Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
15 March 2019
, Pages 299-305
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https://doi.org/10.1016/j.saa.2018.12.022Get rights and content
A novel fluorescence probe L2 based on coumarin has been designed and synthesized. The probe L2 can be used for relay recognition of metal ions Al3+ and anion F− in the aqueous HEPES buffer (0.05 M, pH = 7.4), and build a OFF-ON-OFF detection system. The probe showed high selectivity and sensitivity to target ions in the process of relay recognition, and the corresponding detection limit could be as low as 0.014 μM (Al3+) and 0.03 μM (F−). Besides, the geometry optimizations of probe L2 and [L2 + Al3+] complex were carried out using the Gaussian 16 program based on DFT, and the identification mechanism of the probe was also discussed by the mass spectrometry and theoretical calculations. Moreover, the probe has also been successfully applied to detection of target ions in living cells.
It is well known that the aluminum is the most abundant metal element in nature and its reserves account for about 8% of the earth's crust [1,2]. At the same time, the aluminum has the advantages of small density, good thermal conductivity and good ductility. So it has also been widely used in various fields, such as industrial production, aerospace materials, medical equipment, food additives, drinking-water purification, and so on [, , , ]. But the Al3+ is not a necessary trace element, and the intake of Al3+ ions will remain in various organs of the body. First, Al3+ ions are very easily deposited in brain tissue, which may cause brain damage and serious memory loss. The existence of excessive Al3+ ions can also lead to a series of biochemical reactions, which will affect the normal metabolism of human cells. Meanwhile, Al3+ ions can directly damage the activity of osteoblasts, thus inhibiting bone matrix synthesis [, , ]. Therefore, the harm of Al3+ ions to human body is not to be underestimated.
Similarly, the fluorine also plays a very important role in many chemical and biomedical industry [10,11]. The fluoride is the common ingredient of the anesthetic, hypnotic, psychotropic drugs and military nerve gases. Meanwhile, fluorinated compounds also can be used to prevent dental caries, and they are usually added to some oral hygiene products. Fluorine is widely distributed in natural water, and fluorine is also found in all tissues of human body, mainly accumulated in teeth and bone tendons. A proper amount of F− ions is essential for the human body, but excessive intake of fluoride is also harmful to people's health. The fluorosis is a typical symptom caused by chronic fluorosis [12,13]. High concentration of fluoride can also cause serious pulmonary edema, pulmonary hemorrhage, arrhythmia, nausea and strong irritation in the eyes and upper respiratory tract. Even more, it will also endanger human life [14,15]. From the point of view of environment and human health, it is very necessary to develop effective detection methods for fluoride.
In recent years, fluorescence sensing detection technology has attracted wide attention. Compared with the traditional detection technology, the fluorescence detection technology can show better detection results and have better application value and potential. Therefore, the construction of fluorescent probes with specific recognition performance has become one of the most popular research projects at home and abroad [16,17]. For the fluorescent probes that had been reported, most of them were some metal ions fluorescent probes and anion fluorescent probes. And many of them have some probes can be used for specific detection and identification of Al3+ or F− [, , , , , , , , , , , ]. However, many probes are usually limited by lengthy synthetic routes or high detection limits, which cannot be applied to practical detection applications. Most importantly, most of those probes are single response, although the selectivity of probes to the target ions is good, but the utilization ratio is not high compared to the relay response or the multi response probe. Therefore, the design and synthesis of fluorescent probes with high selectivity, high sensitivity and low cost, which can break through a single response type, is still a challenging subject.
In this paper, coumarin was used as the fluorescent group, a novel fluorescent probe (L2) with simple structure and good fluorescence response performance was designed and synthesized. The probe L2 can be used for relay recognition of metal ions Al3+ and anion F−, and build an OFF-ON-OFF detection system. The optical properties and detection properties of probe L2 were systematically studied through a series of UV–Vis spectra and fluorescence emission spectra. At the same time, the influences of other common anion and cation on the detection effect of probe L2 were also discussed. Finally, probe L2 was used for fluorescence imaging analysis of target ions in living cells.
