A Colorimetric and Fluorescent Indicator for Hg<Superscript>2+</Superscript> Detection Based on Cinnamamide Group-Containing Rhodamine Derivative

A colorimetric and fluorescent indicator based on cinnamamide group-containing rhodamine derivative was synthesized for the detection of Hg²⁺. The rhodamine B and cinnamamide were connected via ethylenediamine as a bridging molecule through a condensation reaction to obtain a colorimetric and fluorescent indicator for the detection of Hg²⁺ in H₂O-EtOH (4:1, v/v). The indicator was excellent in the selectivity of Hg²⁺ and was almost unaffected by other common ions such as Na⁺, K⁺, Mg²⁺, Fe³⁺, Cu²⁺, Zn²⁺, Cr³⁺. The Hg²⁺-containing aqueous solution turned from colorless to red within 7 min after the addition of the indicator, and had an absorption peak at 564 nm in UV-vis, which implies a significant colorimetric phenomenon. Their characteristic peaks varied with the Hg²⁺ content, and they reached a linear relationship at low concentrations. The binding stoichiometry proved to be 1:1. The lowest detection limit was 4.1?×?10^?7 mol/L, ranging from acidic to neutral.     

A Rhodamine Derivative Based Chemosensor with High Selectivity and Quick Respond to Cr<Superscript>3+</Superscript> in Aqueous Solution

In this paper, a new kind of colorimetric chemsensor aiming at detecting Cr³⁺ has been synthesized, and it is based on the “Off-On” effect of a rhodamine derivative. Comparing with other metal irons (Na⁺, K⁺, Ni²⁺, Hg²⁺, Fe³⁺, Mn²⁺, Co²⁺, Cd²⁺, Cu²⁺, Pb²⁺, Zn²⁺, Mg²⁺, Ba²⁺, Ag⁺, Fe²⁺, Ce³⁺), the chemsensor has a quick and accurate response to Cr³⁺ in H₂O-EtOH solution (4/1, v/v). There is an obvious change in color, from colorless to bright pink when Cr³⁺ is detected. According to the fitting curve based on Benesi-Hildebrand equation and working curve of absorption strength in UV-vis spectrum, the binding pattern of Cr³⁺ and the rhodamine derivative follows a 1:1 stoichiometry. The chemsensor shows great potential in monitoring Cr³⁺ in the aqueous medium with high efficiency, which is supposed to complete the recognition in the minimum as 5.2?×?10^?7 mol/L within 5 min.     

A Novel Naphthalene-Immobilized Nanoporous SBA-15 as a Highly Selective Optical Sensor for Detection of Fe<Superscript>3+</Superscript> in Water

A novel organic-inorganic hybrid optical sensor (SBA-NCO) was designed and synthesized through immobilization of isocyanatopropyl-triethoxysilane and 1-amino-naphthalene onto the surface of SBA-15 by post-grafting method. The characterization of materials using XRD, TEM, N₂ adsorption-desorption, and FT-IR techniques confirmed the successful attachment of organic moieties and preserving original structure of SBA-15 after modification step. Fluorescence experiments demonstrated that SBA-NCO was a highly selective optical sensor for the detection of Fe³⁺ directly in water over a wide range of metal cations including Na⁺, Mg²⁺, Al³⁺, K⁺, Ca²⁺, Cr³⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, and Pb²⁺ in a wide pH values.     

A Novel Hg<Superscript>2+</Superscript> Selective Ratiometric Fluorescent Chemodosimeter Based on an Intramolecular FRET Mechanism

A irreversible Hg²⁺ selective ratiometric fluorescence probe FR, a fluorescein fluorophore linked to a rhodamine B hydrazide by a thiourea spacer, was designed and synthesized. The developed probe FR exhibited great ratiometric fluorescence enhancement and remarkable yellow-magenta color change toward Hg²⁺ with excellent selectivity in aqueous acetone solution, and the ratiometric fluorescence response to Hg²⁺ was not interfered by other metal cations including Fe³⁺, Co²⁺, Ni²⁺, Cr³⁺, Zn²⁺, Pb²⁺, Cd²⁺, Ca²⁺, Mg²⁺, Ba²⁺ and Mn²⁺. The linear range and the detection limit of this supposed ratiometric fluorescence method for Hg²⁺ were 0.0–10.0 × 10⁻⁶ and 5 × 10⁻⁸ M, respectively.     

