Silver ion-selective electrodes using pi-coordinate calix

Calix[4]arene derivatives incorporating pi-coordinate substituents such as allyl, benzyl, and propargyl groups were designed as soft neutral carriers for silver ion sensors. Most of all, tert-butylcalix[4]arene tetra(allyl ether) is an excellent neutral carrier for plasticized poly(vinyl chloride)-membrane silver ion-selective electrodes. The ion sensors showed high silver ion selectivity over alkali metal ions and also good selectivity against other soft metal ions such as lead and mercury(II) ions. The electrode potential response was as rapid as that for neutral-carrier-type alkali metal ion electrodes due to the soft interaction between pi-coordinate substituents and silver ion, which was elucidated by 1H NMR spectroscopy.     

Metal complexation of thiacrown ether macrocycles by electrospray ionization mass spectrometry

In the present study, electrospray ionization mass spectrometry is used to evaluate the metal-binding selectivities of an array of novel caged macrocycles for mercury(II), lead(II), cadmium(II), and zinc(II) ions. In homogeneous methanol/chloroform solutions as well as extractions of metals from aqueous solution by macrocycles in chloroform, it is found that the type of heteroatom (S, O, N), cavity size, and presence of other substituents influence the metal selectivities. Several of the macrocycles in this study bind mercury ion very selectively and efficiently in the presence of many other metal ions and have an avidity toward mercury that was tunable by the size and combination of heteroatoms in the macrocycle ring and the number of cage groups attached. The extraction mechanism was further investigated by determining the variation in extraction selectivity as a function of the counterions of the mercury salts.     

Measurement of association and dissociation rate constants for lead(II)/18-crown-6 using square wave voltammetry at a glassy carbon mercury film electrode

Understanding the rate parameters of metal ion-ligand complexes is necessary for sensing, separations, and responsive materials. The complexation between 18-crown-6 and lead(II) is of particular interest due to the potential use of this chemistry in sensors and separations. We have applied square wave voltammetry at a glassy carbon mercury film electrode to this problem. Lead(II) in aqueous solution containing an excess of 18-crown-6, studied with different experimental time scales, yields stoichiometry, binding constants, and rate constants (25 degrees C). For pulse times longer than 10 ms, the glassy carbon mercury film electrode acts as a planar electrode. For shorter pulse times, a roughness correction factor must be used to calculate dimensionless current because of the increase in effective area due to the droplike nature of the adsorbed mercury. Lead(II) forms a 1:1 complex with 18-crown-6 in both nitrate and perchlorate media. Log K for the complex with the nitrate counterion is 4.13 +/- 0.09 (SEM); in the presence of perchlorate it is 4.35 +/- 0.09 (SEM). The formation rate constants, kf, for the nitrate and perchlorate systems are (3.82 +/- 0.89) x 107 and (5.92 +/- 1.97) x 106 M-1 s-1, respectively. The dissociation rate constants, kd, are (2.83 +/- 0.66) x 103 s-1 with nitrate as the counterion and (2.64 +/- 0.88) x 102 s-1 with perchlorate as the counterion. The significant difference in rate constants for the two anions is probably caused by the ion pairing that occurs with lead(II) nitrate.     

Dowex anion exchanger-loaded-baker's yeast as bi-functionalized biosorbents for selective extraction of anionic and cationic mercury(II) species