Materials and Instruments
Unless otherwise noted, all the solvents and inorganic salts were purchased from Sinopharm Chemical Reagent Ltd., The 4-hydroxy-4-biphenylcarbonitrile, hexamethylenetetramine, Rhodamine B and hydrazine hydrate (85%) were purchased from Aladdin Chemical Reagent Ltd., and used without further purification. The 1H NMR spectra were recorded on an AVANCEII 400 MHz spectrometer (Bruker BioSpin) and 13C NMR spectra were recorded on 101 MHz spectrometers. Mass Spectrometry (MS) were measured by a
The Selectivity of Probe L2 to Al3+
The fluorescence respond of the probe L2 were investigated by measuring the fluorescence emission spectra in the presence of different metal ions including Pb2+, Mg2+, Cd2+, Co2+, Cu2+, Ni2+, Fe2+, Al3+, Mn2+, Hg2+, K+, Li+, Na+, Fe3+, Cr3+ and Zn2+. As shown in Fig. 1, the single probe L2 presented an extremely weak fluorescence emission at 461 nm (Φ = 0.02). When 10 equiv. Al3+ was added, the emission peak of the probe system at 461 nm increased significantly (Φ = 0.41). But under the same
A novel schiff base fluorescent probe (L2) based on coumarin fluorescence was designed and synthesized. The probe L2 can be successfully applied to relay recognition detection of Al3+ and F−. First, the probe L2 has high selectivity and anti-interference ability for Al3+. The main phenomenon is that the system changed from no fluorescence to strong blue fluorescence emission. And the titration experiments also showed that the probe L2 has excellent sensitivity to Al3+ and the minimum detection
This work was supported by the National Natural Science Foundation of China (No. 31470434, 21576124, 21507047 and 21676124), the China Postdoctoral Science Foundation funded project (No. 2017M610308), and the project supported by the Science Foundation of Jiangsu Entry-exit Inspection Quarantine Bureau (No.2017KJ47). Meanwhile, thanks to Spartan HPC computing service of University of Melbourne.
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A pyrazole derived “off-on-off” fluorescence sensor for sequential detection of Al<sup>3+</sup> and Fe<sup>3+</sup>
2023, Journal of Photochemistry and Photobiology A: Chemistry
Citation Excerpt :
As the most abundant metal element (8.3% weight) in the earth's crust , aluminum is widely used in a variety of applications, such as construction, automobile manufacturing, household appliances and kitchen utensils [2,3].
A new pyrazole derived Schiff base (E)-N'-(2,3-dihydroxybenzylidene)-1-phenyl-5-(thiophen-2-yl)-1H-pyrazole-3-carbohydrazide (W) was devised and synthesized, which exerted a splendid sensitivity and selectivity fluorescence “turn-on” for Al3+, accompanied by a solution color changed to bright green. The complex W[Al3+] could be applied as a sequential sensor to Fe3+. The lowest detection limits of W for detecting Al3+ and Fe3+ ions were 9.42×10-9 M and 2.1×10-8 M singly. The stoichiometric ratio of W to both Al3+ and Fe3+ was determined to be 1:2 by Job’s Plot, 1H NMR and mass spectrometry titration as well as theoretical arithmetic. Additionally, W was triumphantly applied to detecting Al3+ and Fe3+ in running water.
A novel phenolphthalein-based fluorescent chemosensor for pyrophosphate detection via an Al<sup>3+</sup> displacement approach in real samples and living cells
2022, Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy
Citation Excerpt :
In presence of Al3+ ions, “turn-on” fluorescence of PASB displays pH-dependent emission in the pH range of 3.0–5.5, suggesting that the response was stable at weak acid condition. We infer that the quenched fluorescence emission may be attributed to hydrolysis of Al3+ due to the higher pH . The concentration dependent emission behaviour of PASB towards Al3+ was recorded by a fluorescence titration experiment.
