Sensitive iodate sensor based on fluorescence quenching of gold nanocluster

In this report we described a highly selective and sensitive iodate sensor. Due to its interaction with fluorescent gold nanoclusters, iodate was capable of oxidizing and etching gold core of the nanoclusters, resulting in fluorescence quenching. Furthermore, it was found that extra iodide ion could enhance this etching process, and even a small amount of iodate could lead to significant quenching. Under an optimized condition, linear relationship between the iodate concentration and the fluorescence quenching was obtained in the range 10 nM–1 μM. The developed iodate sensor was found selective and capable of detecting iodate as low as 2.8 nM. The sensor was then applied for the analysis of iodate in real sample and satisfactory recoveries were obtained.     

Ag nanoclusters as probes for turn-on fluorescence recognition of TpG dinucleotide with a high selectivity

CpG dinucleotide in DNA has a great tendency to mutate to TpG dinucleotide and this transition can cause some serious diseases. In this work, fluorescent Ag nanoclusters (Ag NCs) were employed as useful inorganic fluorophores for the potential of selectively discriminating TpG dinucleotide from CpG dinucleotide. Opposite the base Y of interest in YpG dinucleotide (Y = C or T), a bulge site was introduced so as to make the base Y to be unpaired and ready for Ag⁺ binding. Such that the unpaired Y and context base pairs can provide a specific space suitable for creating fluorescent Ag NCs. We found that in comparison with CpG dinucleotide, TpG dinucleotide is much more efficient in growing fluorescent Ag NCs. Therefore, mutation of CpG dinucleotide to TpG can be identified by a turn-on fluorescence response and a high selectivity. More interestingly, Ag NCs exhibit a better performance in the TpG recognition over the other dinucleotides (Y = A and G) than the previously used organic fluorophores. Additionally, the effectiveness of the bulge site design in discriminating these dinucleotides was evidenced by control DNAs having the abasic site structure. We expect that a practical method for TpG dinucleotide recognition with a high selectivity can be developed using the bulge site-grown fluorescent Ag NCs as novel probes.     

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.     

Functionalized cadmium sulfide quantum dots as fluorescence probe for silver ion determination

CdS quantum dots (QDs) modified with l-cysteine has been prepared by one step. They are water-soluble and biocompatible. To improve CdS QDs stability and interaction between silver ion and functionalized CdS QDs in aqueous solution, some amounts of fresh l-cysteine were added to functionalized CdS solution. Based on the characteristic fluorescence enhancement of CdS QDs at 545 nm by silver ions in the presence of some amounts of fresh l-cysteine, simultaneously, a gradual red shift of fluorescence emission bands of CdS QDs from 545 to 558 nm was observed. A simple, rapid, sensitive and specific detection method for silver ion was proposed. Under optimum conditions, the fluorescence intensity of CdS QDs is linearly proportional to silver concentration from 2.0 × 10⁻⁸ to 1.0 × 10⁻⁶ mol/L with a detection limit of 5.0 × 10⁻⁹ mol/L. In comparison with single organic fluorophores, functionalized CdS quantum dots are brighter, more stable against photobleaching, and don’t suffer from blinking. Furthermore, owing to the fluorescence enhancement effect of CdS QDs by silver ion, the proposed method showed lower detection blank and higher sensitivity. Possible fluorescence enhancement mechanism was also studied.     

Label-free aptamer-based colorimetric detection of mercury ions in aqueous media using unmodified gold nanoparticles as colorimetric probe

