An optical sensor for mercury ion based on the fluorescence quenching of tetra(p-dimethylaminophenyl)porphyrin

An optical sensor for mercury ion (Hg²⁺), based on quenching the fluorescence of the sensing reagent porphyrin immobilized in plasticized poly(vinyl chloride) (PVC) membrane, has been developed. The responses to mercury ion were compared for the sensors modified with three porphyrin compounds including 5,10,15,20-tetraphenylporphyrin (TPP), tetra(p-dimethylaminophenyl)porphyrin (TDMAPP) and tetra(N-phenylpyrazole) porphyrin (TPPP). Among them, TDMAPP showed the most remarkable response to Hg²⁺. The drastic decrease of the TDMAPP fluorescence intensity was attributed to the formation of a complex between TDMAPP and Hg²⁺, which has been utilized as the fabrication basis of a Hg²⁺-sensitive fluorescence sensor. The analytical performance characteristics of the TDMAPP modified sensor was investigated. The response mechanism, especially involving the response difference of three porphyrin compounds, was discussed in detail. The sensor can be applied to the quantification of Hg²⁺ with a linear range covering from 4.0 × 10⁻⁸ mol L⁻¹ to 4.0 × 10⁻⁶ mol L⁻¹. The limit of detection was 8.0 × 10⁻⁹ mol L⁻¹. The sensor exhibited excellent reproducibility, reversibility and selectivity. Also, the TDMAPP-based sensor was successfully used for the determination of Hg²⁺ in environmental water samples.     

Oxidation process induced by 2-mercaptopyrimidine at a mercury electrode

The oxidation process induced by 2-mercaptopyrimidine (RSH) at a hanging mercury drop electrode was studied in aqueous media by normal and cyclic voltammetry. The results indicate the formation of a weakly adsorbed HgSR complex according to the reaction Hg+RSH-->HgSR+e(-)+H+. When the surface excess of HgSR is high, a two-dimensional condensation takes place if the potential is positive enough, as proved by phase-sensitive ac and cyclic voltammetry.     

A fluorescent chemical sensor for Hg(II) based on a corrole derivative in a PVC matrix

A fluorescent chemical sensor for Hg(II) using 5,10,15-tris(pentafluorophenyl)corrole (H₃(tpfc)) as fluorophore is described in this paper. The response of the sensor is based on the fluorescence quenching of H₃(tpfc) by coordination with Hg(II). H₃(tpfc) based sensor shows a linear response towards Hg(II) in the concentration range from 1.2 × 10⁻⁷ to 1.0 × 10⁻⁴ M, with a working pH range from 5.0 to 8.0. The response time for Hg(II) concentration ≤1.0 × 10⁻⁵ M is less than 5 min. The sensor shows good selectivity for Hg(II) over alkali, and alkaline earth, and most of transition metal cations. The effect of the composition of the sensor membrane has been studied and the experimental conditions optimized. The corrole based sensor membrane can be easily regenerated just by washing with blank buffer solution after each measurement. The sensor has been used for determination of Hg(II) in water samples with satisfactory results.     

A selective optical chemical sensor for 2,6-dinitrophenol based on fluorescence quenching of a novel functional polymer

A bifurcated optical fiber based chemical sensor for continuous monitoring of 2,6-dinitrophenol (2,6-DNP) has been proposed based on the reversible chemical reaction between a novel functional poly(vinyl chloride) (PVC) as the sensing material and the analytes. The functional PVC (FPVC), containing a fluorescent curcumin moiety, was synthesized by the nucleophilic substitution of a fraction of the chlorine atoms bound to the PVC backbone by curcumin. When plasticized in a membrane of 5 μm thickness, FPVC extracts 2,6-DNP from aqueous solution into the bulk membrane phase and reacts with the analyte to form a complex with low fluorescence efficiency through hydrogen bonding. Formation of the complex gave a significant fluorescence quenching which is suitable for signalling the occurrence of the host-guest interaction. At pH 3.50, the sensor exhibits a dynamic detection range from 2.5 × 10⁻⁶ to 7.0 × 10⁻³ mol L⁻¹ with a limit of detection of 1.0 × 10⁻⁶ mol L⁻¹. As 2,6-DNP can provide an optimal space geometry matches to the formation of hydrogen bonds, the sensor shows excellent selectivity for 2,6-DNP over other nitrophenols. The forward and reverse response time (t₉₅) of the sensor both was within 1 min. The repeatability, reproducibility, and lifetime of the sensor were also satisfied. The sensor was applied to determine 2,6-DNP in water samples successfully.     