Herein, we report a new phenolphthalein appended Schiff base (PASB) as reversible fluorescent sensor for the detection of pyrophosphate (PPi) ions through the metal displacement mechanism. PASB showed sensing exclusively toward Al3+ ions in DMF/H2O (v/v=1/4, pH 5.5) solution, which resulted in a significant fluorescence enhancement at 540nm. The 1: 2 binding stoichiometry for the complex formation between PASB and Al3+ was confirmed by Job’s plot and mass spectroscopic studies. Moreover, a solution of the in situ formed PASB–Al3+ complex displayed a high selectivity to PPi. The addition of PPi to PASB-Al3+ ensemble significantly quenched its fluorescence. Thus, a dual response was established based on “Off–On–Off” strategy for detection of both Al3+ and PPi. The detection limit is 5.86nM and 26nM for Al3+ and PPi, respectively. On this basis, we use PASB to detect Al3+ in food samples. Furthermore, PASB was successfully applicable to detect Al3+ and PPi for intracellular imaging in Human liver cancer cells.
A novel and reversible multifunction probe for Al<sup>3+</sup>and F<sup>−</sup> by fluorogenic and colorimetric method
2022, Journal of Photochemistry and Photobiology A: Chemistry
Citation Excerpt :
As a result, this 1-Al3+ complex can serve as a detecting assemble for F− recognition. Combining with the fluorescence performance of 1 for sensing Al3+, a selective OFF-ON-OFF fluorescent signalling property of 1 is established with the successive addition of Al3+ and F− to it [36-39]. To check the specificity of 1-Al3+ complex towards the detection of F−, changes in emission intensity of 1-Al3+ were then studied by introducing other several anions including S2−, SCN−, I−, ClO4−, SO42−, NO3− and Br− followed by the addition of F−.
A new highly selective and sensitive probe 2-hydroxy-1-formylnaphthalene trihydroxybenzoyl hydrazone (1) was designed and synthesized for sequential detection of Al3+ and F− ions with “OFF-ON-OFF” fluorescent signals. This probe 1 displays high selectivity towards Al3+ among 17 metal cations, the resultant complex [1-Al3+] formed by the coordination of 1 with Al3+ can be recognized as a sequential probe for sensing F−. Moreover, the formation of this 1-Al3+ complex with a 1:1 stoichiometry leads to a significant fluorescence enhancement at 505nm with high selectivity, for that 1 shows “turn-on” fluorescence response to Al3+ with negligible interferences from other various metal cations, and the resultant sequential probe 1-Al3+ complex exhibits the nearly complete quenching of emission intensity with successive addition of F−, which is only specific for F−, without being hampered by the existence of other various anions. The lowest limit of detection (LOD) values of 1 and 1-Al3+ complex for separately sensing Al3+ and F− ions are determined to be 2.55×10−8 M and 1.48×10−7 M, respectively. In addition, 1 can severe as a highly selective probe towards Al3+ and F− ionsby the “naked-eye” detection, for the solution color easily changing from colorless to yellow-green with the introduction of Al3+ and further to colorless upon subsequent addition of F−.
A pyrazine-containing hydrazone derivative for sequential detection of Al<sup>3+</sup> and F<sup>−</sup>
2022, Journal of Molecular Structure
The hydrazone sensor (1) derived from pyrazine-2-carbohydrazide and 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (PMBP) was applied to the fluorescent “turn-on” detection of Al3+ in semi-aqueous solutions. The strongly emissive 1+Al3+ complex could identify F− among other tested anions. The detection limits of sensor 1 for Al3+ and F− were 0.18 and 0.20μM, respectively, which are both much lower than the corresponding values recommended by the World Health Organization, namely, 7.41 and 79μM. Several spectral methods, including single crystal X-ray analysis for the crystal structures of the Cu2+ and Ni2+ complexes of sensor 1, as well as the density-functional theory method, were used to elucidate the binding mode between the sensor and Al3+. 1 can also be used for a selective sensor to continuously monitor Al3+ and F− in living cells.
