Fluorescent Silver Nanoclusters Research Articles

Stirring-Controlled Synthesis of Ultrastable, Fluorescent Silver Nanoclusters.

This paper describes how macroscopic stirring of a reaction mixture can be used to produce nanostructures exhibiting properties not readily achievable via other protocols. In particular, it is shown that by simply adjusting the stirring rate, a standard glutathione-based method-to date, used to produce only marginally stable fluorescent silver nanoclusters, Ag NCs-can be boosted to yield nanoclusters retaining fluorescence for unprecedented periods of over 2 years. This enhancement derives not simply from increased homogenization of the reaction mixture but mainly from an appropriately timed delivery of oxygen from above the reaction mixture. In effect, oxygen serves as a reagent that dictates size, structure, stability, and functional properties of the growing nanoobjects.

Silver nanoclusters stabilized with PVP-BSA conjugate: Optical properties approach

<abstract> <p>The objective of this research was to synthesize fluorescent silver nanoclusters (NC Ag-BSA/PVP) using polyvinylpyrrolidone polymer (PVP) as a stabilizer in conjunction with bovine serum albumin protein (BSA). The nanoclusters were prepared using a wet chemistry reduction technique with two distinctive pathways: the addition of PVP after BSA and the addition of PVP after the metal precursor. The optical properties of the materials were studied in samples with different BSA/PVP molar ratios and varying amounts of metal/reductant. The impact of protein and polymer amounts on fluorescence was determined. The materials were characterized using X-ray diffraction (XRD), infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray energy dispersive spectroscopy (EDS), dynamic light scattering (DLS), fluorescence spectroscopy, and UV-Vis-NIR spectroscopy.</p> <p>It was observed that increasing the BSA/PVP ratio resulted in higher fluorescence intensity at λ = 450 nm and a decrease at λ = 600 nm. Regarding the metal/reductant ratio, the amount of metal ions impacted the intensity obtained at λ = 600 nm. The experiments revealed that BSA had the largest effect on fluorescence intensity at λ = 450 nm, with little effect on fluorescence intensity regardless of the amount of polymer used. Due to its one-step synthesis and favorable reaction conditions, the NC Ag-BSA/PVP obtained under the proposed methodology holds promise as an optical marker material. The use of the stabilizing duo BSA-PVP, as well as the proposed amounts in this research, serves as a precedent for developing new experimental syntheses of colloidal nanoparticles.</p> </abstract>

MicroRNA sensing using integrating DNA-functionalized hydrogels with aggregation-induced emission of silver nanoclusters

Here, a platform consisting of a fluorescent DNA-functionalized hydrogel was created for the measurement of miRNA-141. In the presence of the target, the closed cytosine-rich loop of the three-segment branched DNA structure is formed as a useful template to create fluorescent silver nanoclusters (AgNCs). Then, aggregation-induced emission of AgNCs occurs in the hydrogel, and enhanced fluorescence is observed. Instead of acrylate-modified DNA, we used unmodified penta-adenine (A5) DNA strands for incorporation into polyacrylamide hydrogel in this method. By raising the concentration of target microRNA 141 (miR-141) under optimal conditions, the silver nanocluster's fluorescence intensities increased linearly from 5 pM to 100 nM, with a detection limit (LOD) of 2 pM. In addition, a selectivity analysis against the target demonstrates that the proposed analytical technique has good selectivity for miR-141. Since the creation of nanoclusters only occurs in the presence of the target sequence, this technique has shown significant potential for sensitive, selective, and label-free miRNA detection for clinical disease diagnosis and biomedical applications.

Selective detection of nitrofurantoin by histidine-capped silver nanoclusters with blue luminescence.

In view of the significance of nitrofurantoin, efficient analytical method for accurate nitrofurantoin detection is in urgent demand. Considering the superior fluorescence performance of silver nanoclusters (Ag NCs) and rare report of nitrofurantoin detection by fluorescent Ag NCs, Ag NCs with good stability and uniform size were synthesised through one simple method by protection of histidine (His) and reduction of ascorbic acid (AA). Based on the quenching by nitrofurantoin, Ag NCs were successful applied in nitrofurantoin detection with high sensitivity. In the range of 0.5-150 μM, linear relationship between ln(F0 /F) and nitrofurantoin amounts was found. Static quenching and inner filter effect (IFE) was proved to be the main quenching mechanism. Significantly, the superior selectivity and satisfactory recovery results in bovine serum stated that Ag NCs provided better choice for nitrofurantoin detection.

