Synthesis and Characterization of Chiral Mercury(II) and Cadmium(II) Complexes with 3,3'-Bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl

Two homochiral mercury （1） and cadmium （2） complexes derived from chiral twisted biphenyl pyridine ligand （3,3＇-bipyridine-5,5＇,6,6＇-tetramethyl-2,2＇-dimethoxy-1,1＇-biphenyl） have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038（16）, b = 14.3630（17）, c = 7.0257（8）, V = 1433.3（3）3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F（000） = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I 2σ（I）. For 2, a = 14.212（3）, b = 14.392（3）, c = 7.0498（14）, V = 1442.0（5）3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm–1, F（000） = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I 2σ（I）. The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C–H···π interactions.

Potentiometric Determination of Trace Amounts of Mercury (II) in Water Sample Using a New Modified Palm Shell Activated Carbon Paste Electrode Based on Kryptofix 5

A new modified palm shell activated carbon paste electrode based on 1,13-Bis(8-quinolyl)-1,4,7,10,13-pentaoxat-ride-cane ,8,8-(1,4,7,10,13-Pentaoxatridecylene)-diquinoline (Kryptofix?5) and plasticizing agent was prepared and studied as Hg2+ selective electrode. The best performance was observed with the electrode composition having the iono-phore-palm shell activated carbon-plasticizer composition 10%:50%:40% with Nernstian response over the concentration range of 1.0 × 10–8 - 1.0 × 10–2 M with a slope of 42 ± 1.5 mV per decade of concentration. The detection limit as determined from the calibration plot is 1.0 × 10–7 M. The proposed electrode shows good selectivity for Hg(II) with interfering ions. The response time of the electrode is fast (≤10 s), and can be used in the pH range of 3 - 11. The electrode was used to determine mercury in drinking water.

Highly Efficient and Selective Removal of Pb（II） ions by Sulfur-Containing Calcium Phosphate Nanoparticles

A facile one-step co-precipitation method was demonstrated to fabricate amorphous sulfurcontaining calcium phosphate （SCP） nanoparticles, in which the sulfur group was in-situ introduced into calcium phosphate. The resulting SCP exhibited a noticeable enhanced performance for Pb（II） removal in comparison with hydroxyapatite （HAP）, being capable of easily reducing 20 ppm of Pb（II） to below the acceptable standard for drinking water within less than 10 min. Remarkably, the saturated removal capacities of Pb（II） on SCP were as high as 1720.57 mg/g calculated by the Langmuir isotherm model, exceeding largely that of the previously reported absorbents. Significantly, SCP displayed highly selective removal ability toward Pb（II） ions in the presence of the competing metal ions （Ni（II）, Co（II）, Zn（II）, and Cd（II））. Further investigations indicated that such ultra-high removal efficiency and preferable affinity of Pb（II） ions on SCP may be reasonably ascribed to the formation of rodlike hydroxypyromorphite crystals on the surface of SCP via dissolution-precipitation and ion exchange reactions, accompanied by the presence of lead sulfide precipitates. High removal efficiency, fast removal kinetics and excellent selectivity toward Pb（II） made the obtained SCP material an ideal candidate for Pb（II） ions decontamination in practical application.

1-Pyrenecarboxaldehyde thiosemicarbazone:A novel fluorescent molecular sensor towards mercury(Ⅱ) ion

A novel and simple fluorescent molecular sensor,1-pyrenecarboxaldehyde thiosemicarbazone（Hpytsc）,was synthesized.Its higher sensitivity and selectivity to mercury（Ⅱ） ion were studied through absorption and emission channels.The UV-vis spectra show that the increasing mercury（Ⅱ） ion concentrations result in the decreasing absorption intensity.The fluorescence monomer emission of Hpytsc is enhanced upon binding mercury（Ⅱ） ion,which should be due to the 1：1 complex formation between Hpytsc and metal ion.