Dowex anion exchanger-immobilized-baker's yeast [Dae-yeast] were synthesized and potentially applied as environmental friendly biosorbents to evaluate the up-take process of anionic and cationic mercury(II) species as well as other metal ions. Optimization of mass ratio of Dowex anion exchanger versus yeast (1:1-1:10) in presence of various interacting buffer solutions (pH 4.0-9.0) was performed and evaluated. Surface modification of [Dae-yeast] was characterized by scanning electron microscopy (SEM) and infrared spectroscopy. The maximum metal biosorption capacity values of [Dae-yeast] towards mercury(II) were found in the range of 0.800-0.960, 0.840-0.950 and 0.730-0.900 mmol g(-1) in presence of buffer solutions pH 2.0, 4.0 and 7.0, respectively. Three possible and different mechanisms are proposed to account for the biosorption of mercury and mercuric species under these three buffering conditions based on ion exchange, ion pair and chelation interaction processes. Factors affecting biosorption of mercury from aqueous medium including the pH effect of aqueous solutions (1.0-7.0), shaking time (1-30 min) and interfering ions were se arched. The potential applications of modified biosorbents for selective biosorption and extraction of mercury from different real matrices including dental filling waste materials, industrial waste water samples and mercury lamp waste materials were also explored. The results denote to excellent percentage extraction values, from nitric acid as the dissolution solvent with a pH 2.0, as determined in the range of 90.77-97.91+/-3.00-5.00%, 90.00-93.40+/-4.00-5.00% and 92.31-100.00+/-3.00-4.00% for the three tested samples, respectively.     

Organic–inorganic hybrid mesoporous monoliths for selective discrimination and sensitive removal of toxic mercury ions

Abstract  

The selective optical sensing is attracting strong interest due to the use of “low-tech” spectroscopic instrumentation to detect relevant chemical species in biological and environmental processes. Our development has focused on tailoring specific solid mesoporous monoliths to be used as highly sensitive solid sensors for simple and simultaneous naked-eye detection and removal processes of extremely toxic heavy metal ions such as mercury ions in aquatic samples. The methods are emerging to design optical disc-like sensors by the immobilisation two different organic groups; however, the first organic moiety can enhance the polarity of the inorganic mesoporous disc-like monoliths “additional agents” and the second one can act as a recognition center “probe”. The latter one such as tetraphenylporphine tetrasulfonic acid (TPPS) probe led to facile handling of signal read-out with visual detection of ultra-trace concentrations of mercury ions at the same frequency as the human eye. The facile signaling was quantitatively evident using simple spectrophotometric techniques to indicate the TPPS–Hg(II) ion binding events. Control sensing assays of Hg(II) ions such as contact-time “signal response time”, thickness of support-based sensor, reaction temperature, and pH were established for achieving enhanced signal response and color intensities. Based on our results, these new classes of optical cage sensors exhibited long-term stability of recognition and signaling functionalities of Hg(II) ions that in general provided extraordinary sensitivity, selectivity, reusability, and fast kinetic detection and quantification of Hg(II) ions in our environment.     

Solid phase extraction and determination of sub-ppb levels of hazardous Hg2+ ions

A simple, rapid and reliable method has been developed to selectively separate and concentrate ultra trace amounts of mercury(II) ions from aqueous samples for its highly sensitive measurement by cold vapor atomic absorption spectrometry (CV-AAS). The Hg(2+) ions were adsorbed selectively and quantitatively during the passage of aqueous samples through octadecyl silica membrane disks modified by isopropyl 2-[(isopropoxycarbothiolyl)disulfanyl]ethane thioate (IIDE). The retained Hg(2+) ions were then stripped from the disk with minimal amounts of 0.5 M hydrobromic acid (two 8 ml portions) as eluent, and determined by CV-AAS. The break-through volume of the method is greater than 3000 ml, which results in enrichment factors >150. Maximum capacity of the membrane disks modified with 10mg of the ligand was found to be 350+/-30 microg of mercury(II), and the limit of detection is 0.005 ng ml(-1). The effect of various cationic interferences on the recovery of mercury in binary mixtures was studied. The method was applied to the recovery of Hg(2+) ions from different synthetic and tap water samples, as well as the determination of mercury in human hair samples.     

