Detection of uranium with a wireless sensing method by using salophen as receptor and magnetic nanoparticles as signal-amplifying tags

A new wireless sensing method for the detection of uranium in water samples has been reported in this paper. The method is based on a sandwich-type detection strategy. Salophen, a tetradentate ligand of uranyl ion, was immobilized on the surface of the polyurethane-protected magnetoelastic sensor as receptor for the capture of uranyl ion. The phosphorylated polyvinyl alcohol coated magnetic Fe₃O₄ nanoparticles were used as signal-amplifying tags of uranyl ion. In a procedure of determining uranium, firstly uranyl ion in sample solution was captured on the sensor surface. Then the captured uranyl bound the nanoparticle through its coordination with the phosphate group. The amount of uranium was detected through the measure of the resonance frequency shift caused by the enhanced mass loading on the sensor surface. A linear range was found to be 0.2–20.0 μg/L under optimal conditions with a detection limit of 0.11 μg/L. The method has been applied to determine uranium in environmental water samples with the relative standard deviations of 2.1–3.6 % and the recoveries of 98.0–101.5 %. The present technique is one of the most suitable techniques for assay of uranium at trace level in environmental water samples collected from different sources.     

A simple fluorescent sensor for highly sensitive detection of UO22+

Extensive application of nuclear energy has caused widespread environmental uranium contamination. New detection approaches without complicated sample pretreatment and precision instruments are in demand for on-site and in-time determination of uranyl ions in environmental monitoring, especially in an emergency situation. In this work, a simple and effective fluorescent sensor (Z)-N'-hydroxy-4-(1,2,2-triphenylvinyl)benzimidamide (TPE-A) with aggregation-induced emission (AIE) character was established and studied. It could realize to detect UO₂²⁺ via quenching the fluorescence of its aggregation-induced emission, with good selectivity and sensitivity. Such strategy shows a wide linear range from 5.0 × 10^?8 mol/L to 4.5 × 10^?7 mol/L (R² = 0.9988) with exceptional sensitivity reaching 4.7 × 10^?9 mol/L, which is far below the limit for uranium in drinking water (30 μg/L, ca. 1.1 × 10^?7 mol/L) stipulated by the WHO. A response time less than four minutes make it rapid for uranyl ion measurement. It was applied for detection of uranyl ion in spiked river water samples with recoveries in the range of 98.7%-104.0%, comparable to those obtained by ICP-MS. With the advantages of portable apparatus, rapid detection process and high sensitivity, TPE-A can serve as a promising fluorescent sensor for the detection of UO₂²⁺ in environmental water samples.     

Determination of trace uranium (VI) using its self-assembly with a tetradentate–monodentate ditopic ligand by resonance light scattering

We describe here a resonance light scattering (RLS) method for uranium (VI) detection by using phosphorylethanol-amido-salophen (PAS) as optical probe. PAS is a tetradentate–monodentate ditopic ligand in which the tetradentate and monodentate ligands are salophen moiety and phosphate group, respectively. PAS can chelate uranyl with its salophen moiety. The chelated uranyl can connect phosphate group in another PAS through coordination reaction. This causes the self-assembly of PAS with uranyl to form a metallo-supramolecular polymer, resulting in a production of strong RLS signal. The RLS method was established based on the self-assemble. The RLS intensity is linearly related to the concentration of uranium (VI) in the 0.8–32 ng mL^?1 range, with a detection limit of 0.24 ng mL^?1 detection limit under optimal conditions. The method was successfully applied to determine uranium (VI) in environmental water samples with the recoveries between 97.1% and 102.6%.     

