A nanoparticle autocatalytic sensor for Ag+ and Cu2+ ions in aqueous solution with high sensitivity and selectivity and its application in test paper

A novel nanoparticle autocatalytic sensor for the detection of Ag(+) and Cu(2+) has been constructed based on the oxidative ability of Ag(+) and Cu(2+) toward o-phenylenediamine (OPDA). Ag(+) and Cu(2+) can be reduced to zerovalent silver and copper, respectively, and then such zerovalent Ag and Cu species form silver and copper nanoparticles that can catalyze the reaction between OPDA and Ag(+) and Cu(2+). In the reaction, OPDA is oxidized to 2,3-diaminophenazine (OPDAox), which has a fluorescence emission at 568 nm. Under the optimal conditions, Ag(+) and Cu(2+) can be detected in the concentration ranges from 60 nM to 60 μM and from 2.5 nM to 25 μM, respectively. Through this facile approach, Ag(+) and Cu(2+) can be detected down to 60 nM and 2.5 nM, respectively. In addition, the sensor is utilized for the detection of Ag(+) and Cu(2+) in sewage, and we have obtained very good results that are consistent with those of inductively coupled plasma-mass spectroscopy (ICP-MS). Moreover, such a nanoparticle autocatalytic sensor is applied to test paper for the detection of Ag(+) and Cu(2+) with the naked eye. With such test paper, Ag(+) and Cu(2+) could be detected at levels as low as 0.06 nmol and 0.3 nmol, respectively, with detection ranges of 0.06-60 nmol for Ag(+) and 0.3-60 nmol for Cu(2+), under the irradiation of UV light (365 nm). The test paper could be potentially used in the rapid detection of Ag(+) and Cu(2+) in real samples.     

Electrochemical DNAzyme sensor for lead based on amplification of DNA-Au bio-bar codes

An electrochemical DNAzyme sensor for sensitive and selective detection of lead ion (Pb(2+)) has been developed, taking advantage of catalytic reactions of a DNAzyme upon its binding to Pb(2+) and the use of DNA-Au bio-bar codes to achieve signal enhancement. A specific DNAzyme for Pb(2+) is immobilized onto an Au electrode surface via a thiol-Au interaction. The DNAzyme hybridizes to a specially designed complementary substrate strand that has an overhang, which in turn hybridizes to the DNA-Au bio-bar code (short oligonucleotides attached to 13 nm gold nanoparticles). A redox mediator, Ru(NH3)6(3+), which can bind to the anionic phosphate of DNA through electrostatic interactions, serves as the electrochemical signal transducer. Upon binding of Pb(2+) to the DNAzyme, the DNAzyme catalyzes the hydrolytic cleavage of the substrate, resulting in the removal of the substrate strand along with the DNA bio-bar code and the bound Ru(NH3)6(3+) from the Au electrode surface. The release of Ru(NH3)6(3+) results in lower electrochemical signal of Ru(NH3)6(3+) confined on the electrode surface. Differential pulse voltammetry (DPV) signals of Ru(NH3)6(3+) provides quantitative measures of the concentrations of Pb(2+), with a linear calibration ranging from 5 nM to 0.1 microM. Because each nanoparticle carries a large number of DNA strands that bind to the signal transducer molecule Ru(NH3)6(3+), the use of DNA-Au bio-bar codes enhances the detection sensitivity by five times, enabling the detection of Pb(2+) at a very low level (1 nM). The DPV signal response of the DNAzyme sensor is negligible for other divalent metal ions, indicating that the sensor is highly selective for Pb(2+). Although this DNAzyme sensor is demonstrated for the detection of Pb(2+), it has the potential to serve as a general platform for design sensors for other small molecules and heavy metal ions.     

