Ratiometric fluorescent and colorimetric sensors for Cu based on 4,5-disubstituted-1,8-naphthalimide and sensing cyanide via Cu displacement approach

Two 4,5-disubstituted-1,8-naphthalimide derivatives 1 and 2 were synthesized as ratiometric fluorescent and colorimetric sensors for Cu²⁺, respectively. In 100% aqueous solutions of 1, the presence of Cu²⁺ induces a strong and increasing fluorescent emission centered at 478 nm at the expense of the fluorescent emission of 1 centered at 534 nm. Compound 2 senses Cu²⁺ by means of a colorimetric (primrose yellow to pink) method with a thorough quench in emission attributed to the deprotonation of the secondary amine conjugated to the naphthalimide fluorophore. 1-Cu²⁺ and 2-Cu²⁺ sense cyanide in ratiometric way via colorimetric and fluorescent changes.     

Synthesis and evaluation of a novel pyrenyl-appended triazole-based thiacalix[4]arene as a fluorescent sensor for Ag ion

New fluorescent chemosensors 1,3-alternate-1 and 2 with pyrenyl-appended triazole-based on thiacalix[4]arene were synthesized. The fluorescence spectra changes suggested that chemosensors 1 and 2 are highly selective for Ag⁺ over other metal ions by enhancing the monomer emission of pyrene in neutral solution. However, other heavy metal ions, such as Cu²⁺, and Hg²⁺ quench both the monomer and excimer emission of pyrene acutely. The ¹H NMR results indicated that Ag⁺ can be selectively recognized by the triazole moieties on the receptors 1 and 2 together with the ionophoricity cavity formed by the two inverted benzene rings and sulfur atoms of the thiacalix[4]arene.     

Fluorescent ratioable recognition of Cu in water using a pyrene-attached macrocycle/γ-cyclodextrin complex

A pyrene-functional fluoroionophore, 1 was used to construct a supramolecular 1/γ-CD complex for Cu²⁺ recognition in water. In aqueous γ-CD solution, 1 exhibits pyrene monomer fluorescence emission at 378 nm and 397 nm, while in the presence of Cu²⁺, it shows a pyrene excimer emission at 452 nm with a decrease in the monomer fluorescence due to the formation of a 1:2 metal-liganded complex. Based on the response characteristics of the supramolecular complex, a fluorescent ratiometric method was performed for the determination of Cu²⁺ concentration in water. With the optimum conditions described, Cu²⁺ in aqueous solution can be determined from 1.2 × 10⁻⁶ to 4.5 × 10⁻⁴ M. The Cu²⁺ selectivity of the complex is excellent, and the excimer fluorescence enhancements are very smaller induced by other heavy metal and transition metal ions.     

Fluorescent peptide-based sensors for the ratiometric detection of nanomolar concentration of heparin in aqueous solutions and in serum

New fluorescent peptide-based sensors (1–3) for monitoring heparin in serum sample were synthesized using short peptides (1∼3mer) as a receptor. The peptide-based sensors (2 and 3) showed a sensitive ratiometric response to heparin both in aqueous buffered solution (10 mM HEPES, pH 7.4) and in 2% human serum sample by increase of excimer emission of pyrene at 480 nm and concomitant decrease of monomer emission of pyrene at 376 nm, whereas the peptide-based sensor 1 showed a turn off response only by decrease of monomer emission at 376 nm. 2 and 3 exhibited excellent selectivity toward heparin among various anions and competitors of heparin including chondroitin 4-sulfate (ChS) and hyaluronic acid (HA). Peptide-based sensor 3 showed a more sensitive response to heparin than 2. The detection limit of 3 was determined as 36 pM (R² = 0.998) for heparin in aqueous solution and 204 pM (R² = 0.999) for heparin in aqueous solutions containing 2% human serum. The peptide-based sensors, 2 and 3 provided a practical and potential tool for the detection and quantification of heparin in real biological samples.     

FRET-derived ratiometric fluorescence sensor for Cu

New N-(pyrenylmethyl)naphtho-azacrown-5 (1) was synthesized as an ‘On-Off’ fluorescent chemosensor for Cu²⁺. Excited at 240 nm corresponding to the absorption of naphthalene unit (energy donor) of 1, emission at 380 nm from pyrene unit (energy acceptor) is observed, indicating that intramolecular fluorescence resonance energy transfer (FRET-On) occurs in 1. When Cu²⁺ is added to a solution of 1, however, the fluorescence of pyrene is strongly quenched (FRET-Off) whereas that of naphthalene group is revived. Such FRET ‘On-Off’ behavior of 1 is observed only in the case of Cu²⁺ binding, but not for other metal cations. The high selectivity of 1 toward Cu²⁺ can be potentially applied to a new kind of FRET-based chemosensor. The FRET On-Off behavior is supported by computational studies. The calculated molecular orbitals of HOMO and LUMOs suggest the excited-state interactions leading to FRET from naphthalene to pyrene in 1, but no electron density changes in 1·Cu²⁺ complex.     