Radiative ion-ion neutralization: a new gas-phase atmospheric pressure ion transduction mechanism

All atmospheric pressure ion detectors, including photo ionization detectors, flame ionization detectors, electron capture detectors, and ion mobility spectrometers, utilize Faraday plate designs in which ionic charge is collected and amplified. The sensitivity of these Faraday plate ion detectors are limited by thermal (Johnson) noise in the associated electronics. Thus approximately 10(6) ions per second are required for a minimal detection. This is not the case for ion detection under vacuum conditions where secondary electron multipliers (SEMs) can be used. SEMs produce a cascade of approximately 10(6) electrons per ion impinging on the conversion dynode. Similarly, photomultiplier tubes (PMTs) can generate approximately 10(6) electrons per photon. Unlike SEMs, however, PMTs are evacuated and sealed so that they are commonly used under atmospheric pressure conditions. This paper describes an atmospheric pressure ion detector based on coupling a PMT with light emitted from ion-ion neutralization reactions. The normal Faraday plate collector electrode was replaced with an electrode "needle" used to concentrate the anions as they were drawn to the tip of the needle by a strong focusing electric field. Light was emitted near the surface of the electrode when analyte ions were neutralized with cations produced from the anode. Although radiative-ion-ion recombination has been previously reported, this is the first time ions from separate ionization sources have been combined to produce light. The light from this radiative-ion-ion-neutralization (RIIN) was detected using a photon multiplier such that an ion mobility spectrum was obtained by monitoring the light emitted from mobility separated ions. An IMS spectrum of nitroglycerin (NG) was obtained utilizing RIIN for tranducing the mobility separated ions into an analytical signal. The implications of this novel ion transduction method are the potential for counting ions at atmospheric pressure and for obtaining ion specific emission spectra for mobility separated ions.     

Study of ion feedback in multi-GEM structures

We study the feedback of positive ions in triple and quadruple Gas Electron Multiplier (GEM) detectors. The effects of GEM hole diameter, detector gain, applied voltages, number of GEMs and other parameters on ion feedback are investigated in detail. In particular, it was found that the ion feedback is independent of the gas mixture and the pressure. In the optimized multi-GEM structure, the ion feedback current can be suppressed down to 0.5% of the anode current, at a drift field of 0.1 kV/cm and gain of 10⁴. A simple model of ion feedback in multi-GEM structures is suggested. The results obtained are relevant to the performance of time projection chambers and gas photomultipliers.     

Nontopotactic Reaction in Highly Reversible Sodium Storage of Ultrathin Co9Se8/rGO Hybrid Nanosheets

Transition metal chalcogenide with tailored nanosheet architectures with reduced graphene oxide (rGO) for high performance electrochemical sodium ion batteries (SIBs) are presented. Via one‐step oriented attachment growth, a facile synthesis of Co₉Se₈ nanosheets anchored on rGO matrix nanocomposites is demonstrated. As effective anode materials of SIBs, Co₉Se₈/rGO nanocomposites can deliver a highly reversible capacity of 406 mA h g^?1 at a current density of 50 mA g^?1 with long cycle stability. It can also deliver a high specific capacity of 295 mA h g^?1 at a high current density of 5 A g^?1 indicating its high rate capability. Furthermore, ex situ transmission electron microscopy observations provide insight into the reaction path of nontopotactic conversion in the hybrid anode, revealing the highly reversible conversion directly between the hybrid Co₉Se₈/rGO and Co nanoparticles/Na₂Se matrix during the sodiation/desodiation process. In addition, it is experimentally demonstrated that rGO plays significant roles in both controllable growth and electrochemical conversion processes, which can not only modulate the morphology of the product but also tune the sodium storage performance. The investigation on hybrid Co₉Se₈/rGO nanosheets as SIBs anode may shed light on designing new metal chalcogenide materials for high energy storage system.     

In Situ Intercalation of Bismuth into 3D Reduced Graphene Oxide Scaffolds for High Capacity and Long Cycle‐Life Energy Storage

