Colorimetric Fluoride‐Anion Sensor Based on Intramolecular Hydrogen Bonding and Enol–Keto Tautomerization of a Phenothiazine Derivative

A colorimetric sensor for fluoride ions based on a new sensing mechanism is reported. The colorimetric sensor contains an isomerizable enol–keto moiety as the recognition site and phenothiazine as chromogenic center. A color change visible to the naked eye is observed upon addition of fluoride ions to the solution of sensor 1 in aprotic solvents such as CHCl₃ and MeCN. The sensor shows no colorimetric response for other halide ions. Enol‐keto tautomerization is proposed to be responsible for the anion sensing of 1 , based on UV/VIS absorption, ¹H‐NMR, and single‐crystal structure analysis.     

An All‐solid‐state Polymeric Membrane Ca2+‐selective Electrode Based on Hydrophobic Alkyl‐chain‐functionalized Graphene Oxide

An all‐solid‐state polymeric membrane Ca²⁺‐selective electrode based on hydrophobic octadecylamine‐functionalized graphene oxide has been developed. The hydrophobic composite in the ion‐selective membrane not only acts as a transduction element to improve the potential stability for the all‐solid‐state Ca²⁺‐selective electrode, but also is used to immobilize Ca²⁺ ionophore with lipophilic side chains through hydrophobic interactions. The developed all‐solid‐state Ca²⁺‐selective electrode shows a stable potential response in the linear range of 3.0×10⁻⁷–1.0×10⁻³ M with a slope of 24.7±0.3 mV/dec, and the detection limit is (1.6±0.2 )×10⁻⁷ M (n =3). Additionally, due to the hydrophobicity and electrical conductivity of the composite, the proposed all‐solid‐state ion‐selective electrode exhibits an improved stability with the absence of water layer between the ion‐selective membrane and the underlying glassy carbon electrode. This work provides a simple, efficient and low‐cost methodology for developing stable and robust all‐solid‐state ion‐selective electrode with ionophore immobilization.     

Application of 2‐(benzyliminomethyl)‐6‐methoxy‐4‐(4‐methoxyphenyl‐azo)phenol in construction of ion‐selective PVC membrane electrode for determination of copper (II) in mineral water sample

The potentiometric characteristics of a new Cu²⁺‐selective electrode based on 2‐(benzyliminomethyl)‐6‐methoxy‐4‐(4‐methoxyphenyl‐azo) phenol as an efficient ionophore has been evaluated. The effects of influential parameters on the potentiometric responses such as the amount of plasticizer, the amount of ionophore, pH of the sample solution, and the effect of coexisting ions on the electrode signal were subsequently investigated . The selectivity of the electrode was assessed by calculating the selectivity coefficients using the matched potential method. The optimum ratio of the amount of materials required for the preparation of the electrode was found to be 1.7: 32.1: 64.2: 2.0 corresponding to carboxylated PVC, dimethyl sebacate as solvent mediators, potassium tetrakis (p‐chlorophenyl) borate as the anion localizing agent, and ionophore, respectively. The electrode had a fast response (7s) as well as a satisfactory Nernstian slope (29.26±0.91 mV/decade) to Cu²⁺ over a wide concentration range of 2.0×10^?6‐ 5.0×10^?2 M with a low detection limit of 5.9×10^?7 M. The developed sensor was successfully used for the potentiometric titration of Cu²⁺ ion with EDTA and subsequently, efficient determination of this metal ion in a mineral water sample was performed.     

Solid‐contact Acetate‐selective Electrode Based on a 1,3‐bis(carbazolyl)urea‐ionophore

The construction and study of solid‐contact acetate‐selective electrodes is described using a 1,3‐bis(carbazolyl)urea derivative as a neutral hydrogen‐bonding ionophore and poly(3,4‐ethylenedioxythiophene) as the solid contact. It was shown recently that this ionophore binds acetate (logK_ass=4.98) that is used as primary ion in this study. The electrodes show linearity over the activity range of 10^?4.50–10^?1.10 with a sub‐Nernstian slope of ?51.3 mV per decade and a detection limit of 10^?5.00. The anion‐selectivity pattern of these electrodes deviates markedly from the Hofmeister pattern. When adding ionophore to the membrane the logarithm of the selectivity coefficient (logK) for SCN^? decreased from 6.5 to 1.2, logK for I^? decreased from 5.7 to 0.9, logK for NO₃^? decreased from 4.3 to 0.6 and logK for Br^? decreased from 3.3 to 0.1. The selectivity coefficients of hydrophilic anions such as Cl^?, F^?, HPO₄^2?, and SO₄^2? are significantly lower than in case of the ionophore‐free membrane. It was discovered that the constructed electrodes are also relatively selective to bicarbonate. This work is an important step towards the further development of solid‐contact anion‐selective electrodes.     