Alternative thermodiffusion interface for simultaneous speciation of organic and inorganic lead and mercury species by capillary GC-ICPMS using tri-n-propyl-lead chloride as an internal standard

An alternative thermodiffusion interface (TDI) was designed and constructed for the effective online coupling of capillary gas chromatography (cGC) and inductively coupled plasma mass spectrometry (ICPMS). Pb(2+), (CH3)3Pb(+), (C2H5)3Pb(+), Hg(2+), CH3Hg(+) and C2H5Hg(+) were derived as Pb(C4H9)4, (CH3)3PbC4H9, (C2H5)3PbC4H9, (C4H9)2Hg, CH3HgC4H9, and C2H5HgC4H9 when butyl magnesium bromide was employed as a derivatization reagent for a proof-of-concept study, avoiding the loss of their species specific information. All these derivatives together with the neutral fully saturated (CH3)4Pb and (C2H5)4Pb could be quantitatively separated within 7 min using a 15 m long capillary column, allowing the determination and speciation of organic and inorganic Pb and Hg species in a single run. The method detection limits (3sigma) for Me4Pb, Et4Pb, Me3Pb(3+), Pb(2+), MeHg(+), EtHg(+), and Hg(2+) are 0.07, 0.06, 0.04, 7.0, 0.09, 0.1, and 0.2 pg g(-1), respectively. Moreover, tri-n-propyl-lead chloride was synthesized and used as an alternative internal standard for the accurate and simultaneous speciation analysis of Pb and Hg in complicated environmental and biological samples for the first time. This cGC-TDI-ICPMS method was validated by analyzing Pb and Hg species in certified reference materials and then was applied to simultaneous speciation analysis of Pb and Hg in real-life samples. It is expected that these approaches can be extended to the speciation of other organometallic compounds after suitable modifications and so will aid in monitoring the occurrence, pathways, toxicity, and/or biological effects of these compounds in the environment and in organisms.     

Hg(0) oxidative absorption by K(2)S(2)O(8) solution catalyzed by Ag(+) and Cu(2+)

The aqueous phase oxidation of gaseous elemental mercury (Hg(0)) by potassium persulfate (K(2)S(2)O(8), KPS) catalyzed by Ag(+) and Cu(2+) was investigated using a glass bubble column reactor. Concentrations of gaseous Hg(0) and aqueous Hg(2+) were measured by cold vapor generation atomic absorption spectrometry (CVAAS). The effects of several experimental parameters on the oxidation were studied; these include different types of catalysts, pHs and concentrations of potassium persulfate, temperatures, Hg(0) inlet concentrations and tertiary butanol (TBA). The results showed that the removal efficiency of Hg(0) increased with increasing concentration of potassium persulfate and catalysts Ag(+), Cu(2+) and Ag(+) provided better catalytic effect than Cu(2+). For example, in the presence of 5.0mmoll(-1) KPS, the mercury removal efficiency could reach 75.4 and 97.0% for an Ag(+) concentration of 0.1 and 0.3mmoll(-1), respectively, and 69.8 and 81.9% for 0.1 and 0.3mmoll(-1) Cu(2+). On the other hand, high temperature and the introduction of TBA negatively affect the oxidation. Furthermore, the removal efficiency of Hg(0) was much greater in neutral solution than in either acidic or alkaline solution. But the influence of pH was almost eliminated upon the addition of Ag(+) and Cu(2+), and high Hg(0) inlet concentration also has positive impact on the removal efficiency of Hg(0). The possible catalytic oxidation mechanism of gaseous mercury by KPS was also proposed.     

Manipulation of intraparticle charge delocalization by selective complexation of transition-metal ions with histidine moieties

Ruthenium nanoparticles were cofunctionalized with pyrene and histidine moieties through Ru═carbene π bonds. The selective complexation of the histidine moiety with transition-metal ions led to a marked diminishment of the emission peak at 490 nm which arose from the nanoparticle-bridged pyrene moieties that behaved analogously to pyrene dimers with a conjugated spacer. This is accounted for by the polarization of the core electrons by the added positive charge that impacted the intraparticle charge delocalization between the particle-bound pyrene moieties. This electronic interaction was likely facilitated by the π interactions between the metal ions and the imidazole ring as well as by the conjugated molecular backbone that linked the imidazole ring to the nanoparticle cores. Within the present experimental context, of all the metal ions tested, the impacts were much more drastic with Pb(2+), Co(2+), and Hg(2+) than with Li(+), K(+), Rb(+), Mg(2+), Ca(2+), and Zn(2+) ions, with the most sensitive variation observed with Pb(2+). This is ascribed to the enhanced π interactions of the histidine moiety with the Pb(2+), Co(2+), and Hg(2+) ions because of their capability of donating d electrons, a behavior consistent with prior studies based on conventional histidine-metal ion complexes.     

