Coumarin Based Fluorescent Probe for Colorimetric Detection of Fe<Superscript>3+</Superscript> and Fluorescence Turn On-Off Response of Zn<Superscript>2+</Superscript> and Cu<Superscript>2+</Superscript>

A new coumarin based Schiff-base chemosensor-(E)-7-(((8-hydroxyquinolin-2-yl)methylene) amino)-4-methyl-2H-chromen-2-one (H ₁₁ L) was synthesized and evaluated as a colorimetric sensor for Fe³⁺ and fluorescence “turn on-off” response of Zn²⁺ and Cu²⁺ using absorption and fluorescence spectroscopy. Upon treatment with Fe³⁺ and Zn²⁺, the absorption intensity as well as the fluorescence emission intensity increases drastically compared to other common alkali, alkaline earth and transition metal ions, with a distinct color change which provide naked eye detection. Formation of 1:1 metal to ligand complex has been evaluated using Benesi-Hildebrand relation, Job’s plot analyses, ¹H NMR titration as well as ESI-Mass spectral analysis. The complex solution of H ₁₁ L with Zn²⁺ ion exhibited reversibility with EDTA and regenerate free ligand for further Zn²⁺ sensing. H ₁₁ L exhibits two INHIBIT logic gates with two different chemical inputs (i) Zn²⁺ (IN1) and Cu²⁺ (IN2) and (ii) Zn²⁺ (IN1) and EDTA (IN2) and the emission as output. Again, an IMPLICATION logic gate is obtained with Cu²⁺ and EDTA as chemical inputs and emission as output mode. Both free ligand as well as metal-complexes was optimized using density functional theory to interpret spectral properties. The corresponding energy difference between HOMO-LUMO energy gap for H ₁₁ L, H₁₁L-Zn²⁺ and H₁₁L-Cu²⁺ are 2.193, 1.834 and 0.172 eV, respectively.     

A Phenylbenzothiazole Derived Fluorescent Sensor for Zn(II) Recognition in Aqueous Solution Through “Turn-On” Excited-State Intramolecular Proton Transfer Emission

A highly selective and sensitive fluorescent Zn²⁺ sensor N-(2-(benzo[d]thiazol-2-yl)phenyl)-2-((pyridin-2-ylmethyl)amino)acetamide (1) that derived from 2-(2′-aminophenyl)benzothiazole has been developed. In aqueous solution (HEPES/CH₃CN=4/6, v/v, HEPES 20 mM, pH?=?7.4), sensor 1 displays highly selective recognition to Zn²⁺ over other metal ions with a distinct longer-wavelength emission enhancement. Sensor 1 binds Zn²⁺ through its amide form with a 1:1 binding stoichiometry, which switched on the excited-state intramolecular proton transfer (ESIPT). Graphical Abstract

A simple 2-(2′-aminophenyl)benzothiazole-based fluorescent “off-on” sensor for Zn²⁺ recognition in HEPES/CH₃CN(4/6, v/v, HEPES 20 mM, pH?=?7.4) solution through switching on ESIPT has been developed.     

Urea Based Dipodal Fluorescence Receptor for Sensing of Fe3+ Ion in Semi-Aqueous Medium

Urea based fluorescent chemosensor 1 was synthesized. Receptor 1 shows unique selectivity for the Fe³⁺ion and no such significant response was noticed with other metal ions (Cr³⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Pb²⁺ and Bi³⁺) in DMSO/H₂O (50:50,v/v) semi-aqueous solution. The binding features have been established by absorption and fluorescence spectroscopic methods. The binding constant (K) values obtained from Benesi-Hildebrand, Scatchard and Connor plot for receptor 1 is (8.3?±?0.3) × 10³ M^?1 and has good detection limit 0.7?μM. The stoichiometry of 1.Fe³⁺ complex was confirmed by mass spectroscopy and Job’s plot.

