The authors report on the design of a new Förster resonance energy transfer (FRET) based ratiometric nanoprobe for the determination of arginine. The method is based on the inhibition of the efficiency of FRET in assemblies formed between CdTe quantum dots capped with mercaptopropionic acid (QD-MPA) acting as energy donor, and the dye Cresyl Violet (CV) that acts as an energy acceptor at pH 8. Addition of arginine causes a displacement of the CV by arginine on the surface of the QD/MPA. Hence, the FRET between QD/MPA and CV is interrupted and fluorescence emission of the donor (QD/MPA) is restored. Arginine selectively binds to the QD/MPA via electrostatic and hydrogen bonding interactions between guanidinium and carboxylate. Under optimum conditions, the ratio of the fluorescence emissions peaking at 575 and 620 nm (under 400 nm excitation) is linear in the 1 to 30 μM arginine concentration range, and the detection limit is 0.51 μM. The nanoprobe displays good selectivity over 14 other amino acids, many metal ions, glucose, and ascorbic, tartaric and citric acids. The fluorescent nanoprobe was successfully applied to the determination of arginine in pure and spiked real samples and gave good recoveries. Its good selectivity, sensitivity, low-cost and rapidity make the QD-dye assembly a suitable nanoprobe for the quantitation of arginine.
Graphical abstract Schematic of a FRET ratiometric nanoprobe for arginine. It is based on quantum dots acting as energy donors and Cresyl Violet acting as energy acceptor. The FRET process is interrupted by the addition of arginine which selectively interacts with carboxy groups via a guanidinium-carboxylate salt bridge.
We report on a simple, sensitive and regenerable fluorescent nanoprobe for Zn(II) ion. It is based on the use of glutathione capped CdTe quantum dots (GSH-CdTe Q-dots). The bright fluorescence of these Q-dots is quenched on addition of diethylenetriaminepentaacetic acid (DTPA) due to the binding of DTPA to GSH. If, however, Zn(II) is added, it will bind DTPA and detach it from the surface of the Q-dots, this resulting in the fluorescence recovery. Under optimum conditions, the intensity of the restored fluorescence is proportional to the concentration of Zn(II) in the 0.48 to 90 μmol · L−1 range, with a limit of detection of 0.14 μmol · L−1. The nanoprobe was applied to the determination of Zn(II) in spiked tap water and river water and gave satisfactory results. The findings were also applied to design a molecular logic gate where DTPA acts as the first input to the system by quenching the fluorescence of the GSH-CdTe Q-dots. Zn(II) acts as the second input and causes the detachment of DTPA from the Q-dots and a restoration of fluorescence. This system therefore represents a new IMP (IMPLICATION) logic gate.
We describe a fluorescent nanoprobe for Zn(II) based on quantum dots, and its use in an IMP molecular logic gate. The nanoprobe was successfully applied to the determination of Zn(II) in spiked tap water and river water.
The authors report on a one-pot approach for synthesizing highly fluorescent protamine-stabilized gold nanoclusters. These are shown to be a viable nanoprobe for selective and sensitive fluorometric determination of lead(II) via quenching of fluorescence via Pb(II)-Au(I) interaction. Under optimized conditions, fluorescence measured at excitation/emission peaks of 300/599 nm drops in the 80 nM–15 μM lead(II) concentration range. The detection limit is 24 nM, and relative standard deviations (for n?=?11) at concentrations of 0.10, 4.0 and 15 μM are 1.6, 2.5 and 1.9%, respectively. The relative recoveries of added lead(II) in the water samples ranged from 97.9?±?2.29% to 101.2?±?1.83%.
Graphical abstract Lead(II) ions are found to be able to selectively and sensitively quench the fluorescence of the protamine-gold nanoclusters (PRT-AuNCs). Thereby, an inexpensive, selective and sensitive lead(II) assay was established.
