A new Hg2+-selective fluorescent sensor based on a dansyl amide-armed calix[4]-aza-crown

doi:10.1016/j.tetlet.2004.10.169

Tetrahedron Letters

Volume 46, Issue 1, 3 January 2005, Pages 165-168

https://doi.org/10.1016/j.tetlet.2004.10.169 Get rights and content

Abstract

A new fluorescent chemosensor for Hg²⁺ based on a dansyl amide-armed calix[4]-aza-crown was reported. It exhibits high sensitivity and selectivity toward Hg²⁺ over a wide range of metal ions in MeCN–H₂O (4:1, v/v). The association constant of the 1:1 complex formation for 2-Hg²⁺ was calculated to be 1.31 × 10⁵ M⁻¹, and the detection limit for Hg²⁺ was found to be 4.1 × 10⁻⁶ mol L⁻¹.

Graphical abstract

Section snippets

Acknowledgements

We thank the Chinese Academy of Sciences, the National Natural Science Foundation of China and the Ministry of Science and Technology of China (No. 2002CCA03100) for financial support.

References and notes (14)

L. Prodi et al.
Coord. Chem. Rev.
(2000)
C.D. Gutsche
Calixarene Revisited
(1998)
H.-J. Schneider et al.
Principles and Methods in Supramolecular Chemistry
(2000)
Y.D. Cao et al.
Tetrahedron Lett.
(2003)
G.L. Long et al.
Anal. Chem.
(1983)
A.P. de Silva et al.
Chem. Rev.
(1997)
W. Kaim et al.
Bioinorganic Chemistry; Inorganic Elements in the Chemistry of Life. An Introduction and Guide
(1991)
F.M.M. Morel et al.
Annu. Rev. Ecol. Syst.
(1998)
D.W. Boening
Chemosphere
(2000)
Y.-M. So et al.
J. Org. Chem.
(2004)
L. Prodi et al.
J. Am. Chem. Soc.
(2000)
A.B. Descalzo et al.
J. Am. Chem. Soc.
(2003)
K. Rurack et al.
J. Am. Chem. Soc.
(2000)
J.-Y. Yoon et al.
Tetrahedron Lett.
(1997)
W.-H. Chan et al.
Anal. Chim. Acta
(2001)
R.-C. Na et al.
J. Chem. Soc., Perkin Trans. 2
(2002)
K. Rurack et al.
Chem. Commun.
(2000)
G. Hennrich et al.
Inorg. Chem.
(2001)

There are more references available in the full text version of this article.

Cited by (171)

