Zinc oxide nanostructured platform for electrochemical detection of heavy metals

ZnO nanoparticles (ZnO-NP) were prepared by a facile precipitation technique using di-isopropyl amine as precipitating agent. The morpho-structure and porosity of the as-prepared nano-powder were investigated by FT-IR analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), and BET analysis. By drop-casting, a composite film was deposited to obtain ZnO-NP-Nafion/GCE modified electrode. The modified electrode was investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and square wave anodic stripping voltammetry (SWASV) for the detection of Pb²⁺, Cd²⁺, Cu²⁺, and Fe³⁺, and it was successfully applied for the detection of Pb²⁺ and Cu²⁺ in real water samples.     

Preparation and characterization of thermosensitive polymers grafted onto silica-coated iron oxide nanoparticles

In this study, multifunctional nanoparticles containing thermosensitive polymers grafted onto the surfaces of 6-nm monodisperse Fe(3)O(4) magnetic nanoparticles coated by silica were synthesized using reverse microemulsions and free radical polymerization. The magnetic properties of SiO(2)/Fe(3)O(4) nanoparticles show superparamagnetic behavior. Thermosensitive PNIPAM (poly(N-isopropylacrylamide)) was then grafted onto the surfaces of SiO(2)/Fe(3)O(4) nanoparticles, generating thermosensitive and magnetic properties of nanocomposites. The sizes of fabricated nanoparticles with core-shell structure are controlled at about 30 nm and each nanoparticle contains only one monodisperse Fe(3)O(4) core. For thermosensitivity analysis, the phase transition temperatures of multifunctional nanoparticles measured using DSC was at around 34-36 degrees C. The magnetic characteristics of these multifunctional nanoparticles were also superparamagnetic.     

Liquid crystal-based sensors for the detection of heavy metals using surface-immobilized urease

In this study, a new method for the detection of heavy metals in aqueous phase was developed using liquid crystals (LCs). When UV-treated nematic LC, 4-cyano-4'-pentyl biphenyl (5CB) that was confined in the urease-modified gold grid was immersed in a urea solution, an optical response from bright to dark was observed under a polarized microscope, indicating that a planar-to-homeotropic orientational transition of the LC occurred at the aqueous/LC interface. Since urease hydrolyzes urea to produce ammonia, which would be ionized into ammonium and hydroxide ions, the main product of the photochemically degraded 5CB, 4-cyano-4'-biphenylcarboxylic acid (CBA), was deprotonated and self-assembled at the interface, inducing the orientational transition in the LC. Due to the high sensitivity and rapid response of this system, detection of heavy metal ions was further exploited. The divalent copper ion, which could effectively inhibit the activity of urease, was used as a model heavy metal ion. The optical appearance of the LC did not change when urea was in contact with the copper nitrate hydrate-blocked urease. After the copper-inhibited urease was reactivated by EDTA, a bright-to-dark shift in the optical signal was regenerated, indicating an orientational transition of the LC. This type of LC-based sensor shows high spatial resolution due to its optical characteristics and therefore could potentially be used to accurately monitor the presence of enzyme inhibitors such as heavy metal ions in real-time.     

A layered magnetic iron/iron oxide nanoscavenger for the analytical enrichment of ng-L concentration levels of heavy metals from water

Magnetically driven separation techniques have received considerable attention in recent decade because of their great potential application. In this study, we investigate the application of an unmodified layered magnetic Fe/Fe₂O₃ nanoscavenger for the analytical enrichment and determination of sub-parts per billion concentrations of Cd(II), Pb(II), Ni(II), Cr(VI) and As(V) from water samples. The synthesized nanoscavenger was characterized by BET, TGA, XRD and IR and the parameters influencing the extraction and recovery of the preconcentration process were assessed by atomic absorption spectrometry. The possible mechanism of the enrichment of heavy metals on Fe/Fe₂O₃ was proposed, which involved the dominant adsorption and reduction. The nanoscale size offers large surface area and high reactivity of sorption and reduction reactions. The obtained limits of detection for the metals studied were in the range of 20–125 ng L⁻¹ and the applicability of the nanomaterial was verified using a real sample matrix. The method is environmentally friendly as only 15 mg of nanoscavenger are used, no organic solvent is required for the extraction and the experiment is performed without the need for filtration or preparation of packed preconcentration columns.     