The authors report on a disposable sensor for the differential pulse anodic stripping voltammetric (DPASV) determination of the ions Zn(II), Pb(II) and Cu(II). Simultaneous detection is accomplished by using a screen-printed carbon electrode (SPCE) co-modified with an in-situ plated bismuth (Bi)) film and gold nanoparticles (AuNPs). The synergistic effect of the Bi film, and the large surface and good electrical conductivity of the AuNPs strongly assist in the co-deposition of the three ions. Four well-defined and fully separated anodic stripping peaks, at 540 mV for Zn(II), 50 mV for Pb(II), 140 mV for Bi(III) and 295 mV for Cu(II), all vs. Ag/AgCl, can be seen. The modified SPCE was characterized by scanning electron microscopy, X-ray diffraction, cyclic voltammetry and electrochemical impedance spectroscopy. Under the optimized conditions, the sensor has a good response to these ions. The detection limits (at an S/N ratio of 3) are 50 ng·L?1 for Zn(II), 20 ng·L?1 for Pb(II), and 30 ng·L?1 for Cu(II). The method was applied to the determination of the 3 ions in spiked lake water samples.
Graphical abstract Schematic of screen-printed carbon electrode (SPCE) co-modified with a bismuth film and gold nanoparticles for electrochemical simultaneous determination of Zn(II), Pb(II) and Cu(II) by differential pulse anodic stripping voltammetric (DPASV).
A method is described for ratiometric fluorometric assays of H2O2 by using two probes that have distinct response profiles. Under the catalytic action of ferrous ion, the 615 nm emission of protein-stabilized gold nanoclusters (under 365 nm photoexcitation) is quenched by H2O2, while an increased signal is generated with a peak at 450 nm by oxidizing coumarin with the H2O2/Fe(II) system to form a blue emitting fluorophore. These decrease/increase responses give a ratiometric signal. The ratio of the fluorescences at the two peaks are linearly related to the concentration of H2O2 in the range from 0.05 to 10 μM, with a 7.7 nM limit of detection. The detection scheme was further coupled to the urate oxidase catalyzed oxidation of uric acid which proceeds under the formation of H2O2. This method provides an simple and effective means for the construction of ratiometric fluorometric (enzymatic) assays that involve the detection of H2O2.
Graphical abstract Under catalysis by ferrous ion, hydrogen peroxide quenches the luminescence of gold nanoclusters (AuNCs) and oxidizes coumarin into a fluorescent derivative, which rendered fluorescence ON and OFF at two distinct wavelengths for ratiometric measurements.
Sensing of intracellular singlet oxygen (1O2) is required in order to optimize photodynamic therapy (PDT). An optical nanoprobe is reported here for the optical determination of intracellular 1O2. The probe consists of a porous particle core doped with the commercial 1O2 probe 1,3-diphenylisobenzofuran (DPBF) and a layer of poly-L-lysine. The nanoparticle probes have a particle size of ~80 nm in diameter, exhibit good biocompatibility, improved photostability and high sensitivity for 1O2 in both absorbance (peak at 420 nm) and fluorescence (with excitation/emission peaks at 405/458 nm). Nanoprobes doped with 20% of DPBF are best suited even though they suffer from concentration quenching of fluorescence. In comparison with the commercial fluorescent 1O2 probe SOSG, 20%-doped DPBF-NPs (aged) shows higher sensitivity for 1O2 generated at an early stage. The best nanoprobes were used to real-time monitor the PDT-triggered generation of 1O2 inside live cells, and the generation rate is found to depend on the supply of intracellular oxygen.
Graphical abstract A fluorescent nanoprobe featured with refined selectivity and improved sensitivity towards 1O2 was prepared from the absorption-based probe DBPF and used to real-time monitoring of the generation of intracellular 1O2 produced during PDT.
The authors report that the peroxidase-like activity of Au@Pt core-shell nanohybrids (Au@PtNHs) is selectively inhibited by cysteine. This finding has led to a highly sensitive colorimetric assay for cysteine that is based on the nanohybrid-catalyzed oxidation of TMB by H2O2 to form a blue product. The method has a detection limit of 5.0 nM and a linear range from 10 nM to 20 μM. The assay is highly selective over other amino acids. It was successfully applied to the determination of cysteine in an injection containing a mixture of amino acids.
Graphical abstract The peroxidase-like activity of Au@Pt core-shell nanohybrids (Au@PtNHs) is selectively inhibited by cysteine, enabling the determination of cysteine.