Detection of pyrimidine-rich DNA sequences based on the formation of parallel and antiparallel triplex DNA and fluorescent silver nanoclusters

In this work, the use of DNA-stabilized fluorescent silver nanoclusters for the detection of target pyrimidine-rich DNA sequences by formation of parallel and antiparallel triplex structures is studied by molecular fluorescence spectroscopy. In the case of parallel triplexes, the probe DNA fragments are Watson-Crick stabilized hairpins, and whereas in the case of antiparallel triplexes, the probe fragments are reverse-Hoogsteen clamps. In all cases, the formation of the triplex structures has been assessed by means of polyacrylamide gel electrophoresis, circular dichroism, and molecular fluorescence spectroscopies, as well as multivariate data analysis methods. The results have shown that it is possible the detection of pyrimidine-rich sequences with an acceptable selectivity by using the approach based on the formation of antiparallel triplex structures.

Dual-Functional Capping Agent-Mediated Transformation of Silver Nanotriangles to Silver Nanoclusters for Dual-Mode Biosensing.

The localized surface plasmon resonance (LSPR) property, depending on the structure (morphology and assembly) of nanoparticles, is very sensitive to the environmental fluctuation. Retaining the colorimetric effect derived from the LSPR property while introducing new optical properties (such as fluorescence) that provide supplementary information is an effective means to improve the controllability in structures and reproducibility in optical properties. DNA as a green and low-cost etching agent has been demonstrated to effectively control the morphology and optical properties (the blue shift of the LSPR peak) of the plasmonic nanoparticles. Herein, taking silver nanotriangles (AgNTs) as a proof of concept, we report a novel strategy to induce precisely tunable LSPR and fluorescence-composited dual-mode signals by using mono-DNA first as an etching agent for etching the morphology of AgNTs and later as a template for synthesizing fluorescent silver nanoclusters (AgNCs). In addition, common templates for synthesizing AgNCs, such as l-glutathione and bovine serum albumin, were demonstrated to have the capability to serve as etching agents. More importantly, these biomolecules as dual-functional capping agents (etching agents and templates) follow the size-dependent rule: as the size of the thiolated biomolecule increases, the blue shift of the LSPR peak increases; at the same time, the fluorescence intensity increases. The enzyme that can change the molecular weight (size) of the biomolecular substrates (DNA, peptides, and proteins) through an enzymatic cleavage reaction was explored to regulate the LSPR and fluorescent properties of the resulting nanoparticles (by etching of AgNTs and synthesis of AgNCs), achieving excellent performance in detection of cancer-related proteases. This study can be expanded to other biopolymers to impact both fundamental nanoscience and applications and provide powerful new tools for bioanalytical biosensors and nanomedicine.

Fluorescent paper-based sensor integrated with headspace thin-film microextraction for the detection of acyclic N-nitrosamines following in situ photocatalytic decomposition

BackgroundIn this work, a novel analytical approach based on the photocatalytic decomposition of N-nitrosamines combined with headspace thin-film microextraction of the generated nitrogen oxides such as NO has been developed for the determination of the acyclic N-nitrosamine fraction in drinking water samples. A hydrophilic cellulose substrate modified with fluorescent silver nanoclusters (Ag NCs) was used both as extractant and sensing platform. A quenching effect of Ag NCs fluorescence occurs as the concentration of N-nitrosamines increases. Front-face fluorescence spectroscopy with a solid sample holder was employed for directly measuring the fluorescence quenching onto the cellulose substrate. ResultsIn order to achieve an optimal analytical response, different parameters involved in the photocatalytic reaction as well as those concerning the microextraction step were fully investigated. It is demonstrated that the photodegradation rate of cyclic N-nitrosamines at acidic pH is much lower than that of acyclic ones, which can be the basis for the determination of the later fraction in waters. Under optimal conditions, a detection limit for the acyclic N-nitrosamine fraction around 0.08 μg L−1 using N-nitrosodimethylamine (NDMA) as model compound for calibration was obtained. Several drinking waters were spiked with acyclic N-nitrosamines showing recoveries in the range of 98–102% with a relative standard deviation of 3–4% (N = 3). Significance and noveltyN-nitrosamines generated as by-products during disinfection processes applied to water cause multiple adverse effects on human health being classified as potential human carcinogens.This study highlights the suitability of a fluorescent paper-based sensor for the rapid analysis of the acyclic N-nitrosamine fraction (i.e. the most abundant fraction) as a total index in drinking water, being useful as screening tool before exhaustive chromatographic analysis, which saves costs, time and reduces waste generation.