聚合物纳米光诊疗剂的制备与应用新进展

共轭聚合物纳米颗粒是由π-共轭有机聚合物组成的尺寸在1~100nm范围内的新型有机纳米材料。与传统的有机小分子、半导体量子点和无机纳米材料相比,聚合物纳米颗粒具有光学性质特殊、结构多样、表面易修饰和生物相容性好等优点,因而被广泛应用于生物成像、传感与检测、载药和治疗等领域。本文主要围绕聚合物纳米颗粒的制备方法、性质结构和生物相容性等方面,重点介绍了聚合物纳米颗粒作为光诊疗剂在荧光成像、光声成像,以及光动力和光热治疗领域的研究进展,并对聚合物纳米颗粒的发展前景和未来面临的挑战进行了探讨。     

Trace Determination of Uranyl Ion Using a Blue Led as Excitation Source in Phase-Resolved Luminescence Spectroscopy

Abstract

A phase-resolved luminescence system based on the use of a light emitting diode (LED) is applied to the trace determination of uranyl ion (UO₂ ²⁺). The system performance is evaluated, phase resolved spectra of UO₂ ²⁺ are shown as well as its lifetime determination using multifrequency phase resolved measurements. Analytical figures of merit are also presented for this system. A limit of detection (LOD) of 10 μg/L is obtained at the blue LED excitation wavelength of 460 nm and its results compare well with a conventional system. Also, a linear dynamic range of ca. 5 orders of magnitude is observed. In situ quenching correction of the analytical signal was evaluated and was applied to a real sample for uranyl determination.     

A Novel Surface‐tethered Analysis Method for Mercury (II) ion Detection via Self‐assembly of Individual Electrochemiluminescence Signal Units

A novel analysis strategy based on the analyte‐induced surface‐tethered (AIST) of electrochemiluminescence (ECL) signal nanoparticles was first proposed for detection of Mercury (II) ion (Hg²⁺). In this work, luminol@Au‐cysteamine‐thymine (luminol@Au‐Cys‐T) multifunctional nanoarchitecture was designed as ECL signal units in the experimental process. Through a specific T‐Hg²⁺‐T coordination, luminol@Au‐Cys‐T composites were gravitationally self‐assembled to the electrode surface, which was coated with tris (2‐aminoethyl) amine functionalized graphene oxide@perylene‐3,4,9,10‐tetracarboxylic acid‐thymine (GO@PTCA‐TAEA‐T) complex film. This simple strategy of AIST of signal molecules could amplify the response signal and vastly enhance the sensitivity. Under the optimum condition, the linear relationship of Hg²⁺ concentration variation from 0.005 nM to 5 nM with a limit of detection (LOD) down to 0.002 nM (S/N=3), which also offered an alternative analytical approach with excellent performance of stability and selectivity. The regression equation was y=−414.52+2305.02 lgC_(Hg²⁺₎ (pM). This Hg²⁺ ECL sensor had a good application prospects for the analysis of real samples.     

Capillary electrophoresis–electrochemiluminescence detection method for the analysis of ibandronate in drug formulations and human urine

A simple, rapid and sensitive CE method coupled with electrochemiluminescence (ECL) detection for direct analysis of ibandronate (IBAN) has been developed. Using a buffer solution of 20 mM sodium phosphate (pH 9.0) and a voltage of 13.5 kV, separation of IBAN in a 30‐cm length capillary was achieved in 3 min. ECL detection was performed with an indium tin oxide working electrode bias at 1.6 V (versus a Pt wire reference) in a 200‐mM sodium phosphate buffer (pH 8.0) containing 3.5 mM Ru(bpy)₃²⁺ (where bpy=2,2′‐bipyridyl). Derivatization of IBAN prior to CE‐ECL analysis was not needed. Linear correlation (r=0.9992, n=7) between ECL intensity and analyte concentration was obtained in the range of 0.25–50 μM IBAN. The LOD of IBAN in water was 0.08 μM. The developed method was applied to the analysis of IBAN in a drug formulation and human urine sample. SPE using magnetic Fe₃O₄@Al₂O₃ nanoparticles as the extraction phase was employed to pretreat the urine sample before CE‐ECL analysis. The linear range was 0.2–12.0 μM IBAN in human urine (r=0.9974, n=6). The LOD of IBAN in urine was 0.06 μM. Total analysis time including sample preparation was <1 h.     