A multiplexed graphene oxide (GO) fluorescent nanoprobe is described for quantification and imaging of messenger RNAs (mRNAs) in living cells. The recognizing oligonucleotides (with sequences complementary to those of target mRNAs) were labeled with different fluorescent dyes. If adsorbed on GO, the fluorescence of the recognizing oligonucleotides is quenched. After having penetrated living cells, the oligonucleotides bind to target mRNAs and dissociate from GO. This leads to the recovery of fluorescence. Using different fluorescent dyes, various intracellular mRNAs can be simultaneously imaged and quantified by a high content analysis within a short period of time. Actin mRNA acts as the internal control. This GO-based nanoprobe allows mRNA mimics to be determined within an analytical range from 1 to 400 nM and a detection limit as low as 0.26 nM. Up to 3 intracellular mRNAs (C-myc, TK1, and actin) can be detected simultaneously in a single living cell. Hence, this nanoprobe enables specific distinction of intracellular mRNA expression levels in cancerous and normal cells. It can be potentially applied as a tool for detection of cancer progression and diagnosis.
Graphical abstract A multiplexed graphene oxide (GO)-based fluorescent nanoprobe is described for quantification and imaging of intracellular messenger RNAs. After penetrating living cells, the recovered fluorescence of the dissociated recognizing oligonucleotides can be analyzed , and this allows for simultaneous detection of up to 3 intracellular messenger RNAs.
The authors report on a ratiometric electrochemical sensor for paracetamol (PR) which was fabricated by successively electropolymerizing a layer of Prussian blue (PB) and a layer of molecularly imprinted polypyrrole (MIP) on the surface of a glassy carbon electrode (GCE). The binding of PR molecules to the MIP has two effects: The first is an increase of the oxidation current for PR at 0.42 V (vs. SCE), and the second is a decrease in the current for PB (at 0.18 V) due to partial blocking of the channels which results in reduced electron transmissivity. Both currents, and in particular their ratio, can serve as analytical information. Under optimized conditions, the sensor displays enhanced sensitivity for PR in the 1.0 nM to 0.1 mM concentration range and a 0.53 nM lower limit of detection. The sensor was applied to the determination of PR in tablets and urines where it gave recoveries in the range between 94.6 and 104.9 %. This dual-signal (ratiometric) detection scheme (using electropolymerized Prussian Blue and analyte-specific MIP) in our perception has a wide scope in that it may be applied to numerous other electroactive species for which specific MIP can be made available.
Graphical Abstract Prussian blue (PB) and molecularly imprinted polymer (MIP) were combined to fabricate an electrochemical sensor for paracetamol (PR) detection. The ratio of both currents, increase of PR current and decrease of PB current, was employed for PR selective detection with enhanced sensitivity.
The paper describes a fluorescent method for determination of Au(III) using molybdenum disulfide quantum dots (MoS2 QDs) that were prepared by a hydrothermal route using glutathione as a reductant. The photoluminescence of MoS2 QDs peaks at 416 nm if excited at 340 nm and is temporally stable even in presence of NaCl or when stored in the refrigerator for one year. Its quantum yield is 12.7 %. The blue-green fluorescence of MoS2 QDs is fairly specifically quenched by Au(III) ions and therefore presents a useful nanoprobe for this ion. Fluorescence intensity drops linearly with the concentration of Au(III) in the range from 0.5 to 1000 μM, and the lower detection limit is 64 nM. The quenching mechanism was investigated and it is concluded that the process is due to the reduction of Au(III) and the deposition of Au(0) on the surface of the MoS2 QDs. The nanoprobe was successfully applied to the determination of Au(III) in (spiked) environmental samples. A test stripe for Au(III) was obtained by soaking a piece of paper with a colloidal solution of the MoS2 QDs, and it was found that this stripe, after drying, can also be used to quantify Au(III) via fluorescence.
Graphical abstract Molybdenum disulfide quantum dots (MoS2 QDs) have a high quantum yield and show good stability. MoS2 QDs are shown to be a sensitive fluorescent probe for the determination of Au3+ ions in solution and with a test stripe via fluorescence quenching.