Effects of 1,2,4-Trichlorobenzene and Mercury Ion Stress on Ca^2+ Fluxion and Protein Phosphorylation in Rice

The effects of 5 mg/L 1,2,4-trichlorobenzene （TCB） and 0.1 mmol/L mercury ion （Hg^2＋） stresses on Ca^2＋ fluxion and protein phosphorylation in rice seedlings were investigated by isotope exchange kinetics and in vitro phosphorylation assay. The Ca^2＋ absorption in rice leaves and Ca^2＋ transportation from roots to leaves were promoted significantly in response to Hg^2＋ and TCB treatments for 4-48 h. The Ca^2＋ absorption peaks presented in the leaves when the rice seedlings were exposed to Hg^2＋ for 8-12 h or to TCB for 12-24 h. Several Ca^2＋ absorption peaks presented in the roots during rice seedlings being exposed to Hg^2＋ and TCB, and the first Ca^2＋ absorption peak was at 8 h after being exposed to Hg^2＋ and TCB The result of isotope exchange kinetic analysis confirmed that short-term （8 h） Hg^2＋ and TCB stresses caused Ca^2＋ channels or pumps located on plasmalemma to open transiently. The phosphorylation assay showed that short-term TCB stress enhanced protein phosphorylation in rice roots （TCB treatment for 4-8 h） and leaves （TCB treatment for 4-24 h）, and short-term （4-8 h） Hg^2＋ stress also enhanced protein phosphorylation in rice leaves. The enhancement of protein phosphorylation in both roots and leaves corresponded with the first Ca^2＋ absorption peak, which confirmed that the enhancement of protein phosphorylation caused by TCB or Hg^2＋ stress might be partly triggered by the increases of cytosolic calcium. TCB treatment over 12 h inhibited protein phosphorylation in rice roots, which might be partly due to that TCB stress suppressed the protein kinase activity. Whereas, Hg^2＋ treatment inhibited protein phosphorylation in rice roots, and Hg^2＋ treatment over 12 h inhibited protein phosphorylation in rice leaves. This might be attributed to that not only the protein kinase activity, but also the expressions of phosphorylation proteins were restrained by Hg^2＋ stress.

Co-intensification of cyanide leaching gold by mercury ions and oxidant

The effects of mercury ions on gold cyanidation were studied. The results show that under low cyanide concentration, gold cyanide process is controlled by CN- transfer, while at higher cyanide concentration, there forms passivation on gold surface. Therefore, chemical oxidation of gold in cyanide solution of higher concentration is controlled by surface reaction. Small quantity of additions of mercury ions bring about great increases in anodic gold dissolution rate, decreases the passivation and reduces the equilibrium activated energy. In addition, they also markedly change the effect pattern of cyanide concentration. Mercury ions show positive effects on cathodic reduction of oxygen and raise the rate of electrochemical step of the cathodic reduction of oxygen. Addition of a certain amount of hydrogen peroxide is confirmed to be an effective way for intensification of cathodic process on gold electrode. Active potential range and current peak on anodic dissolution are enlarged when being co-intensified with Hg^2＋ and hydrogen peroxide. Co-intensifying effect may be obtained and gold from gold concentrates. gold leaching rate is considerably increased on cyanide leaching of

Thiol-functionalized MCM-48: an Effective Absorbent of Mercury Ions

Mercaptopropyl groups were grafted onto the pore walls of mesoporous molecular sieves MCM-48. The pore structures were characterized by powder X-ray diffraction and N2 adsorption analYSiS. Elemental analysis confirmed that the material with high organic moiety （2.2 mmol/g） had been obtained. ^13C MAS NMR verified the tethered organic groups. The thiol-functionalized MCM-48 showed effective capture of mercury ions, and all of the organic ligands were accessible for the binding of mercury ions.

Generation of Continuous-Wave 194 nm Laser for Mercury Ion Optical Frequency Standard

A 194-nm cw laser is an essential part in the mercury ion optical frequency standard. We report the generation of over 2mW continuous-wave radiation at 194nm in a beta barium borate crystal using a simple sum frequency mixing （SFM） system. One source beams at 718nm is resonantly enhanced with a cavity and the other at 266mn makes a single pass. Considering the walk-off effect in SFM, the source beam waists are designed to be elliptical, thus the conversion efficiency can be promoted. The 266-nm beam produced by frequency doubling of 532-nm laser is shaped close to the diffraction limit to achieve better mode matching.

