A Novel Chemosensor Based on Rhodamine Derivative for Colorimetric and Fluorometric Detection of Cu<Superscript>2+</Superscript> in Aqueous Solution

A new rhodamine-based reversible chemosensor (2) was synthesized, which exhibits high sensitivity and selectivity for Cu²⁺ but no significant response toward other competitive metal ions in aqueous solution. Upon the addition of Cu²⁺, the spirolactam ring of 2 was opened and the solution color changed from colorless to red. Strangely, an unexpected fluorescence quenching was observed, which is contrary to the fluorescence turn-on of the most rhodamine-based chemosensors. The likely novel sensing mechanism has been proposed.     

A Dansyl-Rhodamine Ratiometric Fluorescent Probe for Hg<Superscript>2+</Superscript> Based on FRET Mechanism

Based on resonance energy transfer (FRET) from dansyl to rhodamine 101, a new fluorescent probe (compound 1) containing rhodamine 101 and a dansyl unit was synthesized for detecting Hg²⁺ through ratiometric sensing in DMSO aqueous solutions. This probe shows a fast, reversible and selective response toward Hg²⁺ in a wide pH range. Hg²⁺ induced ring-opening reactions of the spirolactam rhodamine moiety of 1, leading to the formation of fluorescent derivatives that can serve as the FRET acceptors. Very large stokes shift (220 nm) was observed in this case. About 97-fold increase in fluorescence intensity ratio was observed upon its binding with Hg²⁺.     

A New Reactive 1,8-Naphthalimide Derivative for Highly Selective and Sensitive Detection of Hg<Superscript>2+</Superscript>

A 1,8-naphthalimide derivative with a reactive aliphatic hydroxyl was designed and synthesized as a fluorescent probe. Its structure was characterized by IR, ¹H NMR, ¹³C NMR, LC-MS and HPLC. The probe showed high selectivity and sensitivity to Hg²⁺ over other metal ions such as Pb²⁺, Na⁺, K⁺, Cd²⁺, Cr³⁺, Zn²⁺, Cu²⁺, Ni²⁺, Ca²⁺, Fe³⁺, Fe²⁺, Co²⁺, Mn²⁺ and Mg²⁺ in MeCN/H₂O (15/85, v/v). The increase in fluorescence intensity was linearly proportional to the concentration of Hg²⁺ in the range of 18–40 μM with a detection limit of 1.38 × 10^?7 mol/L. The probe could work in a pH span of 4.3–9.0 and respond to Hg²⁺ quickly with strong anti-interference ability. Job’s plot suggested a 1:2 complex of the probe and Hg²⁺.     

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 Novel Hg<Superscript>2+</Superscript> Selective Ratiometric Fluorescent Chemodosimeter Based on an Intramolecular FRET Mechanism

A irreversible Hg²⁺ selective ratiometric fluorescence probe FR, a fluorescein fluorophore linked to a rhodamine B hydrazide by a thiourea spacer, was designed and synthesized. The developed probe FR exhibited great ratiometric fluorescence enhancement and remarkable yellow-magenta color change toward Hg²⁺ with excellent selectivity in aqueous acetone solution, and the ratiometric fluorescence response to Hg²⁺ was not interfered by other metal cations including Fe³⁺, Co²⁺, Ni²⁺, Cr³⁺, Zn²⁺, Pb²⁺, Cd²⁺, Ca²⁺, Mg²⁺, Ba²⁺ and Mn²⁺. The linear range and the detection limit of this supposed ratiometric fluorescence method for Hg²⁺ were 0.0–10.0 × 10⁻⁶ and 5 × 10⁻⁸ M, respectively.     

A Highly Sensitive and Selective Fluorescent Chemodosimeter for Hg<Superscript>2+</Superscript> in Neutral Aqueous Solution

A fluorescent assay of Hg²⁺ in neutral aqueous solution was developed using N-[p-(dimethylamino)benzamido]-N′-phenylthiourea (1). 1’s fluorogenic chemodosimetric behaviors towards various metal ions were studied and a high sensitivity as well as selectivity was achieved for Hg²⁺. It was because of a strongly fluorescent 1,3,4-oxadiazoles which was produced by the Hg²⁺ promoted desulfurization reaction. The spectra of ESI mass and IR provided evidences for this reaction. According to fluorescence titration, a good linear relationship ranging from 1.0 × 10⁻⁷ to 2.0 × 10⁻⁵ mol l⁻¹ was obtained with the limit of detection as 3.1 × 10⁻⁸ mol l⁻¹. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Organic Material Based Fluorescent Sensor for Hg<Superscript>2+</Superscript>: a Brief Review on Recent Development

