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.     

A Schiff-Based Colorimetric Fluorescent Sensor with the Potential for Detection of Fluoride Ions

A simple Schiff-based colorimetric fluorescent receptor 1 was prepared. It exhibits a “turn-on-type” mode with high sensitivity in the presence of F^?. The change in color is very easily observed by the naked eye in the presence of F^?, whereas other anions do not induce such a change. Job plot indicated a 1:2 complexation stoichiometry between receptor 1 and F^?. The association constant for 1-F^? in CH₃CN was determined as 1.32*10⁵ M^?2 by a Hill plot.

Bis(2-Hydroxy-3-Isopropyl-6-Methyl-Benzaldehyde)Ethylenediamine: A Novel Cation Sensor

Novel substituted phenol-based new symmetrical bis(2-hydroxy-3-isopropyl-6-methyl-benzaldehyde)ethylenediamine (1) has been designed and synthesized. The compound 1 fluorometrically recognized Cu²⁺ ion in CH₃OH/H₂O (90:10, v/v) by exhibiting an increase in emission upon complexation. In addition, Cu²⁺ gave rise to a change in colour of the solution of compound 1, which was clearly visible to the naked eye under UV irradiation. The association constant (K) of compound 1 with Cu²⁺ ion was computed with the Benesi-Hildebrand plot and Scatchard plot at 43,000 M^?1 and 43,011 M^?1 respectively.     

A Novel Series Colorimetric and Off–On Fluorescent Chemosensors for Fe3+ Based on Rhodamine B Derivative

A novel series colorimetric and off–on fluorescent chemosensors (2a, 2b, 2c) were designed and synthesized, which showed reversible and highly selective and sensitive recognition toward Fe³⁺ over other examined metal ions. Upon addition of Fe³⁺, sensors (2a, 2b) exhibit remarkably and 2c exhibits moderate enhanced absorbance intensity and color change from colorless to pink in CH₃OH–H₂O(1:1, v/v). The three compounds (2a, 2b, 2c) may therefore be applicable as rhodamine-based turn-on type fluorescent chemosensors.     

9, 10-Bis(8-Quinolinoxymethyl)Anthracene—A Fluorescent Sensor for Nanomolar Detection of Cu2+ with Unusual Acid Stability of Cu2+-Complex

In this work, the dipod 9,10-bis(8-quinolinoxymethyl)anthracene (1) and for comparison, monopod 9-(8-quinolinoxymethyl)anthracene (2) have been synthesized. The fluoroionophore 1 in pH 7.1 HEPES buffered CH₃CN:H₂O (4:1 v/v) solution shows quenching only with Cu²⁺ with lowest limit of detection 150 nM, amongst various metal ions. Fluoroionophore 1 could also be applied to sense Co²⁺ with lowest limit of detection 600 nM. By modulating the pH of the solution and concentration of Cu²⁺, 1 shows respective “On-Off-On” and “On-Off” fluorescent switching. The self-assembly of two Cu²⁺ ions and two molecules of fluoroionophore 1 to form closed structure [Cu₂(L)₂]⁴⁺ seems to be responsible for nanomolar sensitivity towards Cu²⁺. The combination of delayed second protonation of 1 (pK_a2?=?2.6) and stepwise protonation of [Cu₂ L ₂]⁴⁺ causes unusual stability of [Cu(LH)₂]⁴⁺ even at pH?<?2.

Indole-based Fluorescent Sensors for Selective Detection of Hg2+

A series of indole-based fluorescent chemosensors 1–4 were prepared and investigated characteristick features with transition metal ions. Sensors 1 and 2 were selective for Hg²⁺ ion among a series of metal ions in H₂O–DMSO with association constants of 4.60×10⁴ and 5.90×10⁴?M^?1 and detection limits of 140 and 101.6 μM, respectively.

Fluorescence Turn on Sensor for Sulfate Ion in Aqueous Medium Using Tripodal-Cu2+ Ensemble

We report the selective recognition of sulfate anion in aqueous medium at biological pH 7.2 over the other interfering anions based on naphthoic acid bearing tripodal ligand by applying fluorescence turn off-on mechanism. The carboxylic acid groups in the ligand enhance the solubility in water and enable it to form complex with copper salt. Thus formed L-Cu²⁺ ensemble quench the fluorescence of the parent ligand and in turn recognize sulfate anion via revival of fluorescence intensity. The 1:2 stoichiometry was confirmed by ESI mass spectral data and Job’s plot. The average binding constant was found to be 6.2?×?10⁸ M^?2.

