Determination of Fluoride by Fluorescence Quenching

Abstract

A fluorescence quenching method for the determination of fluoride ion over the concentration range from 10^?9 to 10^?6M is presented. The fluoride ion is added to the fluorescent chelate of aluminum(III) and PAN [1- (2-pyridylazo)-2-naphthol]: the fluoride preferentially complexes the aluminum (III), displacing nonfluorescent PAN. Of the anions tested as possible interferences at equimolar levels, phosphate interferred seriously and iodide interferred somewhat.     

Determination of Total and Fluoride Bound Aluminium in Tea Infusions by Ion Selective Electrode and Flame Atomic Absorption Spectrometry

ABSTRACT

Speciation of metallic compunds is important especially for their bioavailability. In this present study fluoride bound aluminium species were determined in tea infusion. Total aluminium was measured using flame atomic absorption spectrometry (FAAS). Free fluoride and total fluoride were measured by fluoride selective ion electrode (FISE) with the assistance of TISAB buffer solution used for adjustment of pH and total ionic strength, and ALCOA buffer solution which decomposes all of the Al-fluoride complexes in solution.

During the studies, the effects of pH and time on the formation of Al-F complexes and interference of some metal ions found in tea infusion such as Al³⁺, Mg²⁺, Fe²⁺, Fe³⁺ and Mn²⁺ on the concentration of free fluoride were investigated. The concentration of each Al-fluoride complexes in tea fusion were determined indirectly by calculation using pF-Mole Fraction Diagram. It was found that 1.13±0.15 mg 1^? of 12.00±0.86 mg 1^? total aluminium is fluoride bound aluminium, which means that appoximately 10% of total aluminium in tea infusion is complexed with fluoride.     

Xylenol Orange,Zirconium(IV) and Fluoride Color Reaction in Mixed Micelles of N-Hexadecylpyridinium Chloride and Brij 35, and Its Analytical Application1

Abstract

The color reaction between Xylenol orange (XO), zirconium (IV) and fluoride ions in the presence of various surfactants alone or in combination was studied at various pH. The XO -zirconium)IV)-fluoride ion ternary complex in mixed micellar media containing a low concentration of N-hexadecylpyridinium chloride (HPC) as a cationic surfactant and large amounts of (poly{oxyethylene)dodecyl ether (Brij 35) as a nonionic surfactant at weakly acidic media was found to be the most stable, and showed a remarkable bathochromic shift and clear contrast against a reagent blank. The maximum absorbance was at 600 nm in the mixed micellar media at pH 3.5, and the apparent molar absorptivities at 600 nm were 7.0 × 10⁴ 1 mol^?1 cm^?1 for zirconium(IV) and 1.4 × 10⁴ 1 mol^?1 cm^?1 for fluoride ion. The calibration curves covered the ranges of 0.5 ～ 20.0 μg/10 ml zirconium! IV) and 0 ～ 20.0 μg/10 ml fluoride ion with the Sandell sensitivities being 0.0013 μg/cm² for zirconium(IV) and 0.0016 μg/cm² for fluoride ion.     

Highly Sensitive and Selective Fluoride Ion Chemosensing,Fluoroalkylated Polysilane

Summary: This paper reports a new and simple approach for the amplified detection of fluoride ions by a polymer‐based chemosensor made of stiff fluoroalkylated polysilane, poly(3,3,3‐trifluoropropylmethylsilane). This chemosensor exhibited extreme sensitivity and selectivity towards fluoride ions by a decrease in the photoluminescence (PL) intensity with parts per billion concentrations of fluoride ions in solution in tetrahydrofuran (THF). The quenching constant for fluoride ions (K = 1.35 × 10⁷ M ⁻¹) was found to be exceptionally high.

Schematic representation of the polymer amplification mechanism after addition of fluoride ion in tetrahydrofuran.     