An optical redox chemical sensor for determination of iodide

A novel optical sensor based on a redox reaction for the determination of iodide has been developed. The optode membrane is constructed by immobilization of methyltrioctylammonium chloride on triacetylcellulose polymer. The exchange of chloride as counter ion with iodate in the membrane changes the color to yellow, when it is placed in acidic solution of iodide. The sensor can readily be regenerated by 0.1 mol L⁻¹ NaOH in less than 15 s. The optode has a linear range of 3.94 × 10⁻⁶ to 5.51 × 10⁻⁵ mol L⁻¹ of iodide ions with a limit of detection 7.44 × 10⁻⁷ mol L⁻¹. The relative standard deviation for eight replicate measurements of 3.94 × 10⁻⁶ and 1.57 × 10⁻⁵ mol L⁻¹ of iodide was 2.83 and 1.38%, respectively. The sensor was successfully applied to the determination of iodide in tablet, powdered milk and urine samples.     

Dual optical detection of a novel selective mercury sensor based on 7-nitrobenzo-2-oxa-1,3-diazolyl subunits

A novel macromolecule based on 2-[3-(2-aminoethylthio)propylthio]ethanamine covalently bound to two 7-nitrobenzo-2-oxa-1,3-diazolyl moieties was prepared as a fluoroionophore and a chromophore for the selective optical detection of Hg²⁺. The sensor was prepared in two steps and its fluoroionophoric and chromophoric properties toward various transition metal, alkali, and alkali earth cations were investigated. Compound 4 selectively binds Hg²⁺, and the binding is indicated by both fluorescence quenching and a chromogenic change which can be detected by the naked eye. In an 80:20 acetonitrile/water solvent mixture, 4 acts as an ON-OFF fluorescence switch upon Hg²⁺ binding, exhibiting efficient quenching and a detection limit of 10⁻⁷ M or 20 ppb.     

An optical sensor based on H-acid/layered double hydroxide composite film for the selective detection of mercury ion

A novel optical chemosensor was fabricated based on 1-amino-8-naphthol-3,6-disulfonic acid sodium (H-acid) intercalated layered double hydroxide (LDH) film via the electrophoretic deposition (EPD) method. The film of H-acid/LDH with the thickness of 1 μm possesses a well c-orientation of the LDH microcrystals confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The fluorescence detection for Hg(II) in aqueous solution was performed by using the H-acid/LDH film sensor at pH 7.0, with a linear response range in 1.0 × 10⁻⁷ to 1.0 × 10⁻⁵ mol L⁻¹ and a detection limit of 6.3 × 10⁻⁸ mol L⁻¹. Furthermore, it exhibits excellent selectivity for Hg(II) over a large number of competitive cations including alkali, alkaline earth, heavy metal and transitional metals. The specific fluorescence response of the optical sensor is attributed to the coordination between Hg(II) and sulfonic group in the H-acid immobilized in the LDH matrix, which was verified by NMR spectroscopy and UV–vis spectra. In addition, density functional theory (DFT) calculation further confirms that the coordination occurs between one Hg²⁺ and two O atoms in the sulfonic group, which is responsible for the significant fluorescence quenching of the H-acid/LDH film. The results indicate that the H-acid/LDH composite film can be potentially used as a chemosensor for the detection of Hg²⁺ in the environmental and biomedical field.     

Thiourea functionalized CdSe/CdS quantum dots as a fluorescent sensor for mercury ion detection

CdSe/CdS quantum dots(QDs) functionalized by thiourea(TU) were synthesized and used as a fluorescent sensor for mercury ion detection.The TU-functionalized QDs were prepared by bonding TU via electrostatic interaction to the core/shell CdSe/CdS QDs after capping with thioglycolic acid(TGA).It was observed that the fluorescence of the functionalized QDs was quenched upon the addition of Hg~(2+).The quantitative detection of Hg~(2+) with this fluorescent sensor could be conducted based on the linear relationship between the extent of quenching and the concentration of Hg~(2+) added in the range of1-300 μg L~(-1).A detection limit of 0.56 μg L~(-1) was achieved.The sensor showed superior selectivity for Hg~(2+) and was successfully applied to the determination of mercury in environmental samples with satisfactory results.     

