Evaluation of Graphene Oxide as a Thermal Ionization Enhancer for Plutonium in TIMS Measurement.

Thermal ionization mass spectrometry (TIMS) has been extensively employed for the assessment of plutonium (Pu) isotopes in nuclear forensics and environmental monitoring. Recently, great efforts have been made to improve the ionization efficiency (IE) of Pu to achieve better accuracy and precision for trace-level analysis. Herein, the thermal ionization enhancement effect for plutonium of graphene oxide (GO) was investigated and the corresponding mechanism was discussed. The GO layers were homogeneously mounted on the filament's central surface to promote pg-level Pu ion emission. With the excellent structural property of GO, a greatly promoted ionization efficiency of 0.44% for Pu was obtained, and the initial ionization temperature for Pu was remarkably reduced from 1610 to 1390 °C. Average boosts in IE compared to the classical double-filament mode and graphite-loaded single-filament mode were 1640 and 520%, respectively. The analytical accuracy and precision based on the GO-loaded single-filament mode were validated using Pu isotopic certified reference materials. This work demonstrates the excellent property of GO as an ion source additive for Pu ionization, as it provided an interface for the promotion of energy transfer and Pu carbide formation. The operation of GO loading is quite simple and can be finished within 5 min. This rapid filament carburization approach has great potential for improving the measurement precision of trace-level plutonium isotopes and can be applied in nuclear safeguards, nuclear forensics, and environmental monitoring.

Cloud point extraction associated with differential pulse voltammetry: preconcentration and determination of trace uranyl in natural water.

A procedure for the electroanalytical determination of uranyl ions pre-concentrated from natural water by cloud point extraction (CPE) is developed in this study. CPE parameters, such as surfactant concentration, extractant concentration, pH and additive concentration were optimized. After CPE, the solution was diluted for electrochemical determination by differential pulse voltammetry (DPV) with a mercury film electrode (Hg-GCE). The current response of uranyl showed a linear relationship with concentration from 10 nmol L-1 to 1 µmol L-1. The hyphenated method combining CPE and DPV achieved a detection limit of uranyl as low as 0.15 nmol L-1. The presence of some foreign ions interfered greatly with the current response of electrochemical detection. Therefore, the hyphenated technique combining CPE and DPV is important because the CPE step provides selectivity against the co-existing metal ions for electrochemical detection. No interference was seen from the representative foreign metal ions in the CPE-DPV method. The developed method was successfully applied for the determination of uranyl ions in natural water. The average recovery using CPE-DPV in real samples varied from 94.4% to 103.2% and the precision was comparable with that of inductively coupled plasma mass spectrometry (ICP-MS), indicating the good accuracy and precision of the method developed. This hyphenated technique could have greater potential applications for the determination of uranyl ions in aqueous environments.

Plasmon catalytic PATP coupling reaction on Ag-NPs/graphite studied via in situ electrochemical surface-enhanced Raman spectroscopy.

The p-aminothiophenol (PATP) coupling reaction on plasmon substrates such as Ag and Au nanoparticles has received extensive attention since the catalytic effect of the surface plasmon was found. Currently, in situ kinetic studies of this reaction are rare, especially those focusing on the specific role of the hot electron-hole carriers. Here, in situ electrochemical surface-enhanced Raman spectroscopy (SERS) is developed to study the plasmon catalytic reaction of PATP in a controlled aqueous environment involving the factors of O2, electron and hole carriers, and solution pH. Ag nanoparticles supported on graphite serve as a SERS substrate, which could separate hot electron-hole pairs effectively and is beneficial to study the effects of hot carriers on plasmon-driven reactions. In situ electrochemical SERS measurements reveal two reaction paths for the PATP coupling reaction. One is that plasmon-induced hot holes activate the dehydrogenation of PATP and then the radical coupling reaction to form p,p'-dimercaptoazobenzene (DMAB) under O2-free conditions. Another is likely to be that the surface Ag2O/AgOH, which is generated from Ag and 1O2/O2-, catalyzes the oxidation of PATP and then the coupling process under O2-rich conditions. Benefitting from the potential/atmosphere controlled measurements in situ, the intermediate species of PATP(NH)/PATP(N) are observed with vibrational bands at around 1056, 1202, 1253, 1395, 1514 and 1540 cm-1.

Flexible and adhesive tape decorated with silver nanorods for in-situ analysis of pesticides residues and colorants.