Carbon nanotube-based extraction and electrochemical detection of heavy metals

In this mini review, recent trends and challenges in developing carbon nanotube-based extraction and electrochemical detection of heavy metals in water are reviewed. Carbon nanotubes (CNT) have electrical, mechanical, chemical, and structural properties superior to those of conventional materials, for example graphite and activated carbon. CNT-based procedures are also more efficient than traditional techniques and methods, for example liquid?Cliquid extraction, atomic-absorption spectroscopy, flame photometry, and inductively coupled plasma, because they can enable rapid, sensitive, simple, and low-cost on-site detection. Different forms of CNT, including as-grown, oxidised, and functionalised CNT, can be well suited to metal adsorption. The measurement procedure relies on adsorbing the metal on the CNT surface after reasonable contact time, either by applying an electrical potential or under open-circuit conditions, and subsequent quantification. Different types of CNT-based electrode, including composite, paste, and binder-free, can be fabricated and used for metal detection. Application of CNT and their novel properties to the adsorption and detection of heavy metals is discussed in detail.     

基于钨酸镍与氧化锌复合材料的电化学传感平台检测吲哚美辛EI北大核心CSCD

采用一锅法制备了钨酸镍与氧化锌复合材料(NiWO_(4)-ZnO),并对其进行了形貌表征、元素分析及比表面积测试,构筑了一种吲哚美辛电化学传感器。研究发现,NiWO_(4)-ZnO复合材料修饰玻碳电极对吲哚美辛表现出较高的检测灵敏度,在最优的实验条件下,吲哚美辛浓度与氧化峰电流成正比,在250~1082 pmol/L范围内呈现良好的线性关系,线性相关系数为0.9970,检出限为66.6 pmol/L。吲哚美辛电化学传感器应用于实际样品中吲哚美辛的测定,回收率为95.1%~98.3%,相对标准偏差为2.3%~3.8%,该传感器可用于药物分析领域。     

Magnetic relaxation switch and colorimetric detection of thrombin using aptamer-functionalized gold-coated iron oxide nanoparticles

We describe a sensitive biosensing system combining magnetic relaxation switch diagnosis and colorimetric detection of human α-thrombin, based on the aptamer–protein interaction induced aggregation of Fe₃O₄@Au nanoparticles. To demonstrate the concept, gold-coated iron oxide nanoparticle was synthesized by iterative reduction of HAuCl₄ onto the dextran-coated Fe₃O₄ nanoparticles. The resulting core–shell structure had a flowerlike shape with pretty narrow size distribution (referred to as “nanorose”). The two aptamers corresponding to human α-thrombin were conjugated separately to two distinct nanorose populations. Once a solution containing human α-thrombin was introduced, the nanoroses switched from a well dispersed state to an aggregated one, leading to a change in the spin–spin relaxation time (T₂) as well as the UV–Vis absorption spectra of the solution. Thus the qualitative and quantitative detection method for human α-thrombin was established. The dual-mode detection is clearly advantageous in obtaining a more reliable result; the detection range is widened as well. By using the dual-mode detection method, a detectable T₂ change is observed with 1.0 nM human α-thrombin, and the detection range is from 1.6 nM to 30.4 nM.     

Toluene and naphthalene sorption by iron oxide/clay composites

Commercial bentonite (BFN) and organoclay (WS35), as well as iron oxide/clay composite (Mag_BFN) and iron/oxide organoclay composite (Mag_S35) were prepared for toluene and naphthalene sorption. Mag_BFN and Mag_S35 were obtained, respectively, by the precipitation of iron oxide hydrates onto sodium BFN and S35 clay particles. The materials were characterized by powder X-ray diffraction (XRD), X-ray Fluorescence (XRF), and TG and DTA. From XRF results and TG data on calcined mass basis, a quantitative method was developed to estimate the iron compound contents of the composites, as well as the organic matter content present in WS35 and Mag_S35.     

Fluorometric detection of heavy metals with pyrene substituted N-acylthioureas

Summary The new synthesised pyrene substituted ligands N,N-diethyl-N-1-pyreneoylthiourea (DEPyT) and N,N-diethyl-N-4-(1-pyrene)butyrylthiourea (DEPyBuT) form fluorescent complexes with a large number of heavy metal ions. Some of the complex compounds exhibit an especially strong fluorescence — much stronger than that of the free ligands. The complex compounds can be extracted into apolar organic solvents and separated by liquid chromatography. Low detection limits and a wide linear range of detection is achieved by using HPLC with silica gel columns. HPTLC allows the separation of 3 to 6 metals on silica gel layers using chloroform or toluene as mobile phase.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

前驱物热稳定性对氧化铁/氧化锡制备的影响

氧化铁纳米复合材料具有优越的磁学和催化性能,近年来在癌症诊断及治疗[1-3]、污染治理[4-6]、电磁屏蔽[7-8]等多个领域得到广泛研究.目前有许多研究集中于如何对复合材料的组成、结构和形貌进行设计合成,例如:利用机械球磨法将SnO2和α-Fe2O3粉体混合制备α-Fe2O3/SnO2 复合材料[9];通过共沉淀法将SnO2复合在α-Fe2O3 的表面[4];或者在Fe3O4表面复合一层C和相应的盐,然后通过煅烧制备Fe3O4/ZrO2和Fe3O4/TiO2微球[10-11].     

