A reversible fluorescent–colorimetric Schiff base sensor for Hg ion

A simple (R)-(−)-2-phenylglycinol functionalized Schiff base L1 and its characterization as a fluorescent–colorimetric sensor for Hg²⁺ ion are described. The UV–vis and fluorescence analysis in methanol and aqueous solution show complex formation between L1 and Hg²⁺ ion with a micromolar association constant. Competition experiments performed for the acetate salts of Hg²⁺, Zn²⁺, Co²⁺, Pb²⁺, Cd²⁺, Mn²⁺, Cu²⁺, Ni²⁺, and Ba²⁺ revealed that compound L1 exhibits high selectivity toward Hg²⁺ displaying a color change easily detectable by naked-eye and a turn-off fluorescent effect due to a chelation-enhanced quenching (CHEQ) mechanism. Moreover, addition of EDTA to L1–Hg²⁺ recovers the fluorescence and color offering receptor L1 as a reversible sensor for real-time applications.     

A novel colorimetric and “turn-on” fluorescent sensor for selective detection of Cu2+

In this work, a new highly selective and sensitive fluorescent sensor for detecting Cu²⁺ was developed based on rhodamine fluorophore. It displayed strong fluorescence “turn-on” effect upon addition of Cu²⁺, and possessed the function of naked eye recognition. The fluorescence enhancement also enabled the sensor to quantitatively analyze Cu²⁺ due to the formation of a stable 1:1 metal–ligand complex in a short time, and the complex possesses relatively good pH stability. In addition, the density functional theory calculations were adopted to investigate the molecular orbitals as well as the spatial structure. Simultaneously, the cell imaging and zebra fish experiments provided a broader application prospect in biological system.     

A fluorescence “on–off” sensor for the highly selective and sensitive detection of Cu2+ ion

In an attempt to obtain a model of copper(II) ion-selective sensors, a new 1,8-naphthalimide-based fluorescence chemosensor, N-allylamine-4-[(E)-4-(([2-aminoethyl]imino)methyl) benzene-1,3-diol]-1,8-naphthalimide (NABN), was designed and synthesized. The sensor NABN is fully characterized by melting point analysis, fourier transform infrared spectra, Ultraviolet–visible (UV–vis) spectra, fluorescence spectra, ¹H NMR and ¹³C NMR spectroscopy, and mass spectrometry. NABN showed an unrivaled sensing behavior and an ardent selectivity toward copper(II) ion over other competitive metal ions tested in solution (N,N-Dimethylformamide (DMF)/Tris–HCl buffer, 1:1, v/v, pH = 7.2). The sensor showed a linear fluorescence quenching toward copper(II) ion in the range 0–50 μM, with a detection limit of 1.92 × 10⁻⁷ M estimated. Job's method indicated the formation of a 2:1 coordinative mode of the sensor with copper(II) ion with a high threshold of binding constant of 4 × 10¹² M⁻¹. Combining the above results, the quenching response of NABN toward Cu(II) ions could be ascribed to the strong, intrinsic paramagnetic behavior of Cu(II).     

A selective coumarin-based “turn-on” fluorescent sensor for the detection of cysteine and its applications for bioimaging

A coumarin-based compound (1) was designed and synthesized as a new turn-on fluorescent probe for the detection of cysteine. The in vivo imaging of Hi5 cell and Caenorhabditis elegans had further confirmed the cysteine detection by compound 1.     

Multiplex sensor for detection of different metal ions based on on–off of fluorescent gold nanoclusters

In this study, a multiplex fluorescence sensor for successive detection of Fe³⁺, Cu²⁺ and Hg²⁺ ions based on “on–off” of fluorescence of a single type of gold nanoclusters (Au NCs) is described. Any of the Fe³⁺, Cu²⁺ and Hg²⁺ ions can cause quenching fluorescence of Au NCs, which established a sensitive sensor for detection of these ions respectively. With the introduction of ethylene diamine tetraacetic acid (EDTA) to the system of Au NCs and metal ions, a restoration of fluorescence may be found with the exception of Hg²⁺. A highly selective detection of Hg²⁺ ion is, thus, achieved by masking Fe³⁺ and Cu²⁺. On the other hand, the masking of Fe³⁺ and Cu²⁺ leads to the enhancement of fluorescence of Au NCs, which in turn provides an approach for successive determination of Fe³⁺ and Cu²⁺ based on “on–off” of fluorescence of Au NCs. Moreover, this assay was applied to the successful detection of Fe³⁺, Cu²⁺ and Hg²⁺ in fish, a good linear relationship was found between these metal ions and the degree of quenched fluorescent intensity. The dynamic ranges of Hg²⁺, Fe³⁺ and Cu²⁺ were 1.96 × 10⁻¹⁰–1.01 × 10⁻⁹, 1.28 × 10⁻⁷–1.27 × 10⁻⁶ and 1.2 × 10⁻⁷–1.2 × 10⁻⁶ M with high sensitivity (the limit of detection of Fe³⁺ 2.0 × 10⁻⁸ M, Cu²⁺ 1.9 × 10⁻⁸ M and Hg²⁺ 2 × 10⁻¹⁰ M). These results indicate that the assay is suitable for sensitive detection of these metal ions even under the coexistence, which can not only determine all three kinds of metal ions successively but also of detecting any or several kinds of metal ions.     