Magnetite nanoparticles were surface-modified with mercaptoacetic acid (MAA), complexed with Zn(II), and then treated with the dual Schiff base (referred to as imine-based ligand; IBL; obtained by reaction of p-aminobenzoic acid and 2,3-butanedione) to give particles with an architecture of type Fe3O4@MAA@IBL. These are shown to be viable sorbents for magnetic solid phase extraction of organochlorine pesticides (OCPs) from seawater samples. Efficient extraction of the OCPs probably is due to lone pair-π, π-complexation and π-interactions. The sorbent was characterized by transmission electron microscopy, scanning electron microscopy, FT-IR and energy-dispersive X-ray spectroscopy. The effects of the volumes of sample, sorbent dosage and eluent, adsorption and desorption times, and the salinity of the sample on the extraction efficiencies were optimized. The OCPs (heptachlor, aldrin, dieldrin, p,p’-DDE and p,p’-DDT) were quantified by gas chromatography with microelectron capture detection. Under optimal conditions, the limit of detections range was between 1.0 and 1.9 ng L?1. The enrichment factors are between 84.1 and 99.9 %. The sorbent was applied to the rapid extraction of trace quantities of OCPs from seawater samples and gave good relative recoveries (78 to 108 %) and relative standard deviations (<8.3 %).
Graphical Abstract Fe3O4 nanoparticles were functionalized with mercaptoacetic acid. The carboxylate was coordinated with Zn(II) and the ligands were immobilized via coordination with Zn(II). The lone pair-π, π-complexation and π-interaction of modified magnetite nanoparticles made this sorbent effective for extraction of organochlorine pesticides.
The authors described gold nanoclusters (AuNCs) for use on an “on ? off ? on” NIR fluorescent probe for the determination of citrate and Cu(II) ion. The AuNCs were prepared by a microwave-assisted method using BSA as both the stabilizing and reducing agent. The resulting BSA-capped AuNCs display NIR fluorescence peaking at 680 nm under 500 nm excitation, a quantum yield of ~6.0%, an average size of 2.8 ± 0.5 nm, water-dispersibility, stability and biocompatibility. The on?off probe for Cu(II) is based on the interaction between Cu(II) and BSA which causes the fluorescence of the BSA?AuNCs to be quenched. The quenched fluorescence is recovered on addition of vitamin C (VC), obviously due to complexation of Cu(II) by citrate. The probe was employed to image Cu(II) and citrate in HeLa cells and in aqueous solutions. The method works in the 20 nM to 0.1 mM concentration range for Cu(II), and in the 8 nM to 120 μM concentration range for VC.
Graphical abstract Schematic presentation of the gold nanocluster based probe whose fluorescence is quenched by Cu(II) ions and then restored by addition of vitamin C. This is demonstrated for both aqueous solutions and living cells.
The article describes the synthesis of core-shell magnetic nanoparticles (MNPs) of the type Fe3O4@MIL-100 (MIL standing for Material Institut Lavoisier), and their application as sorbent for magnetic solid-phase extraction (MSPE) of triclosan. The MNPs were prepared via circular self-assembly of ferric chloride and benzenetricarboxylic acid. The functionalized MNPs were characterized by transmission electron microscopy, FTIR and thermogravimetry. Following extraction, triclosan was eluted with ammoniacal methanol and then submitted to HPLC with UV detection. The amount of magnetic microspheres, sample pH and ionic strength, adsorption time, desorption time, desorption solvent and the volume of the eluent were optimized. Under optimum conditions, the method showed good linearity in the 0.1 to 50 mg·kg?1 triclosan concentration range in toothpaste samples. Other features include (a) intra-day and inter-day relative standard deviations (RSD, for n = 4) of <5.5 %, (b) a 30 μg·kg?1 limit of detection, and (c) extraction recoveries between 90.86 % and 101.1 %. The method was successfully applied to the determination of triclosan in children’s toothpaste.
Graphical abstract The article describes the synthesis of core-shell magnetic nanoparticles (MNPs) of the type Fe3O4@MIL-100, and their application as sorbent for magnetic solid-phase extraction (MSPE) of triclosan.