A simple rhodanine-based fluorescent sensor for mercury and copper: The recognition of Hg2+ in aqueous solution, and Hg2+/Cu2+ in organic solvent
2019, Journal of Photochemistry and Photobiology A: Chemistry
Detection of copper and mercury attracts important in most environmental and biological systems. In this study, the simple probe 2-OxI-Rh containing rhodanine core was synthesized by a green approach and sensing properties were studied using colorimetric and fluorometric detection. The research indicated that the specific ion affinity for Hg²⁺ ions in aqua systems and the multi-ion affinity for Hg²⁺ and Cu²⁺ in organic solvent results in drastic color and spectral changes. According to the data obtained, while the peak intensity increases at 390 nm, the peak intensity decreased at 272 nm in the absorption spectrum of 2-OxI-Rh and an increase in fluorescence intensity of 2-OxI-Rh were observed in the presence of Hg²⁺ and Cu²⁺ ions. The binding ratio of 2-OxI-Rh to Hg²⁺ and Cu²⁺ were found to be 1:1 according to Job's plot experiments. The binding constants were calculated using the Benesi-Hildebrand equation and found to be 2.15 × 10⁴ M⁻¹ for Hg²⁺ and 1.21 × 10⁴ M⁻¹ for Cu²⁺. Based on these concentration dependent fluorescence changes, the limit of detection (LOD) values were also calculated and found to be 3.36 μM for Hg²⁺ and 2.31 μM for Cu²⁺, which is the range of copper that should be in the blood (11.8–23.6 μM). As a result of all these studies, we can understand that prove 2-OxI-Rh, which is non-toxic, is a good selective candidate turn-on sensor that can be used for Hg²⁺ and Cu²⁺ detection in different solvent systems.
Synthesis of fluorescent di-dansyl substituted ethoxy compound: A selective sensor for antimony and thallium metals detection
2019, Journal of Materials Research and Technology
Fluorescence assays have been widely engaged to assess the affinity of metallic ions. Dansyl chloride or 5-(dimethyl amino)-naphthalene-1-sulfonyl chloride is considered to be the reagent having potential to react with amino groups to yield stable sulfonamide adducts. A fluorescent sensor associated with crown ether moiety could have a potential to be developed as metal ions radar; cations, anions and other biological moieties. This can be further employed to observe relevant biotic processes. The reaction of dansyl sulfonyl chloride with di-ethoxy amine 1 chain in presence of potassium carbonate base resulted in a formation of compound 2. No change was observed on addition of aliquots of anions with compound 2. However, cation binding studies was performed using the series of metallic cations of constant concentration and its influence on a series of cations has been monitored using fluorescence spectrometry. This has been recorded that highest quenching effect was observed for antimony (Sb) and thallium (Tl) while other anions and cations were having no effect. The fluorescent compound 2 was further confirmed with proton-nuclear magnetic resonance (¹H NMR) spectroscopy, ¹³C NMR spectroscopy and ultra violet spectroscopy. It has been concluded that compound 2 is very much selective for the detection of toxic metals like antimony (Sb) and thallium (Tl) even at parts per billion (ppb) levels. This study could be considered as a contemporary development in design and applications of fluorescent investigations containing crown ethers.
Poly(benzodithieno-imidazole-alt-carbazole) based π-conjugated copolymers: Highly selective and sensitive turn-off fluorescent probes for Hg2+
2018, Polymer
In this work, highly emissive and soluble π-conjugated poly(benzodithieno-imidazole-alt-carbazole) π-conjugated copolymers (P1 and P2) have been synthesized through Pd(0)-catalyzed Suzuki coupling polymerization protocol from the corresponding monomers. For solubilizing in common organic solvents, heptyl (in P1) or 2-(2-(2-methoxyethoxy)ethoxy)ethyl (in P2) substituents have been introduced at benzodithieno-imidazole and 9-position of carbazole unit. The well-defined and soluble π-conjugated polymers have been characterized by multinuclear NMR spectra as well as by tetradetector GPC studies showing molecular weight (M_n) of 16.5 and 14.3 kDa with the polydispersity indices of 1.36 and 1.31 respectively. The emissive π-conjugated polymers show remarkable selectivity and sensitivity towards Hg²⁺ ion as turn-off fluorescent probes as a result of molecular wire effect, without interference by other competing metal ions. The detailed photophysical and sensing studies have been demonstrated to understand the insight of polymer-metal ion interaction which is responsible for selective fluorescence quenching of the π-conjugated polymers. DFT studies have been performed to gain the insight of the electronic properties of the sensor by determining the frontier molecular orbitals and the HOMO-LUMO energy levels for a model probe (M1). The polymeric probes (P1 and P2) are reversible in nature, and can also act as secondary sensors for S^2-. The limit of detection of the polymer probes towards Hg²⁺ is found to be in the range of 40–50 ppb with high association constant in the order of 10⁵ M⁻¹ suggesting its high applicability as chemosensor for Hg²⁺. The polymers have also been explored as thin film polymeric sensor towards Hg²⁺ to demonstrate its practical utility.
A selective colorimetric fluorescent chemosensor for Hg2+ in aqueous medium and in the solid state
2018, Journal of Luminescence
A simple colorimetric and turn-on fluorescence receptor RN (Rhodamine-based derivative) was prepared and its cation-sensing properties were investigated. Receptor RN displayed a selective sensing of Hg²⁺ and showed an obvious colorimetric changing in aqueous solution (from colorless to pink color) and in the solid state (from red to pink color), respectively. The association constant of RN-Hg²⁺ complex was calculated to be 8.25×10⁹ M⁻², and the detection limit for Hg²⁺ was found to be 27 ppb.
A novel pyrazoline-based fluorometric “turn-off” sensing for Hg2+
2018, Sensors and Actuators, B: Chemical
A new and non-toxic pyrazoline derivative (4-[3-(4-hydroxyphenyl)-5-(2-thienly)-4,5-dihydro-pyrazol-1-yl]benzenesulfonamide, compound 1) was used for metal ion selectivity based on fluorometric detection. The effects of different metal ions such as Li⁺, Na⁺, K⁺, Ag⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cd²⁺, Zn²⁺, Cu²⁺, Hg²⁺, Cr²⁺, Pb²⁺, Fe²⁺, Mn²⁺, Co²⁺, Fe³⁺, and Al³⁺ were investigated in terms of the photo-physical properties of compound 1 (1 μM). According to the data obtained, the fluorescence intensity of compound 1 has been decreased significantly by Hg²⁺ ion in a concentration dependent manner and without interfering the presence of any other metal ion at the medium in contrast to the other seventeen metal ions. The binding constant (8.06 × 10⁴ M⁻¹) of Hg²⁺ to compound 1, LOD value (14.54 μM) of Hg²⁺, possible interaction mechanism between Hg²⁺ and compound 1 and the possibility of practical uses of compound 1 as selective fluorometric “turn-off” were reported this study. It was determined that the relative standard deviations (RSD) of four measurements were less than 20%. Novel sensor, compound 1 at 1 μM, showed a linear range in the 20–200 μM Hg²⁺ concentration with R = 0.99 value (correlation coefficient). Its response time was less than 1 min. As conclusion, compound 1 seemed as good and selective candidate for fluorometric “turn-off” sensor for Hg²⁺ detection.
Photochromic RAFT reagent helps construct superior photoswitchable fluorescent polymer nanoparticles for rewritable fluorescence patterning and intracellular dual-color imaging
2017, Polymer Chemistry
Superior photoswitchable fluorescent polymer nanoparticles (PFPNs) are highly desirable for photo-rewritable data storage and ultrahigh-resolution bioimaging. Herein, 2-(3′,3′-dimethyl-6-nitrospiro[chromene-2,2′-indolin]-1′-yl)ethyl 2-(((dodecylthio)-carbonothioyl)thio)-2-methylpropanoate (SPTTC), a novel photochromic spiropyran-based reversible addition–fragmentation chain transfer (RAFT) reagent, and 5-dimethylaminonaphthalene-N-allyl-1-sulfonamide (DNS), the energy-level matched green fluorescent dye, were firstly synthesized. Then, they are used as donor and acceptor of the designed fluorescence resonance energy transfer (FRET) system to help fabricate superior dual-color PFPNs via a simple one-pot RAFT miniemulsion method. Thanks to its multiple merits such as the photochromic property, improved miscibility, and the ability to control polymerization rate, not only did the designed SPTTC provide the PFPNs with superior photoswitchable fluorescence properties such as high energy transfer efficiency (up to 91%), high dual-color contrast (green and red), rapid photoresponsiveness (2–4 min) and outstanding photoreversibility upon irradiation with UV and visible light, but it also endowed PFPNs with controllable molecular weight and narrow polydispersity index (PDI), excellent cell membrane permeability and long-term fluorescence stability. Moreover, the as-prepared PFPNs were successfully used for rewritable fluorescence patterning and intracellular dual-color imaging due to its prominent properties.