A new Schiff's base ligand immobilized agarose membrane optical sensor for selective monitoring of mercury ion

A highly selective optical sensor was developed for the Hg(2+) determination by chemical immobilization of 2-[(2-sulfanylphenyl)ethanimidoyl]phenol (L), on an agarose membrane. Spectrophotometric studies of complex formation between the Schiff's base ligand L and Hg(2+), Sr(2+), Mn(2+), Cu(2+), Al(3+), Cd(2+), Zn(2+), Co(2+) and Ag(+) metal ions in methanol solution indicated a substantially larger stability constant for the mercury ion complex. Consequently, the Schiff's base L was used as an appropriate ionophore for the preparation of a selective Hg(2+) optical sensor, by its immobilization on a transparent agarose film. A distinct color change, from yellow to green-blue, was observed by contacting the sensing membrane with Hg(2+) ions at pH 4.5. The effects of pH, ionophore concentration, ionic strength and reaction time on the immobilization of L were studied. A linear relationship was observed between the membrane absorbance at 650 nm and Hg(2+) concentrations in a range from 1×10(-2) to 1×10(-5) mol L(-1) with a detection limit (3σ) of 1×10(-6) mol L(-1). No significant interference from 100 times concentrations of a number of potentially interfering ions was detected for the mercury ion determination. The optical sensor was successfully applied to the determination of mercury in amalgam alloy and spiked water samples.     

Ion-exchange of Pb2+, Cu2+, Zn2+, Cd2+, and Ni2+ ions from aqueous solution by Lewatit CNP 80

Removal of trace amounts of heavy metals can be achieved by means of selective ion-exchange processes. The newly developed resins offered a high resin capacity and faster sorption kinetics for the metal ions such as Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) ions. In the present study, the removal of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) ions from aqueous solutions was investigated. Experimental investigations were undertaken using the ion-exchange resin Lewatit CNP 80 (weakly acidic) and were compared with Lewatit TP 207 (weakly acidic and chelating). The optimum pH range for the ion-exchange of the above mentioned metal ions on Lewatit CNP 80 and Lewatit TP 207 were 7.0-9.0 and 4.5-5.5, respectively. The influence of pH, contact time, metal concentration and amount of ion-exchanger on the removal process was investigated. For investigations of the exchange equilibrium, different amounts of resin were contacted with a fixed volume of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) ion containing solution. The obtained sorption affinity sequence in the presented work was Ni(2+)>Cu(2+)>Cd(2+)>Zn(2+)>Pb(2+). The metal ion concentrations were measured by AAS methods. The distribution coefficient values for metal ions of 10(-3)M initial concentration at 0.1mol/L ionic strength show that the Lewatit CNP 80 was more selective for Ni(2+), Cu(2+) than it was for Cd(2+), Zn(2+) and Pb(2+). Langmuir isotherm was applicable to the ion-exchange process and its contents were calculated. The uptake of metal ions by the ion-exchange resins was reversible and thus has good potential for the removal of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) from aqueous solutions. The amount of sorbed metal ion per gram dry were calculated as 4.1, 4.6, 4.7, 4.8, and 4.7mequiv./g dry resin for Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+), respectively. Selectivity increased in the series: Cd(2+)>Pb(2+)>Cu(2+)>Ni(2+)>Zn(2+). The results obtained showed that Lewatit CNP 80 weakly acidic resin had shown better performance than Lewatit TP 207 resin for the removal of metals. The change of the ionic strength of the solution exerts a slight influence on the removal of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+). The presence of low ionic strength or low concentration of NaNO(3) does not have a significant effect on the ion-exchange of these metals by the resins. We conclude that Lewatit CNP 80 can be used for the efficient removal of Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+) from aqueous solutions.     