Exploration of connexin-43 modulating, multifunctional silver nanocluster-hydrogel system for theranostic management of cancer

Connexin (Cx), a gap junction protein plays an important role in cancer pathophysiology. The enhancement of Cx43, an isoform of Cx, has been reported to improve survival of patients with breast cancer. Since Cxs are expressed in various tissues and organs, their localized modulation is necessary to achieve therapeutic benefits without any side-effects. Therapy combined with diagnostics, i.e. theranostics, is becoming an important facet of cancer management. Thus, considering these two critical aspects, the present study deals with synthesis, bio-imaging, and anti-proliferative effects of a multi-functional chitosan hydrogel incorporating highly fluorescent silver nanoclusters and 4-phenylbutyrate, a histone deacetylase inhibitor for enhancing Cx43 expression. While the remarkable fluorescence of silver nanoclusters enabled cellular uptake and imaging, 4-phenylbutyrate released from the hydrogel specifically upregulated Cx43 expression and induced apoptosis in breast cancer cells. Moreover, the 4-phenylbutyrate released, successfully established gap junction communication between cancer cells as assessed by dye transfer assay. Thus, the current module not only holds potential in cancer theranostics but also for Cx-based cancer therapeutics.

Self-Cascade Nanoenzyme of Cupric Oxide Nanoparticles (CuO NPs) Induced in Situ Catalysis Formation of Polyelectrolyte as Template for the Synthesis of Near-Infrared Fluorescent Silver Nanoclusters and the Application in Glutathione Detection and Bioimaging

In this work, near-infrared fluorescent silver nanoclusters (Ag NCs) were prepared based on the in situ formed poly methacrylic acid (PMAA) as the template and stabilizer, which is synthesized by methacrylic acid (MAA) and hydroxyl radical (·OH) that is generated by the cascade nanoenzyme reaction of cupric oxide nanoparticles (CuO NPs). CuO NPs possess the intrinsic glutathione-like (GPx-like) and peroxidase-like (POD-like) activities, which can catalyze glutathione (GSH) and O2 to produce hydrogen peroxide (H2O2), and then transform into ·OH. The fluorescence intensity of Ag NCs decreases with the addition of GSH, because the -SH can easily anchor on the surface, resulting in the PMAA leaving the Ag NCs, and the coeffect of GSH and PMAA results in the aggregation to form larger Ag NPs. A good linear relationship between the fluorescence quenching rate and the GSH concentration was found in the range 0.01-40 μM with the detection limit 8.0 nM. The Ag NCs can be applied in the detection of GSH in the serum, as well as bioimaging of endogenous and exogenous GSH in cells with high sensitivity. Moreover, the normal and cancer cells can be distinguished through bioimaging because of the different GSH levels. The new method for the preparation of biocompatible nanoprobe based on the nanozyme tandem catalysis and the in situ formed template can avoid the direct usage of polymers or protein templates that hinder preparation and separation, providing a reliable approach for the synthesis, biosensing, and bioimaging of nanoclusters.

Fluorescent silver nanoclusters: from preparation to analytical application

<p indent="0mm"><b/>Owing to their excellent luminescent properties, fluorescent metal clusters show a wide range of applications in the field of analysis chemistry. Ag nanoclusters have attracted a lot of attention because of their adjustable size, good water dispersibility, biocompatibility and excellent optical properties. This review briefly summarizes the synthesis, optical properties and analytical applications of silver nanoclusters, and looks forward to the future development in this field.

Microwave-Assisted Rapid Synthesis of Luminescent Tryptophan-Stabilized Silver Nanoclusters for Ultra-Sensitive Detection of Fe(III), and Their Application in a Test Strip.