Optimal Microwave Radiation Field Parameters for Mercury Ion Microwave Frequency Standards

We propose a method to determine the optimal power of the microwave resonance transition that simultaneously improves the signal-to-noise ratio and reduces line width based on saturation broadening theory and experiment. Saturation broadening spectra of the ground state hyperfine transition of trapped 199Hg＋ ions are measured and analyzed. The value of the optimal microwave power is obtained by using the proposed method and is verified. Rabi oscillations decay spectra of trapped 199Hg＋ ions are observed and the optimal microwave irradiation time for the maximum transition signal intensity is determined. This work will help to improve the short-term frequency stability of the mercury ion microwave frequency standard.

High extraction ability of 1,3-dialkynyl calixarene towards mercury(Ⅱ) ion

The reaction of 1,3-dipropyn-2-yloxycalix[4]arene with mercury（U） acetate could give mercury-containing alkynyl calixarene polymer. The extraction behavior of 1,3-dipropyn-2-yl-oxycalix[4]arene towards mercury（Ⅱ） ion was examined. When the mole ratio of Hg^2＋/calixarene was 1：1, the extractive percent can reach to 99.1%, and the extraction capacity was up to 431 mg/g. It could also decrease the Hg^2＋ concentration from 5 to 0.85 mg/L, which was only 17% of the national standard of effluent and satisfied the national standard of drinking water. The extraction process included chemical reaction.

Bioadsorption of Cd (II) from Contaminated Water on Treated Sawdust: Adsorption Mechanism and Optimization

Sawdust (SD) a very low cost material has been utilized as adsorbent material for the removal of Cd (II) from aqueous solutions after treatment with mono methylol urea (MMU) in the presence of zinc chloride as a catalyst to form MMU-SD. The reaction of MMU-SD was carried out under different conditions including MMU/SD molar ratio, catalyst concentration, and reaction time and temperature. Adsorption studies have been carried out to determine the effect of agitation time, pH, adsorbent and adsorbate concentrations on the adsorption capacity of Cd (II) ions onto MMU-SD. Langmuir, Freundlich and Redlich-Peterson isotherm models were applied in the adsorption studies. The experimental data were analyzed using various sorption kinetic models. The removal processes of Cd (II) onto MMU-SD particles could be well described by the pseudo-second order model. The maximum adsorption capacity of Cd(II) onto MMU-SD was 909 mg/g. Similarly, the Freundlich constant 1/n value was 0.45.

Sesame Husk as Adsorbent for Copper(II) Ions Removal from Aqueous Solution

In this study, the adsorption behavior of copper(II) ions from aqueous solutions onto sesame husk (SH) was investigated. The effect of different parameters such as pH, contact time, adsorbent dosage, adsorbate concentration, temperature and agitation speed was studied. Thermodynamic parameters, equilibrium isotherms and kinetic data have been evaluated. The functional groups and surface morphology of SH adsorbent were characterized by FTIR and SEM. Adsorption equilibrium isotherms were expressed by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) adsorption models and it was found that Langmuir adsorption model fits the experimental data better than Freundlich and D-R models. The adsorption can be best described by the pseudo second-order kinetic model.

Atomic Absorption and Vibrational Spectral Magnetic Studies on the Removal of Cu(II) and Co(II) Ions Using Synthetic Nano Adsorbent Fe₃O₄

Adsorption of Cu(II) and Co(II) from aqueous solutions on synthetic nano Fe3O4 has been studied. The effect of experimental parameters such as initial concentration of the metal ions, adsorbent dosage, contact time and pH has been investigated. Optimum removal efficiency of Cu(II) ion was found to be 97.8% with the dose rate of 1.07 g/L in 60 minutes at pH = 5.5 and for Co(II) ion, it was found to be 99.2% with the dose rate of2.57 g/L in 10 minutes at pH = 5.4. The removal of Co(II) ions require only 10 minutes with the efficient removal of 99.2%, whereas Cu(II) ions require 60 minutes with the maximum removal of 97.8%. In order to understand the effective removal of Cu(II) and Co(II) ions on Fe3O4, room temperature magnetic measurement was carried out using Vibrational Spectrum Magnetometer (VSM), before and after adsorption with a maximum applied magnetic field of 20,000 G.