View all citing articles on Scopus

View full text

Article preview

Tetrahedron Letters

Abstract

Graphical abstract

Section snippets

Acknowledgements

References and notes (14)

Coord. Chem. Rev.

Calixarene Revisited

Principles and Methods in Supramolecular Chemistry

Tetrahedron Lett.

Anal. Chem.

Chem. Rev.

Bioinorganic Chemistry; Inorganic Elements in the Chemistry of Life. An Introduction and Guide

Annu. Rev. Ecol. Syst.

Chemosphere

J. Org. Chem.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

J. Am. Chem. Soc.

Tetrahedron Lett.

Anal. Chim. Acta

J. Chem. Soc., Perkin Trans. 2

Chem. Commun.

Inorg. Chem.

Cited by (171)

A simple rhodanine-based fluorescent sensor for mercury and copper: The recognition of Hg<sup>2+</sup> in aqueous solution, and Hg<sup>2+</sup>/Cu<sup>2+</sup> in organic solvent

Synthesis of fluorescent di-dansyl substituted ethoxy compound: A selective sensor for antimony and thallium metals detection

Poly(benzodithieno-imidazole-alt-carbazole) based π-conjugated copolymers: Highly selective and sensitive turn-off fluorescent probes for Hg<sup>2+</sup>

A selective colorimetric fluorescent chemosensor for Hg<sup>2+</sup> in aqueous medium and in the solid state

A novel pyrazoline-based fluorometric “turn-off” sensing for Hg<sup>2+</sup>

Photochromic RAFT reagent helps construct superior photoswitchable fluorescent polymer nanoparticles for rewritable fluorescence patterning and intracellular dual-color imaging