Catalytic gold nanoparticles for fluorescent detection of mercury(II) and lead(II) ions

In this study, we developed a fluorescence assay for the highly sensitive and selective detection of Hg²⁺ and Pb²⁺ ions using a gold nanoparticle (Au NP)-based probe. The Hg–Au and Pb–Au alloys that formed on the Au NP surfaces allowed the Au NPs to exhibit peroxidase-mimicking catalytic activity in the H₂O₂-mediated oxidation of Amplex UltraRed (AUR). The fluorescence of the AUR oxidation product increased upon increasing the concentration of either Hg²⁺ or Pb²⁺ ions. By controlling the pH values of 5 mM tris–acetate buffers at 7.0 and 9.0, this H₂O₂–AUR–Au NP probe detected Hg²⁺ and Pb²⁺ ions, respectively, both with limits of detection (signal-to-noise ratio: 3) of 4.0 nM. The fluorescence intensity of the AUR oxidation product was proportional to the concentrations of Hg²⁺ and Pb²⁺ ions over ranges 0.05–1 μM (R² = 0.993) and 0.05–5 μM (R² = 0.996), respectively. The H₂O₂–AUR–Au NP probe was highly selective for Hg²⁺ (>100-fold) and Pb²⁺ (>300-fold) ions in the presence of other tested metal ions. We validated the practicality of this simple, selective, and sensitive H₂O₂–AUR–Au NP probe through determination of the concentrations of Hg²⁺ and Pb²⁺ ions in a lake water sample and of Pb²⁺ ions in a blood sample. To the best of our knowledge, this system is the first example of Au NPs being used as enzyme-mimics for the fluorescence detection of Hg²⁺ and Pb²⁺ ions.     

Luminescent ruthenium(II) polypyridyl functionalized gold nanoparticles; their DNA binding abilities and application as cellular imaging agents

The synthesis and photophysical and biological investigation of Ru(II)-polypyridyl stabilized water-soluble, luminescent gold nanoparticles (AuNPs) are described. These structures bind to DNA and undergo rapid cellular uptake, being localized within the cell cytoplasm and nucleus within 4 h.     

Fluorometric determination of cadmium(II) and mercury(II) using nanoclusters consisting of a gold-nickel alloy

A one-pot route has been developed for the preparation of bovine serum albumin-templated nickel-doped bimetallic gold-nickel nanoclusters (BSA-Au-Ni NCs) at a 10:1 M ratio of the precursor salts in a BSA matrix under alkaline conditions. The metal ions are reduced to the metal alloys by BSA. The resulting NCs display strong fluorescence and dual emission with peaks at 405 and 640 nm, respectively, under excitation at 340 nm. Fluorescence is strongly enhanced on addition of Cd(II) ions, but quenched on addition of Hg(II) ions. The findings have been exploited to design a fluorometric method for the separate determination of Cd(II) and Hg(II), respectively. The optimized analytical nanosystem displays relatively good dynamics between enhancement and quenching. Cd(II) and Hg(II) can be quantified in the 0 to 200 and 0 nM to 24 μM, respectively. The limits of detection are ~1.8 nM in both cases, which indicates the highest sensitivity to Cd(II) and Hg(II) ions for a fluorescent probe. This new kind of nanocrystal probe is hardly interfered by a range of commonly encountered metal ions. Its advantages were demonstrated by determining Cd(II) and Hg(II) ions in spiked serum samples.

Dually emitting nanoclusters composed of gold-nickel alloys are shown to act as very sensitive fluorescent probes for the detection of Cd(II) and Hg(II) ions.

     

Determination of the activity of telomerase in cancer cells by using BSA-protected gold nanoclusters as a fluorescent probe

Gold nanoclusters (AuNCs) protected with a bovine serum albumin (BSA) coating are known to emit red fluorescence (peaking at 650 nm) on photoexcitation with ultraviolet light (365 nm). On addition of Cu(II) ions, fluorescence is quenched because Cu(II) complexes certain amino acid units in the BSA chain. Fluorescence is, however, restored if pyrophosphate (PPi) is added because it will chelate Cu(II) and remove it from the BSA coating on the AuNCs. Because PPi is involved in the function of telomerase, the BSA@AuNCs loaded with Cu(II) can act as a fluorescent probe for determination of the activity of telomerase. A fluorescent assay was worked out for telomerase that is highly sensitive and has a wide linear range (10 nU to 10 fM per mL). The fluorescent probe was applied to the determination of telomerase activity in cervix carcinoma cells via imaging. It is shown that tumor cells can be well distinguished from normal cells by monitoring the differences in intracellular telomerase activity.

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Graphical abstract Gold nanoclusters (AuNCs) protected by bovine serum albumin (BSA) and displaying red photoluminescence were prepared as fluorescent probe for the determination of telomerase activity and used for imaging of cervix carcinoma (HeLa) cells.