A Dansyl-Rhodamine Ratiometric Fluorescent Probe for Hg<Superscript>2+</Superscript> Based on FRET Mechanism

Based on resonance energy transfer (FRET) from dansyl to rhodamine 101, a new fluorescent probe (compound 1) containing rhodamine 101 and a dansyl unit was synthesized for detecting Hg²⁺ through ratiometric sensing in DMSO aqueous solutions. This probe shows a fast, reversible and selective response toward Hg²⁺ in a wide pH range. Hg²⁺ induced ring-opening reactions of the spirolactam rhodamine moiety of 1, leading to the formation of fluorescent derivatives that can serve as the FRET acceptors. Very large stokes shift (220 nm) was observed in this case. About 97-fold increase in fluorescence intensity ratio was observed upon its binding with Hg²⁺.     

New dithiacrown–ether butadienyl dyes: synthesis,structure, and complex formation with heavy metal cations

Benzothiazole type butadienyl dyes containing a dithia‐15‐crown‐5 ( 2a ) or dithia‐18‐crown‐6 ether ( 2b ) moieties were synthesized. The structures of dyes 2a , b and their complexes with Ag⁺ and Pb²⁺ were studied by an X‐ray crystallography. It was found that the conformations of dithiacrown–ether moieties of dyes 2a , b are unfavorable for complex formation and change significantly upon binding of Ag⁺ or Pb²⁺. The complexation of 2a , b with Ag⁺, Cd²⁺, Pb²⁺, and Hg²⁺ in water–acetonitrile mixtures with different contents of water (P_W = 0–75%, v/v) was studied by ¹H NMR, UV–Vis spectroscopy, and polarography. In anhydrous acetonitrile, the stability constants of 1:1 complexes change in the sequence Cd²⁺ < Pb²⁺ ≤ Ag⁺ << Hg²⁺ in the case of 2a and in the sequence Cd²⁺ < Ag⁺ < Pb²⁺ << Hg²⁺ in the case of 2b . As P_W increases, the thermodynamic stability of Ag⁺ complexes increases. The opposite effect is observed for the complexes with Cd²⁺, Pb²⁺, and Hg²⁺. When P_W ～ 50%, the stability constants of complexes with Cd²⁺ and Pb²⁺ become too small to be measured. The selectivity of ligands 2a , b toward Hg²⁺ versus Ag⁺ is very high at any P_W values (selectivity coefficients > 10⁴). The complexation of 2a , b with Hg²⁺ at P_W ≤ 50% is accompanied by a substantial hypsochromic effect. This allows dithiacrown‐containing butadienyl dyes to be used as selective optical molecular sensors for heavy metal ions, in particular, in aqueous solutions. Copyright © 2009 John Wiley & Sons, Ltd.     

Improvement of thermal and spectroscopic behavior of Er<Superscript>3+</Superscript>/Ce<Superscript>3+</Superscript> co-doped tellurite glass for lasing materials

Tellurite glasses (TeO₂–ZnO–Nb₂O₅) mono-doped Er³⁺ and co-doped Er³⁺/Ce³⁺ have been prepared using the melt-quenching technique. To evaluate the effect of Ce³⁺ on the structural, thermal stability of glass hosts and fluorescence properties of Er³⁺, X-ray diffraction patterns, Ftir spectra, differential scanning calorimeter curves, absorption spectra, fluorescence emission spectra, fluorescence lifetimes, up-conversion emission spectra of glass samples were measured and investigated. Using Judd–Ofelt theory, we calculated intensity parameters (Ω₂, Ω₄ and Ω₆), spontaneous emission probabilities, the radiative lifetime, luminescence branching factors and the quantum yield of luminescence for ⁴I_13/2 → ⁴I_15/2 transition. The co-doping with Ce³⁺ was effective on the suppression of up-conversion emission of Er³⁺ owing to the phonon-assisted energy transfer: Er³⁺:⁴I_11/2 + Ce³⁺:²F_5/2 → Er³⁺:⁴I_13/2 + Ce³⁺:²F_7/2 which contributed the effective enhancement of 1.53 µm fluorescence emission. The change in optical properties with the addition of Ce³⁺ ions have been discussed and compared with other glasses. Using the Mc Cumber method for the ⁴I_13/2 → ⁴I_15/2 transition, absorption cross-section, calculated emission cross-section, and gain cross-section values support that TZNEr1Ce1 glass is a potential material for developing broad-band and high-gain erbium-doped fiber amplifiers applied for 1.53 µm.     