New Application of a Known Molecule: Rhodamine B 8-hydroxy-2-quinolinecarboxaldehyde Schiff Base as a Colorimetric and Fluorescent “Off-On” Probe for Copper (II)

Rhodamine B 8-hydroxy-2-quinolinecarboxaldehyde Schiff base (1) has been investigated as a colorimetric and fluorescent “off-on” probe for the recognition of Cu²⁺ in aqueous solution. Probe 1 was synthesized by condensation of rhodamine B hydrazide and 8-hydroxy-2-quinolinecarboxaldehyde, which exhibited good selectivity for Cu²⁺ among a range of biologically and environmentally important metal ions. The Cu²⁺ recognition event undergoes a Cu²⁺ promoted hydrolysis of probe 1 to release rhodamine B and the recognition process is barely interfered by other coexisting metal ions.

Selective Fluorescent Detection of Aspartic Acid and Glutamic Acid Employing Dansyl Hydrazine Dextran Conjugate

Highly water soluble polymer (DD) was prepared and evaluated for its fluorescence response towards various amino acids. The polymer consists of dansyl hydrazine unit conjugated into dextran template. The conjugation enhances higher water solubility of dansyl hydrazine moiety. Of screened amino acids, DD exhibited selective fluorescence quenching in the presence of aspartic acid (Asp) and glutamic acid (Glu). A plot of fluorescence intensity change of DD against the concentration of corresponding amino acids gave a good linear relationship in the range of 1?×?10^?4 M to 25?×?10^?3 M. This establishes DD as a potential polymeric sensor for selective sensing of Asp and Glu.

Design and Synthesis of a Pyridine Based Chemosensor: Highly Selective Fluorescent Probe For Pb2+

A pyridine based imine-linked chemosensor has been synthesized and evaluated its binding affinity with library of transition metal ions. It has prominent selectivity towards Pb²⁺ among other metal ions in DMF/H₂O (9:1, v/v) solvent system. The 1:1 stoichiometric was confirmed by job’s plot and has a binding constant (K_a)?=?5.142?×?10³ M^?1 on fluorescence. A B3LYP/6-31G and B3LYP/LanL2DZ basis sets were employed for optimization of 3 and 3.Pb²⁺.     

Salicylaldehyde Phenylhydrazone: A New Highly Selective Fluorescent Lead (II) Probe

The fluorescence intensity of salicylaldehyde phenylhydrazone (L), in 1:1 (v/v) CH₃OH:H₂O was enhanced by ca. 100 times with a blue shift in emission maximum, on interaction with Pb²⁺ ion. No enhancement in fluorescent intensity of L was observed on interaction with metal ions - Na⁺, K⁺, Ca²⁺, Cu²⁺, Ni²⁺, Zn²⁺, Cd²⁺ and Hg²⁺. This signal transduction was found to occur via photoinduced electron transfer (PET) mechanism. A 1:1 complexation between Pb²⁺ and L with log β?=?7.86 has been proved from fluorescent and UV/Visible spectroscopic data. The detection limit of Pb²⁺ was calculated to be 6.3?×?10^?7?M.     

Perylene Diimide Appended with 8-Hydroxyquinoline for Ratiometric Detection of Cu2+ Ions and Metal Displacement Driven “Turn on” Cyanide Sensing

Perylene diimide (PDI) 3 and 4 appended with 8-hydroxyquinoline derivatives have been synthesized and their photophysical and spectroscopic properties have been experimentally determined. Moreover, PDIs 3 and 4 show ratiometric behavior to detect Cu²⁺ colorimetrically with visible color change from coral red to light pink, whereas 3 and 4 show “turn-off” behavior in fluorescence with lowest limit of detection 5?×?10^?7 M. The PDI 3 could be further utilized for ratiometric CN^? detection colorimetrically and as “turn-on” sensor for CN^? detection fluorometrically with lowest limit of detection 8?×?10^?6 M. The comparison of spectroscopic properties of PDI 1-4 highlights the importance of linking 8-hydroxyquinoline units on the PDI core at bay position for achieving Cu²⁺ recognition event into ratiometric signal.