A new preparation method for extreme fluorescent green emission tryptophan-stabilized silver nanoclusters (Tryp-AgNCs) is presented in this scientific research. The produced silver nanoclusters are dependent on tryptophan amino acid which contributes to normal growth in infants and the sublimation and recovery of human protein, muscles, and enzymes. Herein, we have introduced a green method by using microwave-assisted rapid synthesis. The subsequent silver nanoclusters (AgNCs) have excitation/emission peaks at 408/498 nm and display a considerable selectivity to Fe(III) ions. The tryptophan amino acid molecule was used in the synthesis process as a reducing and stabilizing agent. The Tryp-AgNCs’ properties were investigated in terms of morphology, dispersity, and modification of the synthesized particles using different advanced instruments. The luminescent nanoclusters traced the Fe(III) ions by the luminescence-quenching mechanism of the Tryp-AgNCs luminescence. Therefore, the extreme selectivity of the prepared nanoclusters was exhibited to the Fe(III) ions, permitting the sensitive tracing of ferric ions in the lab and in the real environmental samples. The limit of detection for Fe(III) ions based on Tryp-AgNCs was calculated to be 16.99 nM. The Tryp-AgNCs can be efficiently applied to a paper test strip method. The synthesized nanoclusters were used efficiently to detect the Fe(III) ions in the environmental samples. Moreover, we examined the reactivity of Tryp-AgNCs on various human tumor cell lines. The results show that the Tryp-AgNCs exhibited their activity versus the cancer cells in a dose-dependent routine for the perceived performance versus the greatest-used cancer cell lines.

Detection of inflammatory bowel disease (IBD)-associated microRNAs by two color DNA-templated silver nanoclusters fluorescent probes

Researches demonstrated that circulating miRNAs could be used as novel diagnostic and prognostic potential markers for patients with inflammatory bowel diseases (IBD). It is of great significance in clinical to develop rapid and specific detection methods for miRNAs. Herein, we established a fluorescent probe for ulcerative colitis (UC) activity-associated two serum biomarkers (miR-23a and miR-223) simultaneous detection, which used multi-color fluorescent DNA-stabilized silver nanoclusters (DNA-AgNC) illuminated by a close guanine (G)-rich sequence as a signal transducer and two split DNA probes as recognition units. In principle, the two DNA probe sequences containing AgNC nucleation sequence and G-rich sequence respectively, formed a ternary complex when in the presence of target miRNA through base pairing, so as to induce enhancement of fluorescence emission of AgNC by shortening the distance from G-rich sequence. The combined probes for miR-23a and miR-223 detection generated increased fluorescence signals at 460 nm ex/545 nm em and at 560 nm ex/630 nm em, respectively. With this technique, we successfully quantified the two target miRNAs with high selectivity. Furthermore, the potential clinic applicability of this method was verified by testing the spiked standard miRNAs in human serum. Thus, this one-step, low-cost, and homogenous method offers a great opportunity for disease-associated multiplex miRNAs simultaneous detection.

Synthesis of Dual Red‐Emitting Fluorescent Silver Nanoclusters in Aqueous Lipoic Acid‐Based Polymer Solutions and Application for Cu2+ Detection and Cell Imaging

AbstractDual red‐emitting fluorescent and water‐soluble silver nanoclusters (AgNCs) were synthesized in aqueous solutions through the reduce reaction method using lipoic acid‐modified‐poly(vinyl alcohol) as a novel protective ligand and sodium borohydride as a reducing agent. The obtained AgNCs exhibited a large Stokes shift and high stability. The fluorescence lifetime of the obtained AgNCs was 1.4×104 ns and the corresponding quantum yield reached 7.1 %. The obtained AgNCs showed highly sensitive and selective detection of Cu2+, in which the evaluation of Cu2+ was allowed in the range of 0–28 μM with a limit of detection (LOD) as low as 0.71 μM. Moreover, the obtained AgNCs are explored to application for bioimaging through incubation with ID8 cells.

A Novel Fluorescence Aptasensor Based on Magnetic Beads/Gold Nanoparticles/DNA-Stabilized Silver Nanoclusters for Detection of Salmonella Typhimurium.

