Zinc-8-hydroxyquinoline intercalated in calcium bentonite: A promising DO sensor

Zn(II) and 8-hydroxyquinoline were made to react in an in situ solid−solid reaction in the interlayer space of Ca-bentonite from Thailand, resulting in [Zn(8-hydroxyquinoline)₂]²⁺, the well known -Znq₂. X-ray diffraction patterns showed that the interlayer space of the bentonite increased from 1.56 to 1.67 nm on going from Zn(II)-bentonite to Znq₂-bentonite, which confirmed the intercalation of Znq₂ in bentonite. The intercalated Znq₂-bentonite compound was mixed with a solution of polystyrene in toluene and coated as a film on a polystyrene sheet. The fluorescence intensity of Znq₂-bentonite film was measured in the presence of dissolved oxygen (DO). It was found that the fluorescence intensity of the film decreased as dissolved oxygen increased, which is a promising result for developing an optical dissolved oxygen sensor (DO sensor). The fluorescence quenching by oxygen followed the Stern-Volmer plot.     

Fluorescence sensor for Cu(II) based on R6G derivatives modified silicon nanowires

A fluorescence sensor for selective detection of Cu(II) is realized by covalently immobilizing derivatives of rhodamine6G (R6G) on the surface of silicon nanowires (SiNWs). It features the release of R6G from the SiNWs in the presence of Cu(II), which causes a significant enhancement of the fluorescence over other metal ions. The present Cu(II) sensor has good selectivity and sensitivity, and exhibits a linear response in the range of 0.0-7.0 μM Cu(II). Different from conventional Cu(II) sensor with fluorescence quenching, the present sensor based on fluorescence enhancement facilitates the practical application. Especially, the release of the R6G from SiNWs could be utilized as fluorescent labeling for Cu(II) in microenvironment.     

A Highly Selective Turn-On Fluorescent Chemosensor for Zinc Ion in Aqueous Media

In the paper, a novel rhodamine6G based fluorescent chemosensor bearing 3-carbaldehyde chromone was designed and synthesized. According to the fluorescence behavior toward several metal ions, it showed highly selectivity and sensitivity to Zn(II) over other commonly coexistent metal ions (Cu(II), Cd(II), Hg(II), Mg(II), K(I), Pb(II), Fe(III) and Cr(III)) in aqueous environment (pH?=?7.4). Meanwhile the binding constant between Zn(II) and chemosensor achieved 6.21?×?10¹¹ M^?1 in aqueous media. Moreover, according to the Job plot, 1:1 stoichiometry between Zn(II) and sensor was deduced in aqueous media (pH?=?7.4). The good selectivity and sensitivity in aqueous media effectively enhanced the application value of the fluorescent chemosensor for Zn(II).     

Alteration in metal ion induced fluorescence signaling responses of benzofurazan appended acyclic amino-receptor through its structural modification

Fluorescent signaling probes 3 and 4 in the integrated ‘fluorophore-receptor’ format have been synthesized by derivatization of ‘amino-alkyl-amino’ based receptors with 7-chloro-4-nitrobenz-2-oxa-1,3-diazole fluorophore for metal ion induced fluorescence recovery through perturbation of charge-transfer character of fluorophoric D(donor)−π−A(acceptor) segment. Among all the metal ions investigated, the ‘amino-ethyl-amino’ receptor based probe 3 exhibits fluorescence enhancement selectively in presence of Zn(II) ion, while the probe 4 with an structurally modified ‘amino-ethyl-oxy-(phenyl methyl)-amino’ based receptor exhibits fluorescence enhancement with Co(II), Ni(II), Cu(II), Zn(II), and Ag(I). The chemo-selectivity of 3 towards Zn(II) ion fails in 4 due to a structural modification to receptor's framework.     

