Colorimetric photonic hydrogel aptasensor for the screening of heavy metal ions

We have developed a robust method for the visual detection of heavy metal ions (such as Hg(2+) and Pb(2+)) by using aptamer-functionalized colloidal photonic crystal hydrogel (CPCH) films. The CPCHs were derived from a colloidal crystal array of monodisperse silica nanoparticles, which were polymerized within the polyacrylamide hydrogel. The heavy metal ion-responsive aptamers were then cross-linked in the hydrogel network. During detection, the specific binding of heavy metal ions and cross-linked single-stranded aptamers in the hydrogel network caused the hydrogel to shrink, which was detected as a corresponding blue shift in the Bragg diffraction peak position of the CPCHs. The shift value could be used to estimate, quantitatively, the amount of the target ion. It was demonstrated that our CPCH aptasensor could screen a wide concentration range of heavy metal ions with high selectivity and reversibility. In addition, these aptasensors could be rehydrated from dried gels for storage and aptamer protection. It is anticipated that our technology may also be used in the screening of a broad range of metal ions in food, drugs and the environment.     

香豆素类荧光传感器检测金属离子的研究进展

金属离子对自然环境和生物体的生长发育具有重要的影响,因此对环境中及生物体内的金属离子的识别和检测正日益受到人们广泛的关注。在不同的分析方法中,荧光分析法具有灵敏度高、选择性好和实时原位检测等优点,是实现环境中和生物体内金属离子识别和检测的良好工具。本文综述了近5年来香豆素类荧光传感器对一些重金属离子（Hg2+、Pb2+、Cd2+、Ni2+、Ag+）和一些具有重要生物学意义的过渡金属离子（Cu2+、Zn2+、Fe3+）的识别与检测及其应用进展情况,着重介绍了传感器分子的设计合成、识别机理、传感特性及其在环境分析和生物检测中的应用。随着金属离子检测要求的提高,未来香豆素类荧光传感器的设计将向着灵敏度更高、选择性更好、抗干扰性能更强的方向发展。此外,香豆素类传感器在生物检测中的应用研究有望得到进一步发展。     

Enhanced sensitivity of a direct SERS technique for Hg(2+) detection based on the investigation of the interaction between silver nanoparticles and mercury ions

Mercury which is a very important pollutant has drawn significant attention in recent research. So far, among the various detection methods, the strategies based on surface-enhanced Raman scattering (SERS) are quite attractive because of the high sensitivity, and especially as it is reported that Hg(2+) can be directly detected by SERS without tagging. However, the procedure for the direct SERS detection of mercury is still unclear with little experimental evidence, limiting further development of Hg(2+) detection by SERS. Herein, we performed a simple method based on SERS for the detection of mercury ions in water without tagging. It is established that in only 2 min, low concentration of Hg(2+) can be recognized based on the decrease of SERS intensity. The detection procedure is investigated by multiple characterizations and the mechanism proven by the obtained data provides a practical way to further improve the sensitivity of the SERS detection. It is demonstrated that the interaction between Hg(2+) and Ag nanoparticles (Ag NPs) could occur in a short time, which includes the complexation of Hg(2+) with citrate and the formation of amalgam due to the reduction of Hg(2+). This interaction influences the surface plasmon resonance (SPR) property of Ag NPs and thereby decays the electromagnetic enhancement of Ag NPs; meanwhile the interaction also causes the zeta potential decrease of Ag NPs and accordingly affects the adsorption of Raman reporter molecules on the surface of Ag NPs. Therefore, the weakness of SERS intensity in the presence of Hg(2+) should be mainly attributed to the interaction between Hg(2+) and Ag NPs. From the mechanism demonstrated, it can be speculated that using fewer Ag NPs in the detection could improve the sensitivity, because at low Hg(2+) concentration the interaction becomes stronger since every Ag nanoparticle acts with more Hg(2+) ions. Accordingly, we establish that 90.9 pM (18.2 ppt) Hg(2+) is detected in 18 μM Ag NPs, which is much lower than that in reported papers.     