     

Label-free fluorescent detection of copper(II) using DNA-templated highly luminescent silver nanoclusters

Novel luminescent silver nanoclusters (AgNCs) were synthesized utilizing DNA as templates by a simple, rapid and one-pot procedure. Luminescence studies indicated that these DNA-AgNCs exhibited strong emission with peak maximum at 624 nm. The fluorescence of the DNA-AgNCs was found to be quenched by Cu(2+) enabling its detection with high sensitivity and selectivity.     

Microwave-assisted in situ synthesis of fluorescent gold nanoclusters with BSA/montmorillonite and application on latent fingermark imaging

A method for in situ preparation of fluorescent gold nanoclusters(Au NCs) with bovine serum albumin/montmorillonite composite powder(Au NC-BSA/MMT) was developed, and the products were used to detect latent fingermarks. In this work, Au NCs were "grown" both inside and on the surface of BSA/MMT clay using one-step reduction of HAu Cl4 by BSA. The as-prepared Au NC-BSA/MMT nanocomposites emit intensive red fluorescence under the excitation of UV-visible light and show stable chemical features and low toxicity. The obtained fluorescent powders were characterized by UV-visible absorption spectroscopy,fluorescence spectroscopy, infrared spectroscopy, transmission electron microscopy/high-resolution transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction to depict their sizes, structural information and optical features. Given their environmentally friendly preparation, simple operation, low cost, efficient UVvisible radiation-dependent photoluminescence and good affinity with finger residues, the in situ synthesized Au NC-BSA/MMT nanocomposite powders were used as an alternative fluorescent developing reagent for developing latent fingermarks deposited on various object surfaces(such as glass, aluminum foil, painted metal, plastic products and weighing papers) for individual identification. As results, the developed fingermarks with clear patterns and satisfactory level-2(minutiae points) and level-3(sweat pores) ridge details were obtained. Notably, treated prints could be excited by red light and emitted near infrared fluorescence, which was beneficial to avoid background interference and reduce the damage caused by UV light. With the advantages of the simple preparation process and good enhancement performance for latent fingermarks, the proposed method might be used in the preparation of various fluorescent probes for detecting trace evidence in forensic sciences.     

Uptake and imaging of glycine functionalized gold nanoclusters in Spodoptera frugiperda (Sf9) cells

Journal of Cluster Science - Fluorescent gold nanoclusters (Au NCs) have attracted considerable interest in biological application. Here, we reported a novel Au NCs with blue fluorescence,...     

FePt@CoS(2) yolk-shell nanocrystals as a potent agent to kill HeLa cells

We report the evaluation of cytotoxicity of a new type of engineered nanomaterials, FePt@CoS(2) yolk-shell nanocrystals, synthesized by the mechanism of the Kirkendall effect when FePt nanoparticles serve as the seeds. The cytotoxicity of FePt@CoS(2) yolk-shell nanocrystals, evaluated by MTT assay, shows a much lower IC(50) (35.5 +/- 4.7 ng of Pt/mL for HeLa cell) than that of cisplatin (230 ng of Pt/mL). In the control experiment, cysteine-modified FePt nanoparticles exhibit IC50 at 12.0 +/- 0.9 microg of Pt/mL. Transmission electron microscopy confirms the cellular uptake of FePt@CoS(2) nanocrystals, and the magnetic properties analysis (SQUID) proves the release of FePt nanoparticles from the yolk-shell nanostructures after cellular uptake. These results are significant because almost none of the platinum-based complexes produced for clinical trials in the past 3 decades have shown higher activity than that of the parent drug, cisplatin. The exceptionally high toxicity of FePt@CoS(2) yolk-shell nanocrystals (about 7 times higher than that of cisplatin in terms of Pt) may lead to a new design of an anticancer nanomedicine.     

Templated in-situ synthesis of gold nanoclusters conjugated to drug target bacterial enoyl-ACP reductase,and their application to the detection of mercury ions using a test stripe

Fluorescent gold nanoclusters (AuNCs) were synthesized using a drug target bacterial enoyl-ACP reductase (FabI) as a template. The physical and chemical properties of the AuNCs were studied by UV-vis absorption, fluorescence, X-ray photoelectron spectroscopy and TEM. The AuNCs-FabI conjugate was prepared by in situ reduction of tetrachloroaurate in the presence of FabI. The conjugated particles were loaded onto nylon membranes by taking advantage of the electrostatic interaction between the negatively charged AuNCs@FabI and the nylon film which is positively charged at pH 7.4. This results in the formation of a test stripe with sensor spots that can be used to detect Hg(II) ion in the 1 nM to 10 μM concentration range. The test stripes are simple, convenient, selective, sensitive, and can be quickly read out with bare eyes after illumination with a UV lamp.