The Hofmeister Anion Effect on Ionophore‐based Ion‐selective Nanospheres Containing Solvatochromic Dyes

Recently reported ionophore‐based ion‐selective nanospheres contained pH‐independent and positively charged solvatochromic dyes. Here, we evaluate systematically the effect of anions to the fluorescence response of the nanospheres. The anion interference was found significant for anion concentrations above 10 mM. The sensor responses in the presence of various anion background was studied. While target ion (K⁺) causes the fluorescence of the nanospheres to decrease, increasing anion background also leads to lower fluorescence intensity. Lipophilic anions such as ClO₄^?, SCN^?, and I^? exhibited much more interference than hydrophilic anions (e. g., NO₃^?, Cl^?, F^?, SO₄^2?). The trend of the anion interference followed the Hofmeister series. A theoretical model was also demonstrated based on anion adsorption on the surface of the nanospheres.     

Design and evaluation of a thorium (IV) selective optode

A novel optical sensor has been proposed for sensitive determination of thorium (IV) ion in aqueous solutions. The thorium sensing membrane was prepared by incorporating 4-(p-nitrophenyl azo)-pyrocatechol (NAP) as ionophore in the plasticized PVC membrane containing tributyl phosphate (TBP) as plasticizer. The membrane responds to thorium ion by changing color reversibly from yellow to red-brown in glycine buffer solution at pH 3.5. The proposed sensor displays a linear range of 8.66 × 10⁻⁶-2.00 × 10⁻⁴ M with a limit of detection of 6 × 10⁻⁶ M. The response time of the optode was about 8.8-12.5 min, depending on the concentration of Th (IV) ions. The selectivity of optode to Th (IV) ions in glycine buffer is good. The sensor can readily be regenerated by exposure to a solution mixture of sodium fluoride and 5-sulfosalicylic acid (dihydrate) (0.01 M each). The optode is fully reversible. The proposed optode was applied to the determination of thorium (IV) in environmental water samples.     

Synthesis of chromo‐ and fluorogenic poly(ortho‐diaminophenylene) chemosensors for fluoride anion

Two new poly(ortho‐diaminophenylene) derivatives containing fluorene and/or quinoxaline moieties per repeat unit in the main chain were synthesized via Suzuki coupling reaction followed by reduction process. The synthesized polymers were characterized and explored as colorimetric and fluorometric anion‐sensing materials. The polymers in dilute tetrahydrofuran (THF) solution emitted green light (about 530 nm) in their precursor benzothiadiazole forms and blue to green light (477–523 nm) in their reduced forms. The color of polymer solution was dramatically altered upon addition of fluoride anion without noticeable absorption change in UV–vis spectrum. The fluorescence was ratiometrically quenched with a linear relationship between fluorescence intensity and fluoride anion concentration implying static quenching mechanism could be applied judging from the maintenance of constant fluorescence lifetime with variable fluoride anion concentration. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1546–1556, 2007     

Chloride‐Anion‐Templated Synthesis of a Strapped‐Porphyrin‐Containing Catenane Host System

The synthesis, structure and anion‐recognition properties of a new strapped‐porphyrin‐containing [2]catenane anion host system are described. The assembly of the catenane is directed by discrete chloride anion templation acting in synergy with secondary aromatic donor–acceptor and coordinative pyridine–zinc interactions. The [2]catenane incorporates a three‐dimensional, hydrogen‐bond‐donating anion‐binding pocket; solid‐state structural analysis of the catenane?chloride complex reveals that the chloride anion is encapsulated within the catenane’s interlocked binding cavity through six convergent CH????Cl and NH???Cl hydrogen‐bonding interactions and solution‐phase ¹H NMR titration experiments demonstrate that this complementary hydrogen‐bonding arrangement facilitates the selective recognition of chloride over larger halide anions in DMSO solution.     

A Mix‐and‐Read Fluorescence Strategy for the Switch‐On Probing of Kinase Activity Based on an Aptameric‐Peptide/Graphene‐Oxide Platform

Protein kinase plays a vital role in regulating signal‐transduction pathways and its simple and quick detection is highly desirable because traditional kinase assays typically rely on a time‐consuming kinase‐phosphorylation process (ca. 1 h). Herein, we report a new and rapid fluorescence‐based sensing platform for probing the activity of protein kinase that is based on the super‐quenching capacity of graphene oxide (GO) nanosheets and specific recognition of the aptameric peptide (FITC‐IP₂₀). On the GO/peptide platform, the fluorescence quenching of FITC‐IP₂₀ that is adsorbed onto GO can be restored by selective binding of active protein kinase to the aptameric peptide, thereby resulting in the fast switch‐on detection of kinase activity (ca. 15 min). The feasibility of this method has been demonstrated by the sensitive measurement of the activity of cAMP‐dependent protein kinase (PKA), with a detection limit of 0.053 mU μL^?1. This assay technique was also successfully applied to the detection of kinase activation in cell lysate.     