A colorimetric assay method for Co2+ based on thioglycolic acid functionalized hexadecyl trimethyl ammonium bromide modified Au nanoparticles (NPs)

A simple, rapid and sensitive colorimetric assay method for detection of Co(2+) through thioglycollic acid (TGA) functionalized hexadecyl trimethyl ammonium bromide (CTAB) modified Au NPs has been discovered in our work. TGA functionalized CTAB modified Au NPs can be aggregated quickly in the presence of Co(2+) through a cooperative metal-ligand interaction. Transmission electron microscope (TEM), energy dispersive X-ray spectroscopy (EDS), and UV-vis spectra were used to characterize the Au NPs aggregation. The presence of Co(2+) is monitored by a colorimetric response of functionalized Au NPs, and had a detection limit of 3.0 × 10(-7) M. Moreover, the selectivity of this method has been investigated by comparing with other metal ions (Hg(2+), Na(+), Cu(2+), Cd(2+), Ba(2+), Pb(2+), Mn(2+), Ni(2+), Zn(2+), Fe(2+) and Fe(3+)).     

啤酒酵母吸附去除水中Cd~(2+)的影响因素

生物吸附法是一种经济有效的处理大规模低浓度重金属废水的生物技术,其中啤酒酵母(Saccharomyces cerevisiae)是具有实用潜力的生物吸附剂。本文研究了啤酒酵母对Cd2+吸附效果的主要影响因素,结果表明pH值对Cd2+会产生较大的影响,非固定化和固定化啤酒酵母对Cd2+吸附的最佳pH值都为4,过高和过低均不利于吸附的进行。水中常见的K+、Ca2+、Na+、Mg2+四种离子在低浓度时对Cd2+的吸附无显著影响,但当其浓度高于5mg/L时会影响吸附,其影响顺序为K+Na+Ca2+Mg2+;Zn2+、Fe2+、Cu2+、Pb2+对Cd2+的吸附效果影响顺序为Pb2+Zn2+Fe2+Cu2+;当Cu2+浓度≥50mg/L时,啤酒酵母对Cd2+不产生性吸附,而对Cu2+产生专性吸附。     

元素汞在实验室模拟脱硫装置中再析出的影响因素(英文)

Elemental mercury(Hg0)re-emissions from slurries and solutions were evaluated in a lab-scale simulated scrubber.Oxidized mercury(Hg2 +)standard solution was injected into the simulated scrubber at a desired rate to simulate absorbing and dissolving of Hg2 +in the flue gas across wet flue gas desulfurization(WFGD)systems. PS analytical mercury analyzer was used to continuously determine Hg0re-emission concentrations in the carrier gas from the scrubber.Sulfite ion in the slurry of CaSO3 was validated to reduce Hg 2+to Hg 0,while no Hg 0 re-emission occurred from slurries of CaSO4 and CaO.Transitional metal ions with low chemical valence such as Fe2 +,Pb 2+,Ni 2+, 2 AsO-and Cu +were used to prepare solutions with concentration levels of mmol·L-1.Reduction reaction of Hg2 +to Hg 0was observed from these solutions.Reduction capabilities for the different transitional metal ions in the solutions were:Pb2 +Cu +Fe 2+ 2 AsO-Ni 2+.     

重金属离子捕集剂水杨醛双Schiff碱的合成及应用

以2,6-吡啶二甲酸、乙二胺及水杨醛等为原料合成了一种重金属离子捕集剂水杨醛双Schiff碱N,N'-双(2-水杨醛亚胺基乙基)-2,6-吡啶二甲酰胺(Ⅱ),并以其为配体与一些重金属离子(如Cu2+、Pb2+、Hg2+、Cr3+等)进行螯合反应.结果表明,配体化合物Ⅱ能与重金属离子生成稳定性较高且不溶于水的螯合物,可以...     

Alkali preparation and ions detection of Ti3C2 quantum dots

In this paper, a simple lye etching method is used to directly prepare Ti₃C₂ quantum dot (QDs) without fluorine-containing groups at low lye concentration. The as-prepared Ti₃C₂ QDs have a stability fluorescent property in whole pH range of 1–14 and different fluorescence response to different types of heavy metal ions. Due to the unique and irreversible fluorescence quenching ability for Cr³⁺, Ti₃C₂ QDs can be used to detect Cr³⁺ with a low detection limit of 30 mM. Along with the high fluorescent selectivity and stability in pH = 1–14, Ti₃C₂ QDs is a great application prospect as Cr³⁺ ion detection probes in sewage disposal.     