We report a simple and sensitive aptamer-based colorimetric detection of mercury ions (Hg²⁺) using unmodified gold nanoparticles as colorimetric probe. It is based on the fact that bare gold nanoparticles interact differently with short single-strand DNA and double-stranded DNA. The anti-Hg²⁺ aptamer is rich in thymine (T) and readily forms T–Hg²⁺–T configuration in the presence of Hg²⁺. By measuring color change or adsorption ratio, the bare gold nanoparticles can effectively differentiate the Hg²⁺-induced conformational change of the aptamer in the presence of a given salt with high concentration. The assay shows a linear response toward Hg²⁺ concentration through a five-decade range of 1 × 10⁻⁴ mol L⁻¹ to 1 × 10⁻⁹ mol L⁻¹. Even with the naked eye, we could identify micromolar Hg²⁺ concentrations within minutes. By using the spectrometric method, the detection limit was improved to the nanomolar range (0.6 nM). The assay shows excellent selectivity for Hg²⁺ over other metal cations including K⁺, Ba²⁺, Ni²⁺, Pb²⁺, Cu²⁺, Cd²⁺, Mg²⁺, Ca²⁺, Zn²⁺, Al³⁺, and Fe³⁺. The major advantages of this Hg²⁺ assay are its water-solubility, simplicity, low cost, visual colorimetry, and high sensitivity. This method provides a potentially useful tool for the Hg²⁺ detection.     

Solvent-dependent turn-on probe for dual monitoring of Ag and Zn in living biological samples

A novel, solvent-dependent “off–on” probe with benzoylthiourea moiety as the functional receptor and fluorescein as the fluorophore was designed for monitoring of Ag⁺ in EtOH–H₂O (2:8, v/v) solution and Zn²⁺ in CH₃CN–H₂O (2:8, v/v) solution at physiological range with sufficient selectivity and sensitivity. The Ag⁺ promoted desulfurization of thiosemicarbazide functionality in formation of the 1,3,4-oxadiazole and the coordination of Zn²⁺ to the O atom and N atom of the spoirolactam moiety and the S atom of the benzoylthiourea moiety were investigated to be the power that promoted the fluorescent enhancement. This probe was tested highly suitable for mapping Ag⁺ and Zn²⁺ in living human osteosarcoma MG-63 cells and microbial cell–EPS–mineral aggregates, thus, providing a wonderful candidate for tracking Ag⁺ and Zn²⁺ in biological organisms and processes.     

Preparation, characterization and evaluation of water-soluble l-cysteine-capped-CdS nanoparticles as fluorescence probe for detection of Hg(II) in aqueous solution

Water-soluble l-cysteine-capped-CdS nanoparticles were prepared in aqueous solution at room temperature through a straightforward one-pot process by using safe and low-cost inorganic salts as precursors, and characterized by transmission electron microscopy, X-ray diffraction spectrometry, Fourier transform infrared spectrometry, spectrofluorometry and ultraviolet-visible spectrometry. The prepared l-cysteine-capped-CdS nanoparticles were evaluated as fluorescence probe for Hg(II) detection. The fluorescence quenching of the l-cysteine-capped-CdS nanoparticles depended on the concentration and pH of Hg(II) solution. Maximum fluorescence quenching was observed at pH 7.4 with the excitation and emission wavelengths of 360 nm and 495 nm, respectively. Quenching of its fluorescence due to Hg(II) at the 20 nmol l⁻¹level was unaffected by the presence of 5 × 10⁶-fold excesses of Na(I) and K(I), 5 × 10⁵-fold excesses of Mg(II), 5 × 10⁴-fold excesses of Ca(II), 500-fold excesses of Al(III), 91-fold excesses of Mn(II), 23.5-fold excesses of Pb(II), 25-fold excesses of Fe(III), 25-fold excesses of Ag(I), 8.5-fold excesses of Ni(II) and 5-fold excesses of Cu(II). Under optimal conditions, the quenched fluorescence intensity increased linearly with the concentration of Hg(II) ranging from 16 nmol l⁻¹ to 112 nmol l⁻¹. The limit of detection for Hg(II) was 2.4 nmol l⁻¹. The developed method was applied to the detection of trace Hg(II) in aqueous solutions.     