Utilizing a pH‐Sensitive Dye in the Selective Fluorescent Recognition of Sulfate

A receptor containing amidopyrrole binding subunits and free amino groups, conjugated to a naphthalimide dye, has been designed and synthesized. The intrinsic selectivity of the binding motif for phosphate present in DMSO completely disappears in 10 % DMSO aqueous buffer at pH 3.6, at which the receptor is protonated. The electrostatic interactions between the receptor and an anion start to dominate, thus leading to selectivity for sulfate. The ability of the HSO₄^? anion to transfer the proton to the amino group during the recognition event suppresses the photoinduced electron transfer (PET) on the dye, resulting in a selective turn‐on fluorescent response. The choice of pH of the solution for sensing is dictated by the pK_a value of the dye.     

A new procedure for the construction of flow-through optodes. Application to determination of copper (II)

A new procedure for constructing an optical fibre reflectance, bulk optode membrane type, sensor is presented. The optode membrane consists of a plasticized poly (vinyl chloride) membrane in which the ionophore is dissolved, entrapped in a cellulose support. The new optode with the dye indicator 1-(2-pyridylazo)-2-naphthol (PAN) was incorporated in a new flow-through cell and the injection system was optimized to determine Cu (II) at 567 nm in the range 5 × 10^?5–10^?3 M. The response was reproducible and the optode can be regenerated using 10^?2 M EDTA followed by water. The method was applied to the determination of copper in real samples.     

Sensitive and Selective Fluorescent and Colorimetric Sensor for Ag+ Based on the Supramolecular Self‐Assembly in Semi‐Water

Specific recognition of ultratrace levels of ions in semi‐water using super‐quicker methods is still a challenge for environmental monitoring. Herein we report a fluorescent and colormetric sensor ( ZH ) based on supramolecular self‐assembly, whose structure was destroyed by the addition of ultratrace of silver ions. The process promoted either naked eye visible color changes or fluorescence intensity quenched in conjunction with a wide pH range. Systematic studies revealed very high selectivity (0.07 µmol/L) for silver ions, and other common cations, e.g ., Hg²⁺, Cu²⁺, Cd²⁺, Pb²⁺ had nearly no influence on the sensing behavior. This sensor also served as a multiple use of component in sensing materials by addition of I⁻ into the mixture of ZH and Ag⁺ (about 5 times). What's more, ZH containing filter paper emerged distinct color and fluorescence changes upon exposure to silver (Ag⁺), which could be used as a portable method to undertake field testing for Ag ⁺ .     

Di‐ and Triphosphate Recognition and Sensing with Mono‐ and Dinuclear Fluorescent Zinc(II) Complexes: Clues for the Design of Selective Chemosensors for Anions in Aqueous Media

The synthesis of a new ligand (L1) containing two 1,4,7‐triazacyclononane ([9]aneN₃) moieties linked by a 4,5‐dimethylenacridine unit is reported. The binding and fluorescence sensing properties toward Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ of L1 and receptor L2, composed of two [9]aneN₃ macrocycles bridged by a 6,6′′‐dimethylen‐2,2′:6′,2′′‐terpyridine unit, have been studied by coupling potentiometric, UV/Vis absorption, and emission measurements in aqueous media. Both receptors can selectively detect Zn²⁺ thanks to fluorescence emission enhancement upon metal binding. The analysis of the binding and sensing properties of the Zn²⁺ complexes toward inorganic anions revealed that the dinuclear Zn²⁺ complex of L1 selectively binds and senses the triphosphate anion (TP), whereas the mononuclear Zn²⁺ complex of L2 displays selective recognition of diphosphate (DP). Binding of TP or DP induces emission quenching of the Zn²⁺ complexes with L1 and L2, respectively. These results are exploited to discuss the role played by pH, number of coordinated metal cations, and binding ability of the bridging units in metal and/or anion coordination and sensing.     

Design and characterization of a Li-selective optical sensor

An optical ion-sensing system based on a PVC membrane containing a Li⁺ ionophore in combination with a H⁺ selective chromoionophore (ETH 5294) is presented. It exhibits an absorbance response to Li⁺ concentration in pH buffered solutions. The dynamic range and Li⁺/Na⁺ selectivity of this new optode system are discussed.     