联吡啶钌电化学发光传感器测定海洛因

利用离子液体为粘合剂制作碳糊电极,采用高分子聚合法,合成包埋有Ru(bpy)2(dcbpy)2+的高分子聚合物,将钌聚合物掺杂于离子液体碳糊电极中,制作电化学发光传感器.结果表明,此传感器具有很好的电化学发光特性,与用石蜡油为粘合剂制作的电化学发光传感器相比,离子液体为粘合剂的电化学发光传感器检测三丙胺的检出限降低1个数量级.海洛因对电化学发光传感器的发光信号有很好的增强作用,基于此建立了高灵敏度检测海洛因的电化学发光分析法,海洛因浓度与电化学发光信号在2.0×10-9～2.0×10-5 mol/L范围内呈良好的线性关系,检出限为8×10-10 mol/L (S/N=3).将电化学发光传感器在5.0×10-9 mol/L海洛因溶液中采用线性循环电位连续扫描60圈,相对标准偏差小于2.2%.本方法用于血清中海洛因的检测,其回收率为94%～101%.     

Polymer Electrochemiluminescence Featuring Thermally Activated Delayed Fluorescence

Electrochemiluminescence (ECL) based on conjugated polymers or oligomers is persistently being pursued owing to its huge application scope ranging from ultra-sensitive bioanalysis to ultra-resolution imaging and spectroscopy. Because of the theoretical limit in radiative exciton generation yield (typically ∼25 %) of those polymers or oligomers, the corresponding ECL efficiency is still limited, which hampers its ECL performance and its related applications. Herein, we report ECL based on a thermally activated delayed fluorescence (TADF) polymer scaffold, which is characteristic of all-exciton harvesting in the ECL process, and thus potentially capable of achieving ∼100 % ECL efficiency. These desired properties of the TADF polymer ECL is attributed to a fast and efficient up-conversion process from non-radiative triplet to radiative singlet states under thermal activation, which is absent in conventional fluorescent polymers/oligomers, such as F8BT. In this study, various ECL modes, including annihilation or co-reactant mode using TPrA or S₂O₈²⁻ as co-reactant, are confirmed for our model TADF polymer ECL system, which was different from fluorescent polymer ECL counterpart. Furthermore, solid-state ECL sensing on L-cysteine (an important marker of disease) is also evaluated by using the model TADF polymer. Ultralow detection limit in combination with high sensitivity and good specificity are achieved for this model system, indicative of a high potential of the TADF polymer scaffold for applications in the broad field of ECL.     

A resonance light scattering method for the determination of uranium based on a water-soluble salophen and oxalate

A resonance light scattering (RLS) method for the direct detection of uranium (VI) or uranyl in aqueous solution without separation procedure has been reported in this paper. Sulfo-salophen, a water-soluble tetradentate Schiff base ligand of uranyl, reacted with uranyl to form a complex. The complex reacted further with oxalate to form supramolecular dimer with large molecular volume, resulting in a production of strong RLS signal. The amount of uranium (VI) was detected through measuring the RLS intensity. A linear range was found to be 0.2–30.0 ng/mL under optimal conditions with a detection limit of 0.15 ng/mL. The method has been applied to determine uranium (VI) in environmental water samples with the relative standard deviations of less than 5 % and the recoveries of 98.8–105.8 %. The present technique is suitable for the assay of uranium (VI) in environmental water samples collected from different sources.     