大米中重金属检测技术的分析与研究

为提高大米中镉、铅元素检测数据的可靠性,根据GB 5009.12—2017《食品中铅的测定》、GB 5009.15—2014《食品中镉的测定》对大米中镉、铅元素含量进行检测,并以原子吸收分光光度计为测量设备的测量系统进行各类误差分析. 结果表明,两种元素稳定性分析中Xbar控制图均存在超出上下控制界限的点,稳定性不满足要求. 偏倚和线性P值均大于0.05,不存在显著的偏倚和线性误差. 量具研究变异占比（Reproducibility & Repeatability,R&R）分别为54.03%和36.38%,均大于30%,测量误差超出可接受范围. 通过人、机、料、法、环、测等多方面故障排查后稳定性达到统计受控状态,R&R分别降至9.66%和8.95%,均小于10%,测量系统可接受. 利用测量系统分析方法从多方面降低各类测量误差,能够有效保障大米中镉、铅元素含量检测数据的可靠性.     

Selective enrichment of catecholamines using iron oxide nanoparticles followed by CE with UV detection

This study examines the use of unmodified magnetite nanoparticles (Fe₃O₄ NPs) for selective extraction and enrichment of the catecholamines dopamine (DA), noradrenaline (NE), and adrenaline (E), prior to analysis using capillary electrophoresis with UV detection. Coordination between Fe³⁺ on‐the‐surface Fe₃O₄ NPs and the catechol moiety of catecholamines enables Fe₃O₄ NPs to capture catecholamines from an aqueous solution. We obtained maximum loading of catecholamines on the NP surface by adjusting the pH of the solution to 7.0. In addition, catecholamine loading on the Fe₃O₄ NPs increased in conjunction with NP concentrations. H₃PO₄ was found to be efficient for the removal of adsorbed catecholamines on the NP surface. Adding 1.2% poly(diallyldimethylammonium chloride) to the background electrolyte resulted in a baseline separation of the liberated catecholamines within 20 min. Under optimal extraction and separation conditions, the limit of detections at a S/N ratio of 3 for E, NE, and DA were 9, 8, and 10 nM, respectively. Significantly, the combination of a phenylboronate‐containing spin column and the proposed method was successfully applied to the determination of NE and DA in human urine and NE in Portulaca oleracea L. leaves.     

Electroanalytical detection of zinc in whole blood

Three different electroanalytical techniques for the determination of zinc in blood are investigated. The direct determination in diluted blood via anodic stripping voltammetry at glassy carbon and the use of Nafion-coated glassy carbon mercury electrodes are shown to lack the necessary sensitivity whereas an acoustically assisted double extraction followed by sono-ASV using a glassy carbon electrode is found to be rapid, reliable and sensitive.     

Characterization of Co(II) removal from aqueous solution using bentonite/iron oxide magnetic composites

The bentonite/iron oxide magnetic composites were prepared by co-precipitation method, and characterized by Fourier transform infrared spectroscopy, X-ray powder diffraction and scanning electron microscope. The prepared bentonite/iron oxide magnetic composites were used as a sorbent for the removal of Co(II) ions from radioactive wastewater. The results demonstrated that the sorption of Co(II) was strongly dependent on pH and ionic strength at low pH values. The sorption of Co(II) was dominated by outer-sphere surface complexation or ion exchange at low pH whereas inner-sphere surface complexation was the main sorption mechanism at high pH. The presence of iron oxide in the composites also contributes to the sorption of Co(II) ions on the magnetic composites. The experimental data were well described by Langmuir model. The thermodynamic parameters (∆G ^°, ∆S ^°, ∆H ^°) calculated from the temperature-dependent sorption isotherms indicated that the sorption of Co(II) on bentonite/iron oxide magnetic composites was an endothermic and spontaneous processes.     

Determination of heavy metals in sewage-based fertilizer using short-lived isotopes

A fully instrumental method for the neutron activation analysis of heavy metals in sewage sludges has been developed, based on short-lived isotopes, and restricting the total experiment time to 1 hour per sample. The irradiation scheme consists of a cyclic and conventional part, the period of the cyclic irradiation being optimised for the determination of lead, using^207mPb (T=0.8 s). Gamma ray spectra from Ge(Li) detectors are stored on magnetic tape and analysed using the SAMPO programme. An IDENTIFY subroutine enables absolute determinations to be made eliminating the need for standards. Sensitivities and detection limits for 21 heavy metals have been determined and the results for several sludges are presented.     

