Multifunctional Binding Strategy on Nonconjugated Polymer Nanoparticles for Ratiometric Detection and Effective Removal of Mercury Ions.

Developing a multifunctional platform for the selective detection and effective removal of toxic ions is a major challenge when addressing heavy metal contamination in environmental science. Herein, novel nonconjugated polymer nanoparticles (PNPs) called mercaptosuccinic acid-thiosemicarbazide PNPs (MT-PNPs) with appealing fluorescence and stability are synthesized via facile one-step hydrothermal treatment for attractive sensing and simultaneous removal of mercury(II). Interestingly, aggregation-induced fluorescence switch-off and scattering enhancement are found upon the addition of Hg2+, rendering MT-PNPs as a ratiometric sensor for selective and accurate Hg2+ monitoring. A wide linear range (0.1-1471 µM) and a low detection limit (95 nM) are obtained. This dual-signal opposite responses triggered by Hg2+ originate from the formation of MT-PNP-Hg2+ congeries via the multisite binding between S,N,O-containing groups of MT-PNPs and mercury. Meanwhile, target-induced aggregation renders an effective Hg2+ separation from contaminative aqueous media by MT-PNPs, which exhibits a satisfactory absorption efficiency of 90.42% within 50 min. Upon the simple Na2S treatment, the MT-PNPs can be regenerated and reused. This work thus delivers an applicable method for the ratiometric detection and effective removal of mercury with the novel nonconjugated PNPs, offering potential in tackling the problem of heavy metal ion pollution for environmental monitoring and remediation.

A facile and label-free ratiometric optical sensor for selective detection of norepinephrine by combining second-order scattering and fluorescence signals.

In this work, a facile and label-free ratiometric sensor is constructed for selective determination of norepinephrine (NE) by coupling second-order scattering (SOS) and fluorescence, two different and independent optical signals. Herein, polyethyleneimine (PEI) dilute solution medium shows an intensive SOS signal without any fluorescence response. Interestingly, NE can be selectively induced by PEI to emit bright fluorescence, and meanwhile causes an observable decrease in the SOS signal due to the interactions between NE and PEI. The simultaneous variation of the two independent signals can be used for ratiometric sensing of NE. Under the optimal conditions, the resultant ratiometric sensor displays high sensitivity and selectivity toward NE by simultaneously monitoring fluorescence and SOS signals with the same excitation wavelength. The proposed sensor exhibits a good linear relationship versus NE concentration in the range of 10.0 nM-45.0 µM with a detection limit of 2.0 nM (S/N = 3) and has been successfully applied to the determination of NE in real samples without the use of any extra reagent. The combination of fluorescence and SOS signals provides a new scheme for ratiometric sensor design, greatly simplifying experimental procedure and effectively enhancing detection accuracy. Moreover, the proposed analytical strategy further broadens the application of dilute solutions of polymers in research into optical sensor and green analytical chemistry. Graphical abstract.

Supersensitive and selective detection of picric acid explosive by fluorescent Ag nanoclusters.

Picric acid (PA) explosive is a hazard to public safety and health, so the sensitive and selective detection of PA is very important. In the present work, polyethyleneimine stabilized Ag nanoclusters were successfully used for the sensitive and selective quantification of PA on the basis of fluorescence quenching. The quenching efficiency of Ag nanoclusters is proportional to the concentration of PA and the logarithm of PA concentration over two different concentration ranges (1.0 nM-1 µM for the former and 0.25-20 µM for the latter), thus the proposed quantitative strategy for PA provides a wide linear range of 1.0 nM-20 µM. The detection limit based on 3σ/K is 0.1 nM. The quenching mechanism of Ag nanoclusters by PA is discussed in detail. The results indicate that the selective detection of PA over other nitroaromatics including 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (2,4-DNT), p-nitrotoluene (p-NT), m-dinitrobenzene (m-DNB), and nitrobenzene (NB), is due to the electron transfer and energy transfer between PA and polyethyleneimine-capped Ag nanoclusters. In addition, the experimental data obtained for the analysis of artificial samples show that the proposed PA sensor is potentially applicable in the determination of trace PA explosive in real samples.

Sensitive and selective turn-on fluorescence method for cetyltrimethylammonium bromide determination based on acridine orange-polystyrene sulfonate complex.