A flexible adhesive tape decorated with SERS-active silver nanorods (AgNRs) in the form of an array nanostructure is described. The tape was constructed by transferring the AgNRs nanostructures from silicon to the transparent tape by a "paste & peel off" procedure. The transparent, sticky, and flexible properties of commercial tapes allow almost any SERS-inactive irregular surface to be detected in-situ by pasting the SERS tape onto the position to be analyzed. Three examples for an analytical application are presented, viz. determination of (a) tetramethylthiuram disulfide and thiabendazole (two pesticides), (b) colorants in the gel of a writing pen, and (c) the fluorophore Rhodamine B. The tetramethylthiuram disulfide on apple surface was rapidly detected with a LOD of 28.8 ng·cm-2. The AgNRs effectively quenched the fluorescence of the matrix and fluorophores, this enabling the colorants and Rhodamine B to be identified. The results demonstrated that the SERS tape can be used for versatile in-situ detection. Conceivably, it may find applications in food analysis, non-invasive identification, environmental monitoring, and in other areas of daily life. Graphic abstract A flexible and adhesive SERS active tape decorated with silver nanorods (AgNRs) arrays was constructed through a "paste & peel off" method. It can be used as a versatile in situ analysis platform for various applications.

Three-way DNA junction based platform for ultra-sensitive fluorometric detection of multiple metal ions as exemplified for Cu(II), Mg(II) and Pb(II).

A DNA-based fluorometric method is described for simultaneous determination of multiple metal ions. It is based on recycling cleavage of hairpins by using a three-way DNA junction structure. Three DNA sequences containing a binding region and an enzyme-strand (E-DNA) region are hybridized to form a three-way DNA junction. The enzyme strand regions at the end of the DNA sequence binds to the substrate sequence (S-DNA) at the loop of the hairpin to form typical DNAzyme structures. In the presence of analyte metal ions, the DNAzyme structure thus formed cleaves the loop of hairpins. This is accompanied by a release of fluorescently labeled DNA fragments and by quenching of fluorescence. The detection limits are 35 pM for Cu(II), 2 nM for Mg(II), and 8 pM for Pb(II). This method was successfully applied to the simultaneous determination of these ions in spiked human serum. Graphical abstract Schematic presentation of the recycling cleavage of hairpins by using a three-way DNA junction structure. It causes a release of fluorescently labeled DNA fragments and quenching of fluorescence. It was successfully applied to the simultaneous determination of Cu(II), Mg(II) and Pb(II) in spiked human serum.

[Design and Fabrication of Silver Nanoparticles/Graphen Complex Substrate and Its Application for Detecting Uranium (â ¥)].

Uranium is one of the important nuclear materials to nuclear industry. Because of the direct disposal of spent fuel, there is still a huge possibility that uranium migrates into the groundwater, causing water contamination. It is of great importance to understand the concentration and their species distribution in aqueous solutions. Surface-Enhanced Raman Scattering (SERS) technique has been widely used for the detection of uranium (Ⅵ). However, the interactions between uranium (Ⅵ) and SERS substrate cause the symmetric stretching vibration peak of uranium (Ⅵ) shift to low wave number direction, which is unfavorable for confirming the species of uranium (Ⅵ) in aqueous solution. For instance, the normal Raman bands of uranyl in nitric acid solution are 871 cm-1, which belongs to the symmetric stretching mode of UO2+2. However, it moves to 710 cm-1 on the surface of silver nanorods SERS substrtate. What's more, different SERS substrate causes different number of shift. Graphene has advantages of inertness and integrity as well as 2-dimensional thickness. In this paper, graphene-isolated SERS substrate which is silver nanoparticles (AgNPs)/graphene complex substrate, was designed to prevent the interaction between SERS substrate and it was analyzed by using the inert graphene layer. First of all, according to our previous work, AgNPs SERS substrate was fabricated on silicon wafer by using an ascorbic acid-actived self-assembly method. Then, AgNPs/graphene complex substrate was prepared by transfering monolayer graphene onto the self-assembly AgNPs substrate. The morphology of complex substrate was obtained by SEM. Some AgNPs link together closely to form nanochain structures. Nanochain structures were distributed evenly on the surface of silicon wafer. The 2-dimensional thickness of graphene did not affect the morphology of AgNPs. When using the complex substrate to detect uranyl nitrate (5×10-4 mol·L-1)，the Raman peak that appeared around 771 cm-1 is considered to be the symmetric stretching mode of UO2+2, shifting back about 52 cm-1 to high wave number direction when compared with AgNPs substrate, which was about ~719 cm-1. The result indicates that graphene layer isolates the interaction between AgNPs substrate and uranyl in some degree.