Self-powered sensor for trace Hg2+ detection

A self-powered electrochemical sensor has been facilely designed for sensitive detection of Hg(2+) based on the inhibition of biocatalysis process of enzymatic biofuel cell (BFC) for the first time. The as-prepared one-compartment BFC, which was consisted of alcohol dehydrogenase supported on single-walled carbon nanohorns-based mediator system as the anode and bilirubin oxidase as the cathodic biocatalyst, generated an open circuit potential (V(oc)) of 636 mV and a maximum power density of 137 μW cm(-2). It was interestingly found that the presence of Hg(2+) would affect the performance of the constructed BFC (e.g., V(oc)). Taking advantage of the inhibitive effect of Hg(2+), a novel self-powered Hg(2+) sensor has been developed, which showed a linear range of 1-500 nM (R(2) = 0.999) with a detection limit of 1 nM at room temperature. In addition, this BFC-type sensor exhibited good selectivity for Hg(2+) against other common environmental metal ions, and the feasibility of the method for Hg(2+) detection in actual water samples (i.e., tap, ground, and lake water) was demonstrated with satisfactory results.     

Competitive sorption and transport of Pb2+, Ni2+, Mn2+, and Zn2+ in lateritic soil columns

Knowledge of sorption and transport of heavy metals in soils in the presence of other metals is crucial for assessing the environmental risk of these metals. Competitive sorption and transport of four metals, Pb(2+), Ni(2+), Zn(2+), and Mn(2+), were investigated using multi-metal column experiments with lateritic soils obtained from a gold mine impacted by acid mine drainage. Based on Pb(2+) breakthrough time for single-metal system at a pH of approximately 5, the sorption capacity of Pb(2+) was estimated to be higher in lateritic soil than the other metals. For multi-metal systems, the estimated retardation factors for the metals from highest to lowest were: Pb(2+)>Zn(2+)～ Ni(2+)>Mn(2+), suggesting the mobility of metals through lateritic soil for a multi-metal system would be in the order of Mn(2+)>Ni(2+)～ Zn(2+)>Pb(2+). For binary and multi-metal systems, the estimated sorption capacities of individual metals were found to be lower than the sorption capacities in single metal system - indicating possible competition for sorption sites. Mass recoveries estimates showed that the sorption of metals was more reversible under competitive multi-metal systems than in single metal systems.     

Synthesis and metal ion binding properties of thiaaza crown macrocycles

Two new macrocyclic ligands (3) and (4), containing nitrogen-sulfur donor atoms, were designed and synthesized in a multi-step reaction sequence. The macrocycles (3) and (4) were used in solvent extraction of metal picrates such as Ag(+), Hg(2+), Cd(2+), Zn(2+), Cu(2+), Ni(2+), Mn(2+), Co(2+), and Pb(2+) from aqueous phase to the organic phase. The metal picrate extractions were investigated at 25+/-0.1 degrees C by using UV-visible spectrometry. The extractability and selectivity of the mentioned metal picrates were evaluated according to the organic solvents. The values of the extraction constants (logK(ex)) and the complex compositions were determined for the extracted complexes.     

DNAzyme-based colorimetric sensing of lead (Pb(2+)) using unmodified gold nanoparticle probes

Novel functional oligonucleotides, especially DNAzymes with RNA-cleavage activity, have been intensively studied due to their potential applications in therapeutics and sensors. Taking advantage of the high specificity of 17E DNAzyme for Pb(2+), highly sensitive and selective fluorescent, electrochemical and colorimetric sensors have been developed for Pb(2+). In this work, we report a simple, sensitive and label-free 17E DNAzyme-based sensor for Pb(2+) detection using unmodified gold nanoparticles (GNPs) based on the fact that unfolded single-stranded DNA could be adsorbed on the citrate protected GNPs while double-stranded DNA could not. By our method the substrate cleavage by the 17E DNAzyme in the presence of Pb(2+) could be monitored by color change of GNPs, thereby Pb(2+) detection was realized. The detection of Pb(2+) could be realized within 20?min, with a detection limit of 500?nM. The selectivity of our sensor has been investigated by challenging the sensing system with other divalent metal ions. Since common steps such as modification and separation could be successfully avoided, the sensor developed here could provide a simple, cost-effective yet rapid and sensitive measurement tool for Pb(2+) detection and may prove useful in the development of sensors for clinical toxicology and environmental monitoring in the future.     

