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1.

The present study presents a thorough theoretical analysis of the electronic structure and conformational preference of Schiff’s base ligand N,N-bis(2-hydroxybenzilidene)-2,4,6-trimethyl benzene-1,3-diamine (H2L) and its metal complexes with Zn2+, Cu2+ and Ag+ ions. This study aims to investigate the behavior of H2L and the binuclear Zn2+ complex (1) as fluorescent probes for the detection of metal ions (Zn2+, Cu2+ and Ag+) using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The six conformers of the H2L ligand were optimized using the B3LYP/6–311?+??+?G** level of theory, while the L?2-metal complexes were optimized by applying the B3LYP functional with the LANL2DZ/6–311?+??+?G** mixed basis set. The gas-phase and solvated Enol-cis isomer (E-cis) was found to be the most stable species. The absorption spectra of the E-cis isomer and its metal complexes were simulated using B3LYP, CAM-B3LYP, M06-2X and ωB97X functionals with a 6–311?+??+?G** basis set for C, O, N and H atoms and a LANL2DZ basis set for the metal ions (Zn2+, Cu2+ and Ag+). The computational results of the B3LYP functional were in excellent agreement with the experimental results. Hence, it was adopted for performing the emission calculations. The results indicated that metal complex (1) can act as a fluorescent chemosensor for the detection of Ag+ and Cu2+ ions through the mechanism of intermolecular charge transfer (ICT) and as a molecular switch “On–Off-On” via the replacement of Cu2+ by Ag+ ions, as proved experimentally.

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2.

A simple uracil-appended fluorescent sensor (1) has been developed by one pot reaction and characterized by using common spectroscopic methods such as UV-vis, Fluorescence, HRMS and FT-IR analyses. Upon addition of various metal ions to the CH3CN solution of sensor 1, the fluorescence was quenched in the presence of Cu2+ / Hg2+ ions. The limit of detection for Cu2+ and Hg2+ was calculated to be 3.31 and 0.316 µM, respectively. Further, the sensor was applied for real-life applications in the determination of Vitamin B2 (riboflavin) and its presence in milk products. With the incorporation of different sources of vitamin-B to acetonitrile solution of it, there was discernible fluorescence enhancement only in the presence of vitamin B2. Also, it has been successfully applied for the detection of Vitamin B2 (riboflavin) in milk and curd. Moreover, based on the fluorescent color changes, the sensor was utilized for invisible ink applications.

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3.
Chen  Meihui  Cao  Fengying  Huang  Shizhou  Li  Yangping  Zhong  Min  Zhu  Mingguang 《Journal of fluorescence》2022,32(4):1457-1469

Here, three Schiff bases 3a-c, differing by the substitutions (–H, –Cl, and –N(CH3)2) on the phenyl ring, have been designed and synthesized via the reaction of ortho-aminophenol with benzaldehyde, 2,4-dichlorobenzaldehyde and para-dimethylamine benzaldehyde in 1:1 molar ratio with favourable yields of 89–92%, respectively. Their structural characterizations were studied by FT-IR, NMR, MALDI-MS and elemental analysis. The fluorescence behaviours of compounds 3a and 3b exhibited a severe aggregation caused quenching (ACQ) effect in EtOH/water system. On the contrary, compound 3c had an obvious J-aggregation induced emission (AIE) feature in EtOH/water mixture (v/v?=?1:1), and exhibited excellent sensitivity and anti-interference towards Cu2+ with the limit of detection (LOD) of 1.35?×?10–8 M. Job’s plot analysis and MS spectroscopic study revealed the 2:1 complexation of probe 3c and Cu2+. In addition, probe 3c was successfully applied to the determination of Cu2+ in real aqueous samples.

