Velapoldi, R. A.; Barnett, Baruch

doi:10.1063/1.1677427

Cited by 399 publications

(159 citation statements)

References 17 publications

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“…Table 1 summarizes the efficiencies and probabilities of energy transfer in the above sensitizer-activator pairs. (2,27,28). Also Orbach (29,30), Birgeneau (31), Miyakawa and Dexter (32), and Soules and Duke (33) have noted that the transfer rate proportional to the overlap integral was negligible for different no phonon line emission and absorption frequencies.…”

Section: Borate Glassmentioning

confidence: 93%

Excited states and energy transfer from donor cations to rare earths in the condensed phase

Reisfeld

1991

Structure and Bonding

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Section: Borate Glassmentioning

confidence: 93%

Excited states and energy transfer from donor cations to rare earths in the condensed phase

Reisfeld

1991

Structure and Bonding

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“…A r value of 1.27 ms has been reported for Tb(III) in transferrin (2). In order to estimate ro, which strongly depends on environment (25), the integrated absorption of the level in question is required (24). The limited solubility of Tb(III)thermolysin together with the extremely weak absorption of Tb(III) precludes such experimental determinations for this system.…”

mentioning

confidence: 99%

“…§ The study of inter-lanthanide energy transfer in protein systems may also prove fruitful in other protein systems where appropriate hybrid substitutions can be made. Such studies might settle whether inter-lanthanide energy transfer is dipole-dipole (24,28) or dipole-quadrupole (26,27) in nature.…”

mentioning

confidence: 99%

Energy transfer between terbium (III) and cobalt (II) in thermolysin: a new class of metal--metal distance probes.

Horrocks¹,

Holmquist²,

Vallée³

1975

Proc. Natl. Acad. Sci. U.S.A.

106

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The visible fluorescence of terbium(III) when bound to a calcium binding site of thermolysin is greatly enhanced with an excitation maximum at 280 nm but substitution of cobalt(II) for zinc at the-active site decreases the intensity by 89.5%. Treatment with N-bromosuccinimide quenches enzyme tryptophan and Tb(III) fluorescence to a similar extent and suggests the operation of tryptophan Tb(III) -Co(II) energy relay system in the enzyme. Dipoledipole radiationless energy transfer between the Tb(III) donor and the Co(II) acceptor can account for this quenching. The inherent characteristics of the metal pair limits the value of the orientation factor, K2, of the Fbrster equation, thereby reducing uncertainties in distance measurements by energy transfer compared with other systems. A quantum yield of 0.51 yields a value of Bo, the distance for 50% energy transfer, of 19.6 A, and a distance, R, between Tb(III) and Co(II) of 13.7 A, a value identical to that measured for the distance between the active site zinc atom and calcium atom number 1 by x-ray analysis in native thermolysin crystals.The limits of confidence of this measurement are discussed.Energy transfer between two different metal atom sites of a protein provides a new class of probes to measure intramolecular distances of biological macromolecules in solution.The substitution of paramagnetic, chromophoric metal ions, e.g., Co(II), Cu(II), or trivalent lanthanides, for spectroscopically silent ions which are native to metalloenzymes, e.g., Ca(II), Mg(II), or Zn(II), has proven increasingly useful in the study of their structure-function relationships (1). In the arsenal of spectroscopic techniques, fluorescence measurements offer particular advantages, since they can be employed in the study of biological molecules at relatively low concentrations. Certain of the lanthanide ions, principally Tb(III) and Eu(III), can exhibit considerably enhanced fluorescence when replacing Ca(II) in calcium-dependent proteins (2-4) or when bound to nucleic acids (5). Radiationless energy transfer is now an established means to probe distance relationships between organic fluorophoric donors and organic chromophoric acceptors (6, 7).We have now monitored energy transfer between metal ion donors and metal ion acceptors and thereby measured distances between different metal ion sites of thermolysin, a metalloendopeptidase whose metal content and three-dimensional structure are known (8,9 (Fig. 1). * To whom correspondence should be addressed.Hence, Co(II) and Tb(III) substituted thermolysin favors obh servation of inter-ion energy transfer and, owing to its known structure, provides a suitable benchmark for future distance determinations using this technique. EXPERIMENTAL Thermolysin, obtained from Calbiochem (San Diego, Calif.), was recrystallized and rendered zinc free as described (11). Enzyme concentrations were determined by measuring the absorbance at 280 nm, based on the reported absorbance E1%280 = 17.65 (14) and a molecular weight of 34,600 (8).The enzyme was...

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“…On the basis of Dexter's energy transfer theory of exchange and multipolar interaction, the relation can be given by the following formula [27,[29][30][31] …”

Section: Energy Transfer From Ce 31 To Tb 31mentioning

confidence: 99%

Luminescence properties and energy transfer in Ca3(PO4)2:Ce3+, Tb3+ phosphors

Wang

Chen

et al. 2015

Appl. Phys. A

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A series of Ce 3? , Tb 3? and Ce 3? -Tb 3? -doped Ca 3 (PO 4 ) 2 were prepared by high-temperature solid-state reaction, and X-ray diffraction was used to characterize the phase structure. The photoluminescence and energy transfer properties of Ce 3? -and Tb 3? -doped Ca 3 (PO 4 ) 2 host were investigated. Under the 290-nm radiation excitation, the emission spectrum of Ca 3 (PO 4 ) 2 :Ce 3? shows one broad band that peaks at 360 nm, which is attributed to the 5d-4f transition of Ce 3? . Ce 3? and Tb 3? co-doped Ca 3 (PO 4 ) 2 phosphors exhibit both blue emission from Ce 3? ions and intense green emission lines from Tb 3? at the excitation of Ce 3? . These results indicate that there exits valid energy transfer from Ce 3? to Tb 3? . The energy transfer from Ce 3? to Tb 3? in Ca 3 (PO 4 ) 2 was demonstrated to be a resonant type via electric dipole-quadrupole interaction. The critical distance of energy transfer was also calculated. Moreover, the emitting color of Ca 3 (PO 4 ) 2 :Ce 3? , Tb 3? can be tuned by appropriately adjusting the relative doping composition of Ce 3? /Tb 3? .

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Luminescence Quantum Efficiency of Gd and Tb in Borate Glasses and the Mechanism of Energy Transfer between Them

Cited by 399 publications

References 17 publications

Excited states and energy transfer from donor cations to rare earths in the condensed phase

Excited states and energy transfer from donor cations to rare earths in the condensed phase

Energy transfer between terbium (III) and cobalt (II) in thermolysin: a new class of metal--metal distance probes.

Luminescence properties and energy transfer in Ca3(PO4)2:Ce3+, Tb3+ phosphors

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