Polyethyleneimine-capped silver nanoclusters as a fluorescence probe for sensitive detection of hydrogen peroxide and glucose

In this work, we utilized polyethyleneimine-capped silver nanoclusters (PEI-Ag nanoclusters) to develop a new fluorometric method for the determination of hydrogen peroxide and glucose with high sensitivity. The PEI-Ag nanoclusters have an average size of 2 nm and show a blue emission at 455 nm. The photostable properties of the PEI-Ag nanoclusters were examined. The fluorescence of the PEI-Ag nanoclusters could be particularly quenched by H₂O₂. The oxidization of glucose by glucose oxidase coupled with the fluorescence quenching of PEI-Ag nanoclusters by H₂O₂ can be used to detect glucose. Under optimum conditions, the fluorescence intensity quenched linearly in the range of 500 nM–100 μM with high sensitivity. The detection limit for H₂O₂ was 400 nM. And a linear correlation was established between fluorescence intensity (F₀ − F) and concentration of glucose in the range of 1.0 × 10⁻⁶ to 1.0 × 10⁻⁵ M and 1.0 × 10⁻⁵ to 1.0 × 10⁻³ M with a detection limit of 8.0 × 10⁻⁷ M. The method was used for the detection of glucose in human serum samples with satisfactory results. Furthermore, the mechanism of sensitive fluorescence quenching response of Ag nanoclusters to glucose and H₂O₂ has been discussed.     

A fluorescence turn-on probe for the detection of thiol-containing amino acids in aqueous solution and bioimaging in cells

A turn-on fluorescent probe, based on a water-soluble terphenyl derivative, for the detection of cysteine and homocysteine is reported. The aldehyde groups in the probe play crucial roles in providing reaction with thiol groups in the amino acids, leading to a formation of thiazolidine (from cysteine) or thiazinane ring (from homocysteine). As a result, the new formation of such rings alters the electronic property of the conjugated system in the probe and results in emission enhancement. The probe in aqueous solution exhibits a remarkable increase in its quantum yield upon exposure to cysteine (up to 20-fold) and to homocysteine (up to 700-fold), while slight quenching is observed in the presence of glutathione. Moreover, an investigation on time-resolved fluorescence spectra of the probe in the presence of cysteine and homocysteine reveals potential discriminatory detection of cysteine and homocysteine. Bioimaging of the thiols in live HeLa cells was successfully applied.     

A fluorescent sensor for Hg and Ag functions as a molecular switch based on click-generated triazole moiety

The novel (S)-BINOL-based sensor 1 incorporating triazole moieties could be obtained by click reaction. The results show that 1 can exhibit excellent fluorescence response behaviors toward Hg²⁺ (selective switching-off) and Ag⁺ (selective switching-on) without interference from other metal ions, which functions as a molecular switch. This work can expand the application of click reaction in design and synthesis of the novel fluorescence sensor molecules.     

Fluorescent chemosensor for Ag(I) based on amplified fluorescence quenching of a new phthalocyanine bearing derivative of benzofuran

A fluorescent chemosensor for Ag(I) as a new family of peripherally functionalized zinc-phthalocyanine, 2(3),9(10),16(17),23(24)-tetrakis-{6-(-benzofuran-2-carboxylate)-hexylthio} phthalocyaninatozinc(II) {Zn[Pc(β-S(CH₂)₆OCOBz-furan)₄], (ZnPcBzF), (3), which was derivated from 6-(3,4-dicyanophenylthio)-hexyl–2-benzofuranate (BzF), (2), has been synthesized and fully characterized by elemental analysis, FT-IR, ¹H and ¹³C NMR, MS (ESI and Maldi-TOF). An optical silver ion (Ag(I)) sensor based on the fluorescence quenching of benzofuran moiety and ZnPc core was developed. Both absorbance and fluorescence spectra of ZnPcBzF, (3) exhibit distinct changes in visible region in response to treatment with Ag(I) ion in solution. Such properties make compound ZnPcBzF, (3) intriguing candidates for incorporation into the transducer layer in optically based chemical sensors.     

