Electrochemical reduction of Cu(II)-EDTA complex at dropping mercury electrode. An impedance approach

The study of electrochemical reduction of Cu(II)-EDTA system by phase sensitive a.c. impedance method at dropping mercury electrode reveals several interesting features. The complex plane polarograms exhibit loop like shape in contrast to the classical zinc ion reduction where crest like shape is found. Again, the relative placement of peaks of in-phase and quadrature components, and the relative placement of portions before and after the peaks of complex plane polarograms are different from that of zinc ion reduction. The complex plane plots suggest that electrochemical reduction of Cu-EDTA is charge transfer controlled.

Cascaded Cross Flow DBD-Adsorbent Technique for NOX Abatement in Diesel Engine Exhaust

In this paper, a different type of cross flow dielectric barrier discharge (DBD) reactor was designed and tested. Here the gas flow is perpendicular to the barrier discharge electrode. Discharge plasma was utilized to oxidize NO contained in the exhaust gas to NO2 and subsequent NO2 removal can be improved using an adsorbent system. A detailed study of DeNO(X) in a stationary diesel engine exhaust was carried out using pulsed electrical discharges/adsorbent processes. Activated alumina (Al2O3) and MS-13x were used as adsorbents at room temperature. The main emphasis is laid on the removal of NOX from the filtered diesel engine exhaust. In filtered exhaust environment, the cross flow reactor along with adsorbent exhibits a superior performance with regard to NOX removal when compared to that with axial flow of gas. In this paper we bring out a relative comparison of discharge plasma and plasma-adsorbent process at various gas flow rates, ranging from 2 l/min to 25 l/min. The discharge plasma-adsorbent assisted barrier discharge reactor has shown promising results in NOX removal at high flow rates.

Mercury Segregation and Diselenide Self-Assembly on Gold

We have investigated the self-assembly of didecyldiselenide on gold containing mercury using X-ray photoelectron spectroscopy, cyclic voltammetry and infrared spectroscopy. The analysis of intensity and chemical shift of selected Se, Hg, and Au photoelectron lines on samples with increasing Hg content, show that didecyldiselenide adsorption strongly contributed to segregation of bulk Hg to the surface. The voltammetry results support this conclusion and suggest the formation of Hg-Au surface amalgam. The Hg surface segregation effect must be related to the restructuring of the surface following initial adsorption, and to the strong selenophilicity of Hg. The reflectance absorbance infrared spectroscopy studies show that the molecular layer on Hg-Au substrates lacks good order.

DEPRESSION OF MAGNETlCALLY FIXED EMISSION ZONE IN LOW PRESSURE MERCURY ARCS

A transverse magnetic field was used to fix the cathode spot of a low pressure mercury arc with liquid cathode It was noticed that such fixation causes consider-abledepression of the emission zone below the mercury level.This depression varies with the arc current and the magnetic field and is associated with an increase in the arc voltage drop. It indicates appreciable pressure in the emission zone.

Remarkable role of positional isomers in the design of sensors for the ratiometric detection of copper and mercury ions in water

Cation sensing properties of the three positional isomers of rhodamine based sensors (1-3) are studied in water. The sensors differ only in the position of pyridine's nitrogen. The chemosensor 1, with pyridine nitrogen at ortho-position, showed a selective colorimetric detection of Cu(II) ions in water, at physiological pH 7.4 and also in medium containing BSA (bovine serum albumin) and blood serum. Notably the compound 2 and 3, with pyridine end located at meta-and para-positions did not show any color change with Cu(II) ions, although both the compounds showed turn-on change both in color and fluorescence with Hg(II) ions specifically. All the probes showed ratiometric changes with the specific metal ions. The changing position of nitrogen also changed the complexation pattern of the sensors with the metal ions. Probe 1 showed 2 : 1 complexation with Cu(II), whereas 2 and 3 showed 1 : 1 complexation with Hg(II) ions. The mechanism investigation showed that the change in color upon addition of metal ions is due to the ring-opening of the spirolactam ring of the probes. Cu(II) interacted with ligand 1 through a three-point interaction mode comprising carbonyl oxygen, amido nitrogen and pyridine nitrogen end. But in case of 2 and 3, Hg2+ only interacted through pyridine nitrogen ends. Quantitative estimation of Cu2+ and Hg2+ in complex biological media such as bovine albumin protein (BSA) and human blood serum were performed using these sensors. Rapid on-site detection as well as discrimination of these toxic ions was demonstrated using easily prepared portable test-strips.