This work proposed a rapid and novel fluorescence-sensing system using a complex of acridine orange (AO) and polystyrene sulfonate (PSS) to sensitively recognize and monitor cetyltrimethylammonium bromide (CTAB) in an aqueous medium. AO can interact with PSS and a complex is formed via electrostatic attraction and hydrophobic interaction. The fluorescence of AO is greatly quenched after the introduction of PSS. Upon its subsequent addition, CTAB can interact and form a complex with PSS because the electrostatic attraction between CTAB and PSS is much stronger than that between AO and PSS, which results in significant fluorescence recovery. Interestingly, the proposed method can be applied for the discrimination and detection of surfactants with different hydrocarbon chain lengths due to their different binding affinity toward PSS. The detection limit for CTAB is as low as 0.2 µg/mL and the linear range is from 0.5 to 3.5 µg/mL. Moreover, we applied the sensor to the successful detection of CTAB in water samples. Copyright © 2015 John Wiley & Sons, Ltd.

Multidimensional optical sensing platform for detection of heparin and reversible molecular logic gate operation based on the phloxine B/polyethyleneimine system.

A multidimensional optical sensing platform which combines the advantages of resonance Rayleigh scattering (RRS), fluorescence, and colorimetry has been designed for detection of heparin. Phloxine B, a fluorescein derivative showing the special RRS spectrum in the long wavelength region, was selected to develop an easy-to-get system which can achieve switch-on sensing to obtain high sensitivity. The noise level of RRS in the long wavelength region is much weaker, and the reproducibility is much better; in this way, the sensitivity and selectivity can be improved. In the absence of heparin, the phloxine B and polyethyleneimine (PEI) form a complex through electrostatic interaction. Thus, the RRS signal at 554 nm is low; the phloxine B fluorescence is quenched, and the absorption signal is low. In the presence of heparin, competitive binding occurred between phloxine B and heparin toward PEI; then, phloxine B is gradually released from the phloxine B/PEI complex, causing obvious enhancement of the RRS, fluorescence, and absorption signals. Besides, the desorption of phloxine B is less effective for the heparin analogues, such as hyaluronic acid and chondroitin sulfate. In addition, the system presents a low detection limit of heparin to 5.0 × 10(-4) U mL(-1) and can also be applied to the detection of heparin in heparin sodium injection and 50% human serum samples with satisfactory results. Finally, the potential application of this method in reversible on-off molecular logic gate fabrication was discussed using the triple-channel optical signals as outputs.

Polyethyleneimine-templated Ag nanoclusters: a new fluorescent and colorimetric platform for sensitive and selective sensing halide ions and high disturbance-tolerant recognitions of iodide and bromide in coexistence with chloride under condition of high ionic strength.

Ag nanoclusters functioned by hyperbranched polyethyleneimine have been developed as a new fluorescent and colorimetric platform for sensitive and selective recognition of halide ions (e.g., Cl(-), Br(-), and I(-)). The recognition mechanism is based on the unique reactions between halide ions and the silver atoms. In particular, halide-induced oxidative etching and aggregation can produce a strong fluorescence quenching of Ag nanoclusters. This sensing system exhibits a remarkably high selectivity toward halide ions over most of anions and cations and shows good linear ranges and lower detection limits: the linear ranges are 0.5-80 µM for Cl(-), 0.1-14 µM for Br(-), and 0.05-6 µM for I(-), respectively; the limits of detection for Cl(-), Br(-), and I(-), at a signal-to-noise ratio of 3, are estimated to be 200, 65, and 40 nM, respectively. Specifically, Br(-) and I(-) could be recognized selectively in the coexistence with Cl(-) under the condition of higher ionic strength, which is a significant advantage in the detection of Br(-) and I(-) in real samples. In addition, the recognition of halide could be performed by the colorimetric method, which is also attractive and promising because of its simplicity, rapidity, reliability, and low cost. Furthermore, this sensing system has been applied successfully to the detection of Cl(-) in real water samples.

Hydrogen peroxide sensor based on Prussian blue electrodeposited on (3-mercaptopropyl)-trimethoxysilane polymer-modified gold electrode.