A Long Wavelength Excitable Fluorophore; Chloro Phenyl Imino Propenyl Aniline (CPIPA) for Selective Sensing of Hg (II)

In this study, a very sensitive and highly selective irreversible optical chemical sensor (optode) for mercury ions was described. The sensing scheme was based on the interaction of Hg (II) with a newly synthesized fluoroionophore; chloro phenyl imino propenyl aniline (CPIPA) in plasticized PVC membrane. The sensor membranes were tested for the determination of mercury ion in aqueous solutions by batch and flow-through methods. The optodes allow determination of Hg (II) in the working range of 1.0 × 10⁻⁹–1.0 × 10⁻⁵ M with a detection limit of 4.3 ppb. The sensor exhibited excellent selectivity for Hg (II) with respect to several common alkali, alkaline earth and transition metal ions. The association constant of the 1:1 complex formation for Hg (II) was found to be K_a = 1.86 × 10⁵ M⁻¹. The CPIPA exhibited high fluorescence quantum yield, long excitation and emission wavelength and high Stokes’ shift values in the solid matrix which makes it compatible with solid state optics.     

Crystal structure of Ni(II) complex and fluorescence properties of Zn(II) complex with the Schiff base derived from diethenetriamine and PMBP

The Schiff base, H₂L, was derived from 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) and diethenetriamine. The crystal structure of [NiL(C₂H₅OH)]·H₂O obtained from ethanol solution was determined by X-ray diffraction analysis. The coordination geometry of Ni(II) ion is a distorted octahedron with three oxygen atoms and three nitrogen atoms. Under the excitation of ultraviolet light, strong fluorescence of solid Zn(II) complex was observed. In addition, the fluorescence enhancement was obtained in the presence of Zn²⁺ in THF solution of the ligand, indicating that H₂L may be a potential fluorescent sensor for Zn²⁺.     

Fluorescence of the <Emphasis Type="Italic">cis</Emphasis>-dimers of porphyrins containing ethylene bridges

The absorption and fluorescence spectra of solutions of the porphyrin dimers containing ethylene bridges, binding two Zn(II)octaethylporphyrin molecules or one Zn(II)octaethylporphyrin and one octaethylporphyrin molecule into cis conformation, were studied. For both studied cis-dimers, structureless absorption spectra were observed, only in general resembling the spectra of initial molecules, as well as weak fluorescence with a wide bell-shaped spectrum with a maximum at 680–700 nm and a quantum yield of about Φ_f≈3×10^?5, which is three orders of magnitude lower as compared to the fluorescence of initial monomeric porphyrins. A strong dependence of the fluorescence yield on a medium viscosity was revealed. In addition, low-yield irreversible cis-trans photoisomerization of cis-dimers was detected. A mechanism responsible for the strong intramolecular quenching of fluorescence of the porphyrin dimers containing ethylene bridges is suggested to be a conformation transformation in the region of the ethylene bridge, leading the molecular system to the region of “conic crossing” of the energy surfaces of excited and ground electron states.     

Influence of Fe(III) on the Fluorescence of Lysozyme: a Facile and Direct Method for Sensitive and Selective Sensing of Fe(III)

Lysozyme is widely used for the synthesis of nanomaterials (e.g., gold nanoparticle) to fluorescently sense metal ions. However, the effect of metal ions on the fluorescence of lysozyme is not studied yet. Herein, we have explored the interactions of lysozyme with different metal ions to develop a direct sensing platform for Fe(III). It has been observed that the fluorescence of lysozyme was slightly decreased in the presence of Cu(II), Hg(II), As(V), Co(II), Cd(II), Cr(II), Fe(II), Mn(II), Pb(II), and Zn(II), while a significant decrease in the lysozyme fluorescence was observed for Fe(III). The effect of thermal stability on the fluorescence quenching was also studied from 25 to 60 °C. In the present study, the lysozyme sensing probe was able to selectively and accurately detect 0.5–50 ppm of Fe(III) with a LOD of 0.1 ppm (1.8 µM) at 25 °C.