A Probe for the Selective and Parts-per-Billion-Level Detection of Copper(II) and Mercury(II) using a Micellar Medium and Its Utility in Cell Imaging

A novel colorimetric probe 1 based on the picolyl moiety has been designed and synthesized. Probe 1 is composed of a pyrene and a bispicolyl amine (BPA) unit, in which the BPA moiety acts as a binding unit and the binding phenomenon is sensed from the changes in the signaling subunit. The probe detects Cu2+ specifically in water and both Cu2+ and Hg2+ efficiently in neutral Brij-58 micellar media. The probe shows a color change visible to the naked eye upon addition of metal ions. Notably, in a micellar medium, probe 1 can detect both the Cu2+ and Hg2+ ions even at parts-per-billion levels. Furthermore, the probe shows ratiometric detection of both the metal ions making the sensing quantitative. The two metal ions could be discriminated both visibly under a UV lamp and with the use of fluorescence spectroscopy. The probe could be also used in biological cell lines for the detection of both Hg2+ and Cu2+ ions.

Mercury exposure Aasessment in fish and humans from Sundarban Mangrove Wetland of India

Present study had documented total mercury levels in six commonly consumed fish species, and performed across-sectional study on local residents to gauge their intake of fish (via dietary survey) and mercury exposure (via hair biomarker analyses). Mean total mercury content in edible composites of locally-caught fishes (topse, hilsa, mackerel, topse, sardinella, khoira) was low and ranged from 0.01 to 0.11 mu g g(-1) mercury, dry weight. In a cross-sectional study of 58 area residents, the mercury content in hair ranged from 0.25 to 1.23 mu g g(-1), with a mean of 0.65 +/- 0.23 mu g g(-1), Flair mercury level was not influenced by gender, age, or occupation. Mean number of meals consumed per week was 3.1 +/- 1.1, and all participants consumed at least one fish meal per week. When related to fish consumption, a significant positive association was found between number of fish meals consumed per week and hair mercury levels.

Size and temperature dependence of the photoluminescence properties of NIR emitting ternary alloyed mercury cadmium telluride quantum dots

Exciton-phonon coupling and nonradiative relaxation processes have been investigated in near-infrared (NIR) emitting ternary alloyed mercury cadmium telluride (CdHgTe) quantum dots. Organically capped CdHgTe nanocrystals of sizes varying from 2.5-4.2 nm have been synthesized where emission is in the NIR region of 650-855 nm. Temperature-dependent (15-300 K) photoluminescence (PL) and the decay dynamics of PL at 300 K have been studied to understand the photophysical properties. The PL decay kinetics shows the transition from triexponential to biexponential on increasing the size of the quantom dots (QDs), informing the change in the distribution of the emitting states. The energy gap is found to be following the Varshni relation with a temperature coefficient of 2.1-2.8 x 10(-4) eV K-1. The strength of the electron-phonon coupling, which is reflected in the Huang and Rhys factor S, is found in the range of 1.17-1.68 for QDs with a size of 2.5-4.2 nm. The integrated PL intensity is nearly constant until 50 K, and slowly decreases up to 140 K, beyond which it decreases at a faster rate. The mechanism for PL quenching with temperature is attributed to the presence of nonradiative relaxation channels, where the excited carriers are thermally stimulated to the surface defect/trap states. At temperatures of different region (<140 K and 140-300 K), traps of low (13-25 meV) and high (65-140 meV) activation energies seem to be controlling the quenching of the PL emission. The broadening of emission linewidth is found to due to exciton-acoustic phonon scattering and exciton-longitudinal optical (LO) phonon coupling. The exciton-acoustic phonon scattering coefficient is found to be enhanced up to 55 MU eV K-1 due to a stronger confinement effect. These findings give insight into understanding the photophysical properties of CdHgTe QDs and pave the way for their possible applications in the fields of NIR photodetectors and other optoelectronic devices.

Towards rational synthesis of inorganic solids

There have been major advances in the past couple of years in the rational synthesis of inorganic solids: synthesis of mercury-based superconducting cuprates showing transition temperatures up to 150 K; ZrP2-xVxO7 solid solutions showing zero or negative thermal expansion; copper oxides possessing ladder structures such as La1-xSrxCuO2.5; synthesis of mesoporous oxide materials having adjustable pore size in the range 15-100 Angstrom; and synthesis of a molecular ferromagnet showing a critical temperature of 18.6 K. Despite great advances in probing the structures of solids and measurement of their physical properties, the design and synthesis of inorganic solids possessing desired structures and properties remain a challenge today. With the availability of a variety of mild chemistry-based approaches, kinetic control of synthetic pathways is becoming increasingly possible, which, it is hoped, will eventually make rational design of inorganic solids a reality.