A Novel Colorimetric and Fluorescent “Off-On” Chemosensor for Cu2+ Based on a Rhodamine Derivative Bearing Naphthyridine Group

A new rhodamine-based derivative bearing a naphthyridine group (compound 1) was synthesized as a colorimetric and fluorescent “off-on” chemosensor for Cu²⁺ in aqueous solutions. The sensing behaviors of 1 toward various metal ions in neutral aqueous solutions were investigated by absorption and fluorescence spectroscopies. Compound 1 is found to exhibit a significant increase in absorbance at 561 nm and an amplified fluorescence at 590 nm toward Cu²⁺ in a selective, sensitive and rapid manner. The quantification of Cu²⁺ by 1 using an absorption spectroscopy method was satisfactory in the linear working range 0.9–10 μM, with a detection limit of 5.4?×?10^?8?M for Cu²⁺ and good tolerance of other metal ions. Upon addition of Cu²⁺, the spirolactam ring (colorless and nonfluorescent) of 1 was opened to ring-opened amide (red color and fluorescent) and a 1:1 stoichiochemetry for the 1-Cu²⁺ complex was formed with an association constant of 1.57?×?10⁴?M^?1.     

The Smart 2-(2-Fluorobenzoyl)-N-(2-Methoxyphenyl)Hydrazinecarbothioamide Functionalized as Ni(II) Sensor in Micromolar Concentration Level and its Application in Live Cell Imaging

In recent years, fluorescent probes for the detection of environmentally and biologically important metal cations have received extensive attention for designing and development of fluorescent chemosensors. Herein, we report the photophysical results of 2-(2-fluorobenzoyl)-N-(2-methoxyphenyl) hydrazinecarbothioamide (4) functionalized as Ni (II) sensor in micromolar concentration level. Through fluorescence titration at 488 nm, we were confirmed that ligand 4 showed the remarkable emission by complexation between 4 and Ni (II) while it appeared no emission in case of the competitive ions (Cr³⁺, Fe²⁺, Co²⁺, Ba²⁺, Cu²⁺, Ca²⁺, Na⁺, K⁺, Cu⁺, Cs⁺). Furthermore, ligand 4 exhibited no toxicity with precise cell permeability toward normal living cells using L929 cell lines in bio imaging experiment investigated through confocal fluorescence microscope. The non-toxic behavior of ligand 4 (assessed by MTT assay) and its ability to track the Ni²⁺ in living cells suggest its possibility to use in biological system as nickel sensor.

A New Piperidine Derivatized-Schiff Base Based “Turn-on” Cu<Superscript>2+</Superscript>Chemo-Sensor

In this study, we report the synthesis of new Schiff base E-1-(((1-benzylpiperidin-4-yl)imino)methyl)naphthalenee-2-ol (L) and evaluation of its fluorescence response toward Cu²⁺ ion. Preliminary, solvent effect, metal selectivity and metal ligand ratio were analyzed through UV-Visible study. Fluorescence response toward Cu²⁺ was carried to assess the fluorescent property of synthesized Schiff base. The probe exhibited a higher fluorescence enhancement in the presence of Cu²⁺ over other metal ions (Ni²⁺, Zn²⁺, Hg²⁺, Co²⁺, Cd²⁺, Al³⁺, Fe²⁺, and Pb²⁺). The binding stoichiometry between L and Cu²⁺ has been investigated using Job’s plot and Benesi-Hildebrand equation and it was found that ligand L can form 1:1 L-Cu²⁺ complex with binding constant (K _a) of 4?×?10⁴ LM^?1.     

The First Bifluoride Sensor Based on Fluorescent Enhancement

The first fluorescent sensor for HF₂ ^? anion, N¹, N³-di(naphthalene-1-yl)isophthalamide (L) has been derived from α-Napthylamine and isopthaloyl chloride. In 1:1 (v/v) DMSO:H₂O, L exhibits high selectivity towards HF₂ ^? anion with a 4-fold enhancement in fluorescent intensity. Very little enhancement in fluorescence intensity is observed for F^?, Cl^?, Br^?, I^?, SCN^?, PO₄ ^3?, SO₄ ^2?, and CH₃COO^? anions. The stoichiometry interaction between L and HF₂ ^? is found to be 1:1 from fluorescence and UV/Visible spectral data. DFT calculation shows that binding between HF₂ ^? and L is 1:1 and increases the relative planarity between the two naphthyl rings causing fluorescence enhancement. A shift of 0.080 V in oxidation potential of L is observed on interaction with HF₂ ^? by cyclic voltammetry and square wave voltammetry.     