Photoreduced Ag+/sodium alginate supramolecular hydrogel as a sensitive SERS membrane substrate for rapid detection of uranyl ions.

BACKGROUND: In the fields of environmental monitoring and nuclear emergency, in order to obtain the relevant information of uranyl-induced environmental pollution and nuclear accident, it is necessary to establish a rapid quantitative analytical technique for uranyl ions. As a new promising technique, surface-enhanced Raman scattering (SERS) is hopeful to achieve this goal. However, uranyl ions are easily desorbed from SERS substrates under acidic conditions, and the structures of SERS substrates will be destroyed in the strong acidic aqueous solutions. Besides, the quantitative detection ability of SERS for uranyl ions needs to be promoted. Hence, it is necessary to develop new SERS substrates for accurate quantitative detection of trace uranyl in environmental water samples, especially in acidic solutions. RESULTS: In this work, we prepared silver ions/sodium alginate supramolecular hydrogel membrane (Ag+/SA SMH membrane), and the Ag+ ions from the membrane were transformed into Ag/Ag2O complex nanoparticles under laser irradiation. The Raman signal of uranyl was strongly enhanced under the synergistic interaction of electromagnetic enhancement derived from the Ag nanoparticles and charge transfer enhancement between uranyl and Ag2O. Utilizing the peak of SA (550 cm-1) as an internal standard, a quantitative detection with a LOD of 6.7 × 10-9 mol L-1 was achieved due to a good linear relation of uranyl concentrations from 1.0 × 10-8 mol L-1 to 2 × 10-6 mol L-1. Furthermore, foreign metal ions hardly affected the SERS detection of uranyl, and the substrate could determine trace uranyl in natural water samples. Particularly, the acidity had no obvious effect on SERS signals of uranyl ions. Therefore, in addition to the detection of uranyl ions in natural water samples, the proposed strategy could also detect uranyl ions in strong acidic solutions. SIGNIFICANCE AND NOVELTY: A simple one-step method was used to prepare an Ag+/SA SMH membrane for rapid quantitative detection of uranyl ions for the first time. The proposed substrate successfully detected uranyl ions under acidic conditions by immobilizing uranyl ion in hydrogel structure. In comparison with the previous studies, a more accurate quantitative analysis for uranyl ions was achieved by using an internal standard, and the proposed strategy could determine trace uranyl in either natural water samples or strong acidic solutions.

Highly sensitive and selective determination of uranyl ions based on Ag/Ag2O-COF composite SERS substrate.

Uranium is an essential nuclear material in civilian and military areas; however, its extensive application raises concerns about the potential safety issues in the fields of environmental protection and nuclear industry. In this study, we developed an Ag/Ag2O-COF (covalent-organic framework) composite SERS substrate to detect uranyl ions (UO22+) in environmental aqueous solutions. Herein, the strong SERS effect of uranyl adsorbed in Ag/Ag2O composite and the high adsorption efficiency of COF TpPa-1 were combined to realize the trace detection of uranyl ions. This method displayed a linear range of 10-8 mol L-1 to 10-6 mol L-1 with the detection limit of 8.9 × 10-10 mol L-1 for uranyl ions. Furthermore, common metal cations and oxo-ions hardly affected the SERS detection of uranyl, which is helpful for the trace analysis of uranyl in natural water samples. Although the proposed strategy is deployed for uranyl detection, the reusable and high-efficiency system may be expanded to trace detection of other substance with Raman activity.

Enhanced hydrogen production on porous TiO2 nanotube arrays.

Well aligned TiO2 nanotube arrays have been synthesized via anodization in an NH4F and ethylene glycol electrolyte; the resulting carbon-entrained films were treated by oxygen and argon microwave plasma. It was found that as-prepared amorphous TiO2 nanotubes can be easily crystallized into anatase at temperature lower than 150 degrees C. Carbon can be effectively eliminated in oxygen plasma and a new secondary porosity was emerged. It was found such a porous film has obvious photovoltaic and hydrogen production enhancement under simulated solar irradiation compared with that crystallized in inert argon plasma. This phenomenon may be attributed to the improvement of light adsorption and its excellent capability of hole-electron separation derives from highly ordered nanoporous configurations.