Assembly of sol-gel-grown $Li _{(x)} CoO_{2}$ nanocrystals through electromagnetic irradiation

We report the fabrication of assembled nanostructures from the pre-synthesized nanocrystals building blocks through optical means of exciton formation and dissociation. We demonstrate that Li (x) CoO2 nanocrystals assemble to an acicular architecture, upon prolonged exposure to ultraviolet-visible radiation emitted from a 125 W mercury vapor lamp, through intermediate excitation of excitons. The results obtained in the present study clearly show how nanocrystals of various materials with band gaps appropriate for excitations of excitons at given optical wavelengths can be assembled to unusual nanoarchitectures through illumination with incoherent light sources. The disappearance of exciton bands due to Li (x) CoO2 phase in the optical spectrum of the irradiated film comprising acicular structure is consistent with the proposed mechanism of exciton dissociation in the observed light-induced assembly process. The assembly process occurs through attractive Coulomb interactions between charged dots created upon exciton dissociation. Our work presents a new type of nanocrystal assembly process that is driven by light and exciton directed.

Efficient Hg and Ag ion detection with luminescent PbS quantum dots grown in poly vinyl alcohol and capped with mercaptoethanol

PbS quantum dots capped with mercaptoethanol (C2H5OSH) have been synthesized in poly vinyl alcohol and used to investigate their photoluminescence (PL) response to various ions such as zinc (Zn), cadmium (Cd), mercury (Hg), silver (Ag), copper (Cu), iron (Fe), manganese (Mn), cobalt (Co), chromium (Cr) and nickel (Ni). The enhancement in the PL intensity was observed with specific ions namely Zn, Cd, Hg and Ag. Among these four ions, the PL response to Hg and Ag even at sub-micro-molar concentrations was quite high, compared to that of Zn and Cd. It was observed that the change in Pb and S molar ratio has profound effect on the sensitivity of these ions. These results indicate that the sensitivity of these QDs could be fine-tuned by controlling the S concentration at the surface. Contrary to the above, Cu quenched the photoluminescence. In Cd based QDs related ion probing, Hg and Cu was found to have quenching properties, however, our PbS QDs have quenching property only for Cu ions. This was attributed to the formation HgS at the surface that has bandgap higher than PbS. Another interesting property of PbS in PVA observed is photo-brightening mechanism due to the curing of the polymer with laser. However, the presence of excess ions at the surface changes its property to photo-darkening/brightening that depends on the direction of carrier transfer mechanism (from QDs to the surface adsorbed metal ions or vice-versa). which is an interesting feature for metal ion detectivity.

Two-dimensional phase transitions at electrochemical interfaces

A two-state Ising model has been applied to the two-dimensional condensation of tymine at the mercury-water interface. The model predicts a quadratic dependence of the transition potential on temperature and on the logarithm of the adsorbate concentration. Both predictions have been confirmed experimentally.

13c And 1h Nmr Study Of Complexes Of 2-Pyridinethione And 4-Pyridinethione With Zn(Ii), Cd(Ii) And Hg(Ii) Halides

Proton and carbon-13 NMR has been used to study complexes of 2-pyridinethione (in its basic and deprotonated forms) and 4-pyridinethione with zinc(II), cadmium(II) and mercury(II) halides. The variations in the carbon-13 and proton chemical shifts are discussed.

An apparatus for the study of switching characteristics in ferroelectrics

A circuit capable of producing bipolar square pulses of voltages up to +or-400 V, employing an integrated circuit timer and two mercury wetted relays is described. The frequency of the pulses can be varied from a cycle min-1 to 2 kHz. A variable temperature sample chamber and the temperature control and measurement circuits are also described. The performance of the circuit is evaluated using samples of TGS and NaNO2.

Electrochemisorption - A Cluster Approach

A simple semiempirical quantum chemical approach (Extended Huckel Theory) is shown to give a reasonable description of the electronic structural aspects of chemisorption on the mercury model surface. Chemisorptive interaction of alkali metal atoms and cations, halogen atoms and anions, and water molecules with a charge-neutralized hexagonal close-packed cluster of seven Hg atoms is studied. Adsorption of H, C, N and O atoms on the same model cluster is studied for comparison with earlier work. Chemisorption energies, charge transfer, interaction distance and hydration effects are discussed and compared with experimental results where available.