N-benzoate-N′ salicylaldehyde ethynelediamine: A new fluorescent sensor for Zn2+ ion by “off-on” mode

Imbalance of zinc ion (Zn²⁺) in human body causes diseases like Alzheimer’s and Parkinson’s and therefore Zn²⁺ estimation in biological fluids has diagnostic values. Fluorescence “off-on” sensors have advantages of high sensitivity and in situ application over other sensors. A new fluorescent “off-on” Zn²⁺ sensor, N-benzoate-N′ salicylaldehyde ethynelediamine (L), has been synthesisied. In 1:1(v/v) CH₃OH:PBS (PBS?=?phosphate buffer solution), L shows ca. 20 times enhancement in fluorescence intensity on interaction with Zn²⁺, due to snapping of photoinduced electron transfer (PET) process, which is selective over metal ions - Na⁺, K⁺, Ca²⁺, Ni²⁺, Cu²⁺, Cd²⁺, Hg²⁺ and Pb²⁺. These metal ions either individually or all together does not interfere the sensing ability of L towards Zn²⁺. A 1:1 interaction between L and Zn²⁺ ion with binding constant 10^4.25 has been established from spectroscopic data.     

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.

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.     

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.     

Bis-Benzimidazolyl Diamide Based Fluorescent Probe for Copper(II): Synthesis, Structural and Fluorescence Studies

A new fluorescent probe based on a bis-benzimidazole diamide N ²,N ^2′-bis[(1-ethyl-benzimidazol-2-yl)methyl]biphenyl-2,2′-dicarboxamide ligand L ₁ with a biphenyl spacer group and a Copper(II) trinuclear metallacycle has been synthesized and characterized by X-ray single crystallography, elemental and spectral (FT-IR, ¹H & ¹³C NMR, UV-Visible) analysis. The fluorescence spectra of L ₁ in MeOH show an emission band centered at 300 nm. This band arises due to benzimidazolyl moiety in the ligating system. The diamide L ₁ in the presence of Cu²⁺ show the simultaneous ‘quenching’ of (300 nm) and ‘enhancement’ of (375 nm) emission band. Similar fluorescence behavior was found in water–methanol mixture (9:1). The new emission band at 375 nm is attributed to intra ligand π–π* transition of the biphenyl moiety. L ₁ exhibited high selectivity and sensitivity towards Cu²⁺ in both the medium over other common metal ions like Ni²⁺, Co²⁺, Mn²⁺, Mg²⁺, Zn²⁺, Pb²⁺ and Hg²⁺. The binding constant with Cu²⁺ was calculated by the Benesi-Hildebrand equation. Selective “off-on-off” behavior of L ₁ in methanol has also been studied. The fluorescent intensity of 375 nm bands in L ₁ enhances (turns-on) upon addition of Cu²⁺ and quenches (turn-off) upon addition of Na₂-EDTA.     

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.     

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.

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.     

Coordination preference and magnetic properties of FeII assemblies with a bis-azole bearing 1,2,4-triazole and tetrazole

With a new bis-azole molecular fragment (Htt) bearing 1,2,4-triazole and tetrazole, a mononuclear complex [Fe(tt)₂(H₂O)₄]·2H₂O (1), a trinuclear complex [Fe₃(tt)₆(H₂O)₆]·2H₂O (2) and a 1D coordination polymer [Fe(tt)(Htt)₂]BF₄·2CH₃OH (3) were obtained by varying reaction conditions. Htt acts either as an anionic or neutral ligand depending upon the reaction medium and pH. Thermal variation of spin states of 1–3 were investigated in the range 77–300?K by ⁵⁷Fe M?ssbauer spectroscopy. 1 totally remains in high-spin state over the entire temperature range whereas no spin crossover was evidenced in 2. Nearly 1:1 high-spin and low-spin population ratio is found in 3, which remains constant over the entire temperature range investigated.     

Phosphorus(V)corrole- Porphyrin Based Hetero Trimers: Synthesis,Spectroscopy and Photochemistry

‘Axial-bonding’-type hetero trimers have been constructed by employing a simple ‘inorganic’ reaction such as axial bond formation of main group element containing phosphorus corrole. The approach is simple and modular in nature. The architecture of these hetero trimers such that, while a phosphorus(V)corrole forms the basal scaffolding unit, either two free-base porphyrins [(H ₂ ) ₂ –PCor] or Zn^II porphyrins [(Zn) ₂ –PCor] occupy the two axial sites via an aryloxy bridge. Both hetero trimeric species have been completely characterized by mass (FAB), UV/Vis, proton nuclear magnetic resonance spectroscopies and also by the differential pulse voltammetric method. Comparison of their spectroscopic and electrochemical data of these trimers with those of the corresponding reference compounds reveal that there is no apparent ring-to-ring interactions in these ‘vertically’ linked hetero trimers. Reduced fluorescence quantum yields were observed for [(H ₂ ) ₂ –PCor] and [(Zn) ₂ –PCor] when compared to corresponding monomeric chromophores. Finally, a comparison is made between the presently reported phosphorus(V)corrole based hetero arrays and the previously reported analogous arrays based on Ge(IV)corrole with regard to their spectroscopic properties and photochemical activities.     