A highly selective fluorescent sensor for fluoride anion based on pyrazole derivative: Naked eye “no–yes” detection

A new pyrazole-based fluorescent sensor, 5-amino-3-(5-phenyl-1H-pyrrol-2-yl)-1H-pyrazole-4-carboxamide (compound 1), was studied for fluoride anion (F^?) detection in organic or water-containing solution. This compound displayed both changes in UV–vis absorption and fluorescence emission spectra upon addition of F^?. With increasing of F^?, blue emission intensity increases drastically and reaches saturation with 607-fold enhancement at 424 nm. The results indicate that compound 1 has highly selectivity for fluoride detection over other anions, such as Cl^?, Br^?, I^?, HSO₄^?, H₂PO₄^? and AcO^? in DMSO or aqueous DMSO solutions. ¹H NMR titration and other experiments confirm that the sensing process is mainly from the deprotonation of the pyrazole–NH in compound 1.     

Ultrasensitive detection of aliphatic nitro-organics based on “turn-on” fluorescent sensor array

The broad class of explosives includes nitro aromatics as well as challenging aliphatic nitro-organics whose detection is important from counter-terrorism and national security perspectives. Here we report a turn-on fluorescent sensor array based on aggregation-induced emission (AIE) fluorophores as receptors. To achieve a good sensing system with fast response, good sensitivity and low detection limit, three receptors with abundant chemical diversities for target analytes were synthesized. The turn-on response of the individual receptor showed highly variable and cross-reactive analyte-dependent changes in fluorescence. The excellent ability to identify a variety of explosives, especially the challenging aliphatic nitro-organics (2,3-dimethyl-2,3-dinitrobutane (DMNB), 1,3,5-trinitro-1,3,5-triazinane (RDX), cyclotetramethylene tetranitramine (HMX) and entaerythritol tetranitrate (PETN)), was demonstrated in qualitative and quantitative analyses with 100% accuracy. The fluorescence signal amplification in the presence of explosives allows for application of these receptors in a sensor microarray suitable for high-throughput screening. These results suggested that the cross-reactive sensor array based on AIE fluorophores could find a wide range of applications for sensing various analytes or complex mixtures.     

Organic-inorganic hybrid fluorescent sensor thin films of rhodamine B embedded Ag-SBA 15 for selective recognition of Hg (Ⅱ) ions in water

Nowadays, the rapid and effective detection of low doses of heavy metal pollutants in contaminated water is a timely challenge in environmental pollution research. In this study, a rapid and highly sensitive assay for the detection of Hg~(2+)based on quenching of metal-enhanced fluorescence of rhodamine B(RB)has been fabricated. RB and silver nanoparticle were incorporated into the mesoporous siliceous framework spin cast on a quartz glass through post-synthetic incorporation method. The morphology and crystallinity of mesoporous structure and Ag nanoparticle were characterized by transmission electron microscopy and X-ray diffraction analyses. Photoluminescence assays on the hybrid thin film of RB-Ag-SBA15 showed a high enhancement when compared to the intensity of silver free SBA15-RB in the wavelength of 575 nm. The fluorescence of RB-Ag-SBA15 thin film decreased gradually with the increase in the concentration of Hg~(2+)and the detection limits were 10.54 nmol/L. Furthermore, the fluorescence intensity increased linearly with the concentration of Hg~(2+)in the range from 1.0 ? 10à8mol/L to10 ? 10à8mol/L, with a response time of a few seconds. In addition, this system offers a high selectivity over interfering cations such as Cd~(2+) and Pb~(2+). Overall, we have developed an optical assay having a wellordered mesoporous SBA15 containing Ag-RBfor selective detection of Hg~(2+)in aqueous solution. The scheme combines the advantages of specific binding interactions between Hg~(2+)and RB molecule and optical emission properties of RB. The method is suitable for a single-shot and irreversible analytical assay in a quartz glass/microtiter plate.     