Metal anodes, such as zinc and bismuth have been regarded as ideal materials for aqueous batteries due to high gravimetrical capacity, high abundance, low toxicity, and intrinsic safety. However, their translation into practical applications are hindered by the low mass loading (≈1 mg cm^?2) of active materials. Here, the multiscale integrated structural engineering of 3D scaffold and active material, i.e., bismuth is in situ intercalated in reduced graphene oxide (rGO) wall of network, are reported. Tailoring the rapid charge transport on rGO 3D network and facile access to nano‐ and microscale bismuth, the rGO/Bi hybrid anode shows high utilization efficiency of 91.4% at effective high load density of ≈40 mg cm^?2, high areal capacity of 3.51 mAh cm^?2 at the current density of 2 mA cm^?2 and high reversibility of >10 000 cycles. The resulting Ni‐Bi full battery exhibits high areal capacity of 3.13 mAh cm^?2 at the current density of 2 mA cm^?2, far outperforming the other counterpart batteries. It represents a general and efficient strategy in enhancing the battery performance by designing hierarchically networked structure.     

Laser‐Induced Molybdenum Carbide–Graphene Composites for 3D Foldable Paper Electronics

Versatile and low‐cost manufacturing processes/materials are essential for the development of paper electronics. Here, a direct‐write laser patterning process is developed to make conductive molybdenum carbide–graphene (MCG) composites directly on paper substrates. The hierarchically porous MCG structures are converted from fibrous paper soaked with the gelatin‐mediated inks containing molybdenum ions. The resulting Mo₃C₂ and graphene composites are mechanically stable and electrochemically active for various potential applications, such as electrochemical ion detectors and gas sensors, energy harvesters, and supercapacitors. Experimentally, the electrical conductivity of the composite is resilient to mechanical deformation with less than 5% degradation after 750 cycles of 180° repeated folding tests. As such, the direct laser conversion of MCGs on papers can be applicable for paper‐based electronics, including the 3D origami folding structures.     

Golden Bristlegrass‐Like Hierarchical Graphene Nanofibers Entangled with N‐Doped CNTs Containing CoSe2 Nanocrystals at Each Node as Anodes for High‐Rate Sodium‐Ion Batteries

Golden bristlegrass‐like unique nanostructures comprising reduced graphene oxide (rGO) matrixed nanofibers entangled with bamboo‐like N‐doped carbon nanotubes (CNTs) containing CoSe₂ nanocrystals at each node (denoted as N‐CNT/rGO/CoSe₂ NF) are designed as anodes for high‐rate sodium‐ion batteries (SIBs). Bamboo‐like N‐doped CNTs (N‐CNTs) are successfully generated on the rGO matrixed nanofiber surface, between rGO sheets and mesopores, and interconnected chemically with homogeneously distributed rGO sheets. The defects in the N‐CNTs formed by a simple etching process allow the complete phase conversion of Co into CoSe₂ through the efficient penetration of H₂Se gas inside the CNT walls. The N‐CNTs bridge the vertical defects for electron transfer in the rGO sheet layers and increase the distance between the rGO sheets during cycles. The discharge capacity of N‐CNT/rGO/CoSe₂ NF after the 10 000th cycle at an extremely high current density of 10 A g^?1 is 264 mA h g^?1, and the capacity retention measured at the 100th cycle is 89%. N‐CNT/rGO/CoSe₂ NF has final discharge capacities of 395, 363, 328, 304, 283, 263, 246, 223, 197, 171, and 151 mA h g^?1 at current densities of 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, and 20 A g^?1, respectively.     

Biosorption of mercury from aqueous solutions by powdered leaves of castor tree (Ricinus communis L.)

A new biosorbent produced from castor leaves powder [Ricinus communis L.] was used to remove mercury(II) from aqueous solutions. The initial mercury concentrations, contact time and initial pH were evaluated. The ability of castor leaves to remove mercury at various pH (2-8) was studied. The maximum capacity (Qmax) of biomass was found to be 37.2mg Hg(II)/g at pH 5.5. Biosorption equilibrium was established in approximately 1h. The equilibrium data were described well by Langmuir and Freundlich models. The adsorbed mercury on biomass was desorbed using 10 ml of 4M HCl solution. The biomass could be reused for other biosorption assays. The ability of biomass to adsorb mercury(II) in a column was investigated. These studies consider the possibility of using leaves of castor tree as an inexpensive adsorbent for the removal of Hg(II) from contaminated chemical and mining industry wastewaters. It is also suggested that the dried biomass might be simply kept and used in a very low cost metal ion removal system.     