Synthesis and characterization of novel fluoride‐releasing monomers. II. Dimethacrylates containing bis(aminodiacetic acid) and their ternary zirconium fluoride complexes

Novel dimethacrylate monomers containing bis(aminodiacetic acid) chelating ligands with or without additional hydroxyl groups were synthesized, starting from 2,2‐bis(4‐hydroxy‐3‐methylphenyl)propane. The structures of the monomers were characterized by electrospray mass spectrometry (ESMS), ¹H NMR, and ¹³C NMR. The structures and relative stability of fluoride‐releasing monomers containing one or more ternary zirconium fluoride complex moieties were studied by ESMS. The most stable ternary zirconium fluoride complex was in the form of [LZrF]^?, where H₄L is the monomer containing bis(aminodiacetic acid) without additional hydroxyl groups. The synthesized monomer was photopolymerized with camphorquinone and 1‐phenyl‐1,2‐propane‐dione as initiators and N,N‐dimethylaminoethyl methacrylate as the accelerator. The fluoride release, fluoride recharge, compressive strength, and flexure strength were tested on the experimental dental composite containing 13.7 wt % synthesized monomer and three commercial flowable dental composites. The results showed that the experimental composite has significantly higher fluoride release and recharge capabilities than the commercial flowable composites. The compressive strength was comparable to that of the commercial materials. The water sorption and solubility met the requirement of the ISO Specification 4049. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3153–3166, 2005     

Fluorinated,crosslinkable terpolymers based on vinylidene fluoride and bearing sulfonic acid side groups for fuel‐cell membranes

The radical terpolymerization of 8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene with vinylidene fluoride (VDF) and perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride is presented. Changing the feed compositions of these three fluorinated comonomers enabled us to obtain different random‐type poly[vinylidene fluoride‐ter‐perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride‐ter‐8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene] terpolymers containing various sulfonyl fluoride and brominated side groups. Yields higher than 70% were reached in all cases. The hydrolysis of the sulfonyl fluoride group into the ? SO₃Li function in the presence of lithium carbonate was quantitatively achieved without the content of VDF being affected, and so dehydrofluorination of the VDF base unit was avoided. These original terpolymers were then crosslinked via dangling bromine atoms in the presence of a peroxide/triallyl isocyanurate system, which produced films insoluble in organic solvents such as acetone and dimethylformamide (which totally dissolved uncured terpolymers). The acidification of ? SO₃Li into the ? SO₃H function enabled protonic membranes to be obtained. The thermal stabilities of the crosslinked materials were higher than those of the uncured terpolymers, and their electrochemical performances were investigated. According to the contents of the sulfonic acid side functions, the ion‐exchange capacities ranged from 0.6 to 1.5 mequiv of H⁺/g, whereas the water uptake and conductivities ranged from 5–26% (±11%) and from 0.5 to 6.0 mS/cm, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4566–4578, 2006     

Fabrication and Characterization of LaF3/Titania Nanotube Array Electrode for Determination of Fluoride Using a Headspace Single-Drop Microextraction System

LaF₃/titania nanotube array (TNAs) electrodes were fabricated by electrodeposition of LaF₃ on synthesized TNAs. The electrode was characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), and energy dispersive X-ray spectrometer (EDS). The electrode exhibited excellent response to fluoride ion. The linear calibration range achieved four orders of magnitude of F^- concentration (10^?6–10^?2 mg/ml) and the sensitivity of the electrode is higher than that of ordinary fluoride ion selective electrodes (mode PF-1). The limit of detection (LOD) was estimated to be 4.39 × 10^?7 mg/ml (S/N = 3). The novel electrode was applied to the determination of trace fluoride ions in tap water and toothpaste. Finally, a headspace single-drop microextraction (SDME) system coupled with LaF₃/TNAs electrode was successfully applied to determine fluoride in milk samples. The results are satisfactory with an average relative standard deviation (RSD %) of 0.51% and recovery from 96.3% to 107.3%.     