Production of stable aqueous dispersion of poly(3,4-ethylenedioxythiophene) nanorods using graphene oxide as a stabilizing agent and their application for nitrite detection

A stable aqueous dispersion of poly(3,4-ethylenedioxythiophene) (PEDOT) nanorods stabilized by graphene oxide (GO) has been successfully prepared via interface polymerization of EDOT in the presence of GO for the first time. The non-covalent functionalization of PEDOT by GO leads to a PEDOT-GO dispersion that can be stable for several days without the observation of any floating or precipitated particles. Several analytical techniques including Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) have been used to characterize the resultant PEDOT-GO nanocomposites. It is found that such PEDOT-GO nanocomposites exhibit good catalytic activity toward the oxidation of nitrite, leading to a sensor for detection of nitrite. The linear detection range and detection limit are estimated to be 4 μM to 2.48 mM (r = 0.999), and 1.2 μM at a signal-to-noise ratio of 3, respectively.     

Label-free fluorescent sensor for mercury(II) ion by using carbon nanotubes to reduce background signal

A simple, selective and sensitive turn-on fluorescent sensor for the detection of mercury(II) ion was developed using Sybr Green I as the signal reporter and SWCNTs as the quencher. Due to the affinity of SWCNTs towards ssDNA and organic dye, Sybr Green I, thymine-rich ssDNA and SWCNTs could form a self-assembly of three components, resulting in fluorescence quenching. Upon addition of another thymine-rich ssDNA and mercury(II) ion, formation of dsDNA via T-Hg(2+)-T base pairs enabled Sybr Green I to intercalate into the dsDNA, resulting in the restoration of fluorescence. SWCNTs were found to reduce the background signal and improve the analytical sensitivity. A linear relationship between the fluorescence intensity and the concentration of mercury(II) ion was observed in the range of 20-1250 nM (R = 0.9985) with a detection limit of 7.9 nM. The proposed method was applied to detect mercury(II) ion in tap water samples with good results.     

Label-free colorimetric sensor for mercury(II) and DNA on the basis of mercury(II) switched-on the oxidase-mimicking activity of silver nanoclusters

In this paper, a novel colorimetric biosensor for Hg²⁺ and DNA molecules is presented based on Hg²⁺ stimulated oxidase-like activity of bovine serum albumin protected silver clusters (BSA-Ag NCs). Under mild conditions, Hg²⁺ activated BSA-Ag NCs to show high catalytic activity toward the oxidation of 3,3′,5, 5′-tetramethylbenzidine (TMB) using ambient dissolved oxygen as an oxidant. The oxidase-like activity of BSA-Ag NCs was “switched-on” selectively in the presence of Hg²⁺, which permitted a novel and facile colorimetric sensor for Hg²⁺. As low as 25 nmol L⁻¹ Hg²⁺ could be detected with a linear range from 80 nmol L⁻¹ to 50 mmol L⁻¹. In addition, the sensing strategy was also employed to detect DNA molecules. Hg²⁺ is known to bind very strongly and specifically with two DNA thymine bases (T) to form thymine–Hg²⁺–thymine (T–Hg²⁺–T) base pairs. The hairpin-structure was disrupted and Hg²⁺ ions were released after hybridization with the DNA target. By coupling the Hg²⁺ switched-on the oxidase-mimicking activity of BSA-Ag NCs, we developed a novel label-free strategy for facile and fast colorimetric detection of DNA molecules. More important, target DNA can be detected as low as 10 nmol L⁻¹ with a linear range from 30 to 225 nmol L⁻¹. Compared with other methods, this method presents several advantages such as the independence of hydrogen peroxide, high sensitivity and good selectivity, avoiding any modification or immobilization of DNA, which holds a great potential of metal NCs for clinical application in biosensing and biotechnology.     

Enzyme-free colorimetric assay for mercury(II) using DNA conjugated to gold nanoparticles and strand displacement amplification

The authors describe a colorimetric method for the determination of Hg(II) ion. It is based on the color change from red to colorless as displayed by gold nanoparticle (AuNP) modified with thymine - rich DNA. Signal amplification is accomplished by free strand displacement recycling. In this strategy, Hg(II) unfolds the arch-trigger duplex due to the high affinity between Hg(II) and the thymines to form T-Hg(II)-T structures, thereby causing the release of trigger. The liberated trigger unfolds the hairpin structure of H1, and unfolded H1 further unfolds with H2. As a result, the H2 hairpin displaces trigger, and the released trigger unfolds another H1. This results in strong and enzyme-free strand displacement recycling amplification. The aggregation of DNA-AuNPs occurs in the presence of the duplex formed by hairpins H2 and H1. This results in a color change from red to colorless that can be visually observed. Under optimal conditions, the assay has a detection range over 4 orders of magnitude and a 3.4 nM detection limit. The assay is selective, sensitive, rapid and cost-effective. In our perception, it represents a useful platform for determination of Hg(II).

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Graphical abstract Schematic presentation of the  simple, rapid, low cost colorimetric detection of mercury(II) based on enzyme-free strand displacement amplification along with DNA-labeled AuNP.