Chemosensor For Fluoride Anion Research Articles

Hydrogen-Bonded Colorimetric and Fluorescence Chemosensor for Fluoride Anion With High Selectivity and Sensitivity: A Review.

In recent years, the wide application of fluoride materials has grown rapidly, therefore excessive discharge in the surrounding environment, especially in drinking water and organic effluent, has become a potential hazard to humans, and has even resulted in fluorosis disease. The development of a highly effective and convenient method to recognize fluoride anions in surrounding environments seems necessary and urgent. Among which, the development of a colorimetric and fluorescence fluoride chemosensor with obvious color changing allowing for naked-eye detection with high sensitivity and selectivity is more interesting and challenging. In this minireview, current novel colorimetric and fluorescence chemosensors for fluoride anions by hydrogen-bond interaction are introduced, including obvious color changing by naked-eye detection, high sensitivity and selectivity, non-pollution and fluoride extraction ability, aqueous detection, and other additional functions. Finally, the perspective of the fluoride chemosensor design concept and potential evolution trends are pointed out.

Colorimetric and fluorimetric chemosensor based on upper rim-functionalized calix[4]arene for selective detection of fluoride ion

A new colorimetric and fluorescent chemosensor for fluoride anion based on calix [4]arene bearing four sulfonamide-fluorenone subunits on the upper rim was conveniently synthesized. It showed a remarkable color change as well as the fluorescence quenching upon addition of F- even in the presence of a wide range of anions in DMSO. The binding property of L with F- was studied by a combination of various spectroscopic techniques, such as absorption and emission titration, Job's plot and 1H NMR titration. It is anticipated that this design with functional group attached to upper rim of calix[4]arene platform can provide a new approach for the development of F- chemosensor.

Theoretical study on the sensing mechanism of an ON1-OFF-ON2 type fluoride fluorescent chemosensor.

A density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations have been used to study the sensing mechanism of an ON1-OFF-ON2 type fluoride anion fluorescent chemosensor (Bis[[7-(diethylamino)-2-oxo-2H-chromene]methyl-ene]‑carbonothioic dihydrazide (CTC). The current theoretical calculation presents a different sensing mechanism from the experimentally proposed one (Sensor and Actuators B 2016, 222, 823-828). Instead of the combination of CTC deprotonation and poorly emissive excited state tautomer or ICT mechanism, the theoretical results predict the sensing mechanism based on dissociation reaction and excited-state proton transfer (ESPT). The calculated vertical excitation energies both in the ground states and first excited states of different forms of CTC, as well as the potential-energy curves, have completely reproduced the experimental results, providing powerful evidence for our proposed CTC sensing mechanism for fluoride anion.

Novel nitro-substituted formazan derivatives: selective ratiometric and colorimetric chemosensors for fluoride anion sensing detectable by the naked eye

This study is the first report of formazan derivatives designed as chemosensors for fluoride anion recognition.

Synthesis of Stannole-Containing π-Conjugated Polymers by Post-Element Transformation of Organotitanium Polymer.

The synthesis of stannole-2,5-diyl-containing π-conjugated polymers by the post-element transformation of a regioregular organotitanium polymer is described. For example, a 1,1-diphenylstannole-containing polymer is obtained in 83% yield by the reaction of a regioregular organotitanium polymer, which is prepared from 1,4-bis(2-ethylhexyloxy)-2,5-diethynylbenzene and a low-valent titanium complex with diphenyltin dichloride at -50 °C to ambient temperature. The number-average molecular weight and molecular weight distribution (Mn and Mw /Mn ) of the stannole-containing polymer are estimated as 4800 and 1.8, respectively. The obtained polymer is found to have the extended π-conjugated backbone and relatively low-lying lowest unoccupied molecular orbital (LUMO) energy level (-3.12 eV), which is supported by its UV-vis absorption spectrum and cyclic voltammetric (CV) analysis. In addition, the stannole-containing polymer is found to be applicable to a chemosensor for fluoride anion where the color and photoluminescence intensity of the polymer solution exhibits a distinct change in the presence of a fluoride anion.