Salmonella Typhimurium (S. Typhimurium) is a globally distributed foodborne pathogen, which can lead to outbreaks of foodborne infectious diseases. It is essential to guarantee food safety by timely and correct detection of S. Typhimurium. In this investigation, an original fluorescence aptasensor was constructed to detect S. Typhimurium rapidly and sensitively. Through the coupling of magnetic beads, aptamer, and gold nanoparticles (AuNPs), a fluorescence quenching system with a “sandwich structure” was established. The aptamer acted as a link, and its specific binding to S. Typhimurium could release AuNPs from the system. Meanwhile, fluorescent DNA-stabilized silver nanoclusters (DNA-AgNCs) were synthesized. The fluorescence intensity changes caused by the fluorescence resonance energy transfer between DNA-AgNCs and AuNPs were utilized to detect S. Typhimurium. The purposed aptasensor exhibited high selectivity and sensitivity with a linear response to S. Typhimurium, ranging from 3.7 × 102 to 3.7 × 105 cfu/mL. The limit of detection (LOD) was estimated to be 98 cfu/mL within 2 h 10 min. In addition, this method showed excellent application for detection of S. Typhimurium in artificially contaminated milk, with LOD reaching 3.4 × 102 cfu/mL. Therefore, the developed fluorescence aptasensor has great potential to identify S. Typhimurium in foodstuffs.

A fluorescent probe based on tryptophan-coated silver nanoclusters for copper (II) ions detection and bioimaging in cells

Silver nanoclusters (Ag NCs) have been widely used in sensing and bioimaging owing to their excellent photoluminescence properties and biocompatibility. Herein, we fabricated blue fluorescent tryptophan-coated silver nanoclusters (Trp-Ag NCs) by a facile one-step method for Cu2+ detection and multicolour bioimaging. Trp-Ag NCs displayed a strong blue luminescence with a high quantum yield of 35.6% and a long lifetime of 18.48 ns. In the presence of Cu2+, the fluorescence was quenched via static quenching and charge transfer. The developed fluorescence probe for Cu2+ detection showed a high selectivity and sensitivity with a low limit detection of 0.029 μM. Meanwhile, due to their excellent biocompatibility, the demonstration of bioimaging in cells was also provided.

Detection of Norovirus RNA based on catalytic hairpin assembly and magnetic separation of DNA AgNCs

Based on catalytic hairpin assembly (CHA) and magnetic separation, a fluorescence biosensor of Norovirus RNA was developed. In this detection strategy, these two isothermal signal amplification techniques as well as brightly fluorescent DNA-templated silver nanoclusters (AgNCs) of high quantum yield were employed, with the aim of highly sensitive detection of Norovirus RNA at room temperature. Results showed that the designed strategy of sensor could be successfully established and implemented. Under optimal reaction conditions, this sensor showed a good linear response towards the concentrations of target RNA in the range of 1.0–100 nM with a detection limit of 0.82 nM. A quenching phenomenon was found in this sensoring system, which was contributed together by the biotin-avidin complex and magnetic nanoparticles. The phenomenon was confirmed and explained for reference value of AgNCs based biosensors.

Hg2+ Detection with Rational Design of DNA-Templated Fluorescent Silver Nanoclusters

Atomically precise silver nanoclusters (AgNCs) are small nanostructures consisting of only a few atoms of silver. The combination of AgNCs with cytosine-rich single-stranded oligonucleotides results in DNA-templated silver nanoclusters (DNA-AgNCs). DNA-AgNCs are highly luminescent and can be engineered with reproducible and unique fluorescent properties. Furthermore, using nucleic acids as templates for the synthesis of AgNCs provides additional practical benefits by expanding optical activity beyond the visible spectral range and creating the possibility for color tunability. In this study, we explore DNA oligonucleotides designed to fold into hairpin-loop (HL) structures which modulate optical properties of AgNCs based on the size of the loop containing different number of cytosines (HL-CN). Depending on the size of the loop, AgNCs can be manufactured to have either single or multiple emissive states. Such hairpin-loop structures provide an additional stability for AgNCs and further control over the base composition of the loop, allowing for the rational design of AgNCs’ optical properties. We demonstrate the potential of AgNCs in detecting Hg2+ by utilizing the HL-C13 design and its variants HL-T2C11, HL-T4C9, and HL-T6C7. The replacement of cytosines with thymines in the loop was intended to serve as an additional sink for mercury ions extending the detectable range of Hg2+. While AgNC@HL-T0C13 exhibits an interpretable quenching curve, AgNC@HL-T6C7 provides the largest detectable range of Hg2+. The results presented herein suggest that it is possible to use a rational design of DNA-AgNCs based on the composition of loop sequence in HL structures for creating biosensors to detect heavy metals, particularly Hg2+.