A tetraphenylethene based polarity dependent turn-on fluorescence strategy for selective and sensitive detection of Hg in aqueous medium and in living cells

A turn-on fluorescent chemosensor strategy based on the change in the polarity of aggregation induced emission active tetraphenylethene is presented for the detection of Hg²⁺ in aqueous medium and in living cells. The sensing mechanism involves the formation of nonpolar fluorescent aggregates of tetraphenylethene molecules by elimination of polar moieties of TPE with Hg²⁺ interaction.     

Label-free and fluorescence turn-on aptasensor for protein detection via target-induced silver nanoclusters formation

A simple turn-on and homogeneous aptasensor, which relies on target induced formation of silver nanoclusters (Ag NCs), was developed for the determination of platelet-derived growth factor B-chain homodimer (PDGF-BB). The aptasensor contains two hairpin DNA probes termed as P1 and P2. P1 consists of the aptamer sequence of PDGF-BB. Meanwhile, P2 contains the Ag NCs nucleation sequence, which is blocked by the hairpin stem region. P1 and P2 can co-exist metastably in the absence of PDGF-BB and maintain hairpin structure. However, in the presence of PDGF-BB, the binding of PDGF-BB with aptamer will result in the hybridization between P1 and P2, and release the Ag NCs nucleation sequence. In this case, Ag NCs can be formed via the reduction of Ag⁺ by NaBH₄. By monitoring the increase in fluorescence intensity, we could detect the target protein with high sensitivity. The detection limit of this aptasensor is 0.37 nM, which is comparable with that of other reported aptasensors. Furthermore, this proposed aptasensor shows high selectivity toward its target protein. Thus, the proposed aptasensor based on target induced formation of Ag NCs could be used as a sensitive and selective platform for the detection of target protein.     

Label-free fluorescence turn-on detection of microRNA based on duplex-specific nuclease and a perylene probe

A novel fluorescence turn-on microRNA (miRNA) detection method based on duplex-specific nuclease (DSN) and a perylene probe is presented in this study. A positively charged perylene derivative (compound 1) was used as the fluorescent probe. Compound 1 exhibits strong monomer fluorescence in an aqueous buffer solution. It is well known that single-stranded DNA is a polyanion in nature. Thus, it can induce the aggregation of compound 1 through strong electrostatic, hydrophobic and π−π stacking interactions. As a result, the fluorescence of compound 1 was efficiently quenched. When the target miRNA was added, the formation of DNA-RNA hybridized duplex initiated the cleavage of the DNA strand by DSN cycle reaction, which resulted in disaggregation of compound 1. A fluorescence turn-on signal was detected, and a novel miRNA sensing method was therefore established. The presented method is label-free, simple, cost effective, sensitive and selective.     

A functionalized gold nanoparticles and Rhodamine 6G based fluorescent sensor for high sensitive and selective detection of mercury(II) in environmental water samples

A gold-nanoparticles (Au NPs)-Rhodamine 6G (Rh6G) based fluorescent sensor for detecting Hg (II) in aqueous solution has been developed. Water-soluble and monodisperse gold nanoparticles (Au NPs) has been prepared facilely and further modified with thioglycolic acid (TGA). Free Rh6G dye was strongly fluorescent in bulk solution. The sensor system composing of Rh6G and Au NPs fluoresce weakly as result of fluorescence resonance energy transfer (FRET) and collision. The fluorescence of Rh6G and Au NPs based sensor was gradually recovered due to Rh6G units departed from the surface of functionalized Au NPs in the presence of Hg(II). Based on the modulation of fluorescence quenching efficiency of Rh6G-Au NPs by Hg(II) at pH 9.0 of teraborate buffer solution, a simple, rapid, reliable and specific turn-on fluorescent assay for Hg(II) was proposed. Under the optimum conditions, the fluorescence intensity of sensor is proportional to the concentration of Hg(II). The calibration graphs are linear over the range of 5.0 × 10⁻¹⁰ to 3.55 × 10⁻⁸ mol L⁻¹, and the corresponding limit of detection (LOD) is low as 6.0 × 10⁻¹¹ mol L⁻¹. The relative standard deviation of 10 replicate measurements is 1.5% for 2.0 × 10⁻⁹ mol L⁻¹ Hg(II). In comparison with conventional fluorimetric methods for detection of mercury ion, the present nanosensor endowed with higher sensitivity and selectivity for Hg(II) in aqueous solution. Mercury(II) of real environmental water samples was determined by our proposed method with satisfactory results that were obtained by atomic absorption spectroscopy (AAS).     