Design and synthesis ethynyl ferrocene-based multifunctional chemosensors for fluoride anion

To exploit novel ferrocene-based small molecules with long conjugated structures as visible and electrochemical multichannel chemosensors, four conjugated ferrocene ethynyl semicarbazide derivatives (Fc-X-An) were synthesized via the Sonogashira coupling reaction. The synthesized Fc-X-Ans are 2-(4-(ferrocenylethynyl)benzylidene) hydrazine-1-carboxamide (Fc-Ph-An), 2-((5-(ferrocenylethynyl)thiophen-2-yl)methylene)hydrazine-1-carboxamide (Fc-Thie-An), 2-((9-ethyl-6-(ferrocenylethynyl)-9H-carbazol-3-yl) methylene)hydrazine-1-carboxamide (Fc-Cz-An) and 2-((10-ethyl-7-(ferrocenylethynyl)-10H-phenothiazin-3-yl) methylene)hydrazine-1-carboxamide (Fc-PTZ-An). The recognition abilities of the semicarbazide derivative Fc-X-Ans for several anions were evaluated from visible absorption spectra, 1H NMR, and electrochemical technique.

A new fluorescent-colorimetric chemosensor for fluoride anion based on benzimidazolium salt

Two new benzimidazolium salts with the same cationic moiety and different anions 3-(2′-((8″-hydroxy-9″,10″-dioxo-9″,10″-dihydroanthracen-1″-yl)oxy)ethyl)-1-(pyridin-2‴-ylmethyl)-1H-benzo[d]imidazol-3-ium bromide and 3-(2′-((8″-hydroxy-9″,10″-dioxo-9″,10″-dihydroanthracen-1″-yl)oxy)ethyl)-1-(pyridin-2‴-ylmethyl)-1H-benzo[d]imidazol-3-ium hexafluorophosphate were prepared and characterized. The single crystal structure of 3-(2′-((8″-hydroxy-9″,10″-dioxo-9″,10″-dihydroanthracen-1″-yl)oxy)ethyl)-1-(pyridin-2‴-ylmethyl)-1H-benzo[d]imidazol-3-ium bromide was determined by X-ray single crystal diffraction. Particularly, anion recognition using 3-(2′-((8″-hydroxy-9″,10″-dioxo-9″,10″-dihydroanthracen-1″-yl)oxy)ethyl)-1-(pyridin-2‴-ylmethyl)-1H-benzo[d]imidazol-3-ium hexafluorophosphate as a chemosensor was carried out via fluorescence and ultraviolet spectroscopy, 1H NMR titrations, HRMS and IR spectra. The response of this chemosensor to fluoride anion can be observed through both remarkable fluorescence quenching and color change under visible light (from orange to purple). The results indicated that this chemosensor can distinguish fluoride anion from other anions via the instrument and naked eyes, and this is greatly convenient in practical operation.

A novel silicon-oxygen aurone derivative assisted by graphene oxide as fluorescence chemosensor for fluoride anions

A novel silicon-oxygen aurone derivative TBDPSA was synthesized and used for the detection of fluoride anions in aqueous solution based on a specifically F−-triggered silicon-oxygen cleavage. Even though the compound has shown high selectivity, obvious absorption and fluorescence response for fluoride anions in aqueous solution, but it also is suffered from many limits, such as low detection sensitivity and long response time. Here the compound was successfully assembled on the graphene oxide (GO) surface by π-π stacking. GO improves recognition sensitivity and shortens response time of TBDPSA for fluoride anions by taking advantage of the nanocarrier GO. Compared with TBDPSA, the response time of GO/TBDPSA is shortened greatly from 1h to <5s and the detection limit is lowered about four times with fluorescence as detected signal. Generally speaking, GO is an excellent promoter for accelerate recognition.

A “turn on” fluorescent and chromogenic chemosensor for fluoride anion: experimental and DFT studies

A simple, convenient “turn on” fluorescent and chromogenic chemosensor for fluoride anion detection in acetonitrile as well as in water has been developed.