Fluorescent Silver Nanoclusters Embedded in Hydrogel Matrix and Its Potential Use in Environmental Monitoring

The optical absorption and fluorescence of silver nanoclusters (AgNCs) are widely exploited in many different application fields such as sensors, bio-imaging, drug delivery, etc. In the sensor field, optical devices are highly versatile thanks to their ease of fabrication and low costs and, therefore, are optimal candidates to replace expensive apparatuses commonly used. In this study, we synthesized AgNCs in aqueous phase by photochemical synthesis using poly methacrylic acid (PMAA) as a stabilizer. Colloidal water solutions of these NCs showed a very good sensitivity to Pb(II) ions, and in order to fabricate a solid-state sensor, we introduced them in a hydrogel material formed by poly(ethylene glycol) diacrylate with a molecular weight of 700 g/mol (PEGDA700). The systems were characterized using absorption and fluorescence spectroscopy and transmission electron microscopy (TEM). Finally, the sensitivity to Pb(II) ions has been tested with the aim to use these systems as solid-state optical sensors for water quality.

DNA-templated fluorescent silver nanoclusters on-off switch for specific and sensitive determination of organic mercury in seafood

Organic mercury including methyl-mercury and ethyl-mercury (CH3Hg+ and C2H5Hg+) has high toxicity and bio-accumulation, and thus is easy to generate bio-amplification in food chain. Hence, the specific detection of organic mercury has great significance for objectively assessing the health risk of mercury in seafood. We herein designed an aptamer (AS-T7), which consists of a silver nanoclusters (AgNCs) scaffold sequence (AS) and a T-rich sequence (AT7), for simultaneously synthetizing DNA-templated AgNCs and recognizing organic mercury, and further developed a label-free fluorescent method for the sensitive and specific determination of organic mercury (CH3Hg+ and C2H5Hg+ total concentration) by using DNA-templated AgNCs as signal. Without organic mercury, Ag+ in the mixture of aptamer and Ag+ was bond on AS of aptamer to form AS-templated AgNCs after reduction, and thus emitted strong fluorescence. Whereas, in the presence of organic mercury, CH3Hg+/C2H5Hg+ was bond on AT7 of aptamer to generate photoinduced electron transfer (PET) between CH3Hg+/C2H5Hg+ and AS-templated AgNCs, and thus results in fluorescence quenching of AS-templated AgNCs. The fluorescent method could be used to rapidly detect organic mercury with a detection limit of 5.0 nM (i.e. 1.01 ng Hg/g), which meets the U.S. EPA standard of 0.3 mg/kg (wet). The method was successfully used to detect organic mercury in water and fish muscle with a recovery of 96%–104% and an inter-days RSD (n = 5) < 7%. The success of the study promised a reliable method for rapid and specific detection of organic mercury in environmental and biological samples.

Development of General Methods for Detection of Virus by Engineering Fluorescent Silver Nanoclusters.

Viruses have caused significant damage to the world. Effective detection is required to relieve the impact of viral infections. A biomolecule can be used as a template such as deoxyribonucleic acid (DNA), peptide, or protein, for the growth of silver nanoclusters (AgNCs) and for recognizing a virus. Both the AgNCs and the recognition elements are tunable, which is promising for the analysis of new viruses. Considering that a new virus such as severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) urgently requires a facile sensing strategy, various virus detection strategies based on AgNCs including fluorescence enhancement, color change, quenching, and recovery are summarized. Particular emphasis is placed on the molecular analysis of viruses using DNA stabilized AgNCs (DNA-AgNCs), which detect the virus's genetic material. The more widespread applications of AgNCs for general virus detection are also discussed. Further development of these technologies may address the challenge for facile detection of SARS-CoV-2.