Due to the deleterious effects of mercury on human health and natural ecosystems, high reactivity, non-degradability, extreme volatility and relative water and tissue solubility, it would consider as one of the most toxic environmental pollutants among the transition metals. In the present investigation, we have tried to summarized the several organic material based fluorescent sensor including rhodamine, boron-dipyrromethene (BODIPYs), thiourea, crown-ether, coumarine, squaraines, pyrene, imidazole, triazole, anthracene, dansyl, naphthalenedimide/ naphthalene/ naphthalimide, naphthyridine, iridium (III) complexes, polymeric materials, cyclodextrin, phthalic anhydride, indole, calix [4]arene, chromenone, 1,8-naphthalimides, lysine, styrylindolium, phenothiazine, thiocarbonyl quinacridone, oxadiazole, triphenylamine–triazines, tetraphenylethene, peptidyl and semicarbazone for the trace mercury detection in the aqueous, aqueous–organic and cellular media. The present review provides a brief look over the previous development in the organic material based fluorescent sensor for mercuric ion detection. Furthermore, the ligand-metal binding stoichiometry, binding/association/dissociation constants and the detection limit by the receptors have been particularly highlighted which might be useful for the future design and development of more sensitive and robust fluorescent chemosensor/chemodosimeter for the mercuric ion detection.

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Highly Selective and Anions Controlled Fluorescent Sensor for Hg<Superscript>2+</Superscript> in Aqueous Environment

A highly selective PET fluorescent sensor B1 for Hg²⁺ containing a BODIPY fluorophore and a NS₂O₂ penta-chelating receptor has been synthesized and characterized. Its absorption maximum wavelength (498 nm) and emission maximum wavelength (512 nm) are both in the visible range. The fluorescence quantum yields of the B1 and Hg²⁺-bound states of BHg1 are 0.008 and 0.58 in 70% aqueous ethanol solution, respectively. The pKa of 1.97 is the lowest in metal ions PET chemo sensors reported up till now as we know. Thus, B1 can detect the Hg²⁺ in a wide pH span, which indicates that it has more potential and further practical applications for biology and toxicology. Furthermore, BHg1 also displays response to some anions such as Cl⁻(Br⁻), , SCN⁻ and CH₃COO⁻, which is attributed to the significant coordinating ability of these anions to Hg²⁺.     

A Colorimetric and Fluorescent Sensor for Iron Recognition Based on Rhodamine Derivative

A novel rhodamine based fluorescent sensor, L, was developed and investigated as a colorimetric and fluorescent sensor for Fe³⁺ in dimethyl sulfoxide. The compound L showed a good selectivity and sensitivity toward Fe³⁺ in the presence of large excess of other competitive ions. L can be used as a colorimetric and fluorescent sensor for Iron recognition in potential.     

A highly Sensitive Turn-on Fluorescent Sensor for Ba<Superscript>2+</Superscript> Based on G-Quadruplexes

A G-quadruplex-based fluorescent biosensor for highly sensitive detection of barium ion (Ba²⁺) was constructed for the first time. In the absence of Ba²⁺, the G-quadruplex-specific fluorescence ligand N-methyl mesoporphyrin IX (NMM) remained weakly fluorescent when coexisted with a single-stranded G-quadruplex sequence AGRO100. Upon addition of Ba²⁺, AGRO100 was folded into G-quadruplex structures with the aid of Ba²⁺, which bound with NMM by stacking forces and significantly enhanced its fluorescence. The maximum fluorescence intensity of NMM was increased by ca. 22-fold in response to 1 μM Ba²⁺. This simple method exhibites a good linear relationship in the range of 0–600 nM with the detection limit of 4 nM. The detection method is turn-on, fast, economic, high in signal-to-noise ratio and free of participation of toxic organic solvents, demonstrating its great potential for on-site and real-time Ba²⁺ detection.     

A Dual-Target Fluorescent Probe with Response-Time Dependent Selectivity for Cd<Superscript>2+</Superscript> and Cu<Superscript>2+</Superscript>

A novel fluorescent probe (NT) was developed by merging 2-hydrazinylbenzothiazole with 2-hydroxy-1-naphthaldehyde for the detection of Cd²⁺ and Cu²⁺. The probe alone is almost nonfluorescent due to the isomerization of C=N in the excited state. The addition of Cd²⁺ can cause an immediate strong green fluorescence owing to the suppression of C=N isomerization by Cd²⁺-coordination. Furthermore, NT gives a delayed turn-on fluorescence response to Cu²⁺ although it is a vigorous fluorescence quencher, which was thanks to the inhibition of the electron transfer between excited fluorophore and paramagnetic Cu²⁺ by sulfur donor. Based on fluorescence spectra and ESI-MS analysis, the binding modes between NT and Cd²⁺/Cu²⁺ were proposed.     