     

Absorption and fluorescence spectroscopy of 3-hydroxy-3-phenyl-1-o-carboxyphenyltriazene and its copper (II), nickel (II) and zinc (II) complexes: a novel fluorescence sensor

Absorption and fluorescence spectroscopic properties of 3-hydroxy-3-phenyl-1-o-carboxyphenyltriazene (HT) are studied. The mechanism of photo-induced electron transfer (PET) followed by energy transfer process of the ligand and the Cu (II), Ni (II) and Zn (II) metal complexes have been investigated. The excited state photo induced intramolecular hydrogen transfer from N-OH to triazene 1-nitrogen atom is explained. The effect of pH, solvent and concentration on the absorption and fluorescence of the ligand is studied and it has been found that the absorption and fluorescence of HT is highly pH, solvent and concentration dependent. Participation of the N-OH proton of HT in the solvent assisted O to N-proton transfer has also been proposed. The fluorescence band shift and changes in intensity is modulated by protonation and complexation with metal ions. This fluorophore can thus be used as a pH dependent and M⁽ⁿ⁺¹⁾⁺/Mⁿ⁺ redox on/off switchable molecular sensor.     

Fluorescence of N,N-di(2-carboxyethyl)-<Emphasis Type="Italic">p</Emphasis>-anisidine in solution and crystalline states

The fluorescence properties of N,N-di(2-carboxyethyl)-p-anisidine (I) in solvents of various nature and in the crystalline state have been studied at room temperature (273 K) and at the boiling point of liquid nitrogen (77 K). Fluorescence in aqueous solutions of I with protonated (λ _ex /λ _fl ^max = 225/290 nm) and unprotonated (λ _ex /λ _fl ^max = 270/380 nm) amino nitrogen has been detected. On going from aqueous solutions to nonaqueous, the fluorescence band of unprotonated I experiences a blue shift and its intensity rises. The fluorescence intensity of the band in aprotic polar solvents is higher than that in protic solvents. A linear dependence of the fluorescence intensity of deprotonated I on Cu(II) concentration (ranging from 1.0 to 5.0 mg/dm³) in aqueous solution has been found. The fluorescence intensity of I in aqueous solutions at 77 K and pH 1–6 has been shown to increase in the presence of Zn(II) (1–170 mg/dm³) and Cd(II) (2–330 mg/dm³) although a similar dependence is not observed at 293 K.     

Ce (III) - Porphyrin Sandwich Complex Ce<Subscript>2</Subscript>(TPP)<Subscript>3</Subscript>: A Rod-Like Nanoparticle as a Fluorescence Turn-Off Probe for Detection of Hg (II) and Cu (II)

In this study the researcher reports a novel, one step synthesized rod-like nanoparticles of cerium (III)—tetraphenylporphyrin sandwich complex as a spectrofluorometric sensor to measure trace amount of Hg (II) and Cu (II) metal ions. Moreover, the synthesized fluorescent probe was able to detect higher amounts (>10^?4 M) of Hg (II) in aqueous media by changing the color which can also be used as a selective mercury naked-eye sensor. The selectivity and sensitivity of the sensor based on its fluorescence quenching in the presence of Hg (II) and Cu (II) were studied according to the Stern-Volmer equation. The detection limit of the sensor was 16 nM for Hg (II) and about 2.34 μM for Cu (II) ions.

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Graphical Abstract Ce₂(TPP)₃ sandwich complex application as a fluorescent probe for measuring trace amounts of mercury and copper in real samples

     

Fluorescence enhancement of N2O2-type dipyrrin ligand in two step responding to zinc(II) ion

Fluorescence imaging is well-suited for the live imaging of biological Zn(II), which has no facile spectroscopic or magnetic signature. The successful application of this methodology requires the development of robust Zn(II) imaging agents that display high sensitivity, selectivity and temporal fidelity. In this study, a N₂O₂-type dipyrrin based bimolecular zinc(II) complex was produced and shown to have sharper, blue-shifted and more enhanced fluorescence emission. An approximate three-fold fluorescence enhancement was achieved within the micromolar concentration range, which is an important parameter for Zn(II) detection in vivo. The increase in emission intensity was due to the dominant role of aryl-ring rotation in governing the excited state dynamics and fluorescence properties of the dipyrrin dye. Fluorescence titration showed that the ligand complex exhibited very strong zinc(II) binding affinity when compared to that in the binuclear chloro complex. The fluorescence emission changes in the dipyrrin dye to zinc(II) ion could be observed not only using instruments but also by the naked-eye (violet→sky blue).     