A reversible dual-channel chemosensor for fluoride anion

A colorimetric and fluorescent fluoride probe bearing phenolic hydroxy and imine groups has been designed and synthesised. This receptor could visually and spectroscopically recognise F− with high selectivity over other anions. After the addition of fluoride ions to the solution of ([1,1′-biphenyl]-4,4′-diylbis (azanylylidene)) bis (methanylylidene)) bis (naphthalen-2-ol) (TY), since the deprotonation reaction occurred between the sensor and fluoride, the fluorescence intensity of the solution changed significantly. Furthermore, the quenched fluorescence caused by fluoride ions could be recovered upon the addition of calcium ions to this complex solution. This resulted in an ‘OFF-ON-OFF’ type sensing. In particular, an IMP logic gate has been proposed using the output obtained from the fluorescence studies. The fluorescence, UV-vis titration and 1H NMR titration experiments indicated that the effects might occur via a combined process including hydrogen bond and deprotonation between the sensor and F− .

Theoretical study of chemosensors for fluoride anion and optical properties of the derivatives of organosilicon 1,8-naphthalimide

The interactions between chemosensors, organosilicon 1,8-naphthalimide derivatives, and different (F−, Cl−, Br−, and AcO−) anions have been theoretically investigated using Density functional theory (DFT) approaches. Theoretical investigations have been performed to explore the optical and electronic properties of the colorimetric fluoride anion chemosensors. It turned out that the unique selectivity of chemosensors for F− is ascribed to their ability of the cleavage of OSi bond of the host sensors. The frontier molecular orbitals (FMOs) analyses have turned out that the vertical electronic transitions of chemosensors and their anions are characterized as intramolecular charge transfer (ICT). The study of substituent effects suggests that the substituted derivatives with nitrobenzene (1), anisole (2), benzo[c][1,2,5]thiadiazole (3), benzo[c]thiophene (4), and 2-phenylthiophene (5) fragments are expected to be promising candidates for colorimetric fluoride anion chemosensors.

Theoretical study on a chemosensor for fluoride anion-based on a urea derivative

The sensing mechanism of the N-Phenyl-N′-(3-quinolinyl)urea (PQU) chemosensor for fluoride anion has been investigated by density functional theory/time-dependent density function theory. The double intermolecular hydrogen bonds are formed between the three anions (X−F−, AcO−, Cl−) and the urea fragment of PQU. In the S0 states, the HbX− hydrogen bonds are slightly stronger than the HaX− hydrogen bonds and the fluoride-induced deprotonation occurs at the NHb position rather than at the NHa position. Consequently, the absorption peaks, including an intramolecular charge transfer transition and a ππ* transition, are significantly red-shifted. Thermodynamic calculations confirm that the deprotonation in the ground state is favorable in energy only when excess fluoride anion exists. Along with the S0 → S1 transition, the HaX− hydrogen bonds strengthen and the HbX− hydrogen bonds weaken. However, the emission spectra of [PQU-Hb]−, instead of [PQU-Ha]−, are observed upon addition of fluoride anion. © 2013 Wiley Periodicals, Inc.

Highly selective recognition of fluoride anion through direct deprotonation of intramolecularly hydrogen-bonded phenolic hydroxyl groups

Abstract A novel chemosensor for fluoride anion has been developed. This sensor, constructed by merging six phenolyl units into a hexaazatriphenylene (HAT) core, could recognize F− visually and spectroscopically with high selectivity over other anions, which was demonstrated by naked-eye experiment and UV–vis absorption spectroscopy study.

Fluorescence Chemosensor for Fluoride Anion with Coumarin Bipyridine Derivative

E-mail: kcnam@chonnam.ac.krReceived January 21, 2013, Accepted February 5, 2013Key Words : Coumarin, Fluoride, Chemosensor, Fluorescent, Turn-onOn account of the important roles of anion in biological,clinical, environmental, catalysis, and chemical processes,the selective and efficient recognition of anion is an area ofgrowing interest in supramolecular chemistry.

Fluorescent Chemosensors for Fluoride Anion Based on Naphthalene Derivatives Bearing Two Urea Groups

Fluorescent Chemosensors for Fluoride Anion Based on Naphthalene Derivatives Bearing Two Urea Groups

A fluorescent chemosensor for fluoride anions based on a hemicyanine dye

A hemicyanine dye with imidazole as the acceptor was designed and prepared as a chemosensor for fluoride anions. The experimental results demonstrated that it is a fluorometric probe for fluoride anion with good sensitivity and high selectivity. This probe showed obvious changes in UV–Vis absorption and fluorescence spectra in the presence of fluoride anions, which are attributed to the deprotonation of N–H on the imidazole moiety with fluoride anions.