Pyrene-appended calix[4]crowned logic gates involving normal and reverse PET: NOR, XNOR and INHIBIT

As a novel sensing system, N-(1-pyrenylmethyl) amide-appended calix[4]crown-5 (2) and crown-6 (3) have been newly synthesized. Judging from the fluorescence changes upon the addition of cations, 3 having crown-6 ring showed the Pb²⁺ ion selectivity over other cations tested regarding fluorescence quenching. Upon the Pb²⁺ ion coordination to two amide oxygen atoms with aid of crown ring, a reverse-photo-induced electron transfer (PET) occurs in such a way that electrons transfer from the pyrene groups to the electron deficient amide oxygen atoms to give a quenched fluorescence. By the addition of either HClO₄ or triethylamine in the solution of 3, the fluorescence intensity decreased because of the reverse-PET from pyrene groups to protonated amide oxygen atoms and because of normal PET from the nitrogen anion formed by triethylamine to pyrene groups, respectively. For 3, NOR logic gate in which the strong fluorescence signal appears at 395 nm (output: 1) is operated only when neither of triethylamine nor Pb(ClO₄)₂ (inputs A and B) is added (A=B: 0). XNOR gate is also operated only when both of two inputs are added (triethylamine and HClO₄, A=B: 1) or when neither of two inputs is added (A=B: 0). Then, for 3, new INHIBIT gate system was also designed using such combinational inputs as HClO₄, Pb(ClO₄)₂ and triethylamine.     

A ratiometric fluorescent chemosensor, 1,10-phenanthroline-4,7-dione, for anions in aqueous-organic media

A new fluorescent chemosensor, 1,10-phenanthroline-4,7-dione (1), which is capable of the ratiometric sensing of anions in aqueous MeCN, was developed. Chemosensor 1 recognized an anion via two NH groups in the molecule, and showed a much higher affinity for F⁻ than that of 4-quinolone, which binds to an anion at one NH group of the molecule. Upon binding to F⁻, the intensity of the emission band ascribed to the complex of 1-F⁻ was drastically enhanced, while the emission intensity of unbound 1 gradually decreased. The changes in these two emission bands enabled the successful ratiometric sensing.     

Novel 2,2′-bipyridine-modified calix[4]arenes: ratiometric fluorescent chemosensors for Zn ion

Two calix[4]arene derivatives with modified bipyridine as binding sites have been designed and synthesized. Compounds 1 and 2 are the first 2,2′-bipyridine-modified calix[4]arene-based sensors that can detect Zn²⁺ selectively with respect to ratiometric fluorescent changes and red shift. A binuclear complex structure has been demonstrated in the binding modes of 1-Zn²⁺ and 2-Zn²⁺ complexes.     

A specific and ratiometric chemosensor for Hg based on triazole coupled ortho-methoxyphenylazocalix[4]arene

Calix[4]arene 3, which contains two distal triazole groups on the lower rim and two distal o-methoxyphenylazo groups on the upper rim, was synthesized and found to be a specific and ratiometric sensor for Hg²⁺ in a polar protic solvent. A series of o-methoxyphenylazo derivatives (3, 4, 5, 7, and 9) were synthesized, which proved that the lower-rim triazoles and the hydroxyl azophenol(s) were the major ligands for metal ion binding. Though analogues 4 and 10 showed some sensitivity for Hg²⁺, compound 3 was the only ratiometric chemosensor for Hg²⁺ among the series of azocalix[4]arenes synthesized in this work. The formation of 3·Hg²⁺ complex was supported by UV/vis and NMR titration studies and Mass spectrometry. Based on the symmetrical features of NMR spectra of 3·Hg²⁺, the complex is believed to be symmetrical with respect to the calix[4]arene cavity. Furthermore, the complex was determined to be 1:1 binding stoichiometry by Job’s plot, and the association constant was determined to be 4.02×10³ M⁻¹ using Benesi-Hildebrand plot.     

Ferrocenoyl-amino acids: redox response towards di- and trivalent metal ions

The interaction of six ferrocene-amino acid conjugates (Fc-CO-Gly-OH (2a), Fc-CO-Asp-OH (3a), Fc-CO-Glu-OH (4a), 1,1′-Fc(CO-Gly-OH) (2b), 1,1′-Fc(CO-Asp-OH) (3b), and 1,1′-Fc(CO-Glu-OH) (4b)) with Mg²⁺, Ca²⁺, Zn²⁺, La³⁺, and Tb³⁺ was investigated in aqueous solutions using cyclic voltammetry (CV) and differential pulse voltammetry (DPV). Addition of metal ions to solutions caused, in some cases, large changes in the half-wave potential, E_1/2. Our electrochemical results show that the Gly systems, 2a and 2b, show a preference for binding Mg²⁺, whereas the Asp and Glu conjugates prefer binding Ln³⁺.     