Detection of uranium in industrial and mines samples by microwave plasma torch mass spectrometry

Microwave plasma torch (MPT), traditionally used as the light source for atomic emission spectrophotometry, has been employed as the ambient ionization source for sensitive detection of uranium in various ground water samples with widely available ion trap mass spectrometer. In the full‐scan mass spectra obtained in the negative ion detection mode, uranium signal was featured by the uranyl nitrate complexes (e.g. [UO₂(NO₃)₃]^?), which yielded characteristic fragments in the tandem mass spectrometry experiments, allowing confident detection of trace uranium in water samples without sample pretreatment. Under the optimal experimental conditions, the calibration curves were linearly responded within the concentration levels ranged in 10–1000 µg·l^?1, with the limit of detection (LOD) of 31.03 ng·l^?1. The relative standard deviations (RSD) values were 2.1–5.8% for the given samples at 100 µg·l^?1. The newly established method has been applied to direct detection of uranium in practical mine water samples, providing reasonable recoveries 90.94–112.36% for all the samples tested. The analysis of a single sample was completed within 30 s, showing a promising potential of the method for sensitive detection of trace uranium with improved throughput. Copyright © 2016 John Wiley & Sons, Ltd.     

Influence of binary/ternary complex of imprint ion on the preconcentration of uranium(VI) using ion imprinted polymer materials

Ion imprinted polymer (IIP) materials were prepared for uranyl ion (imprint ion) by forming binary (5,7-dichloroquinoline-8-ol (DCQ) or 4-vinylpyridine (VP)) or ternary (5,7-dichloroquinoline-8-ol and 4-vinylpyridine) complexes in 2-methoxy ethanol (porogen) and copolymerizing in the presence of styrene and divinyl benzene as functional and crosslinking monomers, respectively and 2,2′-azobisisobutyronitrile as initiator. IIP particles were obtained by leaching the imprint ion in these polymer materials with 50% (v/v) hydrochloric acid, filtering, drying in an oven at 50 °C and grinding. Control polymer particles were also prepared under identical conditions. The above synthesized polymer particles were characterized by IR, CHN, X-ray diffraction, and pore size analyses. These leached polymer particles can now pick up uranyl ions from dilute aqueous solutions. The IIP particles obtained with ternary complex of uranyl ion alone gave quantitative enrichment of traces of uranyl ions from dilute aqueous solutions. The optimal pH for quantitative enrichment is 4.5-7.5 and eluted completely with 10 ml of 1.0 M HCl. The retention capacity of uranyl IIP particles was found to be 34.05 mg of uranyl ion per gram of polymer. Further, the percent extraction, distribution ratio, and selectivity coefficients of uranium and other selected inorganic ions were also evaluated. Five replicate determinations of 25 μg of uranium present in 1.0 l of aqueous solution gave a mean absorbance of 0.036 with a relative standard deviation of 2.50%. The detection limit corresponding to three times the standard deviation of the blank was found to be 5 μg l⁻¹.     

单个等离子体纳米颗粒在生化分析和生物成像中的应用

等离子体纳米颗粒（PNPs）因其独特的物理、化学、光学和生物学特性而被广泛地应用于材料科学、生物学和医药学等研究领域。PNPs的光学性质是可以通过改变其组成、形状和大小来进行调控的,所以利用可控合成的方式能够筛选出适合的光散射探针。在单分子水平上实时研究PNPs的动态行为对于理解细胞及活体组织的生命活动机制、制备功能型纳米材料和开发新型化学生物传感器等有着重要的意义。基于传统的暗场显微镜（DFM）,通过对光源、检测器及其它光学元件的择优组装和调试,我们开发出了一系列具有高灵敏度、高时空分辨率和高通量的等离子体光散射成像技术,并将其应用于单分子检测、多颗粒传感、单细胞成像以及生物过程示踪等领域。基于具有光学各向异性的PNPs,我们还研制出了活细胞三维扫描成像系统和超连续激光光片成像与高速毛细管电泳联用系统,推进了单分子光谱方面的研究。本文将总结近十年来本课题组在PNP单颗粒分析及成像中的工作,并为该领域未来的发展提出一些新的思路。     

Highly selective electrogenerated chemiluminescence (ECL) for sulfide ion determination at multi-wall carbon nanotubes-modified graphite electrode