Highly selective Markovnikov hydration of Δ24-sterols and triterpenes by oxymercuration–hydrodemercuration

The reaction of mercuric acetate with unsaturated sterols and tetracyclic triterpenes (oxymercuration), followed by reduction with sodium borohydride/sodium hydroxide in water (hydrodemercuration), is highly selective for the side-chain double bonds 24-methylene or 24 (25). The nuclear double bonds, or those on other positions in the side-chain, do not react. The specificity of mercuration is therefore not directly correlated to the degree of substitution of the double bond, but rather to its steric accessibility. This sequence, which has been tested on some 30 sterols and related tetracyclic triterpenes, can be used to separate conveniently some of the constituents of the often-complex mixtures of sterols and of their tetracyclic triterpene precursors present in the unsaponifiable fraction of plant lipids. To cite this article: L. Elkihel et al., C. R. Chimie 6 (2003) 000–000.     

Phenanthrene-imidazole-based fluorescent sensor for selective detection of Ag+ and F− ions: real sample application and live cell imaging

Research on Chemical Intermediates - 4-Methyl-2,6-bis(1H-phenanthro[9,10-d]imidazol-2-yl)phenol (probe-MPIP) conjugate has been designed as a selective fluorescent probe for silver (Ag+) ions. The...     

Azo-pyrene–based fluorescent sensor of reductive cleavage of isomeric azo functional group

In this study we investigated the reductive azo cleavage of an azo compound presenting a pyrene fluorophore (Azo-py). Because of dramatic changes in its fluorescence, Azo-py could be used as a monitoring system for the reductive azo cleavage. Electron transfer from the pyrene unit to the azo moiety induced fluorescence quenching; this quenched fluorescence was recovered after the reductive azo cleavage. IR and NMR spectroscopy were used to study the various structural states. The rate of reductive cleavage of the azo compound, determined through fluorescence monitoring, depended on its structural state: the cleavage of trans-Azo-py was much faster than that of the cis-Azo-py. Furthermore, the Azo-py fluorophore was highly sensitive to the presence of zinc, but not other metal compounds, and the pH.     

Graphene–Au composite sensor for electrochemical detection of para-nitrophenol

A novel electrochemical sensor for para-nitrophenol (p-NP) was constructed with graphene–Au composite containing 10 % Au (G–Au 10 %). In the composite, Au nanoparticles with the size of ca. 11 nm were regularly scattered on graphene sheet without aggregation, which offers dramatically higher electrocatalytic activity on the redox of K₃[Fe(CN)₆]/K₄[Fe(CN)₆] couple than sole Au nanoparticles. Compared to sole Au nanoparticles, the G–Au 10 % also exhibited dramatically improved electrocatalytic activity on the reduction of p-NP. Amperometric detection of p-NP at G–Au 10 % modified electrode displayed a wide linear range of 0.47–10.75 mM with detection limit of 0.47 μM and a high sensitivity of 52.85 μA/mM. Considering the thrifty in utilization of noble Au, the G–Au 10 % can be successfully applied as a low-cost and powerful sensing material for trace detection of p-NP.     

Highly sensitive and selective detection of cytochrome P450 46A1 activity by a ultra-high-performance liquid chromatography–tandem mass spectrometry method

Cytochrome P450 46A1 (CYP46A1) is a key enzyme responsible for metabolizing cholesterol to 24-hydroxycholesterol in the brain, and thus might serve as a therapeutic target for several neurodegenerative disorders including Parkinson's disease, Alzheimer's disease and Huntington's disease. However, an applicable, sensitive and reliable method for the precise measurement of CYP46A1 activities in complex biological samples remains limited. In this study, a novel ultra-high-performance liquid chromatography–tandem mass spectrometry (UPLC–MS/MS) method for highly sensitive and selective determination of 24-hydroxycholesterol was developed to characterize CYP46A1 activity. The mass spectrometric detection was performed using multiple reaction monitoring for 24-hydroxcholesterol at m/z 385.2 → 367.2. The limit of quantification for 24-hydroxycholesterol using this UPLC–MS/MS method was as low as 10 nM, which is lower than those reported previously. The method also showed favorable accuracy and precision. Meanwhile, the short- and long-term stability of this method was fully validated. In addition, the method was successfully applied to investigate the kinetic properties of 24-hydroxycholesterol formation by CYP46A1.     