New strained ferrocenophane-based receptors for the selective electrochemical recognition of Mg in the presence of Ca cations

Ferrocenophane derivatives 3 act as electrochemical sensors of Mg²⁺ ions: a new redox peak appears in the CVs anodically shifted compared to the E_1/2 of the free receptors by 268-382 mV. Receptors 3a, 3c and 3d are selective for Mg²⁺, whilst 3b is also responsive to Ca²⁺ ion (302 mV shift). Receptor 3c also gave a highly visual output response in the presence of Mg²⁺ consisting of a deep purple colour.     

Salicylaldehyde hydrazones as fluorescent probes for zinc ion in aqueous solution of physiological pH

Salicylaldehyde hydrazones of 1 and 2 were synthesized and their potential as fluorescent probes for zinc ion was investigated in this paper. Both of the probes were found to show fluorescence change upon binding with Zn²⁺ in aqueous solutions, with good selectivity to Zn²⁺ over other metal ions such as alkali/alkali earth metal ions and heavy metal ions of Pb²⁺, Cd²⁺ and Hg²⁺. They showed 1:2 metal-to-ligand ratio when their Zn²⁺ complex was formed. By introducing pyrene as fluorophore, 2 showed interesting ratiometric response to Zn²⁺. Under optimal condition, 2 exhibited a linear range of 0-5.0 μM and detection limit of 0.08 μM Zn²⁺ in aqueous buffer, respectively. The detection of Zn²⁺ in drinking water samples using 2 as fluorescent probe was successful.     

Metal ion induced FRET On-Off in naphthyl-pyrenyl pendent tetrahomodioxacalix[4]arene

A novel tetrahomodioxacalix[4]arene (7) bearing both naphthyl- and pyrenyl-amide pendants was synthesized as FRET-based fluorometric sensor for Cu²⁺ ion. Intramolecular FRET from the naphthalene emission to the pyrene absorption affords Cu²⁺ ion selectivity over other metal ions. Upon addition of Cu²⁺ ion, the complex solution of 7 gave a significantly decreased pyrene acceptor emission along with an enhancement of naphthalene donor emission via FRET On-Off event.     

An efficient sensor for relay recognition of Zn and Cu through fluorescence ‘off–on–off’ functionality

A new bis(8-carboxamidoquinoline) dangled binaphthol derivatized fluorescent sensor (L) was designed and synthesized. L behaves ratiometric response to Zn²⁺ with high selectivity accompanied by remarkable emission enhancement and red shift. The resultant L–Zn²⁺ complex can act as a Cu²⁺ sensing probe with fluorescence quenching behavior through direct Zn²⁺ ion replacement. Furthermore, the binding modes of Zn²⁺ and Cu²⁺ with L are elucidated by X-ray crystallographic analysis, respectively.     

Ratiometric fluorescence probe for two-photon bioimaging of Cr in living cells

We presented a ratiometric fluorescent probe dansylamide–rhodamine dyad (DANS–RB) for selectively detecting Cr³⁺ in semi-aqueous solution. The detection mechanism relies on the fluorescent resonance energy transfer (FRET) process from the dansylamide (energy donor) to the rhodamine (energy acceptor) after the addition of Cr³⁺. The cell-permeability of DANS–RB was confirmed by the two-photon fluorescence microscopy experiments, which demonstrated DANS–RB was a good candidate for monitoring the intracellular Cr³⁺ level with the ratiometric fluorescent method. Combining the excellent selectivity, the ratiometric quantitative detection, and the cell-permeability, DANS–RB may find a broad application in the investigation on biologically relevant species in living cells.     

A ratiometric fluorescent probe for iron(III) and its application for detection of iron(III) in human blood serum

A simple and versatile ratiometric fluorescent Fe³⁺ detecting system, probe 1, was rationally developed based on the Fe³⁺-mediated deprotection of acetal reaction. Notably, this reaction was firstly employed to design fluorescent Fe³⁺ probe. Upon treatment with Fe³⁺, probe 1 showed ratiometric response, with the fluorescence spectra displaying significant red shift (up to 132 nm) and the emission ratio value (I₅₂₂/I₃₉₀) exhibiting approximately 2362-fold enhancement. In addition, the probe is highly sensitive (with the detection limit of 0.12 μM) and highly selective to Fe³⁺ over other biologically relevant metal ions. The sensing reaction product of the probe with Fe³⁺ was confirmed by NMR spectra and mass spectrometry. TD-DFT calculation has demonstrated that the ratiometric response of probe 1 to Fe³⁺ is due to the regulation of intramolecular charge transfer (ICT) efficiency. Moreover, the practical utility in fluorescence detection of Fe³⁺ in human blood serum was also conducted, and probe 1 represents the first ratiometric fluorescent probe that can be used to monitor Fe³⁺ level in human blood serum. Finally, probe 1 was further employed in living cell imaging with pancreatic cancer cells, in which it displayed low cytotoxicity, satisfactory cell permeability, and selective ratiometric response to Fe³⁺.     