In the present work, a novel method for immobilization of carbon nanotubes (CNTs) on the surface of graphite electrode was proposed. We further found that superoxide ion was electrogenerated on this CNTs-modified electrode, which can react with sulfide ion combing with a weak but fast electrogenerated chemiluminescence (ECL) emission, and this weak ECL signal could be enhanced by the oxidative products of rhodamine B. In addition, the rate constant of this electrochemical reaction k⁰ was investigated and confirmed that the speed of electrogenerating superoxide ion was in accordance with the subsequent fast CL reaction. Thus, the fast CL reaction of superoxide ion with target brought in the possibility of high selectivity based on time-resolved, relative to other interferences. Based on these findings, an excellently selective and highly sensitive ECL method for sulfide ion was developed. Under the optimum conditions, the enhancing ECL signals were linear with the sulfide ion concentration in the range from 6.0 × 10⁻¹⁰ to 1.0 × 10⁻⁸ mol L⁻¹, and a 2.0 × 10⁻¹⁰ mol L⁻¹ detection limits (3σ) was achieved. In addition, the proposed method was successfully used to detect sulfide ion in environmental water samples.     

Copolymerization of luminol on screen-printed cells for single-use electrochemiluminescent sensors

An efficient electrochemiluminescent (ECL) single-use sensor for H(2)O(2) is presented based on an electropolymerized film prepared on screen-printed gold electrode (gold SPE). A study of the copolymerization of luminol in the presence of different monomers was carried out. The polymeric films were grown potentiodynamically with a potential interval between -0.2 and 1.0 V in 0.2 M H(2)SO(4) and were characterized by their electrochemical, electrochemiluminescent, and superficial features. The polymer with the most efficient growth and ECL emission was poly(luminol-3,3',5,5'-tetramethylbenzidine) at 1:5 ratio. These prepared SPE cells present good mechanical and photoemissive properties. A semi-logarithmic linearization shows a noticeable four decade-width concentration range with a limit of detection (LOD) of 2.6 × 10(-9) M and a precision of 10.2% (n = 5; as relative standard deviation, RSD) in the medium range level. The described SPE ECL sensors will be useful for the determination of oxidase substrates in ECL single-use biosensors.     

Highly sensitive detection of protein and small molecules based on aptamer-modified electrochemiluminescence nanoprobe

Amplified optical detection of biomolecules using nanoparticle as the carrier has attracted considerable interest in the scientific community. In this study, a promising aptasensor was developed for highly sensitive detection of protein and small molecules based on the construction of aptamer-modified electrochemiluminescence (ECL) nanoprobe. Specifically, thrombin and ATP serve as the examples for detection. By taking advantage of sandwich binding of two affinity aptamers for high specificity, tris-(2,2'-bipyridyl)ruthenium (TBR)-cysteamine loaded in gold nanoparticle (GNP) as barcodes for signal amplification, and micromagnetic particles (MMPs) based ECL technology for rapid detection, a novel assay for biomolecules quantification was developed. The sandwich complex containing targets could be selectively captured by MMPs and then quantified by ECL intensity. We have demonstrated that the detection limits of human thrombin and ATP are 1 pM and 10 pM, respectively, with high specificity. The proposed technology is expected to become a powerful tool for biomolecule analysis.     

离子色谱法检验血液中的亚硝酸盐

建立了使用离子色谱检验血液中亚硝酸盐含量的方法。血液样品经乙腈沉淀蛋白,过DionexOnGuardⅡRP,Ag/Na前处理柱后,经IonPacAS-19阴离子色谱柱分离,用KOH淋洗液自动发生器(EG)进行梯度淋洗,抑制器采用外加水模式,电导检测器检测。NO2-标准溶液的浓度在0.214～21.4mg/L时线性关系良好,线性方程为Y=0.0209X+0.5189,相关系数r2=0.9999,血中NO2-的检出限为0.39μg/L,回收率为96.5%～101.2%。检验方法快捷,操作简便,回收率高,重现性好,可满足案件需要。     

Design of two-dimensional biomimetic uranyl optrode and its application to the analysis of natural waters