A highly selective turn-on colorimetric and luminescence sensor based on a triphenylamine-appended ruthenium(Ⅱ) dye for detecting mercury ion

A dual colorimetric and luminescent sensor based on a heteroleptic ruthenium dye[Ru(Hipdpa)(Hdcbpy)(NCS)_2]~-·0.5H~+ 0.5[N(C_4H_9)_4]~+ Ru(Hipdpa) {where Hdcbpy = monodeprotonted-4,4'-dicarboxy-2.2'-bipyridineand Hipdpa = 4-(1H-imidazo[4,5-f][l,10]phenanthroIin-2-yl)-N,N-diphenylaniIine} for selective detection of Hg~(2+) is presented.The results of spectrophotometric titrations revealed an evident luminescence intensity enhancement(I/I_0 =11) and a considerable blue shift in visible absorption and luminescence maxima with the addition of Hg~(2+).The sensitive response of the optical sensor on Hg~(2+) was attributed to the binding of the electron-deficient Hg~(2+) to the electron-rich sulfur atom of the thiocyanate(NCS) ligand in the Ru(Hipdpa).which led to an increase in the energy gap between the highest occupied molecular orbital(HOMO) and the lowest unoccupied molecular orbital(LUMO).Accordingly,the blue shift in the absorption spectrum of Ru(Hipdpa) due to the binding of Hg~(2+) was obtained.Ru(Hipdpa) was found to have decreased Hg~(2+) detection limit and improved linear region as compared to di(tetrabutylammonium) ris-bis(isothiocyanato)bis(2,2'-bipyridine-4-carboxylic acid-4'-carboxylate)ruthenium(Ⅱ) N719.Moreover,a dramatic color change from pink to yellow was observed,which allowed simple monitoring of Hg~(2+) by either naked eyes or a simple colorimetric reader.Therefore,the proposed sensor can provide potential applications for Hg~(2+) detection.     

1-Pyrenecarboxaldehyde thiosemicarbazone:A novel fluorescent molecular sensor towards mercury(Ⅱ) ion

<正>A novel and simple fluorescent molecular sensor,1-pyrenecarboxaldehyde thiosemicarbazone(Hpytsc),was synthesized.Its higher sensitivity and selectivity to mercury(Ⅱ) ion were studied through absorption and emission channels.The UV-vis spectra show that the increasing mercury(Ⅱ) ion concentrations result in the decreasing absorption intensity.The fluorescence monomer emission of Hpytsc is enhanced upon binding mercury(Ⅱ) ion,which should be due to the 1:1 complex formation between Hpytsc and metal ion.     

Development of an optical chemical sensor based on 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol in Nafion for determination of nickel ion

An optical chemical sensor based on immobilization of 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol (Br-PADAP) in Nafion membrane is described. The membranes were cast onto glass substrates and were used for the determination of nickel in aqueous solutions by spectrophotometry. The sensor system is highly transparent, mechanically stable and showed no evidence of reagent leaching. The influence of several parameters such as pH, ligand concentration, and type and concentration of regenerating solution were optimized. The sensor system showed good sensitivity in the range 0.5-20 μg ml⁻¹ with a detection limit of 0.3 μg ml⁻¹ Ni(II). The sensor has been incorporated into a home-made flow-through cell for determination of nickel in flowing streams with improved sensitivity, precision and detection limit. The calibration curve in the flow system was linear in the range 0.1-16 μg ml⁻¹ with a detection limit of 0.07 μg ml⁻¹. The sensor is easily regenerated by dilute nitric acid solution. The proposed method was successfully applied to the determination of nickel content in vegetable oil and chocolate samples and the results were compared with those obtained using atomic absorption spectrometry.     

