How can aluminium(III) generate fluorescence?

Mulon, Jean-Baptiste; Destandau, Émilie; Alain, Valérie; Bardez, Élisabeth

doi:10.1016/j.jinorgbio.2005.06.005

Cited by 35 publications

(13 citation statements)

References 32 publications

(38 reference statements)

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“…When HNAQ undergoes electronic excitation, the acidity of the naphtholic group and the basicity of the quinolyl nitrogen become considerably enhanced, promoting tautomerization of this ligand, as illustrated in Scheme . A coupling between the intramolecular proton transfer and an intramolecular charge transfer from naphtholate oxygen to the quinolyl ring results in the formation of a low emissive keto phototautomer presumably due to a partial loss of planarity of the molecule (39). The increase in fluorescence intensity upon complexation of the ligand is attributed to the inhibition of the phototautomerization.…”

Section: Resultsmentioning

confidence: 99%

Spectrofluorimetric determination of aluminium using 2‐hydroxy‐1‐naphthylidene‐(8‐aminoquinoline)

et al. 2010

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A sensitive and selective spectrofluorimetric method has been developed for the rapid determination of aluminium. This method is based on the complex formation between aluminium and 2-hydroxy-1-naphthylidene-(8-aminoquinoline) (HNAQ). The optimum conditions for the complex formation were a metal-to-ligand (M : L) stoichiometric ratio of 1:1, a pH of 5.5 and a 0.20 m acetate buffer. The fluorescence of the complex was monitored at an emission wavelength of 502 nm with excitation at 438 nm. Under these conditions, linear calibration curves were obtained in the ranges 0.05-1 and 1-5 ppm. The detection limit was 3.4 ppb for the former and 13.5 ppb for the latter. The maximum relative standard deviation of the method for an aluminium standard of 200 ppb was 1.5% (n = 5). This method was successfully applied for the determination of aluminium in drinking water, pharmaceutical antacid tablets and suspension samples.

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Section: Resultsmentioning

confidence: 99%

Spectrofluorimetric determination of aluminium using 2‐hydroxy‐1‐naphthylidene‐(8‐aminoquinoline)

et al. 2010

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“…An increase of the fluorescence intensity can also be observed, for example in the case of complexation of 8-hydroxyquinoline by Al 3+ . The charge transfer at play in bare 8-hydroxyquinoline tends to quench the fluorescence; complexation by Al 3+ prevents it and results in the enhancement of local emission . The same behavior is observed in anthraceno-cryptands. , …”

Section: Resultsmentioning

confidence: 66%

Role of Conformational Isomerism in Solvent-Mediated Charge Transfer in Chiral (S) 1,2,3,4-Tetrahydro-3-isoquinoline Methanol (THIQM): Condensed-Phase to Jet-Cooled Spectroscopic Studies

et al. 2011

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Intramolecular charge-transfer reaction in chiral (S) 1,2,3,4-tetrahydro-3-isoquinoline methanol (THIQM) has been investigated in the condensed phase and in jet-cooled conditions by means of laser-induced fluorescence, dispersed emission, resonance-enhanced two-photon ionization, and IR-UV double resonance experiments, as well as quantum chemical calculations. In the condensed phase, THIQM only shows local emission in nonpolar and protic solvents and dual emission in aprotic polar solvents, where the solvent-polarity dependent Stokes shifted emission is ascribed to a state involving charge transfer from the nitrogen lone pair to the benzene π-cloud. Ab initio calculations reveal two low-energy conformers, which are observed in jet-cooled conditions. In the most stable conformer, THIQM(I), the CH(2)OH substituent acts as a hydrogen bond donor to the nitrogen lone pair in the equatorial position, while the second most stable conformer, THIQM(II), corresponds to the opposite NH···O hydrogen bond, with the nitrogen lone pair in the axial position. The two low-energy jet-cooled conformers of THIQM evidenced from the laser-induced fluorescence and dispersed emission spectra only show structured local emission. Complexes with usual solvents reproduce the condensed phase properties. The jet-cooled complex with aprotic polar solvent acetonitrile shows both local emission and charge transfer emission as observed in solution. The jet-cooled hydrate mainly shows local emission due to the unavailability of the nitrogen lone pair through intermolecular hydrogen bonding.

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“…The disadvantages of the FIA method were key to selecting the RP-HPLC method. The chemistry employed in the FIA method was clearly superior to alternatives (Ahmed and Hossan 1995;Mulon et al 2005 and references there in), however, the analytical set-up had many limitations. Changing the inline sample treatment (as employed in the FIA method) with a pre-column (batch) reagent mixing step, separated the detection mechanism (formation of the Al-lumogallion complex) from the concentration mechanism (the focusing of the Al-lumogallion complex onto the C 18 guard column), allowing independent optimization.…”

Section: Discussionmentioning

confidence: 99%

Reversed phase high performance liquid chromatographic determination of dissolved aluminium in open ocean seawater

Remenyi

Nesterenko

Butler

et al. 2012

Limnology & Ocean Methods

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Popular shipboard techniques to determine dissolved aluminium in open ocean seawater have two major disadvantages: relative to HPLC techniques, they require large sample volumes; and, in practice they are are only semi-automated. To address these two issues, the application of a reversed-phase high performance liquid chromatographic (RP-HPLC) method for the determination of the aluminium in open ocean seawater was developed. With this method, dissolved aluminium in the sample was complexed with lumogallion at pH 5.5 by the addition of a reagent, producing the fluorescent aluminium-lumogallion complex. This complex was concentrated onto a Chromolith ® RP-18e Guard (10 × 4.6 mm) column and eluted with 95% methanol into a fluorescence detector (λ ex = 505 nm, λ em = 574 nm). Sample pre-treatment required 10 h (>100 samples can be prepared simultaneously) and sample analysis required 375 mL of sample per vial analysed, with 10 mL and 2.7 min per injection. Total required sample volume (including rinses) was 1.5 mL. Limit of detection was 0.13±0.05 nM, with precision of 2.7% at 1 nM on SAFe reference samples. Agreement with SAFe reference samples was within 4.6±4.6% (n = 13). The technique is robust, inherently automated and could easily be applied shipboard for open ocean analyses. It provides improvements in sample efficiency, operational robustness and automation relative to popular shipboard techniques, especially when applied to samples with dissolved aluminium concentrations that approach the limit of detection. This project was a contribution to the GEOTRACES program.

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How can aluminium(III) generate fluorescence?

Cited by 35 publications

References 32 publications

Spectrofluorimetric determination of aluminium using 2‐hydroxy‐1‐naphthylidene‐(8‐aminoquinoline)

Spectrofluorimetric determination of aluminium using 2‐hydroxy‐1‐naphthylidene‐(8‐aminoquinoline)

Role of Conformational Isomerism in Solvent-Mediated Charge Transfer in Chiral (S) 1,2,3,4-Tetrahydro-3-isoquinoline Methanol (THIQM): Condensed-Phase to Jet-Cooled Spectroscopic Studies

Reversed phase high performance liquid chromatographic determination of dissolved aluminium in open ocean seawater

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