CT-Operated Bifunctional Fluorescent Probe Based on a Pretwisted Donor–Donor–Biphenyl

Taking into account the structural requirements for TICT-type sensor molecules, a general synthetic route to derive pH and cation-responsive pretwisted donor (D)–donor (D) biphenyls (b) equipped with donor receptors is developed and a first model compound containing a mono aza-15-crown-5 and a DMA receptor is synthesized, see Scheme 1. The spectroscopic properties of this new bifunctional D–D biphenyl are studied in the non-polar and polar solvents cyclohexane, acetonitrile, and methanol. Protonation as well as complexation studies are performed with the representative metal ions Na(I), K(I), Ca(II), Ag(I), Zn(II), Cd(II), Hg(II), and Pb(II) to reveal the potential of this molecule for communication of whether none, only one, or both binding sites are engaged in analyte coordination by spectroscopically distinguishable outputs. The results are compared to those obtained with closely related donor (D)–acceptor (A) substituted biphenyl-type sensor molecules and are discussed within the framework of neutral and ionic D – A biphenyls.     

Synthesis,Characterization, DNA Binding Properties,Fluorescence Studies and Antioxidant Activity of Transition Metal Complexes with Hesperetin-2-hydroxy Benzoyl Hydrazone

A novel Schiff-base ligand (H₅L), hesperetin-2-hydroxy benzoyl hydrazone, and its copper (II), zinc (II) and nickel (II) complexes (M·H₃L) [M(II) = Cu, Zn, Ni], have been synthesized and characterized. The ligand and Zn (II) complex exhibit green and blue fluorescence under UV light and the fluorescent properties of the ligand and Zn (II) complex in solid state and different solutions were investigated. In addition, DNA binding properties of the ligand and its metal complexes have been investigated by electronic absorption spectroscopy, fluorescence spectra, ethidium bromide displacement experiments, iodide quenching experiments, salt effect and viscosity measurements. Results suggest that all the compounds bind to DNA via an intercalation binding mode. Furthermore, the antioxidant activity of the ligand and its metal complexes was determined by superoxide and hydroxyl radical scavenging methods in vitro. The metal complexes were found to possess potent antioxidant activity and be better than the free ligand alone and some standard antioxidants like vitamin C and mannitol.     

Highly Selective and Sensitive Benzimidazole Based Bifunctional Sensor for Targeting Inedible Azo Dyes in Red Chilli,Red Food Color,Turmeric Powder,and Cu(Ii) in Coconut Water

In this study, a simple Benzimidazole based bifunctional chemosensor 4-(2-(3,4-dimethoxyphenyl)-1H-benzo[d]imidazol-6-yl) benzene-1,2-diamine, L was synthesized and characterized. The sensor proved to be selective and sensitive towards detecting banned azo dyes Sudan Dye I, II, and Metanil Yellow via fluorescence turn-off response. The proposed mechanism of fluorescence quenching was the inner filter effect. LODs for Sudan I, II, and Metanil Yellow were found to be 0.009 µM, 0.012 µM, and 0.0073 µM, respectively. The developed chemosensor also showed a colorimetric response towards Cu (II) ions via an apparent color change from yellow to pink. LOD for Cu (II) ions was found to be 1.2 µM. The synthesized benzimidazole based bifunctional chemosensor was adequately tested to determine Sudan I in Red chili powder and red Food color samples, Metanil yellow in turmeric powder, and Cu(II) packaged coconut water.

     

A new fluorescence probe for trace metal ions: Cation-dependent spectroscopic properties

The fluorescence behavior of a new bipyridyl ligand, 2,2-bipyridyl-3,3-diol (BPDO), was studied as a function of the metal ion complexed. At pH 7.6, the fluorescence of BPDO is strongly decreased by complexation to Cu(II), but binding to Zn(II) leads to an increase in fluorescence intensity. Time-resolved fluorescence measurements suggest that in the case of Cu(II), a nonfluorescent complex is formed, whereas in the presence of Zn(II), a new, longer decay component appears.     