A New On-fluorescent Probe for Manganese (II) Ion

A new fluorescent probe for Mn²⁺ ion, (6E)-N-((E)-1,2-diphenyl-2-(pyridin-2-ylimino)ethylidene)pyridin-2-amine (L), has been synthesized from benzil and 2-amino pyridine and characterized. In 1:1 (v/v) CH₃CN:H₂O (pH 4.0, universal buffer) L exhibits fluorescent intensity with emission peak at λ_max 360 nm on excitation with photons of 310 nm. Fluorescent intensity of L increases distinguishingly on interaction with Mn²⁺ ion compared to metal ions—Na⁺, K⁺, Ca²⁺, Mg²⁺, Ba²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Pb²⁺ and Ag⁺ individually or all together. The enhancement in fluorescent intensity is due to snapping of photoinduced electron transfer (PET) prevailed in free L. Fluorescence and UV/visible spectral data analysis shows that binding stoichiometry between Mn²⁺ and L is 1:1 with log β?≈?3.0. Both L and its Mn²⁺ complex were optimised using density functional theory (DFT) and vibrational frequency calculations confirm that both are at local minima on the potential energy surfaces.     

Bay Functionalized Perylenediimide with Pyridine Positional Isomers: NIR Absorption and Selective Colorimetric/Fluorescent Sensing of Fe<Superscript>3+</Superscript> and Al<Superscript>3+</Superscript> Ions

Bay functionalized perylene diimide substituted with pyridine isomers, (2-pyridine (2HMP-PDI), 3-pyridine (3-HMP-PDI) and 4-pyridine (4-HMP-PDI)) have been synthesized and explored for selective coloro/fluorimetric sensing of heavy transition metal ions. HMP-PDIs showed strong NIR absorption (760–765 nm) in DMF. The absorption and fluorescence of HMP-PDIs have been tuned by make use of pyridine isomers. Reddish-orange color was observed for 2-HMP-PDI (λ_max = 437, 551, 765 nm) whereas 4-HMP-PDI exhibited light green (λ_max = 432, 522, 765 nm). 3-HMP-PDI showed orange-yellow (λ_max = 431, 524, 762 nm). The fluorescence spectra of 2-, 3- and 4-HMP-PDI showed λ_max at 585, 538, 546 nm, respectively. Interestingly, HMP-PDI dyes showed selective color change (intense pink color) and fluorescence quenching for Fe³⁺ and Al³⁺ metal ions in DMF. Absorbance spectra revealed complete disappearance of NIR absorption and intensification/appearance of new peak at lower wavelength. The concentration dependent studies suggest that 4-HMP-PDI can detect up to 36.52 ppb of Fe³⁺ and 43.12 ppb of Al³⁺ colorimetrically. The interference studies in presence of other metal ions confirmed the good selectivity for Fe³⁺ and Al³⁺. The mechanistic studies indicate that Lewis acidic character of Fe³⁺ and Al³⁺ ions were responsible for selective color change and fluorescence quenching.     

A New Fluorescent Chemosensor Detecting Co<Superscript>2+</Superscript> and K<Superscript>+</Superscript> in DMF Buffered Solution

A new fluorescent chemosensor 2-(2-thiophene)imidazo [4,5,f]-1,10-phenanthroline (L) was prepared and characterized. By adding univalent or divalent metal ions such as Na⁺, K⁺, Mg²⁺, Ba²⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Ag⁺, Zn²⁺, Cd²⁺ and Hg²⁺ ions into the solution of L in DMF under buffered conditions with the working pH ranging from 7.0 to 8.0, we found that L could be used to detect K⁺ ratiometricly and it could also be applied to sense Co²⁺ with the phenomenon of fluorescence quenching of L. While the response behavior of L was not discernibly affected by other examined metal ions.     

Adsorption kinetics,isotherms, and thermodynamic studies for the adsorption of Pb<Superscript>2+</Superscript> and Hg<Superscript>2+</Superscript> metal ions from aqueous medium using Ti(IV) iodovanadate cation exchanger

In the current study, Ti(IV) iodovanadate cation exchanger (TIV) was synthesized and applied for the removal of Pb²⁺ and Hg²⁺ metal ions from the aqueous medium. The adsorption studies were performed by the batch techniques and adsorption parameters viz. contact time, pH, initial metal ion concentration, and temperature were also investigated. The optimum adsorption of Pb²⁺ (95 %) and Hg²⁺ (65 %) were observed at pH 6. The pseudo-second order equation represented the adsorption kinetics with high correlation coefficient. Langmuir model showed the best fitting to the isotherm equilibrium data, with a maximum adsorption capacity of 18.8 mg g^?1 for Pb²⁺ and 17.2 mg g^?1 for Hg²⁺. Furthermore, thermodynamic factors, i.e., ΔG, ΔH, and ΔS, indicated that adsorption of Pb²⁺ and Hg²⁺ onto TIV were spontaneous, endothermic, and feasible in the temperature range of 293–323 K.     