A hydrogen peroxide (H(2)O(2)) sensor was developed by electrodepositing Prussian blue (PB) on a gold electrode modified with (3-mercaptopropyl)-trimethoxysilane (MPS) polymer. The characterization of the self-assembled electrode was investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The results of electrochemical experiments showed that such constructed sensor had a favorable catalytic ability to reduce H(2)O(2). The MPS film on the modified gold electrode greatly enhanced the pH-adaptive range of PB. Large surface-to-volume ratio property of double-layer 2d-network MPS-modified PB electrode enabled stable and highly sensitive performance of the non-enzymatic H(2)O(2) sensor. The linear range of H(2)O(2) determined is from 2.0 × 10(-6) to 2.0 × 10(-4) mol L(-1) with a correlation coefficient of 0.9991 and a detection limit for H(2)O(2) of 1.8 × 10(-6) mol L(-1). The influences of the potentially interfering substances on the determination of H(2)O(2) were investigated. This modified electrode exhibits a good selectivity and high sensitivity with satisfactory results.

Label-free fluorescent discrimination and detection of epinephrine and dopamine based on bioinspired in situ copolymers and excitation wavelength switch.

A simple and label-free fluorescence turn-on method is proposed for the discrimination and detection of epinephrine (Ep) and dopamine (DA) via polyethyleneimine (PEI)-initiated in situ copolymerization and excitation wavelength switch. The PEI solution in the presence of Ep, DA and the mixture of Ep and DA are denoted as PEp-PEI, PDA-PEI and MEp+DA, respectively. In this study, PEI aqueous solution medium initiates the auto-oxidization of Ep and DA and the bioinspired copolymerization. These resultant copolymers emit yellow-green fluorescence color with a fluorescence emission maximum at 515 nm. Interestingly, these fluorescent copolymers exhibit distinct different excitation spectra, although Ep and DA are structurally very similar. PDA-PEI exhibits only one excitation peak at 385 nm, and PEp-PEI shows dual-excitation mode with two significant excitation peaks at 328 nm and 405 nm, respectively. MEp+DA also shows dual-excitation mode with two excitation peaks at 330 nm and 395 nm, respectively. Thus, individual Ep, DA, and their mixture can be discriminated based on the different excitation spectral shapes and peak locations of PEp-PEI, PDA-PEI and MEp+DA. Furthermore, the quantitative analysis of Ep and DA in mixture can also be achieved by switching excitation wavelength between 330 and 395 nm and monitoring the fluorescence emission intensity of MEp+DA at 515 nm. The fluorescence intensity of MEp+DA only related to the concentration of Ep when excited at 330 nm. Moreover, the concentration of DA can also be calculated by subtracting the fluorescence intensity of PEp-PEI from the total fluorescence intensity when excited at 395 nm. The resultant method has been used to simultaneously detect Ep and DA in human urine samples. The proposed fluorescence system is facile, eco-friendly, low-cost, and time-saving, and also provides a new and simple path for discriminating analogues.

Characterization and electrocatalytic properties of Prussian blue electrochemically deposited on nano-Au/PAMAM dendrimer-modified gold electrode.

Gold electrode was modified with 3-mercaptopropionic acid (MPA) and further reacted with poly(amidoamine) (PAMAM) dendrimer (generation 4.0) then attached the nano-Au to obtain films on which Prussian blue (PB) was electrochemically deposited to afford much wider pH adaptive range, much better electrochemical stability and excellent electrochemical response. The microstructure and electrochemical behavior of Au/MPA/PAMAM/nano-Au/PB electrode were investigated by scanning electron microscopy (SEM) and cyclic voltammetry. The electrochemical response of the Au/MPA/PAMAM/nano-Au/PB-modified electrode for the electrocatalytic reduction of hydrogen peroxide was investigated, and it was found that the sensitivity as well as the corresponding detection limits were improved as compared to the voltammetric response of a Au/PB-modified electrode and Au/MPA/PAMAM/PB electrode. Based on this, a new electrochemical sensor for determination of hydrogen peroxide has been developed.

A Sensitive "Turn-On" Fluorescent Sensor for Melamine Based on FRET Effect between Polydopamine-Glutathione Nanoparticles and Ag Nanoparticles.

In this work, Ag nanoparticles (AgNPs) were synthesized quickly by a one-step method utilizing polydopamine-glutathione nanoparticles (PDA-GNPs) as a reducing agent. The PDA-GNPs and the generated AgNPs acted as the energy donor and acceptor, respectively. Accordingly, the fluorescence of PDA-GNPs was quenched on the basis of fluorescence resonance energy transfer (FRET). In the presence of melamine, the preferential combination of Ag(I) and melamine to form Ag(I)-melamine complex prevents Ag(I) from forming AgNPs, together with fluorescence enhancement compared with the absence of melamine. Under the optimal conditions including the concentration of AgNO3, reaction time, reaction temperature, and pH, the fluorescence enhancement efficiency has a linear response to the concentration of melamine from 0.1 to 40 µM with a detection limit of 23 nM for melamine. The proposed method is simple, time-saving, and low-cost, which was further applied to detect melamine in real milk products with satisfactory results.