A novel HPQ-based turn-on fluorescent probe for detection of fluoride ions in living cells

2-(2′-Hydroxyphenyl)-4(3H)-quinazolinone (HPQ) has been reported as a precipitating fluorescent molecule with excellent optical properties, such as large Stokes shift and strong fluorescence intensity. HPQF, a novel HPQ-based turn-on probe for localizable detection of fluoride ions, was designed, synthesized and fully characterized by ¹H NMR, ¹³C NMR and HRMS. As a chemogenic fluoride probe, the tert-butyldiphenylsilane moiety of HPQF can be easily cleaved by fluoride. After spontaneous 1,6-elimination, HPQ molecule was generated to emit fluorescence under the excitation light. Further study shows that HPQF exhibited high selectivity and sensitivity for detection of fluoride. In addition, HPQF was utilized for the detection of fluoride in living cells.     

Removal of fluoride from water by electrocoagulation using Mild Steel electrode

Electrocoagulation process was used for defluoridation of synthetic fluoride containing water. In the process Mild Steel (MS) was used as sacrificial electrode and experiments were performed with different varying parameters such as pH and current density (CD). The fluoride removal efficiency was found to be maximum at pH 6 and CD 75.44 A/m² (2 A). At these conditions fluoride concentration reduces from initial concentration of 50 ​mg/dm³ to 5.2 ​mg/dm³. Kinetic study of electrocoagulation process revealed that the order of the reaction was in the range 1.61–1.64 with respect to fluoride concentration. It was observed that fluoride removal efficiency of the present MS electrode is comparable to the other electrodes used in electrocoagulation process available in the literature.     

Organoboron compounds as Lewis acid receptors of fluoride ions in polymeric membranes

Newly synthesized organoboron compounds – 4-octyloxyphenylboronic acid (OPBA) and pinacol ester of 2,4,6-trifluorophenylboronic acid (PE-PBA) – were applied as Lewis acid receptors of fluoride anions. Despite enhanced selectivity, the polymer membrane electrodes containing the lipophilic receptor OPBA exhibited non-Nernstian slopes of the responses toward fluoride ions in acidic conditions. Such behavior was explained by the lability of the B–O bond in the boronic acids, and the OH⁻/F⁻ exchange at higher fluoride content in the sample solution. In consequence, the stoichiometry of the OPBA–fluoride complexes in the membrane could vary during the calibration, changing the equilibrium concentration of the primary anion in membrane and providing super-Nernstian responses. The proposed mechanism was supported by ¹⁹F NMR studies, which indicated that the fluoride complexation proceeds more effectively in acidic solution leading mainly to PhBF₃⁻ species. Finally, the performances of the membranes based on the phenylboronic acid pinacol ester, with a more stable B–O bond, were tested. As it was expected, Nernstian fluoride responses were recorded for such membranes with worsened fluoride selectivity.     

Removal of fluoride ions using cuttlefish bones

Because of the high toxicity of fluoride to mankind, there is an urgent need to treat fluoride-contaminated drinking water to make it safe for human consumption. This work investigated the possibility of eliminating, by sorption, the excess of fluoride in overloaded water according to World Health Organization WHO recommendations. We tested the cuttlefish bone as an adsorbent material (available in Tunisia) for the defluoridation of water. Initially, we determined the optimal conditions of use (contact time, pH effect, adsorbent dose, initial fluoride concentration) of the cuttlefish bone on synthetic solutions of sodium fluoride. The second step was to verify the effectiveness of the sorption process on the cuttlefish bone by testing it on natural waters loaded with fluoride. The results obtained showed that sorption on the cuttlefish bone could be an effective method for the removal of fluoride. The efficacy of cuttlefish bone to remove fluoride from water was found to be 80% at pH 7.2, 1 h contact time, 15 g L⁻¹ adsorbent dose and 5 mg L⁻¹ initial fluoride concentration. Despite the different anions (Cl⁻ and SO₄²⁻) generally present in natural waters, a fluoride concentration in agreement with the norm (<1.5 mg L⁻¹) could be reached whatever the water treated. The regeneration of the cuttlefish bone was performed with a NaOH solution (10 g of cuttlefish bone/1000 mL NaOH 3 M). After 1 h of agitation, 95% of fluorides were desorbed. Following regeneration, the adsorbent can be used for further removal of fluoride.     