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4.
A new pyrene derivative (chemosensor 1) containing a picolinohydrazide moiety exhibits high selectivity for Cu2+ ion detection in mixed aqueous media (CH3OH:H2O = 7:3). Significant fluorescence enhancement was observed with chemosensor 1 in the presence of Cu2+. However, the metal ions Ag+, Ca2+, Cd2+, Co2+, Cu2+, Fe2+, Fe3+, Hg2+, K+, Mg2+, Mn2+, Ni2+, Pb2+, and Zn2+ produced only minor changes in fluorescence for the system. The apparent association constant (K a) of Cu2+ binding in chemosensor 1 was found to be 2.75*103 M−1. The maximum fluorescence enhancement caused by Cu2+ binding in chemosensor 1 was observed over the pH range 5–8. Moreover, by means of fluorescence microscopy experiments, it is demonstrated that 1 can be used as a fluorescent probe for detecting Cu2+ in living cells.  相似文献   

5.
Liu SR  Wu SP 《Journal of fluorescence》2011,21(4):1599-1605
A new 7-nitrobenz-2-oxa-1,3-diazole (NBD) derived fluorescent probe (1) exhibiting high selectivity for Cu2+ detection, produced significant fluorescence quenching in the presence of Cu2+ ion, while the metal ions Ca2+, Cd2+, Co2+, Fe2+, Hg2+, Mg2+, Mn2+, Ni2+ and Zn2+ produced only minor changes in fluorescence. The apparent association constant (K a) for Cu2+ binding in chemosensor 1 was found to be 1.22 × 103 M−1. The maximum fluorescence quenching activity caused by Cu2+ binding to 1 was observed over the pH range 6–10.  相似文献   

6.

A simple fluorescent chemosensor 5-(4-methylphenyl)-3-(5-methylfuran-2-yl)-1-phenyl-4, 5-dihydro-1H-pyrazole (PY) has been synthesized for the detection of Cd2+ ion.The fluorescent probe PY shows high selectivity for Cd2+in the presence of othermetal ions (Co2+, Cu2+, Hg2+, Mn2+, Zn2+, Fe3+, Pb2+, Ni2+, and Al3+). The fluorescence intensity of the PY has been strongly quenched with increasing concentration of Cd2+ (0–0.9 μM)via photoinduced electron transfer mechanism. The binding constant of Cd2+ to PY for the 1:1 complex isfound to be 5.3?×?105 M?1with a detection limit of 0.09 μM. The chemosensor was successfully applied for determination of Cd2+ in different water samples (tap, river, and bottled water) showing good recovery values in the range of 94.8–101.7% with RSD less than 3%. Density functional theory (DFT) calculations were also performed to investigate electronic and spectral characteristics which are quite agreeable with the experimental value. The results show that the synthesized fluorescent chemosensor shows good selectivity towards Cd2+ and can be readily applied for the detection of Cd2+ in real samples including water samples.

Graphical Abstract
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7.

The development of a highly sensitive, selective, and efficient sensor for the determination and detection of Cr(III) ions remains a great challenge. Recently, some fluorescent chemosensors have been developed for the recognition of Cr(III) ions. But, the main drawbacks of the reported fluorescent chemosensors are the lack of selectivity and interference of anions and other trivalent cations. Herein, we designed and synthesized a novel thiazole-based fluorescent and colorimetric Schiff base chemosensor SB2 for the detection of Cr(III) ion by chemodosimetric approach. Using different analytical techniques including UV–vis, 13C-NMR, 1H-NMR, and FT-IR analysis the chemosensor SB2 was structurally characterized. The fully characterized chemosensor SB2 was used for the spectrofluorimetric and colorimetric detection of Cr(III) ions. Interestingly, chemosensor SB2 upon interaction with various metal cations including Ni2+, Na+, Cd2+, Ag+, Mn2+, K+, Zn2+, Cu2+, Hg2+, Co2+, Pb2+, Mg2+, Sn2+, Al3+ and Cr3+ displays highly selective and sensitive fluorescent (turn-on) and colorimetric (yellow to colorless) response toward Cr(III) ions. The fluorescence and UV–vis techniques confirmed the selective hydrolysis of azomethine group (-C?=?N-) of Schiff base chemosensor SB2 by Cr(III) ions. As a result, the fluorescence enhancement was observed that is corresponding to 2-hydroxy-1-nepthaldehyde (fluorophore). The chemosensor SB2 exhibits high interference performance towards Cr(III) ions over other metal cations in a wide pH range. Mover, the quite low detection limit was calculated to be 0.027 µg ml-1 (0.5 µM) (3σ/slop), lower than the maximum tolerable limits of Cr(III ions (10 µM) in drinking water permitted by the United States Environmental Protection Agency (EPA). These results show that chemosensor SB2 has great potential to detect selectively Cr(III) ions in the agricultural, environmental and biological analysis system.