A DFT study of pyrrole-isoxazole derivatives as chemosensors for fluoride anion.

The interactions between chemosensors, 3-amino-5-(4,5,6,7-tetrahydro-1H-indol-2-yl)isoxazole-4-carboxamide (AIC) derivatives, and different anions (F− Cl−, Br−, AcO−, and H2PO4−) have been theoretically investigated using DFT approaches. It turned out that the unique selectivity of AIC derivatives for F− is ascribed to their ability of deprotonating the host sensors. Frontier molecular orbital (FMO) analyses have shown that the vertical electronic transitions of absorption and emission for the sensing signals are characterized as intramolecular charge transfer (ICT). The study of substituent effects suggests that all the substituted derivatives are expected to be promising candidates for fluoride chemosensors both in UV-vis and fluorescence spectra except for derivative with benzo[d]thieno[3,2-b]thiophene fragment that can serve as ratiometric fluorescent fluoride chemosensor only.

Theoretical study of chemosensor for fluoride anion and optical properties of the derivatives of diketopyrrolopyrrole

The interactions between chemosensors, diketopyrrolopyrrole (DPP) derivatives, and different halides (F−, Cl−, and Br−) anions have been theoretically investigated using DFT approaches. Theoretical investigations have been performed to explore the optical, electronic, charge transport, and stability properties of DPP derivatives as charge transport and/or luminescent materials. It turned out that the unique selectivity of DPP derivatives for F− is ascribed to their ability of deprotonating the host sensors. The atoms in molecules theory and natural bond orbitals charge analysis of the complexes consisting of DPP derivatives and X− (X = F, Cl, and Br) confirm that the protons are almost completely abstracted by F−. The study of substituent effects suggests that all the substituted derivatives are expected to be promising candidates for ratiometric fluorescent fluoride chemosensors as well as chromogenic chemosensors. Furthermore, the derivatives with biphenyl, 2-(thiophen-2-yl)thiophene, and benzo[d]thieno[3,2-b]thiophene fragments are expected to be promising luminescent materials. In addition, derivatives with 2-(thiophen-2-yl)thiophene and 4,9-dihydrothieno[3,4-b]quinoxaline fragments can serve as good electron transport materials for OLEDs as well.

Theoretical study of coumarin derivatives as chemosensors for fluoride anion

The interactions between chemosensor, coumarin derivative (1), and F−, Cl−, Br−, NO3-, AcO−, and H2PO4- anions have been theoretically investigated at the B3LYP/6-31G(d,p) level with the BSSE correction. It turned out that the unique selectivity of 1 for F− is ascribed to its ability of deprotonating the amido group of host sensor. The intermolecular proton transfer (IPT) causes the colorimetric signaling of 1 for F−. The deprotonated anion 1− is formed for the deprotonation process of chemosensor. The study of substituent effects suggest that both electron-donating (–CH3 and –OCH3,) and electron-withdrawing (–NO2, –CN, and –COCH3) substituted derivatives are expected to be promising candidates for chromogenic fluorescent F− chemosensors, except the electron-donating –N(CH3)2 substituted derivative does not suit to be a chromogenic F− chemosensor.

Theoretical study of thiazole derivatives as chemosensors for fluoride anion

The interactions between chemosensor, 2-(2′-hydroxyphenyl)-4-phenylthiazole ( 1), and different halides (F −, Cl −, and Br −) and NO 3 − anions have been theoretically investigated at the B3LYP/6-31G(d) level with the BSSE correction. It turned out that the unique selectivity of 1 for F − is ascribed to its ability of deprotonating the hydroxy group of host sensor. The intermolecular proton transfer (IPT) causes the colorimetric and fluorescent signaling of 1 for F −. The deprotonated complex 1 −·HF is formed for the deprotonation process of chemosensor. The study of substituent effects suggest that the electron-donating –CH 3 and –OCH 3 substituted derivatives are expected to be promising candidates for ratiometric fluorescent F − chemosensors as well as chromogenic chemosensors, while electron-donating –N(CH 3) 2 substituted derivative can serve as chromogenic F − chemosensors only. Furthermore, the electron-withdrawing (–NO 2 and –Br) substituted derivatives can serve as chromogenic F −/CH 3COO − chemosensors.