A two-dimensional biomimetic optrode for the detection and quantification of uranium in natural waters was fabricated. The sensing element was designed by the inclusion of uranyl ion imprinted polymer particles into polymethyl methacrylate followed by casting a thin film on a glass slide without any plasticizer. The ion imprinted polymer material was prepared via covalent immobilization of the newly synthesised ligand 4-vinyl phenylazo-2-naphthol by thermal polymerization. Operational parameters such as pH, response time and the amount of sensing material were optimized. The response characteristics of the imprinted and the corresponding non-imprinted polymer inclusion optrodes of uranium were compared under optimum conditions. The imprinted polymer inclusion optrode responds linearly to uranium in the concentration range 0–1.0 μg mL⁻¹ with a detection limit of 0.18 μg mL⁻¹, which is much better than the solution studies using 4-vinyl phenylazo-2-naphthol (1.5 μg mL⁻¹). Triplicate determinations of 100 μg of uranium(VI) present in 250 mL of solution gave a mean absorbance of 0.018 with a relative standard deviation of 8.33%. The superior sensitivity of imprinted polymer inclusion optrode is exemplified by lower detection limits and broader dynamic range over non-imprinted polymer inclusion optrode. The developed imprinted polymer inclusion optrode was found to give stable and precise response for 3 months and can be used without any loss in sensitivity. The applicability for analysing ground, lake and tap-water samples collected in the vicinity of uranium deposits was successfully demonstrated.     

Polymer Zwitterions for Stabilization of CsPbBr3 Perovskite Nanoparticles and Nanocomposite Films

Functional polymers with sulfobetaine or phosphorylcholine zwitterions as pendent groups are demonstrated as both ligands and host matrices for CsPbBr₃ perovskite nanoparticles (PNPs). These polymers produce nanocomposite films with excellent NP dispersion, optical transparency, and impressive resistance to NP degradation upon exposure to water. Multidentate interactions of the zwitterion‐containing copolymers with the PNPs induce dispersed or weakly aggregated nanocomposite morphologies, depending on the extent of zwitterionic functionality in the polymer. Incorporating additional functionality into the polymers, such as benzophenone pendent groups, yields lithographically patternable films, while time‐resolved photoluminescence measurements provide insight into the electronic impact of PNPs in zwitterionic polymer matrices.     

Potential controlling highly-efficient catalysis of wheat-like silver particles for electrochemiluminescence immunosensor labeled by nano-Pt@Ru and multi-sites biotin/streptavidin affinity

The potential controlling silver catalysis for Ru(bpy)(3)(2+) electrochemiluminescence (ECL) signal at a special potential -0.4～1.25 V was newly developed as the new ECL signal amplification strategy for ultrasensitive protein detection. Firstly, the wheat-like deposited silver (DpAg) particles were modified on the bare glass carbon electrode (GCE) surface by cyclic voltammetry deposition to capture the primary antibodies and then bind the antigen analytes. Secondly, as a sandwich immunoreaction format, the secondary antibodies conjugated with the Ru(bpy)(3)(2+)-doped Pt (Pt@Ru) nanoparticles by the multi-sites biotin/streptavidin (SA) affinity can be captured onto the electrode surface to generate ECL signal. In the proposed Ru(bpy)(3)(2+) ECL system without any co-reactant, the detected ECL signal was amplified due to following multiple amplification strategies: (1) the ECL catalysis for Ru(bpy)(3)(2+) was performed by electro-inducing the DpAg particles to generate Ag(+) ion and controlled by the special potential. The catalyzer Ag(+) was produced near the electrode surface and reproduced by cyclic potential scan, which improved the catalytic efficiency. (2) The amount of the ECL signal probes linked to secondary antibodies were amplified by the adsorption of Pt nanoparticles and the multiple sites bridge linkage of biotin/SA. These new multiple signal amplification strategies made the proposed ECL immunosensor achieve ultrasensitive detection for model protein human IgG with a detection limit down to 3 pg mL(-1), which can be further extended to the detection of disease biomarkers.