Polyol-thermal synthesis of silver nanowires for Hg<Superscript>2+</Superscript> sensing detection

This study demonstrates a facile but effective polyol-thermal reaction method for the synthesis of silver nanowires in autoclaves (160–180 °C). By this approach, the generated silver nanowires show an average diameter of ~40 nm and length up to tens of micrometers with a high yield and potential for large-scale production. To achieve shape- and size-controlled Ag nanowires, several experimental parameters were investigated and optimized, including surface controller(s), molar ratio of surfactant(s) to silver ions, temperature, and concentration of reactants. The structure and composition of silver nanowires were characterized by transmission electron microscopy (TEM), high-resolution TEM (HRTEM), scanning electron microscopy (SEM), and X-ray diffraction (XRD) techniques. In particular, the twinned crystal structure observed in both spherical particles and nanowires was analyzed by HRTEM technique, and the possible formation and growth mechanisms were discussed. The optical property of the as-prepared product was measured by ultraviolet–visible (UV–vis) spectroscopy. The sensing detection of metal ions (e.g., Hg²⁺) using the obtained silver nanowires in aqueous media was finally investigated.     

A Turn-on Fluorescent Chemosensor for Zn<Superscript>2+</Superscript> Based on Quinoline in Aqueous Media

A simple “off-on fluorescence type” chemosensor 1 3-((2-(dimethylamino)ethyl)amino)-N-(quinolin-8-yl)propanamide has been synthesized for Zn²⁺. The receptor 1 comprises the quinoline moiety as fluorophore and the N,N^′-dimethylethane-1,2-diamine as a binding site. 1 showed a remarkable fluorescence enhancement in the presence of Zn²⁺ in aqueous solution. Importantly, the chemosensor 1 could be used to detect and quantify Zn²⁺ in water samples. In particular, this chemosensor could clearly distinguish Zn²⁺ from Cd²⁺. The binding properties of 1 with Zn²⁺ ions were investigated by UV-vis, fluorescence, electrospray ionization mass spectroscopy and ¹H NMR titration.     

A Rhodamine Derivative Based Chemosensor with High Selectivity and Quick Respond to Cr<Superscript>3+</Superscript> in Aqueous Solution

In this paper, a new kind of colorimetric chemsensor aiming at detecting Cr³⁺ has been synthesized, and it is based on the “Off-On” effect of a rhodamine derivative. Comparing with other metal irons (Na⁺, K⁺, Ni²⁺, Hg²⁺, Fe³⁺, Mn²⁺, Co²⁺, Cd²⁺, Cu²⁺, Pb²⁺, Zn²⁺, Mg²⁺, Ba²⁺, Ag⁺, Fe²⁺, Ce³⁺), the chemsensor has a quick and accurate response to Cr³⁺ in H₂O-EtOH solution (4/1, v/v). There is an obvious change in color, from colorless to bright pink when Cr³⁺ is detected. According to the fitting curve based on Benesi-Hildebrand equation and working curve of absorption strength in UV-vis spectrum, the binding pattern of Cr³⁺ and the rhodamine derivative follows a 1:1 stoichiometry. The chemsensor shows great potential in monitoring Cr³⁺ in the aqueous medium with high efficiency, which is supposed to complete the recognition in the minimum as 5.2?×?10^?7 mol/L within 5 min.     

A Coumarin-Based Fluorescent Chemosensor for Zn<Superscript>2+</Superscript> in Aqueous Ethanol Media

A coumarin-based fluorescent chemosensor 1 for Zn²⁺ was designed and synthesized. Compound 1 exhibits lower background fluorescence due to intramolecular photoinduced electron transfer. However, upon mixing with Zn²⁺ in 30% (v/v) aqueous ethanol, a “turn-on” fluorescence emission is observed. The fluorescence emission increases linearly with Zn²⁺ concentration in the range 0.5–10 μmol L⁻¹ with a detection limit of 0.29 μmol L⁻¹. No remarkable emission enhancement was, however, observed for other metal ions. The proposed chemosensor was applied to the determination of Zn²⁺ in water samples with satisfactory results.     

A New Fluorescent Chemosensor Detecting Co<Superscript>2+</Superscript> and K<Superscript>+</Superscript> in DMF Buffered Solution

A new fluorescent chemosensor 2-(2-thiophene)imidazo [4,5,f]-1,10-phenanthroline (L) was prepared and characterized. By adding univalent or divalent metal ions such as Na⁺, K⁺, Mg²⁺, Ba²⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Ag⁺, Zn²⁺, Cd²⁺ and Hg²⁺ ions into the solution of L in DMF under buffered conditions with the working pH ranging from 7.0 to 8.0, we found that L could be used to detect K⁺ ratiometricly and it could also be applied to sense Co²⁺ with the phenomenon of fluorescence quenching of L. While the response behavior of L was not discernibly affected by other examined metal ions.     