Determination by Fluorescence Spectroscopy of Cadmium at the Subnanomolar Level: Application to Seawater

This paper reports the development of a molecular fluorescence spectroscopy-based approach for the determination of cadmium in seawater. Anthrylazamacrocycle derivatives—the fluorescence of which is enhanced when chelated to zinc or cadmium—are used as chemosensors. A detection limit of 5 nM has been found at pH 10 for both metals, and spectral shifts allow simultaneous Cd(II)/Zn(II) determination using multiwavelength analysis. While cadmium emission behavior is similar at pH 13, zinc is not detected anymore. This enables the selective detection of cadmium even at a high Zn(II)/Cd(II) ratio. The detection limit is 1 nM. Interferent removal and preconcentration have been developed using a Dowex resin, with a view to determine cadmium in seawater. A global procedure including interferent elimination, cadmium preconcentration (30 fold), and fluorescence detection at pH 13 has been evaluated on certified reference material SLEW-2.     

Fluorescence of metal complexes of 8-hydroxyquinoline derivatives in aqueous micellar media

The fluorescence characteristics of 8-hydroxyquinoline derivative complexes of A1(III), Ga(III), In(III), Zn(II), and Be(II) in differently charged micellar media are reported. For most of the chelates studied, large increases are observed in micellar media compared with those obtained in hydroorganic solvents. However, some exceptions are observed, of which the low fluorescence of Zn(II) chelates in anionic sodium lauryl sulfate media is the most noticeable.     

硒杂环-金属离子在乙醇溶液中的发光

研究了不同分子结构的硒杂环化合物 金属离子在乙醇溶液中的发光 ,硒杂环均为苤硒脑类化合物(Piazselenoles,简称Pis) :Piazselenole(PS) ;4 ,5 benzopiazselenole(BP) ;5 methyl piazselenole(MP) ;4 ,4 ' dipi azselenole(DP)。结果表明 :Pis的Em随分子共轭体系增大或共轭效应增强而出现有规律地红移 ;Sn(Ⅳ )对Pis的发光有明显的增敏作用 :使DP的Em蓝移 ;对MP荧光减弱 ,对BP和DP均有明显的荧光增强作用 ,对常温下不发光的PS ,在Sn(Ⅳ ) PS乙醇溶液有较强的特征荧光 (Ex =35 5nm ,Em =4 2 6nm) ;此外 ,Cr(Ⅲ ) ,Cd(Ⅱ ) ,Cu(Ⅱ ) ,Sb(Ⅲ )和Sn(Ⅳ )均使BP荧光增强 ,Fe(Ⅲ )和Fe(Ⅱ )浓度较大时使BP荧光减弱 ,Zn(Ⅱ )却几乎没有影响     

Synchrotron study of metal localization in Typha latifolia L. root sections

Understanding mechanisms that control plant root metal assimilation in soil is critical to the sustainable management of metal‐contaminated land. With the assistance of the synchrotron X‐ray fluorescence technique, this study investigated possible mechanisms that control the localization of Fe, Cu, Mn, Pb and Zn in the root tissues of Typha latifolia L. collected from a contaminated wetland. Metal localizations especially in the case of Fe and Pb in the dermal tissue and the vascular bundles were different. Cluster analysis was performed to divide the dermal tissue into iron‐plaque‐enriched dermal tissue and regular dermal tissue based on the spatial distribution of Pb and Fe. Factor analysis showed that Cu and Zn were closely correlated to each other in the dermal tissues. The association of Cu, Zn and Mn with Fe was strong in both regular dermal tissue and iron‐plaque‐enriched dermal tissue, while significant (p < 0.05) correlation of Fe with Pb was only observed in tissues enriched with iron plaque. In the vascular bundles, Zn, Mn and Cu showed strong association, suggesting that the localization of these three elements was controlled by a similar mechanism. Iron plaque in the peripheral dermal tissues acted as a barrier for Pb and a buffer for Zn, Cu and Mn. The Casparian strip regulated the transportation of metals from dermal tissues to the vascular bundles. The results suggested that the mechanisms controlling metal localization in root tissues varied with both tissue types and metals.