A resonance Rayleigh scattering sensor for detection of Pb2+ ions via cleavage-induced G-wire formation.

A resonance Rayleigh scattering (RRS) aptasensor was fabricated for detection of Pb2+via hairpin-like label-free substrate and G-wire for signal amplification. A hairpin-like DNA substrate contains a sequence in the loop labeled with ribonucleobase A and c-myc sequence in the stem. When hybridized with 8-17 DNAzyme in the presence of Pb2+, the sequence in the loop was activated and cleaved. Hundreds of c-myc sequences departing from the 8-17 DNAzyme yield nanowires superstructure called G-wire in the presence of Mg2+. The polymer G-wire was demonstrated by the RRS spectrum, polyacrylamide gel electrophoresis, and AFM. The RRS intensity was enhanced by the product G-wires, and the RRS signal at 370nm was linear with the logarithm of Pb2+ concentration in the range of 2.0nM to 5.0µM. This method was selective for Pb2+ even coexisting with other metal ions at high concentrations and was successfully applied to the determination of Pb2+ in real samples. The aptasensor holds a great promise for universal RRS sensing platform for sensitive detection of various metal ions just by changing the sequence of the probe in the loop and DNAzyme.

Simultaneous voltammetric measurement of ascorbic acid, epinephrine and uric acid at a glassy carbon electrode modified with caffeic acid.

A stable electroactive thin film of poly(caffeic acid) has been deposited on the surface of a glassy carbon electrode by potentiostatic technique in an aqueous solution containing caffeic acid. Poly(caffeic acid) was used as a modified electrode for the detection of ascorbic acid (AA), epinephrine (EP), uric acid (UA) and their mixture by cyclic voltammetry. This modified electrode exhibits potent and persistent electron-mediating behavior followed by well-separated oxidation peaks towards AA, EP and UA with activation overpotential. For the ternary mixture containing AA, EP and UA, the three compounds can well separate from each other at the scan rate of 20 mVs(-1) with a potential difference of 156, 132 and 288 mV between AA and EP, EP and UA and AA and UA, respectively, which was large enough to determine AA, EP and UA individually and simultaneously. The catalytic peak current obtained, was linearly dependent on the AA, EP and UA concentrations in the range of 2.0 x 10(-5) to 1.0 x 10(-3) mol l(-1), 2.0 x 10(-6) to 8.0 x 10(-5) mol l(-1) and 5.0 x 10(-6) to 3.0 x 10(-4) mol l(-1), and the detection limits for AA, EP and UA were 7.0 x 10(-6), 2.0 x 10(-7) and 6.0 x 10(-7) mol l(-1), respectively. The modified electrode shows good sensitivity, selectivity and stability, and has been applied to the determination of EP in practical injection samples and that of EP, UA and AA simultaneously with satisfactory results.

Enzyme-free fluorescent biosensor for the detection of DNA based on core-shell Fe3O4 polydopamine nanoparticles and hybridization chain reaction amplification.

A novel, highly sensitive assay for quantitative determination of DNA is developed based on hybridization chain reaction (HCR) amplification and the separation via core-shell Fe3O4 polydopamine nanoparticles (Fe3O4@PDA NPs). In this assay, two hairpin probes are designed, one of which is labeled with a 6-carboxyfluorescein (FAM). Without target DNA, auxiliary hairpin probes are stable in solution. However, when target DNA is present, the HCR between the two hairpins is triggered. The HCR products have sticky ends of 24 nt, which are much longer than the length of sticky ends of auxiliary hairpins (6 nt) and make the adsorption much easier by Fe3O4@PDA NPs. With the addition of Fe3O4@PDA NPs, HCR products could be adsorbed because of the strong interaction between their sticky ends and Fe3O4@PDA NPs. As a result, supernatant of the solution with target DNA emits weak fluorescence after separation by magnet, which is much lower than that of the blank solution. The detection limit of the proposed method is as low as 0.05 nM. And the sensing method exhibits high selectivity for the determination between perfectly complementary sequence and target with single base-pair mismatch. Importantly, the application of the sensor for DNA detection in human serum shows that the proposed method works well for biological samples.

Differential pulse anodic stripping voltammetric determination of traces of copper with a tobramycin-Nafion modified electrode.