磺化煤对重金属离子的吸附效果研究

磺化煤是一种价格低廉、原料广泛的具有较强吸附性能的新型吸附剂。介绍了磺化煤的制备方法采用静态法测定了磺化煤对几种重金属离子的吸附量,结果显示吸附量的顺序为Pb^2 ＞Cu^2 ＞Ni^2 ＞Zn^2 。研究了吸附时间、pH值对吸附量的影响及磺化煤在电镀废水处理中的实际应用效果,探讨了磺化煤吸附重金属离子的机理。结果表明,pH值是影响磺化煤吸附作用的主要因素,且其对实际电镀废水的吸附净化效果较好,对重金属的去除率高达99％、     

汞离子荧光传感的研究进展

荧光传感提供了方便,快捷,廉价的分析检测重金属离子的方法,并具有很高的灵敏度和选择性。它在环境科学,分析化学以及生命科学等领域有着广泛的应用前景。综述了Hg2+荧光传感的最新研究进展,并展望了该领域的发展趋势。     

Removal of Cd(II), Hg(II), and Pb(II) ions from aqueous solution using p(HEMA/chitosan) membranes

An interpenetration network (IPN) was synthesized from 2‐hydroxyethyl methacrylate (HEMA) and chitosan, p(HEMA/chitosan) via UV‐initiated photo‐polymerization. The selectivity to different heavy metal ions viz Cd(II), Pb(II), and Hg(II) to the IPN membrane has been investigated from aqueous solution using bare pHEMA membrane as a control system. Removal efficiency of metal ions from aqueous solution using the IPN membranes increased with increasing chitosan content and initial metal ions concentrations, and the equilibrium time was reached within 60 min. Adsorption of all the tested heavy metal ions on the IPN membranes was found to be pH dependent and maximum adsorption was obtained at pH 5.0. The maximum adsorption capacities of the IPN membrane for Cd(II), Pb(II), and Hg(II) were 0.063, 0.179, and 0.197 mmol/g membrane, respectively. The adsorption of the Cd(II), Hg(II), and Pb(II) metal ions on the bare pHEMA membrane was not significant. When the heavy metal ions were in competition, the amounts of adsorbed metal ions were found to be 0.035 mmol/g for Cd(II), 0.074 mmol/g for Hg(II), and 0.153 mmol/g for Pb(II), the IPN membrane is significantly selective for Pb(II) ions. The stability constants of IPN membrane–metal ions complexes were calculated by the method of Ruzic. The results obtained from the kinetics and isotherm studies showed that the experimental data for the removal of heavy metal ions were well described with the second‐order kinetic equations and the Langmuir isotherm model. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Metal‐chelating properties of poly(2‐hydroxyethyl methacrylate–methacryloylamidohistidine) membranes

Metal‐chelating membranes have advantages as adsorbents in comparison with conventional beads because they are not compressible and they eliminate internal diffusion limitations. The aim of this study was to explore in detail the performance of poly(2‐hydroxyethyl methacrylate–methacryloylamidohistidine) [poly(HEMA–MAH)] membranes for the removal of three toxic heavy‐metal ions—Cd(II), Pb(II), and Hg(II)—from aquatic systems. The poly(HEMA–MAH) membranes were characterized with scanning electron microscopy and ¹H‐NMR spectroscopy. The adsorption capacity of the poly(HEMA–MAH) membranes for the selected heavy‐metal ions from aqueous media containing different amounts of these ions (30–500 mg/L) and at different pH values (3.0–7.0) was investigated. The adsorption capacity of the membranes increased with time during the first 60 min and then leveled off toward the equilibrium adsorption. The maximum amounts of the heavy‐metal ions adsorbed were 8.2, 31.5, and 23.2 mg/g for Cd(II), Pb(II), and Hg(II), respectively. The competitive adsorption of the metal ions was also studied. When the metal ions competed, the adsorbed amounts were 2.9 mg of Cd(II)/g, 14.8 mg of Pb(II)/g, and 9.4 mg of Hg(II)/g. The poly(HEMA–MAH) membranes could be regenerated via washing with a solution of nitric acid (0.01M). The desorption ratio was as high as 97%. These membranes were suitable for repeated use for more than three adsorption/desorption cycles with negligible loss in the adsorption capacity. The stability constants for the metal‐ion/2‐methacryloylamidohistidine complexes were calculated to be 3.47 × 10⁶, 7.75 × 10⁷, and 2.01 × 10⁷ L/mol for Cd(II), Pb(II), and Hg(II) ions, respectively, with the Ruzic method. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1213–1219, 2005     

Dissimilar roles of the four conserved acidic residues in the thermal stability of poly(a)-specific ribonuclease

Divalent metal ions are essential for the efficient catalysis and structural stability of many nucleotidyl-transfer enzymes. Poly(A)-specific ribonuclease (PARN) belongs to the DEDD superfamily of 3'-exonucleases, and the active site of PARN contains four conserved acidic amino acid residues that coordinate two Mg(2+) ions. In this research, we studied the roles of these four acidic residues in PARN thermal stability by mutational analysis. It was found that Mg(2+) significantly decreased the rate but increased the aggregate size of the 54 kDa wild-type PARN in a concentration-dependent manner. All of the four mutants decreased PARN thermal aggregation, while the aggregation kinetics of the mutants exhibited dissimilar Mg(2+)-dependent behavior. A comparison of the kinetic parameters indicated that Asp28 was the most crucial one to the binding of the two Mg(2+) ions, while metal B might be more important in PARN structural stability. The spectroscopic and aggregation results also suggested that the alterations in the active site structure by metal binding or mutations might lead to a global conformational change of the PARN molecule.     