An acylhydrazone coumarin as chemosensor for the detection of Ni<sup>2+</sup> with excellent sensitivity and low LOD: Synthesis, DFT calculations and application in real water and living cells
2021, Inorganica Chimica Acta
A novel acylhydrazone coumarin fluorescent chemosensor C4 for detection of Ni2+ was designed and synthesized. The experimental results revealed a low detection limit of 2.1×10−11 M with high selectivity and excellent sensitivity towards Ni2+. C4 showed a good linear relationship with the concentration of Ni2+ from 1.3×10−6 to 1.6μM. Moreover, a stable complex was formed between C4 and with Ni2+ and the binding ratio was proved to be 2: 1 by Job’s plot and mass spectrum. The sensing ability of C4 towards Ni2+ was attributed to parity-forbidden transition according to fluorescence titrations and DFT calculations. The detection of Ni2+ in water samples illustrated C4 could be successfully applied for the detection of Ni2+ in real environmental samples. What’s more, the fluorescence microscopy images of Hela cells demonstrated the high potential of the novel biosensor for the investigation of biological processes involving Ni2+, as well.
Pyrans and Benzo Derivatives: Applications
2021, Comprehensive Heterocyclic Chemistry IV
Pyrans constitute an important class of 6-member heterocycles with one oxygen atom. This article outlines applications of pyrans and their benzo derivatives for the time period 2008–18. Together with benzo derivatives, pyrans form a wide variety of scaffolds for pharmaceutical applications with many approved drugs, promising candidates in clinical trials and recently isolated bioactive natural products. In the last decade, cyclodextrins and carbohydrate-based polymers have been investigated for innovative biomedical applications. Pyran dyes have also emerged as promising photoredox catalysts and key components in solar cells and sensors. Finally, applications of pyrans as catalysts and “chiral pool” reagents in chemical synthesis are summarized.
A new fluorescent-colorimetric chemosensor based on a Schiff base for detecting Cr3+, Cu2+, Fe3+ and Al3+ ions
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Volume 214, 2019, pp. 7-13
A new Schiff base derivative fluorescence-colorimetric chemosensor 2-hydroxy-5-[(2-hydroxy-1-naphthyl)methylideneamino]benzoic acid (H3L), has been designed and synthesized. H3L displayed high selectivity and sensitivity for detecting Cr3+, Cu2+, Fe3+ and Al3+ ions in DMF/H2O (v/v = 1/1) solution. When Cr3+, Cu2+ or Fe3+ ions were added, the solution of H3L in DMF/H2O exhibited different color changes. While with the addition of Fe3+ or Al3+ ions, the solution of H3L in DMF/H2O displayed different fluorescence responses. The bonding modes and bonding ratios of H3L and metal ions were explored by the Job's plot, 1H NMR titration, and electrospray ionization mass spectrometry (ESI-MS). The detection limits of H3L with Cr3+, Cu2+, Fe3+and Al3+ ions were 3.37 × 10−7 M, 4.65 × 10−7 M, 3.58 × 10−7 M and 4.89 × 10−7 M, respectively.
A coumarin based azo-phenol ligand as efficient fluorescent “OFF-ON-OFF” chemosensor for sequential detection of Mg2+ and F−: Application in live cell imaging and as molecular logic gate
Sensors and Actuators B: Chemical, Volume 253, 2017, pp. 317-325
A novel coumarin based azo-phenol ligand (H2L) has been synthesized and characterized by several spectroscopic techniques. An almost 16 fold enhancement of emission intensity has been observed upon gradual addition of Mg2+ to H2L in DMSO:H2O (1:5v/v) medium while it has no significant effect in emission intensity even in presence of other metal ions. The emission intensity of L-Mg2+ complex has almost quenched on gradual addition of F− to it. The limit of detection for both Mg2+ and F− are of 10−8M order, hence the newly developed chemosensor is highly efficient in detecting Mg2+ and F− in very minute levels. The chemosensor can even detect Mg2+ in the intracellular region of human lung cancer cells (A549 cells).