Investigati on sonsimultaneous determination of silver and mercury in catalytic－ligandsub stitution reaction with stopped－flow technique calibrated by synergistic effect

Ｉｎｖｅｓｔｉｇａｔｉｏｎｓｏｎｓｉｍｕｌｔａｎｅｏｕｓｄｅｔｅｒｍｉｎａｔｉｏｎｏｆｓｉｌｖｅｒａｎｄｍｅｒｃｕｒｙｉｎｃａｔａｌｙｔｉｃ－ｌｉｇａｎｄｓｕｂｓｔｉｔｕｔｉｏｎｒｅａｃｔｉｏｎｗｉｔｈｓｔｏｐｐｅｄ－ｆｌｏｗｔｅｃｈｎｉｑｕｅｃａｌ...

Demineralised Lignite Fly Ash for the Removal of Zn(II) Ions from Aqueous Solution

Among the various possibilities of limiting the disposal of fly ashes (lignite), their reutilization as adsorbent materials is worthy of consideration. To this end, proper ashes beneficiation techniques can be put into practice. The adsorption of toxic compounds from industrial wastewater is an effective method for both treating these effluents and recycling lignite fly ash. The aim of this paper is to give a contribution for understanding the relationships among beneficiation treatments, adsorbent properties and adsorption mechanism and efficiency. In this context, the lignite fly ash was demineralised using concentrated HCl and HF (FA-DEM) and was used as adsorbent for Zn(II) ions from aqueous solutions. Batch experiments were carried out under various adsorbent dosages, pH, contact time and different metal ion concentrations. For FA-DEM, the 57.7% removal of Zn(II) ion was achieved under the optimum conditions of adsorbent dosages of 4 g/L, pH at 6, temperature at 303 K and the contact time of 1.15 h. The adsorption of Zn(II) ions onto FA-DEM followed the pseudo second order kinetics. The Langmuir isotherm model best represented the equilibrium data.

Preparation, Characterization, and Application of Manganese Oxide Coated Zeolite as Adsorbent for Removal of Copper(II) Ions from Seawater

The present study is aimed to examine the adsorption characteristics of Cu(II) by using the novel cellulose acetate composite and to apply it for the removal of Cu(II) from real wastewater samples. In order to achieve this objective, ethylenediamine, diethylenetriamine, triethylenetetramine and te-traethylenepentanene were used for immobilization of grafted cellulose acetate-nanoscale manganese dioxide. Cellulose was extracted from mangrove species Avicennia marina and converted to cellulose acetate then it was formed composite with nano-manganese dioxide via precipitation of nano-manganese dioxide on it. The composite was grafted with acrylamide monomer before immobilization. The synthesized compounds were used for adsorption of Cu(II) and characterized by FT-IR, TGA and SEM. The adsorption characteristics of synthesized sorbents were optimized. Langmuir and Freundlich models were used to establish sorption equilibria. The analytical applications of these modified materials were applied successfully for the removal of Cu(II).

Application of 3A Zeolite Prepared from Venezuelan Kaolin for Removal of Pb (II) from Wastewater and Its Determination by Flame Atomic Absorption Spectrometry

This work consists in the use of a 3A zeolite (K-LTA) obtained by a process of exchange of sodium for potassium (4A zeolite), synthesized from Venezuelan kaolin for the removal of Pb (II) ions from aqueous solutions by batch process mode in order to consider its application in treating industrial wastewaters. The 3A zeolite was characterized for X-ray powder diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR) and scanning electron microscopy and energy dispersive X-ray microanalysis (SEM-EDX). The metal concentration in the equilibrium Ce (mg·L-1) after adsorption with 3A zeolite was analyzed using flame atomic absorption spectrometry (FAAS). The influences of the solution pH, contact time, metal initial concentration and adsorbent dosage have been studied. The retention of metal occurring at pH values around 6.5 and the adsorption equilibrium was obtained at 60 min. The equilibrium process was well described by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. The Langmuir parameters qm (mg·g-1) and b (L·mg-1) (which are related to the sorption capacity and constant of sorption energy) obtained were 14.64 and 5.42 respectively. The Pb (II) experimental uptake was about 14.56 mg·g-1, a little smaller than the theoretical one given by Langmuir isotherm model. The regression parameters and correlation coefficients (R) indicate that the adsorption data for Pb (II) removal fit better the Langmuir isotherm model. Moreover, 0 1/n 1 (1/n is 0.13), indicating that adsorption of metal ions on the zeolite, is a favorable physical process. The application of removing of the metal lead from real samples was examined by industrial wastewater samples. For all samples, the percentage of recovery was found with accuracy of more than 98%. The present work suggests 3A zeolite used as a sorbent material with relatively low cost, obtained from Venezuelan raw material;it is a candidate for removal lead ion and probably other cationic heavy metal species from wastewater.