Single-fluorophore-based fluorescent probes enable dual-channel detection of Ag and Hg with high selectivity and sensitivity

A new type of fluorescent probe capable of detecting Ag⁺ and Hg²⁺ in two independent channels was developed in the present work. Specifically, in CH₃CN–MOPS mixed solvents with CH₃CN/MOPS ratio (v/v) of 15/85, this type of probe fluoresced weakly, and the addition of Ag⁺ remarkably induced fluorescence enhancement of the probe. In CH₃CN–MOPS mixed solvents with the percentage of CH₃CN increased up to 65%, the probe was highly fluorescent and addition of Hg²⁺ dramatically induced the fluorescence quenching. Thus, using such single-fluorophore-based probe and tuning the polarity of the mixed solvent, Ag⁺, and Hg²⁺ can be detected in independent channels with high selectivity and sensitivity. As a result, the mutual interference usually encountered in most cases of Ag⁺ and Hg²⁺ sensing owing to the similar fluorescence response that these two ions induced, can be effectively circumvented by using the probes developed herein.     

Gold Nanoclusters Templated by Poly-cytosine DNA as Fluorescent Probes for Selective and Sensitive Detection of Thiocyanate

Gold nanoclusters(AuNCs) were prepared in the presence of the nucleobases of poly-cytosine DNAs in this paper. We have demonstrated tliat the fluorescence of the AuNCs is quenched by thiocyanate(SCN^-) through the interaction between SCN^- and gold atoms. AuNCs can receive energy from nucleobases to boost their emission intensity, while in the presence of SCN^-, they coordinate with Au atoms and influence the energy transfer between the nucleobases and AuNCs, leading to the fluorescence quenching. The decreased fluorescence intensity was in proportion to the concentration of SCN^- in the range of 8.0×10^-7-1.5×10^-5 mol/L with a limit of detection of 4.2×10^-7 mol/L(3σ). We further validated the practice of this probe througli the detection of SCbT in natural water samples.     

An optical sensor for mercury ion based on the fluorescence quenching of tetra(p-dimethylaminophenyl)porphyrin

An optical sensor for mercury ion (Hg²⁺), based on quenching the fluorescence of the sensing reagent porphyrin immobilized in plasticized poly(vinyl chloride) (PVC) membrane, has been developed. The responses to mercury ion were compared for the sensors modified with three porphyrin compounds including 5,10,15,20-tetraphenylporphyrin (TPP), tetra(p-dimethylaminophenyl)porphyrin (TDMAPP) and tetra(N-phenylpyrazole) porphyrin (TPPP). Among them, TDMAPP showed the most remarkable response to Hg²⁺. The drastic decrease of the TDMAPP fluorescence intensity was attributed to the formation of a complex between TDMAPP and Hg²⁺, which has been utilized as the fabrication basis of a Hg²⁺-sensitive fluorescence sensor. The analytical performance characteristics of the TDMAPP modified sensor was investigated. The response mechanism, especially involving the response difference of three porphyrin compounds, was discussed in detail. The sensor can be applied to the quantification of Hg²⁺ with a linear range covering from 4.0 × 10⁻⁸ mol L⁻¹ to 4.0 × 10⁻⁶ mol L⁻¹. The limit of detection was 8.0 × 10⁻⁹ mol L⁻¹. The sensor exhibited excellent reproducibility, reversibility and selectivity. Also, the TDMAPP-based sensor was successfully used for the determination of Hg²⁺ in environmental water samples.