8-Hydroxyquinoline Functionalized Graphene Oxide: an Efficient Fluorescent Nanosensor for Zn<Superscript>2+</Superscript> in Aqueous Media

A nanosensor, based on 8-hydroxyquinoline functionalized graphene oxide, was developed for the fluorescence detection of Zn²⁺. It showed high selectivity and sensitivity for Zn²⁺ion in aqueous solution over other metal ions such as Li⁺, Na⁺, Ca²⁺, Mg²⁺, Al³⁺, Cd²⁺, Co²⁺, Cu²⁺, Hg²⁺, Ni²⁺, Pb²⁺, Fe²⁺, Fe³⁺and Cr³⁺. Due to the linearity of the emission intensity toward Zn²⁺ concentration, fluorescent technique could be used for the detection of Zn²⁺ ion even at very low concentrations.     

Novel Pyrazoline-Based Selective Fluorescent Sensor for Hg2+

This paper presents the preparation of a pyrazoline compound and the properties of its UV–Vis absorption and fluorescence emission. Moreover, this compound can be used to determine Hg²⁺ ion with selectivity and sensitivity in the EtOH:H₂O?=?9:1 (v/v) solution. This sensor forms a 1:1 complex with Hg²⁺ and shows a fluorescent enhancement with good tolerance of other metal ions. This sensor is very sensitive with fluorometric detection limit of 3.85?×?10^?10 M. In addition, the fluorescent probe has practical application in cells imaging.     

Study of Specific Interaction between bis(<Emphasis Type="Italic">p</Emphasis>-phenylene)-34-crown-10-based Substituted Macrocycle and Ni<Superscript>2+</Superscript>

A novel macrocyclic host has been synthesized for the determination of Ni (II) ions in aqueous solution (H₂O-CH₃CN, v/v?=?1:1). Its molecular structure has been verified by ¹H-NMR, ¹³C NMR and mass spectrometry (ESI).This probe shows selectivity towards the presence of Ni (II) ion among various alkali, alkaline earth, and transition metal ions. The formation of a new fluorescence band at 311 nm has been detected due to possible complex formation with increasing Ni²⁺ concentration in the range of 10^?5–10^?4 M. The detection limit is calculated to be 5.22 μM. To our knowledge, it will be the first case for bis(p-phenylene)-34-crown-10 based molecules to recognize Ni²⁺ ions.     

A Pyrene-based Highly Selective Turn-on Fluorescent Chemosensor for Iron(III) Ions and its Application in Living Cell Imaging

A new pyrene-based chemosensor (1) exhibits excellent selectivity for Fe³⁺ ions over a wide range of tested metal ions Ag⁺, Ca²⁺, Cd²⁺, Co²⁺, Cu²⁺, Fe²⁺, Hg²⁺, K⁺, Mg²⁺, Mn²⁺, Ni²⁺, Pb²⁺, and Zn²⁺. The binding of Fe³⁺ to chemosensor 1 produces an emission band at 507 nm due to the formation of a Py-Py* excimer that is induced by Fe³⁺-binding. The binding ratio of 1-Fe³⁺ was determined to be 1:1 from a Job plot. The association constant of 1-Fe³⁺ complexes was found to be 1.27?×?10⁴ M^?1 from a Benesi-Hildebrand plot. In addition, fluorescence microscopy experiments show that 1 can be used as a fluorescent probe for detecting Fe³⁺ in living cells.     

Absolute cross-sections and kinetic-energy-release distributions for electron-impact ionization and dissociation of CD<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack>

Absolute cross-sections have been measured for electron-impact dissociativeexcitation and ionization of CD ₂ ⁺ leading toformation of CD ₂ ²⁺ , CD⁺, C⁺,D ₂ ⁺ and D⁺. The animated crossed-beams methodis applied in the energy range from the reaction threshold up to 2.5 keV.The maximum total cross-sections are found to be (1.2±0.1)×10^-17 cm², (6.1±0.7)×10^-17 cm², (6.4±0.7)×10^-17 cm², (26.3±3.8)×10^-19 cm² and (14.9±1.4)×10^-17 cm² forCD ₂ ²⁺ , CD⁺, C⁺,D ₂ ⁺ and D⁺ respectively. Individualcontributions for dissociative excitation and dissociative ionization aredetermined for each singly-charged product, which are of significantinterest in fusion plasma edge modelling and diagnostics. Conforming to thescheme recently applied in the CD ₄ ⁺ and in theCD ₃ ⁺ articles, the cross-sections are presented inclosed analytic forms convenient for implementation in plasma simulationcodes. Kinetic-energy-release distributions are determined for each ionicfragment at selected electron energies.     