Phenolphthalein immobilized membrane for an optical pH sensor

A phenolphthalein immobilized cellulose membrane for an optical pH sensor was described. The phenolphthalein was first reacted with the formaldehyde to produce a series of prepolymers with many hydroxymethyl groups. In this paper, the prepolymers was abbreviated to phenolphthalein-formaldehyde (PPF). Then the PPF was covalently immobilized to the diacetylcellulose membrane via hydroxymethyl groups. Finally the membrane was hydrolyzed in the 0.1 M NaOH solution for 24 h to reduce the response time. Advantageous features of the pH-sensitive membrane include (a) a large dynamic range from pH 8.0 to 12.50, or even broader, (b) rapid response time (2–30 s), (c) easy of fabrication, and (d) a promising material for determination of high pH values. The immobilized PPF has a broader dynamic range from 8.0 to 12.50 than the free phenolphthalein from pH 8.0 to 11.0, and this was due to the newly produced methylenes in our investigation.     

Magnesium optical one-shot sensor based on a coumarin chromoionophore

The characterization of a new irreversible optical absorption-based one-shot sensor for magnesium is described. The magnesium photoactive probe is 7-diethylamino-3-(3,4-ethylendioxybenzoyl)coumarin immobilized in a plasticized polymeric membrane. The magnesium selectivity can be explained in terms of size and charge density of magnesium and charge-separated resonance forms contribution in the excited state of coumarin. The selectivity obtained for magnesium over a variety of naturally occurring species in natural waters meets the requirements for the determination of this ion in water. The one-shot sensor responds between 0.14 and 14mgL(-1) with a sensor-to-sensor reproducibility of 1.3% as [Formula: see text] , at the medium level of the range. The performance of the optical one-shot sensor was tested in the analysis of magnesium in different types of natural waters and soft drinks validating results against a reference procedure.     

Lead ion selective PVC membrane electrode based on 5,5'-dithiobis-(2-nitrobenzoic acid)

A PVC membrane electrode for lead ions based on 5,5′-dithiobis-(2-nitrobenzoic acid) as membrane carrier was prepared. The electrode exhibits a Nernstian response for Pb²⁺ over a wide concentration range (1.0×10⁻²–4.0×10⁻⁶ M). It has a relatively fast response time and can be used for at least 3 months without any divergence in potentials. The proposed electrode revealed good selectivities for Pb²⁺ over a wide variety of other metal ions and could be used in a pH range of 2.0–7.0. It was used as an indicator electrode in potentiometric titration of lead ions and in direct determination of lead in water samples.     

An MSFIA system for mercury speciation based on an anion-exchange membrane

A new methodology for the in-line preconcentration, clean-up and speciation of mercury by use of an anion-exchange membrane is proposed. The speciation of mercury is based on retention of its tetrachloro complex onto the membrane while organic mercury flows freely through it. A multisyringe is used as a liquid driver and a cold vapour atomic fluorescence detector is employed to ensure a high sensitivity. Organic mercury is decomposed into to inorganic mercury by using a UV lamp. The carrier and reductant streams consist of 1.5% (m/v) hydrochloric acid and 2% (m/v) tin chloride, respectively. Certified reference material DORM-2 was digested with 37% hydrochloric acid and analysed directly without the need for extraction. The proposed system is more environmental friendly than the classical liquid-liquid extraction procedure. Mercury recoveries from spiked samples and the reference material were all close to 100%. An LOD of 14 and 16 ng/L was obtained for total and organic mercury, respectively, both with an RSD less than 1.3%.     

Novel fluorescent sensor for Ag and Hg based on the BINOL-pyrene derivative via click reaction

A novel BINOL-pyrene derivative sensor 1 for Ag⁺ and Hg²⁺ incorporating the triazole moieties and pyrenes was synthesized via click reaction. Binding of Ag⁺ ion induces the formation of 1:1 Ag⁺-1 chelating complex, and occurs in a ratiometric manner through an enhanced monomer and declining excimer emission, which make it possible to ratiometrically detect Ag⁺. The competitive experiment shows 1 can be used as an Ag⁺ specific fluorescence sensor over a wide range of competing cations. In the meanwhile, the sensor 1 was found to be selectively quenched by only Hg²⁺ at both monomer and excimer emission. Furthermore, we obtained evidences for different fluorescence signaling behaviors with Ag⁺ and Hg²⁺ by ¹H NMR titration experiments.     