In Situ Surface-Enhanced Raman Spectroscopy Detection of Uranyl Ions with Silver Nanorod-Decorated Tape.

Surface-enhanced Raman spectroscopy (SERS) has been utilized for rapid analysis of uranyl ions (UO2 2+) on account of its fast response and high sensitivity. However, the difficulty of fabricating a suitable SERS substrate for in situ analysis of uranyl ions severely restricts its practical application. Hence, we proposed flexible and adhesive SERS tape decorated with silver nanorod (AgNR) arrays for in situ detection of UO2 2+. The SERS tape was fabricated through a simple "paste & peel off" procedure by transferring the slanted AgNR arrays from silicon to the transparent tape surface. UO2 2+ can be easily in situ detected by placing the AgNR SERS tape into an aqueous solution or pasting it onto the solid matrix surface due to the excellent transparent feature of the tape. The proposed SERS tape with well-distributed AgNRs effectively improved the reproducibility and sensitivity for UO2 2+ analysis. UO2 2+ with concentration as low as 100 nM was easily detected. Besides, UO2 2+ adsorbed on an iron disc and rock surface also can be rapidly in situ detected. With its simplicity and convenience, the AgNR SERS tape-based SERS technique offers a promising approach for environmental monitoring and nuclear accident emergency detection.

Surface-Enhanced Raman Scattering Detection of Pesticide Residues Using Transparent Adhesive Tapes and Coated Silver Nanorods.

The efficient extraction of analytes from complex and severe environments is significant for promoting the surface-enhanced Raman scattering (SERS) technique to actual applications. In this paper, a proof-of-concept strategy is proposed for the rapid detection of pesticide residues by utilizing the flexible, transparent, and adhesive properties of commercial tapes and SERS performance of Al2O3-coated silver nanorod (AgNR@Al2O3) arrays. The function of tapes is to rapidly transfer the analytes from the actual surface to the SERS substrate. The novel "tape-wrapped SERS (T-SERS)" approach was constructed by a simple "paste, peel off, and paste again" procedure. The easily obtained but clearly distinguished SERS signals allow us to quickly determine the constituents of complex surfaces, such as tetramethylthiuram disulfide and thiabendazole pesticides from fruits and vegetables, which may be practically applied to food safety, environmental monitoring, and industrial production process controlling.

Rapid and sensitive detection of uranyl ion with citrate-stabilized silver nanoparticles by the surface-enhanced Raman scattering technique.

Uranium contamination poses a huge threat to human health due to its widespread use in the nuclear industry and weapons. We proposed a simple and convenient wet-state SERS method for uranyl detection based on the citrate-stabilized silver nanoparticles. The effect of citrate on the detection performance was also discussed. By using the citrate as an internal reference to normalize the peak of uranyl, a quantitative analysis was achieved and a good linear relationship of uranyl concentration from 0.2 to 5 µM with the limit of detection of 60 nM was obtained. With its simplicity, convenience and cost-effectiveness, this method has great potential for the detection of other molecules also.

Ultrasensitive visual detection of DNA with tunable dynamic range by using unmodified gold nanoparticles and target catalyzed hairpin assembly amplification.

A simple and novel strategy for enzyme-free ultrasensitive DNA detection platform has been present here based on gold nanoparticles (AuNPs) colorimetry and target catalyzed hairpin assembly amplification. Three hairpin auxiliary probes (H1, H2, and H3) are designed with signal-stranded DNA (ssDNA) sticky ends which could effectively stabilize AuNPs against salt-induced aggregation. However, a cascade of assembly steps with H1, H2, and H3 are activated in the presence of the target DNA, followed by a disassembly step in which H3 displaces the target DNA from the complex, freeing the target DNA to catalyze the self-assembly of additional branched junctions. The formed branched junction consisted with dsDNA is stiffer, and cannot prevent salt-induced AuNPs aggregation, corresponding to a red-to-blue color change. The result can be read out by naked eyes or UV-vis spectrometer. The detection limit of this method is 0.1 pM by naked eyes, and this result is comparable or even better than enzyme or hybridization chain reaction (HCR) based amplification AuNPs colorimetric assays. Moreover, the dynamic range of sensor could be tuned by using different concentration of hairpins. Importantly, this strategy provides a versatile ultrasensitive detection platform for the DNA and related filed targets including metal ions, small molecules, proteins, cells et al. by combining with specific DNAzymes and aptamers.