Graphical Abstract
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8.

We have prepared Schiff base functionalized 1,2,4-triazole and pyrene derivative for selective, sensitive, and naked eye colorimetric detection of Cu2+ in the mixed organic- aqueous media. Amongst the 18 different metal ions studied for absorption and fluorescence titration, only Cu2+ ion encourages the modification in spectral properties of Schiff base functionalized 1,2,4-Triazole and Pyrene Probe. The stoichiometric ratio of the TP-Cu2+ complex was determined to be 2:1 according to Job’s plot. The lower detection limit estimated for Cu2+ is 0.234 nM which shows excellent sensitivity and selectivity of the present analytical method towards detection of Cu2+ ion in the mixed organic-aqueous media. The present approach has been successfully utilized for the quantitative determination of Cu2+ ion from environmental aqueous solution.

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9.

In this work, we introduce a highly selective and sensitive fluorescent sensor based on pyrene derivative for Fe(III) ion sensing in DMSO/water media. 2-(pyrene-2-yl)-1-(pyrene-2-ylmethyl)-1H-benzo[d]imidazole (PEBD) receptor was synthesized via simple condensation reaction and confirmed by spectroscopic techniques. The receptor exhibits fluorescence quenching in the presence of Fe(III) ions at 440 nm. ESI–MS and Job’s method were used to confirm the 1:1 molar binding ratio of the receptor PEBD to Fe(III) ions. Using the Benesi-Hildebrand equation the binding constant value was determined as 8.485?×?103 M?1. Furthermore, the limit of detection (LOD, 3σ/K) value was found to be 1.81 µM in DMSO/water (95/5, v/v) media. According to the Environmental Protection Agency (EPA) of the United States, it is lower than the acceptable value of Fe3+ in drinking water (0.3 mg/L). The presence of 14 other metal ions such Co2+, Cr3+, Cu2+, Fe2+, Hg2+, Pb2+, K+, Ni2+, Mg2+, Cd2+, Ca2+, Mn2+, Al3+, and Zn2+ did not interfere with the detection of Fe(III) ions. The fluorescence life-time of the receptor PEBD with and without Fe3+ ion was found to be 1.097?×?10?9 s and 0.9202?×?10?9 s respectively. Similarly, the quantum yield of the receptor PEBD with Fe3+ and without Fe3+ ion was calculated, and found as 0.05 and 0.25 respectively. Computational studies of the receptor PEBD were carried out with density functional theory (DFT) using B3LYP/ 6-311G (d, p), LANL2DZ level of theory.

Graphical Abstract
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10.
ABSTRACT

The interaction between metal complex Cu2+–ARS (Alizarin Red S) and l-cysteine was investigated via fluorescence and absorption spectroscopies. In pH 5.2 Britton–Robinson buffer, the addition of L-cysteine into Cu2+–ARS system resulted in a fluorescence enhancement because cysteine reduced Cu2+ to Cu+, which led to Cu2+–ARS decompound, and ARS was released. The result was also supported by absorption spectroscopy change. A good linear response of fluorescence intensity as a function of cysteine concentration was obtained ranging from 1.0 × 10?6 to 4.0 × 10?5 mol L?1 with the detection limit as 1.08 × 10?7 mol L?1. The introduced method has high selectivity over other amino acids such as cystine, tyrosine, tryptophan, methionine, and glycine. It was applied to determine cysteine in protein hydrolysate of fresh pig blood with recovery of 88.4–100.2%.  相似文献   