One-pot synthesis of hybrid nanospheres with multistructure for selective adsorption of Hg<Superscript>2+</Superscript>

Novel complex nanospheres with core/shell structure for selective adsorption of Hg²⁺ have been prepared by a simple one-pot method. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) images showed the nanospheres had perpendicularly thiol-functionalized mesoporous SiO₂ hybrid shell and Fe₃O₄@SiO₂ core (Fe₃O₄@nSiO₂@mSiO₂–SH). XRD patterns of as-synthesized nanospheres confirmed the observation of the SEM and TEM. The size of the nanospheres is about 100 nm. Based on the analysis of N₂ sorption–desorption isotherm, the surface area and pore volume of the adsorbent are 861 m²/g and 0.48 cm³/g, respectively. The saturation magnetization value for Fe₃O₄@nSiO₂@mSiO₂–SH is as high as 6.87 emu g⁻¹. The nanospheres showed more accessible active sites and high dispersibility in water, exhibited excellent performance for selective Hg²⁺ adsorption, had a stable structure, and could be recycled easily with magnet.     

A Fluorescence Turn-on Sensor for Hg<Superscript>2+</Superscript> with a Simple Receptor Available in Sulphide-Rich Environments

Detection of Hg²⁺ in complex natural environmental conditions is extremely challenging, and no entirely successful methods currently exist. Here we report an easy-to-prepare fluorescent sensor B3 with 2-aminophenol as Hg²⁺ receptor, which exhibits selective fluorescence enhancement toward Hg²⁺ over other metal ions. Especially, the fluorescence enhancement was unaffected by anions and cations existing in environment and organism. Moreover, B3 can detect Hg²⁺ in sulphide-rich environments without cysteine, S^2- or EDTA altering the fluorescence intensity. Consequently, B3 is capable of distinguishing between safe and toxic levels of Hg²⁺ in more complicated natural water systems with detection limit ≤2 ppb.     

Bay Functionalized Perylenediimide with Pyridine Positional Isomers: NIR Absorption and Selective Colorimetric/Fluorescent Sensing of Fe<Superscript>3+</Superscript> and Al<Superscript>3+</Superscript> Ions

Bay functionalized perylene diimide substituted with pyridine isomers, (2-pyridine (2HMP-PDI), 3-pyridine (3-HMP-PDI) and 4-pyridine (4-HMP-PDI)) have been synthesized and explored for selective coloro/fluorimetric sensing of heavy transition metal ions. HMP-PDIs showed strong NIR absorption (760–765 nm) in DMF. The absorption and fluorescence of HMP-PDIs have been tuned by make use of pyridine isomers. Reddish-orange color was observed for 2-HMP-PDI (λ_max = 437, 551, 765 nm) whereas 4-HMP-PDI exhibited light green (λ_max = 432, 522, 765 nm). 3-HMP-PDI showed orange-yellow (λ_max = 431, 524, 762 nm). The fluorescence spectra of 2-, 3- and 4-HMP-PDI showed λ_max at 585, 538, 546 nm, respectively. Interestingly, HMP-PDI dyes showed selective color change (intense pink color) and fluorescence quenching for Fe³⁺ and Al³⁺ metal ions in DMF. Absorbance spectra revealed complete disappearance of NIR absorption and intensification/appearance of new peak at lower wavelength. The concentration dependent studies suggest that 4-HMP-PDI can detect up to 36.52 ppb of Fe³⁺ and 43.12 ppb of Al³⁺ colorimetrically. The interference studies in presence of other metal ions confirmed the good selectivity for Fe³⁺ and Al³⁺. The mechanistic studies indicate that Lewis acidic character of Fe³⁺ and Al³⁺ ions were responsible for selective color change and fluorescence quenching.     

A Label-Free Oligonucleotide Based Thioflavin-T Fluorescent Switch for Ag<Superscript>+</Superscript> Detection with low Background Emission

A novel fluorescent Ag⁺ sensor was developed based on the label-free silver (I) specific oligonucleotide (SSO) and Thioflavine T (ThT) monomer-excimer switch. C-rich SSO which contain C-C mismatched base pairs can selectively bind to Ag⁺ ions and the formed duplexes which constructed by C-Ag⁺-C structure are thermally stabilized without largely altering the double helical structure. ThT give very weak fluorescent in bulk solution and/or in the presence of SSO. However ThT shows high fluorescence in the presence of SSO and Ag⁺ at the same time mainly because ThT excimer, which has the high quantum yield, formed and stabilized in the minor or major groove. Based on the discovery, we developed the novel Ag⁺ sensor. Under the optimum condition, the selectivity of this system for Ag⁺ over other metal ions in aqueous solution is remarkably high, and Ag⁺ can be quantified over the dynamic range of 30–450 nM, with a limit of detection of ~16 nM and a linear correlation coefficient of 0.995.