The authors describe double-shell magnetic nanoparticles functionalized with 2-mercaptobenzothiazole (MBT) to give nanospheres of the type MBT-Fe3O4@SiO2@C). These are shown to be viable and acid-resistant adsorbents for magnetic separation of the heavy metal ions Ni(II), Cu(II) and Pb(II). MBT act as a binding reagent, and the carbon shell and the silica shell protect the magnetic core. Following 12 min incubation, the loaded nanospheres are magnetically separated, the ions are eluted with 2 M nitric acid and then determined by inductively coupled plasma-mass spectroscopy. The limits of detection of this method are 2, 82 and 103 ng L￣1 for Ni(II), Cu(II), and Pb(II) ions, respectively, and the relative standard deviations (for n = 7) are 6, 7.8, and 7.4 %. The protocol is successfully applied to the quantitation of these ions in tap water and food samples (mint, cabbage, potato, peas). Recoveries from spiked water samples ranged from 97 to 100 %.
Graphical abstract Mercaptobenzothiazole-functionalized magnetic carbon nanospheres of type Fe3O4@SiO2@C were synthesized. Then applied for magnetic solid phase extraction of Ni(II), Cu(II) and Pb(II) from water and food samples with LOD of 0.002, 0.082 and 0.103 μg L?1 respectively.
The present paper reports on a chelation enhanced fluorescence (CHEF) effect that is observed on addition of certain metal ions to phosphorus doped carbon nanodots (P-CNDs). The effect is accompanied by a large shortwave shift of the emission peak. Highly passivated P-CNDs with sizes of around 3 nm were prepared from lactose and phosphoric acid, using a one-pot low temperature solvothermal method. The nanoparticles were purified according to polarity and size. The extent of blue shift and strength of enhancement depend on metal ions and actual pH value. For instance, the P-CND complex with Al(III) has a fluorescence that is shifted to shorter wavelengths, and the fluorescence quantum yield is enhanced from 12% (for the free P-CNDs) to almost 62% at 490 nm. The fluorescence is also enhanced and shifted by the ions Zn(II) and Cd(II). It is quenched by the ions Fe(II), Fe(III), Hg(II), Cu(II) and Sn(II), among others. The enhancement is attributed to the chelation of metal ions with the passivated surface functional groups of P-CNDs, mainly those of phosphorus. Phosphorous free CNDs (prepared via HCl instead of H3PO4) and low-passivated P-CNDs (prepared for longer period of time; typically 8 h) show no enhancement. The metal ion induced enhancement led to the design of a fluorometric assay for the detection of these ions. The detection limits are 4 nM for Al(III) and 100 nM for Zn(II). The two ions were quantified in spiked pharmaceutical formulations. Recoveries typically are 102% (for n = 7).
Graphical abstract The fluorescence emission of phosphorous doped carbon nanodots is significantly enhanced and tuned after binding to Al3+, Zn2+ and Cd2+. The enhancement mechanism is attributed to chelation enhanced fluorescence (CHEF).
Near infrared (NIR) emitting semiconductor quantum dots can be excellent fluorescent nanoprobes, but the poor biodegradability and potential toxicity limits their application. The authors describe a fluorescent system composed of graphene quantum dots (GQDs) as NIR emitters, and novel MnO2 nanoflowers as the fluorescence quenchers. The system is shown to be an activatable and biodegradable fluorescent nanoprobe for the “turn-on” detection of intracellular glutathione (GSH). The MnO2-GQDs nanoprobe is obtained by adsorbing GQDs onto the surface of MnO2 nanoflowers through electrostatic interaction. This results in the quenching of the NIR fluorescence of the GQDs. In the presence of GSH, the MnO2-GQDs nanoprobe is degraded and releases Mn2+ and free GQDs, respectively. This gives rise to increased fluorescence. The nanoprobe displays high sensitivity to GSH and with a 2.8 μM detection limit. It integrates the advantages of NIR fluorescence and biodegradability, selectivity, biocompatibility and membrane permeability. All this makes it a promising fluorescent nanoprobe for GSH and for cellular imaging of GSH as shown here for the case of MCF-7 cancer cells.
Graphical abstract A biodegradable NIR fluorescence nanoprobe (MnO2-GQDs) for the “turn-on” detection of GSH in living cell was established, with the NIR GQD as the fluorescence reporter and the MnO2 nanoflower as the fluorescence quencher.