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.

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⁺.     

Theoretical studies of ground and excited states in a series of Zn(II) complexes,derived from thiourea and thiosemicarbazide

Theoretical studies for a series of mono- and binuclear zinc (II) complexes Zn(CH₃COO)₂(H₂L)₂ [H₂L = N-2-propenyl-N ^′-2-pyridinylthiourea] (A), Zn₂(CH₃COO)₂(H₃L-a)₂ [H₃L-a = 2-[(2-hydroxy phenyl)methylene]hydrazine-N-phenylcarbothioamide] (B), and Zn(H₃L-b)₂ [H₃L-b = 2-[(2-hydroxy phenyl)methylene]hydrazine-N-(2-propenyl)carbothioamide] (C) have been performed on their structures and excited-state absorption spectra. The singlet ground-state geometries are fully optimised at three DFT levels, i.e., B3LYP, B3PW91, and M06. Different geometries, i.e., strongly distorted tetrahedral coordination environment in complex A, distorted square-pyramidal environment in complex B, and irregular octahedral mode in complex C are identified. Consequently, the spectroscopic properties are calculated by means of time-dependent density functional theory (TDDFT) with the Polarisable Continuum Model (PCM) based on the optimised gas-phase geometries. Three absorption peaks are identified for every complex, which are in good agreement with the experimental ones. For complex A, all three absorption peaks centered at 280.33 nm, 268.09 nm, and 250.87 nm, respectively, are ascribed to the (p,π) → π* transition with a mixed intraligand charge-transfer (ILCT)/ligand-ligand charge-transfer (LLCT) character. The composition of frontier orbitals involved in major absorption bands for the three complexes shows similarities, which results in the almost homologous transition attributions and characteristics. A remarkable bathochromic shift in the lowest-lying absorption band is observed for complexes B and C as compared with complex A, which is attributed to the decreased H (HOMO)-L (LUMO) energy gap (ΔE |HOMO-LUMO|) by the formation of conjugate metallocycles in complexes B and C.     

A New Thiosemicarbazone-Based Fluorescence “Turn-on” Sensor for Zn<Superscript>2+</Superscript> Recognition with a Large Stokes Shift and its Application in Live Cell Imaging

Selective fluorescence turn on Zn²⁺ sensor with long-wavelength emission and a large Stokes shift is highly desirable in Zn²⁺ sensing area. We reported herein the synthesis and Zn²⁺ recognition properties of a new thiosemicarbazone-based fluorescent sensor L. L displays high selectivity and sensitivity toward Zn²⁺ over other metal ions in DMSO-H₂O (1:1, v/v, HEPES 10 mM, pH = 7.4) solution with a long-wavelength emission at 572 nm and a large Stokes shift of 222 nm. Confocal fluorescence microscopy experiments demonstrate that L is cell-permeable and capable of monitoring intracellular Zn²⁺.

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Graphical Abstract We report a new thiosemicarbazone-based fluorescent sensor (L) for selective recognition of Zn²⁺ with a long wavelength emission and a large Stokes shift.

     

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.     

Theory of spatial dispersion of dielectric and magnetic constants in magnetic uniaxial gyrotropic crystals

The theory of spatial dispersion of dielectric and magnetic constants of magnetic uniaxial crystals based on generalized Maxwell’s equations D = ε?E = (ε + inγ E = ?ns ^× H and B = μ?H = (μ + inδ)H = ns ^× E with spatial dispersion parameters γ and δ is considered. Generalized Fresnel’s and polarization equations for the obtained vectors E, D, H, and B are analyzed for the wave normal direction s ⊥ C (where C is the optic axis of a crystal). The possibility of the existence of a third natural wave in a crystal is proved.     

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.