1,2-dithioglycol functionalised carbon nitride quantum dots as a “turn – off” fluorescent sensor for mercury ion detection

A kind of 1,2-dithioglycol (DTG) functionalised carbon nitride quantum dots (DTG-CNQDs) was designed for the first time by modifying DTG on the surface of carbon nitride quantum dots (CNQDs). The as-prepared DTG-CNQDs exhibit strong blue fluorescence under ultraviolet light and have a high quantum yield of 27%. Experiments show that Hg²⁺ has a good quenching effect on the fluorescence of DTG-CNQDs. In phosphate buffer (PBS, 10 mM, pH 6.0), the fluorescence quenching rate (F₀/F) has a good linear relationship with the concentration of Hg²⁺ in the range of 0.020–0.50 μM with detection limit of 0.63 nM. This fluorescent probe possesses high sensitivity and good selectivity, which can be applied in the rapid detection of Hg²⁺ in tap and lake water samples.     

Utilization of a spiropyran derivative in a polymeric film optode for selective fluorescent sensing of zinc ion

Spiropyrans are the most studied families of func- tional materials due to their reversible structural con- version in response to external optical, chemical, and thermal stimulation[1]. Irradiation with ultraviolet light causes formation of an extended π-conjugation open form (merocyanine form) by heterolytic cleavage of the C (spiro)-O bond, which generates an intense ab- sorption in the visible region. Under the irradiating of visible light, the opened form will come back to the closed spi…     

A ratiometric electrochemical biosensor for sensitive detection of Hg based on thymine–Hg–thymine structure

In this paper, a simple, selective and reusable electrochemical biosensor for the sensitive detection of mercury ions (Hg²⁺) has been developed based on thymine (T)-rich stem–loop (hairpin) DNA probe and a dual-signaling electrochemical ratiometric strategy. The assay strategy includes both “signal-on” and “signal-off” elements. The thiolated methylene blue (MB)-modified T-rich hairpin DNA capture probe (MB-P) firstly self-assembled on the gold electrode surface via Au–S bond. In the presence of Hg²⁺, the ferrocene (Fc)-labeled T-rich DNA probe (Fc-P) hybridized with MB-P via the Hg²⁺-mediated coordination of T–Hg²⁺–T base pairs. As a result, the hairpin MB-P was opened, the MB tags were away from the gold electrode surface and the Fc tags closed to the gold electrode surface. These conformation changes led to the decrease of the oxidation peak current of MB (I_MB), accompanied with the increase of that of Fc (I_Fc). The logarithmic value of I_Fc/I_MB is linear with the logarithm of Hg²⁺ concentration in the range from 0.5 nM to 5000 nM, and the detection limit of 0.08 nM is much lower than 10 nM (the US Environmental Protection Agency (EPA) limit of Hg²⁺ in drinking water). What is more, the developed DNA-based electrochemical biosensor could be regenerated by adding cysteine and Mg²⁺. This strategy provides a simple and rapid approach for the detection of Hg²⁺, and has promising application in the detection of Hg²⁺ in real environmental samples.     

Highly sensitive and selective DNA-based detection of mercury(II) with α-hemolysin nanopore

The duplex formation mediated by Hg(2+) in a properly designed ssDNA generates a stable hairpin structure, which greatly alters the translocation profile of the ssDNA through α-hemolysin nanopore. From the 2D-events contour plot, the presence of Hg(2+) can be confirmed in as little as 30 min at ～7 nM or higher. The sensor is highly selective to Hg(2+), without interference from other metal ions. It can be fabricated from readily available materials, without the processes of synthesis, purification, probe-making, and so forth. This sensing strategy opens new possibilities for detecting many types of analytes which have specific interactions with DNA molecules.     

Light element analysis in steel by high–energy heavy–ion time of flight elastic recoil detection analysis

Time of flight elastic recoil detection analysis (TOF–ERDA) using high–energy heavy ions has been applied to determining the composition of light elements in stainless–steel (SUS304) samples before and after welding in order to monitor the variation in the composition of light elements in sample surfaces during a welding process. An argon–welding method using a welding rod (SUS304) and an arc–welding method using a welding rod were used to prepare samples. Four samples, welded and non–welded using two welding methods, were measured. ⁴⁰Ar ions accelerated to 40.3 MeV were used as a probe. Carbon, oxygen and sodium were measured. It was found that the oxygen distributions near to the surfaces of the welded samples increased compared with those of the non–welded samples. However, variations in the carbon distributions were relatively smaller than that of oxygen distributions.