A simple method is described for the determination of copper(II) ions based on the cathodic electrochemiluminescence (ECL) of lucigenin which is quenched by Cu(II). The blue ECL is best induced at ?0.45 V (vs. Ag/AgCl) at a scan rate of 50 mV·s?1. Under optimum conditions, the calibration plot is linear in the 3.0 to 1000 nM Cu(II) concentration range. The limit of detection is 2.1 nM at a signal-to-noise ratio of 3. Compared to other analytical methods, the one presented here is simple, fast, selective and cost-effective. It has been successfully applied in the analysis of copper ions in spiked tap water samples with recoveries ranging from 93.0% (at 50 nM concentration) to 105.7% (at 150 nM).
Graphical abstract The inhibitory effect of Cu(II) on the cathodic electrochemiluminescence of lucigenin enables determination of Cu(II) with a 2.1 nM detection limit.
The authors describe a fluorometric glucose assay that is based on the use of MnO2 nanosheets and copper nanoclusters (CuNCs) acting as nanoprobes. The CuNCs were synthesized by using bovine serum albumin as a template by chemical reduction of copper(II) sulfate. On addition of MnO2 nanosheets to a colloidal solution of CuNCs, the fluorescence of CuNCs (measured at excitation/emission wavelengths of 335/410 nm) is quenched. However, in the presence of enzymatically generated H2O2, the MnO2 nanosheets are reduced to form Mn(II) ions. As a result, fluorescence intensity recovers. The glucose assay is based on the enzymatic conversion of glucose by glucose oxidase to generate H2O2 and glucuronic acid. The calibration plot is linear in the 1 μM to 200 μM glucose concentration range, and the detection limit is 100 nM. The method was successfully applied to the determination of glucose in spiked human serum samples.
Graphical abstract A sensitive fluorescent bioassay is reported for the detection of glucose based on the hydrogen peroxide-induced decomposition of a quencher system composed of MnO2 nanosheets and copper nanoclusters (CuNCs).
Functionalized nitrogen-doped graphene quantum dots (N-GQD) with mean particle size of 8.5?±?0.5 nm were covalently linked to β-cyclodextrin (β-CD) to form a β-CD@N-GQD nanoprobe. The probe is shown to enable voltammetric determination of cholesterol via selective host-guest recognition and by using ferrocene (FC) as the redox indicator. FC is first included in β-cyclodextrin. Cholesterol has a higher affinity for β-CD (in comparison to FC). It forms a strong inclusion complex with β-CD and can replace FC from its cavities. The quantity of released FC is proportional to the concentration of cholesterol. The differential pulse voltammetric signal for FC (with a peak at typically 0.22 V vs Ag/AgCl) increases linearly in the 0.5–100 μM cholesterol concentration range, with a limit of detection as low as 80 nM. The assay is found to be highly selective over 15 potentially interfering species. The method was successfully applied to the detection of cholesterol in spiked serum samples which gave recoveries between 96 and 101%. The probe can be stored for at least 28 days after which the activity still is 87%.
Graphical abstract This scheme illustrates the detection of cholesterol by differential pulse voltammetry (DPV) technique. The β-cyclodextrin functionalized nitrogen-doped graphene quantum dot (β-CD@N-GQD) probe was developed to enable voltammetric determination of cholesterol using selective host-guest recognition.
Diphenyl diselenide was immobilized on chitosan loaded with magnetite (Fe3O4) nanoparticles to give an efficient and cost-effective nanosorbent for the preconcentration of Pb(II), Cd(II), Ni(II) and Cu(II) ions by using effervescent salt-assisted dispersive magnetic micro solid-phase extraction (EA-DM-μSPE). The metal ions were desorbed from the sorbent with 3M nitric acid and then quantified via microflame AAS. The main parameters affecting the extraction were optimized using a one-at-a-time method. Under optimum condition, the limits of detection, linear dynamic ranges, and relative standard deviations (for n?=?3) are as following: Pb(II): 2.0 ng·mL?1; 6.3–900 ng·mL?1; 1.5%. Cd(II): 0.15 ng·mL?1; 0.7–85 ng·mL?1, 3.2%; Ni(II): 1.6 ng·mL?1,.6.0–600. ng·mL?1, 4.1%; Cu(II): 1.2 ng·mL?1, 3.0–300 ng·mL?1, 2.2%. The nanosorbent can be reused at least 4 times.
Graphical abstract Fe3O4-chitosan composite was modified with diphenyl diselenide as a sorbent for separation of metal ions by effervescent salt-assisted dispersive magnetic micro solid-phase extraction.