Some Hybrid Systems of Chiral Schiff Base Zn(II) Complexes and Photochromic Spiropyrans for Environmental Ion Sensing

This is a review article including our recent results and some previous photo functional hybrid system having potential applications for environmental ion sensing. We have prepared several new and known chiral Schiff base Zn(II) complexes and measured (and also calculated) absorption and fluorescence spectra for sole complexes. After assembling hybrid systems with 1,3,3-trime- thylindolino-6’-nitrobenzopyrylospiran (SP) in methanol solutions, we measured spectral changes before and after alternate irradiation of UV and visible light. Intensity of fluorescence spectra for pale yellow Zn(II) complexes (λem = 450 nm, λex = 270 and 360 nm) was quenched by colorless SP (λem = 533 nm, λex = 612 nm). After UV light irradiation to form purple merocyanine (MC), photoisomerization resulted in changes of the intensity of absorption spectra as well as fluorescence spectra. Thus the hybrid systems could successfully act as molecular logic circuit by input (excitation by light) and output (intensity of fluorescence peaks). Moreover, we investigated concentration dependence of doped Zn(II) and Cu(II) ions to confirm quenching of intensity of fluorescence peaks by Zn(II) and Cu(II) MC complexes for metal ion sensing in solutions.

Bioremediation of Lead(II) from Polluted Wastewaters Employing Sulphuric Acid Treated Maize Tassel Biomass

The ability to modify a waste by-product precursor, maize tassel biomass using sulfuric acid as the activating agent with specific focus on Lead(II) ion from water has been proposed. The treating of maize tassel using sulphuric acid is believed to enhance sorption capacity of Lead(II) ions. For this, batch adsorption mode was adopted for which the effects of initial pH, adsorbent dosage, contact time and initial concentration were investigated. Consequently, it was found that the adsorbent capacity depends on pH;since it increases up to 4.5 and then decreases. The highest percentage of Lead(II) ion removal was achieved in the adsorbent dosage of 1.2 g and at an initial concentration of 10 mg/L metal ion. In an attempt to determine the capacity and rate of Lead(II) removal, isotherm and kinetic data were modeled using appropriate equations. To this end, the adsorption data fitted best into the Langmuir model with an R2 (0.9997) while kinetically the Lead(II) adsorption followed the pseudo-second-order model. Furthermore, as a way to address issues related to sustainability, maize tassel is recommended since the process is considered to be a dual solution for environmental cleaning. From one side, it represents a better way to dispose the maize tassel which has no use after fertilization and on the other hand it is an economic source of carbonaceous materials.

Effect of Hg(II) and Pb(II) Ions on C-Phycocyanin (<i>Spirulina</i><i>platensis</i>)

Influence of Hg(II) and Pb(II) ions on C-Phycocyanin (C-PC) from cyanobacteria Spirulina platensis was investigated using Fluorescence spectroscopy. Fluorescence measurements demonstrate quenching of C-PC emission by Hg(II) and Pb(II), and blue shifts in the fluorescence spectra. The effect of DNA on the fluorescence of Hg(II)-and Pb(II)-C-PC (from Spirulina platensis) complexes was also studied. It was shown that the fluorescence intensity of Hg-C-PC after addition of DNA gave rise to the fluorescence buildup. At the same time, addition of DNA to the Pb(II)-C-PC complexes showed no such effect. In the case of Hg(II)-C-PC, fluorescence intensity significantly decreases in time, while for Pb(II)-C-PC, decrease of the fluorescence intensity is not significant, but blue shift of the peak takes place.