Preparation and characterization of magnetic polymethylmethacrylate microbeads carrying ethylene diamine for removal of Cu(II), Cd(II), Pb(II), and Hg(II) from aqueous solutions

Magnetic polymethylmethacrylate (mPMMA) microbeads carrying ethylene diamine (EDA) were prepared for the removal of heavy metal ions (i.e., copper, lead, cadmium, and mercury) from aqueous solutions containing different amount of these ions (5–700 mg/L) and at different pH values (2.0–8.0). Adsorption of heavy metal ions on the unmodified mPMMA microbeads was very low (3.6 μmol/g for Cu(II), 4.2 μmol/g for Pb(II), 4.6 μmol/g for Cd(II), and 2.9 μmol/g for Hg(II)). EDA‐incorporation significantly increased the heavy metal adsorption (201 μmol/g for Cu(II), 186 μmol/g for Pb(II), 162 μmol/g for Cd(II), and 150 μmol/g for Hg(II)). Competitive adsorption capacities (in the case of adsorption from mixture) were determined to be 79.8 μmol/g for Cu(II), 58.7 μmol/g for Pb(II), 52.4 μmol/g for Cd(II), and 45.3 μmol/g for Hg(II). The observed affinity order in adsorption was found to be Cu(II) > Pb(II) > Cd(II) > Hg(II) for both under noncompetitive and competitive conditions. The adsorption of heavy metal ions increased with increasing pH and reached a plateau value at around pH 5.0. The optimal pH range for heavy‐metal removal was shown to be from 5.0 to 8.0. Desorption of heavy‐metal ions was achieved using 0.1 M HNO₃. The maximum elution value was as high as 98%. These microbeads are suitable for repeated use for more than five adsorption‐desorption cycles without considerable loss of adsorption capacity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 81–89, 2000     

A sensitive and selective near-infrared fluorescent probe for mercuric ions and its biological imaging applications

A new mercury(II) near-infrared region fluorescent probe 3,9-dithia-6-monoazaundecane-tricarbocyanine has been designed and synthesized. It consists of two functional moieties: the tricarbocyanine performs as the near-infrared region fluorophore, and the 3,9-dithia-6-monoazaundecane acts as the selected binding site for metal ions. The near-IR excitation and emission profiles of the probe can minimize cell and tissue damage and avoid native fluorescence from natural cellular species. It exhibits fluorescence increase upon the binding of the Hg(2+) based on the inhibition of the photoinduced electron transfer quenching mechanism. Excellent sensitivity and selectivity for mercuric ions are observed with this probe. The value of the system is demonstrated by its use in monitoring the real-time uptake of Hg(2+) within HepG2 cells and five day old zebrafish. The synthesis and remarkable properties of it help to extend the development of metal ions fluorescent probes for biological applications.     

Two-photon ratiometric sensing of Hg2+ by using cysteine functionalized Ag nanoparticles

We have demonstrated a novel two-photon sensing strategy to detect mercury ions with high selectivity and sensitivity. This sensing approach is based on the observation that addition of Hg(2+) into a cysteine functionalized Ag nanoparticle solution could significantly enhance their two-photon emission. An enhancement factor of up to 100 fold was obtained when mercury was added. A detection limit of as low as 65 nM could be achieved. The sensitivity and sensing range can be easily tuned. Compared to the conventional colorimetric or extinction spectrum based methods, this scheme offers improved sensitivity, quantitative detection of Hg(2+) with a larger dynamic range, and allows detection deep into biological environments such as cells and tissues where deep penetration is required. The sensitivity could be further improved by using two-photon microscopy with the additional advantages of 3D detection and mapping.     