A PVC-based pentathia-15-crown-5 membrane potentiometric sensor for mercury(II)

Poly(vinyl chloride) (PVC)-based membrane of pentathia-15-crown-5 exhibits good potentiometric response for Hg²⁺ over a wide concentration range (2.51 × 10⁻⁵ to 1.00 × 10⁻¹ mol dm⁻³) with a slope of 32.1 mV per decade of Hg²⁺ concentration. The response time of the sensor is as fast as 20 s. The electrode has been used for a period of six weeks and exhibits fairly good discriminating ability towards Hg²⁺ in comparison to alkali, alkaline and some heavy metal ions. The electrode can be used in the pH range from 2.7 to 5.0.     

A squaraine based fluorescent probe for mercury ion via coordination induced deaggregation signaling

Due to the high affinity between dithiocarbamate(DTC) and Hg2+,a fluorescent probe based on squaraine chromophore with DTC side arm for Hg2+via coordination induced deaggregation signaling has been designed and synthesized.Squaraine has a high tendency to aggregate in aqueous solution,and such self-aggregation usually results in a dramatic absorption spectral broadening with fluorescence emission quenching.The combination of the DTC side arm of the probe with Hg2+induces steric hindrance,leading to the deaggregation of the dye complex,companying with a fluorescence emission restoration.In EtOH–H2O(20:80,v/v) solution,this ‘‘turn on' fluorescent probe has high selectivity and sensitivity toward Hg2+over other metal ions,and the limit of detection for Hg2+was estimated as2.19 ? 10à8mol/L by 3s/k.     

A fluorescent chemical sensor for Fe based on blocking of intramolecular proton transfer of a quinazolinone derivative

In this paper, 2-(2′-hydroxy-phenyl)-4(3H)-quinazolinone (HPQ), a typical compound that exhibits excited state intramolecular proton transfer (ESIPT) reaction and possesses good photophysical properties, is synthesized and used as fluoroionophore for Fe³⁺ sensitive optochemical sensor. The decrease of fluorescence intensity of HPQ membrane upon the addition of Fe³⁺ was attributed to the blocking of ESIPT reactions of HPQ and quenching its fluorescence. The effect of the composition of the sensing membrane was studied, and experimental conditions were optimized. The sensor shows a linear response toward Fe³⁺ in the concentration range of 7.1 × 10⁻⁷ M to 1.4 × 10⁻⁴ M with a limit of detection of 8.0 × 10⁻⁸ M, and a working pH range from 2.5 to 4.5. It shows excellent selectivity for Fe³⁺ over a large number of cations such as alkali, alkaline earth and transitional metal ions. The proposed sensor is applied to the determination of the content of iron ions in pharmaceutical preparations samples with satisfactory results.     

Novel colorimetric sensor for mercury (Ⅱ) based on layer-by-layer assembly of unmodified silver triangular nanoplates

A simple layer-by-layer deposition technique was used to fabricate the multilayer thin films of unmodified silver triangular nanoplates(AgTNPs).The multilayer of AgTNPs thin films were fabricated by alternate deposition of each anionic sodium citrate stabilized AgTNPs and cationic poly(diallyldimethylammonium chloride).All prepared AgTNPs multilayer thin films were exhibited a strong plasmon band at the wavelength of 667 nm,which confirmed the formation of AgTNPs onto the substrate.The characteristics of the multilayer thin films were investigated using contact angle measurement,UV-visible spectroscopy,X-ray diffraction analysis(XRD),atomic force microscope(AFM)and field emission scanning electron microscope(FESEM).As these films are to be used as a mercury(II)colorimetric sensor,the changes in optical properties of the films were evaluated for various mercury(Ⅱ)concentrations.AgTNPs assembled into thin films showed a strong color shift from blue to mauve and colorless when exposed to mercury(Ⅱ).The constructed multilayer thin films exhibited excellent color changes of mercury(II) with a linear range between 0.5 and 20 ppm.The limit of detection(LOD) and limit of quantitation(LOQ) were 0.45 ± 0.002 and 1.52 ± 0.002 ppm,respectively.The recovery values of AgTNPs multilayer thin films are satisfactory in the range of 100.1%-106.4%when applied to determining mercury(Ⅱ) in water samples.