Effect of evolved hydrogen fluoride on radiation-induced crosslinking and dehydrofluorination of poly(vinylidene fluoride)

Poly(vinylidene fluoride) (PVdF) was irradiated by ⁶⁰Co γ-rays with and without potassium hydroxide (KOH) under vacum. KOH tablets were added to absorb completely hydrogen fluoride (HF) which is the main volatile product of radiolysis of PVdF in the irradiation cell. In the presence of HF, the rates of radiation-induced crosslinking and dehydrofluorination of PVdF were lower than those in the absence of HF. The experimental results are discussed from the standpoint of stabilization of alkyl free radicals in PVdF by reaction with hydrogen fluoride.     

Voltammetric,potentiometric and amperometric studies with a rotated aluminum wire electrode : Amperometric titration of fluoride with aluminum

The rotated aluminum electrode is a suitable indicator electrode in the amperometric titration of fluoride, Fluoride in concentrations varying between 1.10^-4 and 2.10^-3M was titrated with a standard aluminum nitrate solution in aqueous buffer solutions (pH between 3.6 and 46) Equilibrium was established within 15 mim. The fluoride-aluminum ratio at the (true) end-point was found to increase from 2 2 in 10^-4M fluoride to 28 in. 2.10^-3M fluoride. The titration calculated from the stability constants of the various aluminum-fluoride complexes were found to be in excellent agreement with the experimental curves.From a practical point of view titration in an acetate buffer in 50% alcohol in the presence of 0 5 M potassium or sodium nitrate is recommended. The fluoride-aluminum ratio at the end-point was found to be 5 9 ± 0 1 and independent of the fluoride concentration.     

Fluoride ion transfer and stabilisation of reactive ions

Some general guidelines for the generation of salts with high fluoride ion donor ability are discussed. A preliminary scale for a limited number of fluoride ion donors is presented, cations are classified according to their anion-cation interaction properties. Examples for fluoride ion transfer reactions are given and the influence of anion-cation interaction on the stabilisation of reactive anions is discussed. In our work mainly TAS fluoride (Me₂N)₃S⁺Me₃SiF₂⁻ has been used as fluoride ion source: (a) for fluoride ion transfer to coordinatively unsaturated sulfur species, to SN and SO multiple bond systems, to SN, PN and CN heterocycles, (b) for the stabilisation of primary products of nucleophilic attacks and of intermediates in isomerisation processes or of intermediates in polymerisation processes, (c) for the generation of “naked” anions by silicon-element bond cleavage, and (d) for the activation of element-fluorine bonds by anion formation.     

[F]Fluoroamines via ring-opening of N-Cbz-2-methylaziridine with [F]-fluoride

A highly regioselective method was developed for ring-opening benzyloxycarbonyl (Cbz)-protected 2-methylaziridine with [¹⁸F]-labelled fluoride. Following catalytic hydrogenation, 1-[¹⁸F]fluoro-2-propanamine ([¹⁸F]1) and 2-[¹⁸F]fluoro-1-propanamine ([¹⁸F]2) were prepared as the major and minor products, respectively (85:15), and were characterized following acylation with benzyl chloride. This methodology is applicable towards the generation of new [¹⁸F]-labelled amines for incorporation into radiopharmaceuticals.     

Flow-injection spectrophotometric determination of fluoride based on alizarin fluorine blue in the presence of sodium dodecyl sulphate

The stopped-flow reagent-injection method proposed for the spectrophotometric determination of fluoride with lanthanum (III)/alizarin fluorine blue in the presence of sodium dodecyl sulphate at pH 4.6 (λ_max=574 nm) provides a linear calibration graph for 0.08–1.2 mg l^?1 fluoride. The relative standard deviation (n=10) was 0.2% at 0.60 mg l^?1 fluoride. The sampling rate was 60 h^?1. The method is applied to sea and bottled mineral waters with satisfactory results.     

Oxidation of organic substances with compounds of trivalent manganese: XXIII. Preparation,stability, and determination of the titer of standard solutions of the fluoride complex of trivalent manganese

A method of preparation of 10^?2 ?10^?3M standard solutions of the fluoride complex of manganese(III) by the reaction of manganese(II) with permanganate in a medium of potassium fluoride acidified with sulfuric acid has been developed. It has been found that in a medium of 1 M sulfuric acid, 0.5 M manganese(II) sulfate, and 0.1 M potassium fluoride these solutions are sufficiently stable for both direct and indirect titrimetric determinations. The titer was determined using potassium iodide as a primary standard and potentiometric, bipotentiometric, or biamperometric titration.     