Wide range pH measurements using a single H(+)-selective chromoionophore and a time-based flow method

A hydrophilic transparent triacetyl cellulose membrane was adopted as a pH optode by immobilizing highly selective and sensitive Nile blue indicator on the membrane. Contrary to the common procedure for determinations using optodes, in which a steady state response is measured, a new approach is introduced in which the dynamic response of the optode is used as the analytical signal. While in common procedures, pH optodes exhibit limited linear dynamic range (often 2–4 pH units only), it is shown that in a time-based flow method, an optode with only one acid-base indicator can be used for measurement in the pH range of 0–10. The procedure is simple, inexpensive and rapid.     

Investigation of Protein Binding With All Solid‐State Ion‐Selective Electrodes

A potentiometric sensor for studying charge based adsorption of proteins was created using a single‐piece polyaniline‐PVC ion‐selective electrode (ISE). Three different ISEs, two for Na⁺ and one for Cl^? ion determination, were studied. The Na⁺‐ISEs consisted of a neutral calixarene‐based ionophore and one with a charged carrier dinonylnapthalenesulfonic acid (DNNSA) whereas for the Cl^? ISE, an anion exchanger tridodecylmethylammonium chloride (TDDMA⁺Cl^?), was used. The Na⁺ ISE with DNNSA as the charged carrier was successfully able to discriminate the binding of two different proteins (bovine serum albumin and lysozyme) based on their intrinsic charge.     

A novel optical sensor for uranium determination

A metal ion indicator, Alizarin Red S, was tested for its potential use in uranium selective optode membrane. The water-soluble indicator was lipophilized in the form of an ion pair with tetraoctylammonium bromide, and subsequently immobilized on a triacetyl cellulose membrane. The membrane responds to uranium ions, giving a color change from yellow to violet in acetate buffer pH 5. This optode has a linear range of (1.70-18.7) × 10⁻⁵ M of UO₂²⁺ ions with a limit of detection of 5 × 10⁻⁶ M. The response time of optode was within 6 min depending on the concentration of UO₂²⁺ ions. The sensor can readily be regenerated with hydrochloric acid solution (0.01 M). The optode is fully reversible.     

Fluoride anion sensing mechanism of a BODIPY‐linked hydrogen‐bonding probe

The sensing mechanism of a fluoride‐anion probe BODIPY‐amidothiourea ( 1c ) has been elucidated through the density functional theory (DFT) and time‐dependent density functional theory (TDDFT) calculations. The theoretical study indicates that in the DMSO/water mixtures the fluorescent sensing has been regulated by the fluoride complex that formed between the probe 1c /two water molecules and the fluoride anion, and the excited‐state intermolecular hydrogen bond (H‐B) plays an important role in the fluoride sensing mechanism. In the first excited state, the H‐Bs of the fluoride complex 1cFH₂ are overall strengthened, which induces the weak fluorescence emission. In addition, molecular orbital analysis demonstrates that 1cFH₂ has more obvious intramolecular charge transfer (ICT) character in the S₁ state than 1cH₂ formed between the probe 1c and two water molecules, which also gives reason to the weaker fluorescence intensity of 1cFH₂ . Further, our calculated UV‐vis absorbance and fluorescence spectra are in accordance with the experimental measurements. © 2018 Wiley Periodicals, Inc.     

一种具有吡咯酰胺和脲的杂双位点受体的选择性氟离子比色识别

本文合成了一种具有吡咯酰胺和脲杂双识别位点的阴离子受体。利用紫外光谱法研究了该受体在乙腈溶液中对阴离子的识别作用。结果表明,该受体的识别能力比具有两个相同识别位点的受体的阴离子识别能力有所提高。同时,当仅当添加氟离子时,受体溶液的颜色会从无色变为黄色。表明,受体在氟离子的选择比色传感方面具有潜在的应用能力。     

Polyion Detection via All‐solid‐contact Paper‐based Polyion‐sensitive Polymeric Membrane Electrodes

The first all‐solid‐contact paper‐based single‐use polyion‐sensitive ion‐selective electrodes (ISEs) are described. These polyion‐sensitive ISEs are fabricated using cellulose filter paper coated with a carbon ink conductive layer. A polyanion sensing membrane is cast on a section of the coated paper and the sensor is insulated, resulting in a disposable, single‐use device. Various polyanions are shown to yield large negative potentiometric responses when using these disposable devices for direct polyanion detection. These new sensors are further demonstrated to be useful in indirect polycation detection when polycations (i. e., polyquaterniums (PQs)) are titrated with polyanionic dextran sulfate (DS). Titrations monitored using these paper‐based, all‐solid‐contact devices yield endpoints proportional to the given PQ concentration present in the test sample.