Direct Generation of Mn‐Doped ZnS Quantum Dots/Alginate Nanocomposite Beads Based on Gelation and In Situ Synthesis of Quantum Dots

Herein, a concise and novel method is developed to directly generate Mn‐doped ZnS QDs/alginate nanocomposite beads. In this method, the ionic gelation of alginate is employed to produce alginate gel beads in a solution of Zn²⁺ and Mn²⁺ ions. Subsequently, the gel beads serve as the reaction support for in situ synthesis of Mn‐doped ZnS QDs in the beads through the reaction of sodium sulfide with Zn²⁺ and Mn²⁺ ions. The method has many benefits such as the simple preparation, the environmentally friendly process, the mild conditions, and the easy post‐treatment for the beads. The resulting QDs/alginate beads are homogeneous and stable gel spheres which show clear fluorescence. TEM images demonstrate that Mn‐doped ZnS QDs are homogeneously distributed within the QDs/alginate nanocomposite, and their average size is 2.4 ± 0.3 nm. Potentially, the QDs/alginate beads can be utilized for fluorescence bioimaging, as well as fluorescence detection toward metal ions.     

Poly(hydroxamic acid) ligand from palm-based waste materials for removal of heavy metals from electroplating wastewater

Heavy metals pollutants are nonbiodegradable and their bioaccumulation results in detrimental environmental consequences. Therefore, it is important to effectively remove toxic heavy metal waste from industrial sewage. Thus, the main goal of this research is to synthesize an ideal cellulose-based adsorbent from palm-based waste materials (agro waste) in order to be utilized in real-life practical applications with low cost as such removing common toxic heavy metals from industrial effluents. A poly(methyl acrylate) grafted palm cellulose was synthesized via a free-radical initiation process, followed by an oximation reaction to yield poly(hydroxamic acid) ligands. The adsorption capacity (q_e) of poly(hydroxamic acid) ligands for metal ions such as copper (Cu²⁺), iron (Fe³⁺), and lead (Pb²⁺) were 325, 220, and 300 mg g⁻¹, respectively at pH 6. In addition, the X-ray photoelectron spectrometry results are to be proved the binding of metal ions, for instance, Cu(II) ions showed typically significant BEs of 932.7 and 952.0 eV corresponding to the Cu2p3/2 and Cu2p1/2 species. The heavy metal ions adsorption followed a pseudo-first-order kinetic model pathway. The adsorption capacity (q_m) is also derived from the Langmuir isotherm linear plot, which does not showed good correction coefficients. However, the results were correlated to the Freundlich isotherm model, where the R² value showed significance (>0.98), indicating that multiple layer adsorption occurs on the synthesized ligand. The synthesized polymeric ligand is an excellent adsorbent for the removal of heavy metals from the industrial wastewater. In addition, the metal analysis results showed that about 98% removal of copper and iron ions from electroplating wastewater including lead, nickel, and chromium can be removed up to 85–97%.     

Separation and extraction of some heavy and toxic metal ions from their wastes by grafted membranes

Preparation and characterization of a series of ion‐exchange membranes for the purpose of separation and extraction of some heavy and toxic metal ions from their wastes were studied. Such ion‐exchange membranes were prepared by γ‐radiation grafting of acrylonitrile (AN) and vinyl acetate (VAc) in a binary monomer mixture onto low‐density polyethylene (LDPE) using the direct technique of grafting. The reaction conditions at which the grafting process proceeds successfully were determined. Many modification treatments were attempted for the prepared membranes to improve their ion‐exchange properties. The possibility of their practical use in waste‐water treatment to remove some heavy and toxic metal ions such as Pb²⁺, Cd ²⁺, Cu²⁺, Fe³⁺, Sr²⁺, and Li⁺ were investigated. These grafted membranes showed great promise for possible use in the field of extraction and removal of some heavy and toxic metals from their wastes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 849–860, 2001     

Adsorption of heavy-metal ions (Pb2+, Cu2+) on perm-lotion-treated human hair

Removal of toxic heavy metal ions from environmental and biological systems is important, but the use of commercially available heavy metal adsorbents is complicated by the need for specific pretreatment steps. We chose to study human hair treated with perm lotion as a heavy metal adsorbent because it is readily available and contains a large number of sulfur atoms for strong coordination to heavy metal ions. The optimal pH of adsorption by perm lotion-treated human hair was 4.16, which was slightly higher than the isoelectric point (pI) of the hair. The maximum removal ratio at pH 4.16 was 88.5% for a 50 ppm Cu²⁺ solution, and 96.79% for a 50 ppm Pb²⁺ solution. Almost 90% of the Pb²⁺ was removed from a 120 ppm Pb²⁺ solution. The perm-lotion-treated human hair was a cation-selective adsorbent.