Novel fluorescent sensor for Ag and Hg based on the BINOL-pyrene derivative via click reaction

A novel BINOL-pyrene derivative sensor 1 for Ag⁺ and Hg²⁺ incorporating the triazole moieties and pyrenes was synthesized via click reaction. Binding of Ag⁺ ion induces the formation of 1:1 Ag⁺-1 chelating complex, and occurs in a ratiometric manner through an enhanced monomer and declining excimer emission, which make it possible to ratiometrically detect Ag⁺. The competitive experiment shows 1 can be used as an Ag⁺ specific fluorescence sensor over a wide range of competing cations. In the meanwhile, the sensor 1 was found to be selectively quenched by only Hg²⁺ at both monomer and excimer emission. Furthermore, we obtained evidences for different fluorescence signaling behaviors with Ag⁺ and Hg²⁺ by ¹H NMR titration experiments.     

A pyrene-benzthiazolium conjugate portraying aggregation induced emission,a ratiometric detection and live cell visualization of HSO3

The present study deals with the photophysical property of a pyrene-benzthiazolium conjugate R1, as a strong intramolecular charge transfer (ICT) probe exhibiting long wavelength emission in the red region. Unlike traditional planar polyaromatic hydrocarbons whose aggregation generally quenches the light emission, the pyrene based R1 was found to display aggregation-induced emission (AIE) property along with simultaneous increase in its quantum yield upon increasing the water content of the medium. The R1 exhibits high specificity towards HSO₃⁻/SO₃²⁻ by interrupting its own ICT producing there upon a large ratiometric blue shift of ∼220 nm in its emission spectrum. The lowest detection limit for the above measurement was found to be 8.90 × 10⁻⁸ M. The fluorescent detection of HSO₃⁻ was also demonstrated excellently by test paper strip and silica coated TLC plate incorporating R1. The live cell imaging of HSO₃^─ through R1 in HeLa cells was studied using fluorescence microscopic studies. The particle size and morphological features of R1 and R1-HSO₃⁻ aggregates in aqueous solution were characterized by DLS along with SEM analysis.     

2D and 3D alkaline earth metal carboxyphosphonate hybrids: Anti-corrosion coatings for metal surfaces

Reactions of Mg²⁺ (1), Ca²⁺ (2), Sr²⁺ (3), or Ba²⁺ (4) salts with hydroxyphosphonoacetic acid (HPAA) at a 1:1 ratio yield M-HPAA layered coordination polymers. The crystal structures of 3 (two phases) and 4 have been determined by single crystal X-ray crystallography. Both stereoisomers (R and S) of HPAA are incorporated in the metal-HPAA materials. Synergistic combinations of Sr²⁺ or Ba²⁺ and HPAA at pH 7.3 are effective corrosion inhibitors for carbon steel, but are ineffective at pH 2.0.     

Zn selective luminescent ‘off-on’ probes derived from diaryl oxadiazole and aza-15-crown-5

New photo-induced electron transfer (PET) probes OMOX and OBOX, carrying an additional binding site in the form of ‘oxadiazole nitrogen’ have been designed to evaluate binding interactions with biologically significant Li⁺, Na⁺, K⁺, Ca²⁺, Mg²⁺, and Zn²⁺ including environmentally toxic Ba²⁺ and Cd²⁺ using optical spectral techniques. While Li⁺, Na⁺, and K⁺ did not appreciably perturb either the absorption or emission spectra, Ba²⁺, Ca²⁺, Mg²⁺, Zn²⁺, and Cd²⁺ induced slight red shifts (2-8 nm) in the UV-visible spectra as well as pronounced chelation induced enhanced fluorescence (CHEF). Both OMOX and OBOX exhibited the highest CHEF in contact with the zinc ion, whereas Ba²⁺, Ca²⁺, Mg²⁺, and Cd²⁺ induced relatively less emission enhancements. OBOX, which is a poorer emitter (Φ_f=0.0062) than OMOX (Φ_f=0.015), showed highly promising 160-fold emission enhancement in the presence of Zn²⁺. Potential, therefore is available in OBOX to function as a selective luminescent ‘off-on’ sensor for Zn²⁺ in the presence of coordinatively competing Ba²⁺, Ca²⁺, Mg²⁺, and Cd²⁺ ions.