A New Thiophenyl Pyrazoline Fluorescent Probe for Cu2+ in Aqueous Solution and Imaging in Live Cell

A new thiophenyl pyrazoline probe for Cu²⁺ in aqueous solution was synthesized and characterized by IR, NMR, HRMS and X-ray analysis. The probe displays remarkably high selectivity and sensitivity for Cu²⁺ with a detection limit of 1.919?×?10^?7 M in aqueous solution (EtOH:HEPES = 1:1, v/v, 0.02 M, pH?=?7.2). In addition, the probe is further successfully used to image Cu²⁺ in living cells and the probe possesses good reversibility.

A Highly Selective and Sensitive Fluorescent Chemosensor for Aluminum Ions Based on Schiff Base

An efficient “off–on” type fluorescent chemosensor, (E)-N′-(4-(diethylamino)-2-hydroxybenzylidene)-2-hydroxybenzohydrazide (H ₂ L), based on Schiff base for the determination of Al³⁺ has been designed, synthesized, and evaluated. Upon treated with Al³⁺, the fluorescence of H ₂ L was enhanced 45-fold due to the chelation-enhanced fluorescence (CHEF) effect based on the formation of a 1:1 complex between the chemosensor and Al³⁺. Other metal ions, such as Na⁺, K⁺, Mg²⁺, Ca²⁺, Cu²⁺, Ga³⁺, Zn²⁺, Cr³⁺, Cd²⁺, Ag⁺, Fe³⁺, In³⁺, Mn²⁺, Pb²⁺, Co²⁺, and Ni²⁺ had little effect on the fluorescence. The results demonstrate that the chemosensor H ₂ L has stronger affinity with Al³⁺ than other metal ions. The detection limit of H ₂ L for sensing Al³⁺ is 3.60 × 10^?6 M in EtOH–H₂O (3:7, v/v) solution. And the recognizing behavior has been investigated both experimentally and computationally.     

Aging effect in CaLaBa{Cu1???xFex}3O7???�� with 0 �� x �� 0.07 studied by M?ssbauer spectroscopy

In this work, we study the long-term aging effect caused by Fe atoms in the superconductor CaLaBa{Cu_1???xFe_x}₃O_7????? with 0 ?? x ?? 0.07. XRD confirms that this system has a YBCO-like structure. The critical temperature (T_c) is strongly affected by aging and depends on the amount of Fe in the structure. Room temperature Mössbauer spectroscopy reveals the presence of the typical species A, B?CB ??, C and new species E ?? and F. Interestingly; A, which corresponds to the Fe^3?+? atom located in the Cu(1) of the chains with spin S _z = 3/2, shows a drastic reduction which means migration to the species B, B ?? and C. Species B and B ?? correspond to the Fe^3?+? in the Cu(2) site forming planar quasi-octahedral and planar square pyramidal, while the C specie is a square pyramidal with O(5) respectively (spin S_z = 3/2 in all these cases). Aging causes loss of superconductivity in the samples with 5 and 7% of iron content.     

Off-on Fluorescent Sensor from On-off Sensor: Exploiting Silver Nanoparticles Influence on the Organic Fluorophore Fluorescence

Turn-off fluorescence of organic fluorophore, 2-{[4-(2H-Naphtho[1,2-d][1,2,3]triazol-2-yl)-phenyl]carboxylic acid (NTPC), with metal ions (Fe³⁺, Cu²⁺, Pb²⁺) was converted into turn-on fluorescent sensor for biologically important Zn²⁺, Cu²⁺ and Fe³⁺ metal ions in aqueous solution at ppb level by exploiting strong fluorescence quenching phenomena of metal nanoparticles when organic fluorophores assembled in the vicinity of metallic surface. Amino acid attached phenolic ligands (L) were used as reducing as well as functional capping agents in the synthesis of silver nanoparticles (AgNPs). The hydrogen bonding functionality of L facilitated the assembling of NTPC in the vicinity of metallic surfaces that leads to complete quenching of NTPC fluorescence. The strong and selective coordination of L with metal ions (Zn²⁺, Cu²⁺ and Fe³⁺) separates the NTPC from the AgNPs surface that turn-on the NTPC fluorescence. HR-TEM and absorption studies confirm the metal coordination with L and separation of NTPC from the AgNPs surface. Mn²⁺ showed selective red shifting of NTPC fluorescence after 12 h with all sample. Effects of different amino acid attached phenolic ligands were explored in the metal ion sensitivity and selectivity. This approach demonstrates the multifunctional utility of metal NPs in the development of turn-on fluorescence sensor for paramagnetic heavy metal ions in aqueous solution.