A coumarin derivative as a “turn-on” fluorescence probe toward Cd2+ in live cells
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Volume 218, 2019, pp. 359-365
A novel coumarin-derived Schiff base fluorescence probe (CTB) has been successfully designed and synthesized through exploiting tris-(2-aminothyl)-amine moiety as a recognition unit for the highly selective and sensitive detection of Cd2+. It is based on CN isomerization and the photo-induced electron transfer (PET) mechanism. The investigation into the sensing processes showed that CTB exhibited an excellent selectivity for Cd2+. The sensitivity exceeded that of other competing metal ions, and had a high sensitivity, a detection limit of 1.16 × 10−7 M with the association constants of 1.37 × 1011 M−2. The experiments including Job's plot, UV–Vis titration, 1H NMR titration and ESI-MS spectrum established that the probe CTB binds to Cd2+ in a 1:2 ratio. Further studies also demonstrated that probe CTB can be successfully applied to the fluorescence imaging of Cd2+ in HepG-2 cells.
A highly selective and sensitive fluorescent chemosensor and its application for rapid on-site detection of Al3+
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Volume 193, 2018, pp. 415-421
In this paper, a simple naphthalene-based derivative (HL) has been designed and synthesized as a Al3+-selective fluorescent chemosensor based on the PET mechanism. HL exhibited high selectivity and sensitivity towards Al3+ over other commonly coexisting metal ions in ethanol with a detection limit of 2.72nM. The 1:1 binding stoichiometry of the complex (HL-Al3+) was determined from the Job's plot based on fluorescence titrations and the ESI-MS spectrum data. Moreover, the binding site of HL with Al3+ was assured by the 1H NMR titration experiment. The binding constant (Ka) of the complex (HL-Al3+) was calculated to be 5.06×104M−1 according to the Benesi-Hildebrand equation. In addition, the recognizing process of HL towards Al3+ was chemically reversible by adding Na2EDTA. Importantly, HL could directly and rapidly detect aluminum ion through the filter paper without resorting to additional instrumental analysis.
A multifunctional fluorescence sensor for Cd2+, PO43− and Cr3+ in different system and the practical application
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Volume 201, 2018, pp. 216-222
A fluorescence probe based on thiosemicarbazide has been synthesized and well characterized by 1H NMR, 13C NMR, Elemental analysis, Electrospray ionization mass spectra. The probe 1 functions as a multitarget ion sensor, detect biologically and ecologically important Cd2+, PO43− and Cr3+. Meanwhile, probe 1 displays selectivity for Cd2+ over other metal ions and anions in DMF by emission spectrum. Interestingly, probe 1 has been explored to recognize PO43− in CH3OH-H2O (v:v = 1:9). The binding stoichiometry of probe 1 with Cd2+ and PO43− are 2:1 and 1:1, respectively, which are confirmed by Electrospray ionization mass spectra. Probe 1 is selective, sensitive and reversibility/reusability to Cd2+ and PO43− with the detection limit as low as 0.035 μM and 0.011 μM respectively. Besides, the designed probe 1 has shown potential applications in the area of photo-printing.
A targetable fluorescent probe for real-time monitoring of fluoride ions in mitochondria
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Volume 204, 2018, pp. 777-782
Fluorion are pivotal anions in biology because they play an important role in dental care, treating osteoporosis, preventing tooth decay and promoting the healthy growth of bone. Studies have shown that high levels of fluoride will lead to the inactivation of the mitochondria. Therefore, it is urgent to develop a method to detect the fluoride anions in the mitochondria. Herein, we have developed a novel mitochondrial-target fluorescent probe for detecting F− in living cells. The probe exhibited excellent sensitivity and high selectivity for F− over the other relative species. With changing fluoride ions, the fluorescence spectrum of the probe changed significantly with a large turn-on fluorescence signal. Cell imaging indicated that the probe can penetrate viable cell membranes and rapidly detects and images fluorion over other anions in the mitochondria.
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