Novel Turn-on Fluorescence Probes for Al<Superscript>3+</Superscript> Based on Conjugated Pyrazole Schiff Base

One novel turn-on fluorescence probe founded on conjugated pyrazole Schiff base for detecting Al³⁺ was invented. The UV–vis and fluorescence spectrometer were employed to explore optical properties of this probe. The results got from those experiments indicated that this fluorescence probe manifested excellent sensitivity and selectivity for Al³⁺ compared with other cations examined(Ag⁺, Co²⁺, Mg²⁺, Cu²⁺, Ni²⁺, Pb²⁺,and Zn²⁺). In addition, this probe displayed a more rapid response and remained stable between pH 6 and 9 by investigating the fluorescence intensity under different response time and various pH values. Remarkably, the detection limit for Al³⁺ could lower to 1.0×10^?9M. Therefore, the probe could be potentially applied to the environment for the detection of Al³⁺, and the availability in biological range of pH that could be further studied to make this probe apply to biological systems in the future.     

Synthesis and Evaluation of a Schiff-Based Fluorescent Chemosensors for the Selective and Sensitive Detection of Cu<Superscript>2+</Superscript> in Aqueous Media with Fluorescence Off-On Responses

Copper being an essential nutrient; also pose a risk for human health in excessive amount. A simple and convenient method for the detection of trace amount of copper was employed using an optical probe R1 based on Schiff base. The probe was synthesized by Schiff base condensation of benzyl amine and 2-hydroxy-1-napthaldehyde and characterized by single X-ray diffraction, ¹H NMR and FTIR. By screening its fluorescence response in a mixture of DMSO and H₂O (20:80, v/v) R1 displayed a pronounced enhancement in fluorescence only upon treatment with copper. Other examined metal ions such as alkali, alkaline and transition had no influence. Within a wide pH range 5–12 R1 could selectively detect copper by interrupting ICT mechanism that results in CHEF. From Job’s plot analysis a 2:1 binding stoichiometry was revealed. The fluorescence response was linear in the range 1–10?×?10^?9 M with detection limit 30?×?10^?9 M. Association constant was determined as 1?×?10¹¹ M^?2 by Benesi-Hilderbrand plot. As a fast responsive probe it possesses good reproducibility and was employed for detection of copper in different water samples.     

Dual-Functional Fluorescein-Based Chemosensor for Chromogenic Detection of Fe<Superscript>3+</Superscript> and Fluorgenic Detection of HOCl

A novel fluorescein-based dual probe was designed and synthesized. The probe exhibited highly sensitive and selective colormetric response to Fe³⁺ and turn-on fluorescence response towards OCl^? with very low detection limits of 100 and 50 nM, respectively. It was successfully applied for quantitative detection of Fe³⁺ and OCl^? in real water samples. Moreover, probe 1 was expected to be a potentially powerful tool for studying and providing further insights into OCl^? and Fe³⁺ chemistry in the near future.     

A New Sensitive and Selective Off-On Fluorescent Zn<Superscript>2+</Superscript> Chemosensor Based on 3,3′,5,5′-Tetraphenylsubstituted Dipyrromethene

3,3′,5,5′-Tetraphenyl-2,2′-dipyrromethene was described as a highly sensitive and selective Off-on fluorescent colorimetric chemosensor for Zn²⁺ based on the chelation-enhanced fluorescence (CHEF) effect. The reaction of dipyrromethene ligand with Zn²⁺ induces the formation of the [ZnL₂] complex, which exhibits the increasing fluorescence in 120 fold compared with ligand in the propanol-1/cyclohexane (1:30) binary mixture. The Zn²⁺ detection limit was 1.4 × 10^?7 М. The UV-Vis and fluorescence spectroscopic studies demonstrated that the dipyrromethene sensor was highly selective toward Zn²⁺ cations over other metal ions (Na⁺, Mg²⁺, Co²⁺, Ni²⁺, Fe³⁺, Cu²⁺, Mn²⁺, Cd²⁺ and Pb²⁺), excluding Hg²⁺.