Immobilization of heavy metals by Pseudomonas putida CZ1/goethite composites from solution

Bacterial–mineral composites are important in the retention of heavy metals due to their large sorption capacity under a wide range of environmental conditions. This study provides the first quantitative comparison of the metal-binding capacities of P. putida CZ1–goethite composite to its individual components. When the same amount (on a dry weight basis) of living and nonliving cells of P. putida CZ1, goethite or their composites was separately exposed to solutions of 0.5 mM Cu(II) and Zn(II) in 0.01 M KNO₃, the living cells removed the largest quantity of heavy metals. The results of calculated metal retention values indicated that the adsorption of goethite to bacteria has not mask or neutralize chemically reactive adsorption sites normally available to metal ions. Moreover, the nonliving cells–goethite composite retained approximately 82% more Zn than that predicted by their individual behavior. The preferential association of Zn with P. putida CZ1 was observed by TEM and EDS analyses of a mixture consisting of the bacteria and goethite. Desorption of Cu and Zn with 1.0 M CH₃COOK solution from P. putida CZ1 and goethite indicated the differences in the functional groups able to bind heavy metals.     

Synthesis and ferromagnetic properties of composites of a water-soluble polyaniline copolymer containing iron oxide

Composites of water-soluble conducting polyaniline copolymers, poly(aniline-co-aminobenzenesulfonic acid) (PAOABSA), containing γ-Fe₂O₃magnetic particles with nanometer size, were synthesized by a chemical method. The ferromagnetic properties of the resulting PAOABSA composites were measured as a function of the pH value of the reaction solution, the sulfonated degree of the copolymer, and the concentration of FeCl₂. The structure of the composites was characterized by means of elemental analysis, FTIR, XPS, and X-ray diffraction. It was found that increasing the pH value of the reaction solution and the concentration of FeCl₂ is favorable for an enhancement of the saturated magnetization. As high as 33.2 emu/g of saturated magnetization for the PAOABSA composites was observed. No hysteresis loop (i.e. H_c = 0) was observed, which is independent of the preparation conditions. Structure characterizations show that iron oxide existing in the composite is mainly γ- Fe₂O₃, which is responsible for the ferromagnetic properties of the PAOABSA composites, whereas γ- Fe₂O₃ magnetic particles nanometer in size (∼85 nm) may be attributed to a lower coercive force (i.e. H_c = 0) of the composites. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2749–2755, 1998     

Amperometric detection of unithiol complexes of heavy metals in high-performance liquid chromatography

It was demonstrated that Pb(II), Cd(II), Hg(II), Ni(II), Co(II), and Cu(II) can be indirectly determined as their unithiol complexes by amperometric detection under static and HPLC conditions. Factors affecting the Chromatographic separation and amperometric detection of metal complexes of unithiol were studied. Two designs of flow electrochemical cells (thin-layer and wall-jet cells) and three electrode materials (platinum, graphite, and glassy carbon) were compared. The best sensitivity was attained for an amperometric detector with wall-jet flow cell and a graphite indicator electrode. The detection limits for Hg(II), Pb(II), and Cd(II) were 0.9, 0.3, and 0.1 μg/mL, respectively. The Chromatographic determination of heavy metals in a sample of waste water was carried out using the amperometric detector     

Synthesis of iron oxide nanoparticles using chitosan and starch templates

Natural polymers like chitosan and starch have been employed as templates for the preparation of iron oxide nanoparticles. The templates offer selective binding sites for Fe(II) under aqueous conditions. Controlled drying and subsequent removal of the template backbone enables the synthesis of spatially separated iron oxide nanoparticles. The crystalline character of the iron oxide and near narrow particle size distribution pattern have been confirmed through powder XRD, Photon Correlation Spectroscopy, and TEM measurements. The crystallite sizes of the particles were found to be 26–35 nm irrespective of the nature of the template.     

Fast and simultaneous detection of heavy metals using a simple and reliable microchip-electrochemistry route: An alternative approach to food analysis

This paper reports, for the first, the fast and simultaneous detection of prominent heavy metals, including: lead, cadmium and copper using microchip CE with electrochemical detection. The direct amperometric detection mode for microchip CE was successfully applied to these heavy metal ions. The influences of separation voltage, detection potential, as well as the concentration and pH value of the running buffer on the response of the detector were carefully assayed and optimized. The results clearly show that reliable analysis for lead, cadmium, and copper by the degree of electrophoretic separation occurs in less than 3min using a MES buffer (pH 7.0, 25mM) and l-histidine, with 1.2kV separation voltage and -0.8V detection potential. The detection limits for Pb(2+), Cd(2+), and Cu(2+) were 1.74, 0.73 and 0.13microM (S/N=3). The %R.S.D. of each peak current was <6% and migration times <2% for prolonged operation. To demonstrate the potential and future role of microchip CE, analytical possibilities and a new route in the raw sample analysis were presented. The results obtained allow the proposed microchip CE-ED acts as an alternative approach for metal analysis in foods.