Metal ion (silver, cadmium and zinc ions) modified CdS quantum dots for ultrasensitive copper ion sensing

Metal ion (Ag(+), Cd(2+), Zn(2+)) modified CdS quantum dots (QDs) were synthesized and used for Cu(2+) sensing. Modification by these metal ions could enhance the PL intensity of CdS QDs with the extent of the PL enhancement being related to the concentration of the metal ions. Different metal ion (Ag(+), Cd(2+), Zn(2+)) modified CdS QDs also showed different analytical characteristics for Cu(2+) sensing. In particular, Ag( + ) modified CdS QDs showed greatly enhanced sensitivity for Cu(2+) determination than did the unmodified CdS QDs. A limit of detection (LOD) of 2.0 × 10(-10) M was obtained for Ag(+) modified CdS QDs, which is the lowest LOD obtained using QDs as fluorescence probes for Cu(2+) sensing. This study demonstrates the important role of surface state of QDs in fluorescence sensing.     

Ultrasensitive sensing of Hg(2+) and CH(3)Hg(+) based on the fluorescence quenching of lysozyme type VI-stabilized gold nanoclusters

This study presents a one-step approach to prepare lysozyme type VI-stabilized gold nanoclusters (Lys VI-AuNCs) for the ultrasensitive detection of Hg(2+) and CH(3)Hg(+) based on fluorescence quenching. The optical properties and size of Lys VI-AuNCs are highly dependent on the concentration of Lys VI, which acts as both a reducing and a stabilizing agent. With an increase in the concentration of Lys VI, we observed a systematic blue shift in the fluorescence maxima, an increase in the quantum yields, and a reduction in the particle size. When using 25 mg/mL Lys VI as a reducing agent, the formed Lys VI-AuNCs (denoted as Au-631) were found to be highly stable in a high-concentration glutathione or NaCl. Additionally, the Au-631 were capable of sensing Hg(2+) and CH(3)Hg(+) through the interaction between Hg(2+)/CH(3)Hg(+) and Au(+) on the Au surface; the limits of detection (LODs) for Hg(2+) and CH(3)Hg(+) were 3 pM and 4 nM, respectively. The selectivity of this probe is more than 500-fold for Hg(2+) over any metal ions. As compared to bovine serum albumin-stabilized AuNCs, Au-631 provided an approximately 330-fold improvement in the detection of Hg(2+). To the best of our knowledge, Au-631 not only provide the first example for detecting CH(3)Hg(+) but also have the lowest LOD value for Hg(2+) when compared to other AuNC-based Hg(2+) sensors. Importantly, this probe was successfully applied to the determination of Hg(2+) and CH(3)Hg(+) in seawater.     

Comparison of synthesis of chelating resin silica-gel-supported diethylenetriamine and its removal properties for transition metal ions

Four kinds of silica-gel (SG)-supported diethylenetriamine (DETA) chelating resins SG-DETA-1, SG-DETA-2, SG-DETA-3, and SG-DETA-4 were prepared by functionalization of silica-gel via so-called "heterogeneous-direct-amination" (hetero-DA), "homogeneous-direct-amination" (homo-DA), "heterogeneous end-group protection" (hetero-EGP), and "homogeneous end-group protection" (homo-EGP) routes, respectively. These functionalized reactions on silica-gel were confirmed through elemental analysis, infrared spectroscopy, X-ray diffractometry, porous analysis, and thermogravimetry. Element analysis revealed that the direct-amination routes and homogeneous condition were more beneficial than the corresponding end-group protection routes and heterogeneous condition to the syntheses of chelating resins with high N content. Several metal ions, such as Ag(+), Cu(2+), Ni(2+), Hg(2+), Zn(2+) and Pb(2+), were chosen as representatives to investigate the relationship between adsorption capacities and N content of ligands onto the surface of silica-gel. The experiments results showed that all resins, SG-DETA-1, SG-DETA-2, SG-DETA-3 and SG-DETA-4, had a better adsorption for Hg(2+) and Cu(2+) than others. One conclusion should be drawn from the above compared experiments, that is, higher N content of silica-gel resins does not ensure a higher utilization ratio of N.     