Temperature profile investigation of SnO/sub 2/ sensors for CO detection enhancement

SnO/sub 2/ sensors are widely used for the detection of air contaminants such as CO. Nevertheless, their application encounters several problems, mainly the effect of interfering gases. The low selectivity is, in fact, a well-known problem of these sensors. Moreover, the high operating temperature of metal oxide sensors implies, in general, high power consumption. We present a study aimed at the selection of an appropriate measurement technique for detection of CO for indoor applications (lower threshold 100 ppm), in the presence of high concentrations of ethanol (up to 1000 ppm), by using only one sensor. Moreover, the paper aims at developing portable CO detectors that are very small, low power, and could be battery operated.     

Synthesis and characterization of binary transition metal oxide/reduced graphene oxide nanocomposites and its enhanced electrochemical properties for supercapacitor applications

SnO₂/Co₃O₄ (BTMO) with reduced graphene oxide (rGO) nanocomposite were synthesized by co-precipitation method to determine its electrochemical properties for the betterment of Supercapacitor applications. The XRD pattern of BTMO/rGO nanocomposite shows tetragonal rutile and spinal cubic structure. The XRD peak of BTMO/rGO nanocomposite is comparatively broader than the BTMO nanocomposite and bare nanoparticles due to the presence of high surface area rGO. From the SEM image it is observed that the BTMO nanocomposite has comparatively larger particles than the bare nanoparticles and BTMO/rGO nanocomposites. Hence, the BTMO/rGO nanocomposite has alteration in surface to volume ratio and improved electron conductivity were observed with increased integral area and current such as 2.5117?×?10^?4 A/s and 3.1686?×?10^?4 A respectively in CV behavior, when it is compared to BTMO nanocomposite and bare nanoparticles. The BTMO/rGO nanocomposite also has an increased specific capacitance value of 317.2 F/g at 1 A/g. The increased specific capacitance value of BTMO/rGO nanocomposites are mainly due to the synergistic effect between SnO₂/Co₃O₄ and rGO. Hence, it may be responsible for the improved electron conductivity, due to the free diffusion pathway for the fast ion movement and also it has easily ion accessibility nature to the storage sites makes the materials with both the electric double layer capacitance and pseudocapacitance behavior. Hence, BTMO/rGO nanocomposite would be a promising candidate material for energy storage supercapacitor application.     

Detection of mercury(II) by quantum dot/DNA/gold nanoparticle ensemble based nanosensor via nanometal surface energy transfer

An ultrasensitive fluorescent sensor based on the quantum dot/DNA/gold nanoparticle ensemble has been developed for detection of mercury(II). DNA hybridization occurs when Hg(II) ions are present in the aqueous solution containing the DNA-conjugated quantum dots (QDs) and Au nanoparticles. As a result, the QDs and the Au nanoparticles are brought into the close proximity, which enables the nanometal surface energy transfer (NSET) from the QDs to the Au nanoparticles, quenching the fluorescence emission of the QDs. This nanosensor exhibits a limit of detection of 0.4 and 1.2 ppb toward Hg(II) in the buffer solution and in the river water, respectively. The sensor also shows high selectivity toward the Hg(II) ions.     

Removal and recovery of mercury(II) from hazardous wastes using 1-(2-thiazolylazo)-2-naphthol functionalized activated carbon as solid phase extractant

As a part of removal of toxic heavy metals from hazardous wastes, solid phase extraction (SPE) of mercury(II) at trace and ultra trace levels was studied using 1-(2-thiazolylazo)-2-naphthol (TAN) functionalized activated carbon (AC). The SPE material removes traces of mercury(II) quantitatively in the pH range 6.0 +/- 0.2. Other parameters that influence quantitative recovery of mercury(II), viz. percent concentration of TAN in AC, amount of TAN-AC, preconcentration time and volume of aqueous phase were varied and optimized. The possible means of removal of Hg(II) from other metal ions that are likely to be present in the wastes of the chloroalkali industry is discussed. The potential of TAN-functionalized AC SPE material for decontaminating mercury from the brine sludge and cell house effluent of a chloralkali plant has been evaluated.     