11.
A new rhodamine derivative (RhB-NSal) bearing an electron-withdrawing group –NO2 at the 5-position of 2-hydroxyphenyl moiety was synthesized and its sensing behaviors for Cu2+ in acetonitrile and aqueous acetate-buffer/acetonitrile (2/3, v/v, pH 4.8) media were investigated. In each medium, significant absorption and fluorescence enhancements accompanied by an instant color change from colorless to pink were observed for RhB-NSal upon addition of Cu2+. RhB-NSal binds with Cu2+ forming a 1:1 stoichiometric complex with an association constant of 6.72 (±0.03) × 104 M?1 and 4.23 (±0.03) × 104 M?1, respectively. RhB-NSal displayed high selectivity for Cu2+ over possibly competitive metal ions except that Fe3+ and Bi3+ ion can respectively bring about a little interference in absorption and fluorescence with its sensing for Cu2+. In dry acetonitrile, pronounced enhancements in the absorbance and emission of RhB-NSal were induced by Cu2+, with a detection limit of 0.49 μM, exhibiting higher sensitivity than that of a known analogue bearing no substituent on its phenol ring, RhB-Sal. In aqueous solution, RhB-NSal displayed likewise a high selectivity but a lower sensitivity for Cu2+ than that in acetonitrile, with a detection limit of 14.98 μM, still more sensitive than RhB-Sal in absorption. By virtue of these properties, RhB-NSal could be used as an “Off-On” fluorescent and colorimetric chemosensor for Cu2+ in acetonitrile medium, and be developed to be a promising candidate of “Off-On” eye-naked chemosensor for Cu2+ in a weakly acidic aqueous medium.  相似文献   

12.

A Fluorescent chemosensor based on pyrene scaffold, 5-diethylamino-2-(pyren-1-yliminomethyl)-phenol (PDS) is synthesized using condensation method. It displays novel aggregation-induced emission (AIE) phenomena in its aggregated/solid state. The AIE characteristic of PDS is studied in CH3CN/H2O mixtures at different volume percentage of water and morphology of the aggregated particles are investigated by DLS and optical fluorescence microscopic study. The probe is aggregated into ordered one-dimensional (1-D) rod like microcrystals and exhibit high efficiency of solid-state emission with green colour. By taking advantage of its interesting AIE feature, the aggregated hydrosol has been utilized as ‘off–on’ type fluorescence switching chemosensor with superb selectivity and sensitivity towards Cu2+ions and the limit of detection (LOD) was calculated as low as 6.3 µM. A high Stern–Volmer quenching constant was estimated to be 2.88?×?105 M?1. The proposed chemosensor with AIE feature reveals a prospective view for the on-site visual recognition of Cu2+ ions in fluorescent paper strips and the synthesized probe is also exploited to find out the concentration of Cu2+ions in real water samples.

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13.
We report the synthesis and characterization two coumarin-based fluorescence probes, N′-{[7-(diethylamino)-2-oxo-2H-chromen-3-yl]carbonyl}pyridine-3-carbohydrazide (3) and N′-benzoyl-7-(diethylamino)-2-oxo-2H-chromene-3-carbohydrazide (4), proposed as a novel fluorescent chemosensor. The two probes designed showed an instant turn-off fluorescence response to Cu2+ over other metal ions in ethanol-water mixture based on intramolecular charge transfer (ICT). It was found that pyridine-analogue coumarin is highly selective and sensitive sensor for Cu2+. The 3 sensor coordinates Cu2+ in 1:1 stoichiometry with a binding constant, Ka = 5.22 M?1 and the detection limit was calculated 1.97 × 10?9 M.  相似文献   