FTIR spectrophotometry, kinetics and adsorption isotherms modeling, ion exchange, and EDX analysis for understanding the mechanism of Cd(2+) and Pb(2+) removal by mango peel waste

Mango peel waste (MPW) was evaluated as a new sorbent for the removal of Cd(2+) and Pb(2+) from aqueous solution. The maximum sorption capacity of Cd(2+) and Pb(2+) was found to be 68.92 and 99.05mgg(-1), respectively. The kinetics of sorption of both metals was fast, reaching at equilibrium in 60min. Sorption kinetics and equilibria followed pseudo-second order and Langmuir adsorption isotherm models. FTIR analysis revealed that carboxyl and hydroxyl functional groups were mainly responsible for the sorption of Cd(2+) and Pb(2+). Chemical modification of MPW for blocking of carboxyl and hydroxyl groups showed that 72.46% and 76.26% removal of Cd(2+) and Pb(2+), respectively, was due to the involvement of carboxylic group, whereas 26.64% and 23.74% was due to the hydroxyl group. EDX analysis of MPW before and after metal sorption and release of cations (Ca(2+), Mg(2+), Na(+), K(+)) and proton H(+) from MPW with the corresponding uptake of Cd(2+) and Pb(2+) revealed that the main mechanism of sorption was ion exchange. The regeneration experiments showed that the MPW could be reused for five cycles without significant loss in its initial sorption capacity. The study points to the potential of new use of MPW as an effective sorbent for the removal of Cd(2+) and Pb(2+) from aqueous solution.     

Computer-Readable DNAzyme Assay on Disc for ppb-Level Lead Detection

A method for the convenient detection of lead at the parts-per-billion (ppb)-level has been developed; it uses a conventional compact disc (CD) as the platform for preparing DNAzyme assays and an unmodified optical drive of ordinary desktop/laptop computers as the readout device. In particular, by immobilization of Pb(2+)-specific DNAzyme sensing constructs on the "transparent side" of a conventional CD-R via mild surface reactions, the Pb(2+) concentration can be determined by a free diagnostic program that checks the error distribution on the CD (i.e., it extracts the number of errors in a prerecorded audio file). The reading errors increase monotonically over a wide range of Pb(2+) concentrations (from 10 nM to 1 mM), and the selectivity is confirmed by testing several other divalent cations (Zn(2+), Ba(2+), Mg(2+), Ca(2+), Cu(2+), and Hg(2+)).     

The study of various parameters affecting the ion exchange of Cu2+, Zn2+, Ni2+, Cd2+, and Pb2+ from aqueous solution on Dowex 50W synthetic resin

A gel resin containing sulfonate groups (Dowex 50W) was investigated for its sorption properties towards copper, zinc, nickel, cadmium and lead metal ions. The use of selective ion exchange to recover metals from aqueous solution has been studied. The ion exchange behavior of five metals on Dowex 50W, depending on pH, temperature, and contact time and adsorbate amount was studied. Experimental measurements have been made on the batch sorption of toxic metals from aqueous solutions using cation exchanger Dowex 50W. The maximum recoveries (about 97%) Cu(2+), Zn(2+), Ni(2+), Cd(2+) and (about 80%) Pb(2+) were found at pH ranges 8-9. The amount of sorbed metal ion was calculated as 4.1, 4.6, 4.7, 4.8, and 4.7mequiv./gram dry resin for Pb(2+), Cu(2+), Zn(2+), Cd(2+), and Ni(2+), respectively. The precision of the method was examined at under optimum conditions. Selectivity increased in the series: Pb>Cd>Cu>Zn>Ni. It has been observed that, selectivity of the -SO(3)H group of the resin increases with atomic number, valance, degree of ionization of the exchanged metals. The equilibrium ion exchange capacity of resin for metal ions was measured and explored by using Freundlich and Langmuir isotherms. Langmuir type sorption isotherm was suitable for equilibrium studies.     