Effects of chemical competition for multi-metal binding by Medicago sativa (alfalfa).

Alfalfa shoot biomass has demonstrated the ability to bind an appreciable amount of cadmium(II), chromium(III), copper(II), lead(II), nickel(II), and zinc(II) separately from aqueous solutions. Since most heavy metal contaminated waters contain more than one heavy metal ion, it was necessary to determine the binding abilities of the alfalfa biomass with multi-metal solutions. Batch laboratory experiments were performed with a solution containing 0.1 mM of each of the following metal ions: cadmium(II), chromium(III), copper(II), lead(II), nickel(II), and zinc(II). We determined the pH profile, time dependency, and binding capacity by the alfalfa biomass of each metal ion under multi-elemental conditions. For all the metal ions studied, the alfalfa biomass showed to have a high affinity for metal binding around pH 5.0 within a time period of approximately 5 min. The binding capacity experiments showed that there was a preferential binding of the metal ions from the multi-elemental solution with the following amounts of metal ion bound per gram of biomass: 368.5 micromol/g for copper(II), 215.4 micromol/g for chromium(III), 168.0 micromol/g for lead(II), 56.9 micromol/g for zinc(II), 49.2 micromol/g for nickel(II), and 40.3 micromol/g for cadmium(II). Reacting the biomass from the capacity experiments with 0.1 M HCl resulted in 90% or greater recovery of bound cadmium, copper, lead, nickel, and zinc. However, only 44% of the bound chromium was recovered. These experiments show the ability of Medicago sativa (alfalfa) to bind several metal ions under multi-contaminant conditions. Similar results were obtained when the experiments were performed under flow conditions using silica-immobilized alfalfa biomass. Chromium bound on the silica-immobilized biomass was also difficult to be desorbed with 0. 1 M HCl. The information obtained will be useful for the future development of an innovative technology to remove heavy metal contaminants from polluted ground waters.     

Monolithic Graphene Trees as Anode Material for Lithium Ion Batteries with High C‐Rates

Monolithically structured reduced graphene oxide (rGO), prepared from a highly concentrated and conductive rGO paste, is introduced as an anode material for lithium ion batteries with high rate capacities. This is achieved by a mixture of rGO paste and the water‐soluble polymer sodium carboxymethylcellulose (SCMC) with freeze drying. Unlike previous 3D graphene porous structures, the monolithic graphene resembles densely branched pine trees and has high mechanical stability with strong adhesion to the metal electrodes. The structures contain numerous large surface area open pores that facilitate lithium ion diffusion, while the strong hydrogen bonding between the graphene layers and SCMC provides high conductivity and reduces the volume changes that occur during cycling. Ultrafast charge/discharge rates are obtained with outstanding cycling stability and the capacities are higher than those reported for other anode materials. The fabrication process is simple and straightforward to adjust and is therefore suitable for mass production of anode electrodes for commercial applications.     

Electrical characterization of functionalized platinum electrodes and ISFET sensors for metal ion detection

This paper reports the application of functionalized platinum (Pt) electrodes and ChemFETs sensors for metal ion detection. The sensitive part of the sensors consists in a film of ethyl 2-thienylglyoxalate (ETGO) deposited by a spin-coating process. Electrochemical impedance spectroscopy was used to investigate the electrical properties of functionalized Pt electrodes. The optimized working conditions of the sensors have been studied with regard to the sensitivity performances, in particular, the polarization was adjusted to − 0.85 V/ESC in order to neglect the Warburg effects at low frequencies. The functionalized Pt electrodes have shown a good sensitivity towards Cu(II) ions, whereas low response towards Ca(II) ions was observed. The ETGO/ISFET devices have shown good sensitivity (14 mV/decade) and linear responses over at least two decades of Cu(II) activity compared to (0.5 mV/decade) for Ca(II) ions.