14.
A new fluorescent sensor, 4-allylamine-N-(N-salicylidene)-1,8-naphthalimide (1), anchoring a naphthalimide moiety as fluorophore and a Schiff base group as receptor, was synthesized and characterized. The photophysical properties of sensor 1 were conducted in organic solvents of different polarities. Our study revealed that, depending on the solvent polarity, the fluorescence quantum yields varied from 0.59 to 0.89. The fluorescent activity of the sensor was monitored and the sensor was consequently applied for the detection of Cu2+ with high selectivity over various metal ions by fluorescence quenching in Tris-HCl (pH = 7.2) buffer/DMF (1:1, v/v) solution. From the binding stoichiometry, it was indicated that a 1:1 complex was formed between Cu2+ and the sensor 1. The fluorescence intensity was linear with Cu2+ in the concentration range 0.5–5 μM. Moreso, the detection limit was calculated to be 0.32 μM, which is sufficiently low for good sensitivity of Cu2+ ion. The binding mode was due to the intramolecular charge transfer (ICT) and the coordination of Cu2+ with C = N and hydroxyl oxygen groups of the sensor 1. The sensor proved effective for Cu2+ monitoring in real water samples with recovery rates of 95–112.6 % obtained.  相似文献   

15.
The present article describes the solvatochromic effect including solvent system selection, time study and a detailed complexation study along with exploration of extraction properties of 5,11,17,23-tetrakis[(diethylamino)methyl]-25,26,27,28-tetrahydroxycalix[4]arene (4) that bears nitrogen atom as a donor group available for chelating metal ions. Complexation properties of 4 toward selected transition metal ions have been investigated by UV-visible and fluorescence spectroscopies. The% efficiency of 4 toward selected transition metal ions was found in order Cu2+> Ni2+> Hg2+> Zn2+> Co2+> Cd2+> Pb2+. It has been noticed that 4 is not only proved to be an efficient Cu2+ selective chromoionophore but also possesses an effective extraction property for transferring Cu2+ ions from an aqueous to dichloromethane layer. The FT-IR spectroscopic method has also been applied for further confirmation of the complexation phenomenon of 4 with Cu2+ ion and found adequate.  相似文献   

16.
A novel fluorescent rhodamine based chemosensor (E)-3′,6′-bis(diethylamino)-2-((2-(pyridin-2-ylmethoxy)benzylidene)amino)spiro[isoindoline-1,9′-xanthen]-3-one, RSP, had been successfully developed and well characterized by NMR, FT-IR and Mass spectroscopy. The chemosensor exhibits high selectivity for Hg2+ over other ions (Ag+, Pb2+, Cu2+, Ni2+, Fe3+, Co2+, Zn2+ and Cd2+) with fluorescence enhancement in ethanol solution. More over the detection limit of the sensor is in the 10?6 M level. The binding ratio of RSP-Hg2+ complex was determined to be 1:1 according to the Job plot. Test strips based on RSP were fabricated, which showed the application of the sensor for detection of mercuric ions in water by naked eyes.  相似文献   

17.
Abstract

(50?x/2)Na2O–xCuO–(50?x/2)P2O5 glasses (x=1, 5, 15, or 30 mol%) have been prepared and characterized by electron paramagnetic resonance (EPR) and magnetic susceptibility measurements. The shape of the Cu2+ EPR spectrum depends on the Cu content, and the corresponding computer simulations suggest that the Cu2+ ions occupy two different sites in these glasses: one of them is preponderant at low Cu content and the other is preponderant at high content, in which the Cu2+–Cu2+ interactions are more important. From EPR parameters, it was found that for the site at low content, the covalency of copper ion bonding with the surrounding ligands is appreciable. The magnetic susceptibility data appear to follow the Curie–Weiss law (χ=C/(Tp)) with negative paramagnetic Curie temperature θp indicating antiferromagnetic interactions between Cu2+ ions that are more significant in the samples with high Cu content, in agreement with EPR results.  相似文献   

18.