Synthesis and characterization of a novel,fluoride‐releasing dimethacrylate monomer and its dental composite

A novel, fluoride‐releasing dimethacrylate monomer containing zirconium fluoride chelate for use in dental composites was synthesized by an efficient four‐step procedure starting from 4,4‐bis‐(4‐hydroxyphenyl)‐pentanoic acid and was characterized by electrospray mass spectrometry, Fourier transform infrared (FTIR), and ¹H and ¹³C NMR spectroscopies. The synthesized monomer was photopolymerized with camphorquinone and 1‐phenyl‐1,2‐propane‐dione as initiators and N,N‐dimethylaminoethyl methacrylate as an accelerator. The photopolymerization process was investigated by FTIR spectroscopy. The experimental composite containing 13.7 wt % of the synthesized monomer was tested for fluoride release, fluoride recharge, compressive strength, and flexure strength, each in comparison to three commercial flowable dental composites. The results showed that the experimental composite had significantly higher fluoride release and fluoride recharge capabilities than the commercial flowable composites. The flexure strength was comparable to the commercial materials. The water sorption and solubility met the requirements of the International Organization for Standardization 4049 and the American National Standards Institute/American Dental Association Specification Number 27. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 985–998, 2004     

The reaction of 1,2-diiodo-tetrafluoroethane with sulfur trioxide

As an extension of our studies on the reaction of I(CF₂CF₂)_nI (n = 2 and 3) with sulfur trioxide¹⁾, the reaction of 1,2-diiodo-tetrafluoroethane with sulfur trioxide was studied.1,2-Diiodo-tetrafluoroethane was reacted with an excess of sulfur trioxide at reaction temperature ranging from 0°C to 115°C.The products were not the expected iododifluoroacetyl fluoride and/ or oxalyl fluoride, but thermally stable derivatives with polysulfate structures.These derivaties could be converted nearly quantitatively into iododifluoroacetyl fluoride and ethyl iododifluoroacetate by potassium fluoride and by ethanol, respectively.The possible structures of these derivatives will be discussed based on these results and ¹⁹F-NMR studies.     

Fluoride accumulation in barnacles and mussels in the lagoon of Venice.

As some industries are likely to discharge fluoride into the Lagoon of Venice, especially in the area of Portomarghera, a survey was undertaken of the environmental levels of this element. Fluoride concentrations in the waters surrounding the industrial area ranged from 1.53 mg 1^?1 (chlorinity: 16.6‰) to 3.14 mg 1^?1 (15.1‰) and all values exceeded the levels considered normal for seawater having the same chlorinity.However determination of the fluoride content of water alone tells little about the entrance of this element into food chains. It therefore seemed appropriate to monitor the environment by examining organisms for their ability to accumulate fluoride in tissues. The organisms chosen for this purpose were the crustacean $\text{Balanus}$$\text{amphitrite}$ (barnacles) and the mollusk $\text{Mytilus galloprovincialis}$ (mussels). Both species were found to accumulate fluoride in their soft tissues to above-ambient levels. Maximum fluoride concentrations found for barnacles and mussels were 81 ± 6 μg g^?1 and 85 ± 20 μg g^?1 (dry weight) respectively; the concentration factor, calculated as the ratio of mean concentration of fluoride in dry soft tissue of the animal to mean concentration in water, was of the order of 10² for both species. Moreover seasonal variations in soft tissue fluoride concentrations were recorded. These seasonal variations are probably related to the reproductive cycle; in both species the highest fluoride levels were found during the spawning periods, that is in summer in the case of the barnacle and in winter and spring in the case of the mussel.These species, especially during their spawning periods, are indirectly or directly included in the human diet. Since fluoride can be toxic, more attention should be paid to levels in environments, like the Lagoon of Venice, in the vicinity of highly industrialized comunities in which a large amount of local seafood is included in the diet.