Adsorptive features of polyacrylamide-apatite composite for Pb2+, UO(2)2+ and Th4+

Micro-composite of polyacrylamide (PAA) and apatite (Apt) was prepared by direct polymerization of acrylamide in a suspension of Apt and characterized by means of FT-IR, XRD, SEM and BET analysis. The adsorptive features of PAA-Apt and Apt were then investigated for Pb(2+), UO(2)(2+) and Th(4+) in view of dependency on ion concentration, temperature, kinetics, ion selectivity and reusability. Experimentally obtained isotherms were evaluated with reference to Langmuir, Freundlich and Dubinin-Radushkevich (DR) models. Apt in PAA-Apt had higher adsorption capacity (0.81, 1.27 and 0.69 mol kg(-1)) than bare Apt (0.28, 0.41 and 1.33 mol kg(-1)) for Pb(2+) and Th(4+), but not for UO(2)(2+). The affinity to PAA-Apt increased for Pb(2+) and UO(2)(2+) but not changed for Th(4+). The values of enthalpy and entropy changed were positive for all ions for both Apt and PAA-Apt. Free enthalpy change was DeltaG<0. Well compatibility of adsorption kinetics to the pseudo-second-order model predicated that the rate-controlling step was a chemical sorption. This was consistent with the free energy values derived from DR model. The reusability tests for Pb(2+) for five uses proved that the composite was reusable to provide a mean adsorption of 53.2+/-0.7% from 4x10(-3)M Pb(2+) solution and complete recovery of the adsorbed ion was possible (98+/-1%). The results of this investigation suggested that the use of Apt in the micro-composite form with PAA significantly enhanced the adsorptive features of Apt.     

Experimental platform to study heavy metal ion-enzyme interactions and amperometric inhibitive assay of Ag+ based on solution state and immobilized glucose oxidase

The heavy metal (HM) ion-enzyme interaction is an important research topic in many areas. Using glucose oxidase (GOx) as an example, a comprehensive experimental platform based on quartz crystal microbalance and electroanalysis techniques is developed here to quantitatively study the HM ion-enzyme interactions and amperometric inhibitive assays of HM ions. The effects of some common HM ions on the bioactivities of solution-state GOx (GOx(s)), electrode surface-adsorbed GOx (GOx(ads)), and polymer-entrapped GOx (GOx(e)) are comparatively examined on the basis of anodic amperometric detection of enzymatically generated H(2)O(2). Ag(+) shows the strongest inhibition effect among the HM ions examined, and the inhibitive assays of Ag(+) based on GOx(s), GOx(ads), and GOx(e) entrapped in poly(l-noradrenalin) (PNA) give limits of detection (LOD) of 2.0, 8.0, and 5.0 nM (S/N = 3), respectively. Inhibition effects of Hg(2+), Cu(2+), and Co(2+) are detectable only at 15 μM or higher concentrations, and the other HM ions show undetectable inhibition even at 1.0 mM. The developed experimental platform allows one to quantify the number of the bound HM ions per GOx(ads) molecule at various inhibition percentages. In addition, the electrosynthesized PNA matrix to entrap GOx for an inhibitive assay of Ag(+) shows the lowest competitive affinity to HM ions and gives the highest sensitivity, as compared with several other polymer matrixes commonly used for the inhibitive assay. The suggested experimental platform is recommended for wide applications in enzymatic inhibitive assays and quantitative studies of the inhibition effects of HM ions on many other redox-event-relevant enzymes.     

Cu2+, Cd2+ and Pb2+ adsorption from aqueous solutions by pyrite and synthetic iron sulphide

In this study, removal of Cu(2+), Cd(2+) and Pb(2+) from aqueous solutions by adsorption onto pyrite and synthetic iron sulphide (SIS) was investigated as a function of pH, contact time, adsorbent dosage, initial metal concentration and temperature. It has been determined that the adsorption of metal ions onto both adsorbents is pH dependent and the adsorption capacities increase with the increasing temperature. The mechanisms governing the metal removal processes were determined as chemical precipitation at low pH (<3) due to H(2)S generation and adsorption at high pH (in the range of 3-6). The metal adsorption yields also increased with the increasing adsorbent dosage and contact time and reached to equilibrium for both adsorbents. The Cu(2+), Cd(2+) and Pb(2+) adsorption capacities of both adsorbents decrease in the order of Pb(2+)>Cu(2+)>Cd(2+). Except for cadmium, little fraction of copper and lead in the solid adsorption residues was desorbed in acidic media.