To utilize the nanomaterials as an effective carrier for the drug delivery applications, it is important to study the interaction between nanomaterials and drug or biomolecules. In this study GSH functionalized Mn2+-doped CdTe/ZnS QDs has been utilized as a model nanomaterial due to its high luminescence property. Folic acid (FA) gradually quenches the FL of GSH functionalized Mn2+???doped CdTe/ZnS QDs. The Stern-Volmer quenching constant (Ksv), binding constant (Ks) and effective quenching constant (Ka) for the FA-QDs system is calculated to be 1.32?×?105 M?1, 1.92?×?105 and 0.27?×?105 M?1, respectively under optimized condition (Temp. 300 K, pH 8.0, incubation time 40 min.). The effects of temperature, pH, and incubation time on FA-QDs system have also been studied. Statistical analysis of the quenched FL intensity versus FA concentration revealed a linear range from 1?×?10?7 to 5.0?×?10?5 for FA detection. The LOD of the current nano-sensor for FA was calculated to be 0.2 μM. The effect of common interfering metal ions and other relevant biomolecules on the detection of FA (12.0 μM) have also been investigated. L-cysteine and glutathione displayed moderate effect on FA detection. Similarly, the common metal ions (Na+, K+, Ca2+ and Mg2+) produced minute interference while Zn2+ Cu2+ and Fe3+ exert moderate interference. Toxic metal ions (Hg2+ and Pb2+) produced severe interferences in FA detection.

Graphical abstract

GSH-Mn2+ CdTe/ZnS QDs based Fluorescence Nanosensor for Folic acid

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19.

Calixarenes, which have a great place in supramolecular chemistry, have become the most prominent macrocyclic compounds in synthetic organic chemistry due to their easy synthesis and functionalization. In this study, p-tert-butyl calix[4]arene dihydrazide derivative was synthesized and then reacted with 3-oxo-3,4-dihydro-2 H-benzo[b][1,4] thiazin-2-ylideneacetyl chloride to prepare new calixarene based chromophore compound 4. The structure of the synthesized compound was elucidated by spectroscopic methods such as 1H NMR 13C NMR and FT-IR spectroscopy. Chromogenic and fluorescence properties of compound 4 were evaluated. It was observed from both studies that compound 4 was Co2+ selective and shows fluorescence Switched-off behavior. Stoichiometry, binding constant and the detection limit were calculated. The stoichiometry between compound 4 and Co2+ was found to be 1:1. The binding constant value (K) was calculated as 666.67 M??1 using Benesi–Hildebrand equation, while the detection limit for Co2+ ion was calculated as 0.0465 µM.

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20.
A fluorescent chemosensing ensemble for the detection of cysteine is designed based on the fluorescence inner filter effect. The method employs the coordination of Cu2+ ion with salicylaldehyde rhodamine B hydrazone (I), a colorless and non-fluorescent rhodamine B spirolactam derivative to form I-Cu(II), a pink color but weakly fluorescent complex. When rhodamine B was introduced to the I-Cu(II) complex solution, the fluorescence signal of rhodamine B is dramatically decreased because of the fluorescence inner filter effect (IFE). Upon adding cysteine to the above solution, it can complex preferentially to Cu2+ compared to I, and the I-Cu(II) complex dissociates, which thus decreases the fluorescence IFE of the solution, and in turn leading to the fluorescence increase of the chemosensing system. Based on the above mechanism, a fluorescent chemosensing ensemble for cysteine is developed. The fluorescence increase is linearly with cysteine concentration up to 10.0 μ mol L−1, with a detection limit of 1.4 × 10−7 mol L−1 (3σ). The optimal conditions of the proposed method were studied and the selectivity of the proposed method was investigated in this paper.  相似文献   

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