Species-differentiable sensing of phosphate-containing anions in neutral aqueous solution based on coordinatively unsaturated lanthanide complex probes

doi:10.1016/j.ab.2004.05.024

Analytical Biochemistry

Volume 331, Issue 2, 15 August 2004, Pages 235-242

https://doi.org/10.1016/j.ab.2004.05.024 Get rights and content

Abstract

A new chromogenic/fluorogenic molecular probe was developed for highly selective and species-differentiable detection of phosphate-containing anions in neutral aqueous solution. The coordinatively unsaturated lanthanide complex, made from Eu(III) ion and 2-[(8-hydroxy-5-sulfo-7-quinoline)azo]-1,8-dihydroxy-3,6-naphthalene disulfonic acid, changed its conformation when binding to the incoming target anions, which resulted in differential absorption or fluorescence responses. It was demonstrated that not only phosphate and pyrophosphate but also DNA and RNA could be clearly distinguished by visible absorption or fluorescence spectra. Also, differential responses in absorption spectra were observed when AMP, ADP, and ATP were added into the sensing system. Selective quantitation of these phosphate-containing anions in aqueous solutions, therefore, can be easily available. DNA and RNA were distinguished by different colors and independent fluorescence emissions due to their intrinsic differences in β-d-ribose residues. Simultaneous or independent quantitation of DNA and RNA in a mixture sample, therefore, is possible without pretreatment with nuclease. Furthermore, the influence from the base selectivity can be eliminated by the use of the probe. The detection limits of phosphate and 5^′-ATP in neutral water were 6.0 × 10⁻⁷ and 9.0 × 10⁻⁷ M, respectively, by the UV/Vis spectrophotometric method; the detection limits were 12.3 ng/mL for DNA by fluorimetry and 2.3 mg/L for RNA by UV/Vis spectrophotometry.

Section snippets

Reagents

HQSAC was prepared as described elsewhere [15]. 5^′-AMP, 5^′-ADP, and 5^′-ATP were purchased from Sangon Biotech. (Shanghai, China); herring sperm DNA, calf thymus DNA, and yeast RNA were purchased from Sino-American Biotech.; buffer reagents, Tris(hydroxymethyl)aminomethane, and 3,3^′-dimethylglutaric acid were purchased from Acros Organics and used without any further purification. All other reagents were of analytical grade or better and used without further purification.

The lanthanide complex

Results and discussion

The UV/Vis spectral responses of 1a toward many anions were tested; the results are shown in (Fig. 2). When a series of buffered (0.020 M Tris–HCl, pH 7.40 at 23 °C) 1a aqueous solutions with the same concentration were titrated by different anion solutions, it was observed that the color shifted from pink to blue and royal for HPO₄²⁻ and P₂O₇⁴⁻, respectively, while other anions including F⁻, Cl⁻, Br⁻, I⁻, SCN⁻, NO₃⁻, SO₃²⁻, SO₄²⁻, HCO₃⁻, NO₂⁻, and HPO₂⁻ induced no color changes. This phenomenon

Acknowledgements

This work was supported by the National Natural Science Foundation of China (No. 20275033). We gratefully acknowledge Dr. Yuan Yan for presenting the synthesized reagents HQSAC and HQSAH.

References (28)

N. DiCesare et al.
New sensitive and selective fluorescent probes for fluoride using boronic acids
Anal. Biochem.
(2002)
L.A. Cabell et al.
A Competition Assay for determining glucose-6-phosphate concentration with a tris-boronic acid receptor
Tetrahedron Lett.
(1999)
J. Yguerabide et al.
Quantitative fluorescence method for continuous measurement of DNA hybridization kinetics using a fluorescent intercaltor
Anal. Biochem.
(1995)
Y.X. Ci et al.
Fluorescence reaction of terbium(III) with nucleic acids in the presence of phenanthroline
Anal. Chim. Acta
(1991)
H.S. Rye et al.
Fluorometric assay using dimericdyes for double- and single-stranded DNA and RNA with picogram sensitivity
Anal. Biochem.
(1993)
H. Zheng et al.
Near-infrared fluorimetric determination of nucleic acids by shifting the ion-association equilibrium between heptamethylene cyanine and Alcian blue 8GX
Anal. Chim. Acta
(2002)
A.A. Killeen
A visible spectrophotometric assay for submicrogram quantities of DNA, including PCR- amplified DNA
Microchem. J.
(1995)
R. Martı́nez-Máñez et al.
Fluorogenic and chromogenic chemsoensors and reagents for anions
Chem. Rev.
(2003)
M.E. Huston et al.
Chelation enhanced fluorescence detection of non-metal ions
J. Am. Chem. Soc.
(1989)
D.H. Vance et al.
Real-time assay of inorganic pyrophosphatase using a high-affinity chelation-enhanced fluorescence chemosensor
J. Am. Chem. Soc.
(1994)

M.T. Albelda et al.

Thermodynamics and fluorescence emission studies on potential molecular chemosensors for ATP recognition in aqueous solution

J. Chem. Soc. Perkin Trans.

(1999)

F. Sancenón et al.

A colorimetric ATP sensor based on 1,3,5-triarylpent-2-en-1,5-diones

Angew Chem. Int. Ed.

(2001)

M.S. Han et al.

Naked-eye detection of phosphate ions in water at physiological pH: a remarkable selective and easy-to-assemble colorimetric phosphate-sensing probe

Angew. Chem. Int. Ed.

(2002)

S. Mizukami et al.

A fluorescent anion sensor that works in neutral aqueous solution for bioanalytical application

J. Am. Chem. Soc.

(2002)

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Species-differentiable sensing of phosphate-containing anions in neutral aqueous solution based on coordinatively unsaturated lanthanide complex probes

Abstract

Section snippets

Reagents

Results and discussion

Acknowledgements

Anal. Biochem.

Tetrahedron Lett.

Anal. Biochem.

Anal. Chim. Acta

Anal. Biochem.

Anal. Chim. Acta

Microchem. J.

Fluorogenic and chromogenic chemsoensors and reagents for anions

Chem. Rev.

Chelation enhanced fluorescence detection of non-metal ions

J. Am. Chem. Soc.

Real-time assay of inorganic pyrophosphatase using a high-affinity chelation-enhanced fluorescence chemosensor

J. Am. Chem. Soc.

Thermodynamics and fluorescence emission studies on potential molecular chemosensors for ATP recognition in aqueous solution

J. Chem. Soc. Perkin Trans.

A colorimetric ATP sensor based on 1,3,5-triarylpent-2-en-1,5-diones

Angew Chem. Int. Ed.

Naked-eye detection of phosphate ions in water at physiological pH: a remarkable selective and easy-to-assemble colorimetric phosphate-sensing probe

Angew. Chem. Int. Ed.

A fluorescent anion sensor that works in neutral aqueous solution for bioanalytical application

J. Am. Chem. Soc.