A Nafion-modified glassy carbon electrode incorporated with tobramycin for the voltammetric stripping determination of Cu2+ has been explored. The electrode was fabricated by tobramycin containing Nafion on the glassy carbon electrode surface. The modified electrode exhibited a significantly increased sensitivity and selectivity for Cu2+ compared with a bare glassy carbon electrode and the Nafion modified electrode. Cu2+ was accumulated in HAc-NaAc buffer (pH 4.6) at a potential of -0.6 V (vs. SCE) for 300 s and then determined by differential pulse anodic stripping voltammetry. The effects of various parameters, such as the mass of Nafion, the concentration of tobramycin, the pH of the medium, the accumulation potential, the accumulation time and the scan rate, were investigated. Under the optimum conditions, a linear calibration graph was obtained in the concentration range of 1.0 x 10(-9) to 5.0 x 10(-7) mol l(-1) with a correlation coefficient of 0.9971. The relative standard deviations for eight successive determinations were 4.3 and 2.9% for 1.0 x 10(-8) and 2.0 x 10(-7) mol l(-1) Cu2+, respectively. The detection limit (three times signal to noise) was 5.0 x 10(-10) mol l(-1). A study of interfering substances was also performed, and the method was applied to the direct determination of copper in water samples, and also in analytical reagent-grade salts with satisfactory results.

Polyethylenimine-capped silver nanoclusters as a fluorescence probe for highly sensitive detection of folic acid through a two-step electron-transfer process.

A highly sensitive folic acid (FA) detection method based on the fluorescence quenching of polyethylenimine-capped silver nanoclusters (PEI-AgNCs) was put forward. In the sensing system, FA and PEI-AgNCs were brought into close proximity to each other by electrostatic interaction, and a two-step electron-transfer process, in which the electron was transferred from FA to AgNCs through PEI molecule, led to fluorescence quenching. The fluorescence quenching efficiency of PEI-AgNCs was linearly related to the concentration of FA over the range from 0.1 nM to 2.75 µM. Good linear correlation (R(2) = 0.9981) and a detection limit of 0.032 nM were obtained under optimum conditions. Moreover, the proposed method was used for the determination of FA in real samples with satisfactory results, and those coexistent substances could not cause any significant decrease in the fluorescence intensity of AgNCs. Therefore, the proposed research system is of practical significance and application prospects.

Fluorescent detection of hydrogen peroxide and glucose with polyethyleneimine-templated Cu nanoclusters.

An interesting, simple, and label-free strategy for the detection of hydrogen peroxide and glucose has been developed with polyethyleneimine (PEI)-capped copper nanoclusters as a fluorescence probe in aqueous solution. The PEI-templated Cu nanoclusters which we have synthesized have an average diameter of 1.8 nm and show a blue emission at 480 nm. In the presence of hydrogen peroxide, the fluorescence of the Cu nanoclusters is quenched. Similarly, glucose oxidase catalyzes the oxidation of glucose to gluconic acid and H2O2, so we can also use this probe to detect glucose. Because of the high zymolyte specificity of glucose oxidase, the detection of glucose has good selectivity. Under the optimized experimental conditions, the linear ranges for H2O2 and glucose are 0.5-10 µM and 10-100 µM, respectively. And the detection limits for H2O2 and glucose are 0.4 and 8 µM, respectively. Furthermore, we discussed the mechanism of fluorescence quenching which is caused by the interaction between H2O2 and Cu nanoclusters. This sensing system has been applied successfully to the detection of glucose in human serum samples.

Sensitive signal-on fluorescent sensing for copper ions based on the polyethyleneimine-capped silver nanoclusters-cysteine system.

In this work, we present a label-free sensor for copper ions. This sensor is composed of silver nanoclusters and cysteine. The fluorescence of the silver nanoclusters was quenched by cysteine, which was recovered in the presence of copper ions. This binding of silver nanoclusters to cysteine promoted agglomeration of silver nanoclusters to yield larger non-fluorescent silver nanoparticles. The presence of copper ions resulted in the oxidation of cysteine to form a disulfide compound, leading to recovery of fluorescence of the silver nanoclusters. The fluorescence of the silver nanoclusters in the presence of cysteine increased with increasing concentration of copper ions in the range of 10-200 nM. The detection limit of this sensor for copper ions was 2.3 nM. The silver nanoclusters-cysteine sensor provides a simple, cost-effective, and sensitive platform for the detection of copper ions.