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.

Fe(II)改性蒙脱石对土壤汞的吸附固定机理探究

为明确Fe-MMT对土壤汞离子(Hg^(2+))的吸附、解吸特性及潜在作用机理,采用FeSO_(4)·7H_(2)O改性钠基蒙脱土(Na-MMT),合成了Fe(II)基蒙脱石(Fe-MMT),并探究了不同pH值、吸附剂用量、Hg^(2+)初始浓度和反应时间等条件下,Fe-MMT对土壤Hg^(2+)的吸附解吸特性、吸附动力学和等温吸附模型。结果发现:在pH=5、吸附剂用量为0.5 g、Hg^(2+)初始浓度为170 mg/L、反应时间为0.5 h的条件下,Fe-MMT对土壤Hg^(2+)的去除率高达76.8%;Fe-MMT对Hg^(2+)+的吸附过程符合Langmuir等温吸附模型,伪二阶动力学模型可较好地拟合吸附动力学行为,表明该吸附过程主要为单分子层吸附,且主要发生在吸附剂表面的均相反应位点上;结合微观结构表征,发现Fe-MMT对土壤Hg^(2+)的吸附主要通过-S^(2-)、-SH和-OH与Hg^(2+)进行络合,以及Fe^(2+)与Hg^(2+)的原位共沉淀络合引起的;Fe-MMT在水-土混合体系中的解吸率为9.7%,表明Fe-MMT对土壤Hg^(2+)具有较强的固定作用。可见,Fe-MMT具有修复Hg污染土壤的潜力。

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.

Inhibition of cysteine protease papain by metal ions and polysulfide complexes,especially mercuric ion

Aim Cysteine proteases are closely associated with many human and non-human pathological processes and are potential targets for metal ions especially Hg^2＋ and the related species. In the present work, on the basis of to the general study on the effects of some metal ions on the activity of papain, a well-known representative of cysteine protease family, the inhibitory effects of Hg^2＋ and polysulfide complexes were studied. Results All the metal ions tested （Hg^2＋, Cu^2＋, Ag^＋, Au^3＋, Zn^2＋, Cd^2＋, Fe^3＋, Mn^2＋, Pb^2＋, Yb^3＋） inhibit the activity of papain anda good correlation between the inhibitory potency and softness-and-hardness was observed. Among the metals, Hg^2＋ was shown to be a potent inhibitor of papain with a Kiof 2 × 10^-7 mol·L^-1 among. Excessive amounts of glutathione and cysteine could reactivate the enzyme activity of papain deactivated by Hg^2＋. These evidences supported that Hg^2＋ might bind to the catalytic site of papain. Interestingly, Hg （Ⅱ） polysulfide complexes were for the first time found to inhibit papain with a Ki of 7 × 10^-6 mol·L^-1, whose potency is close to a well known mercury compound, thimerosal （Ki=2.7 × 10^-6）. In addition, Hg （Ⅱ） polysulfide complexes exhibit good permeability （ 1.9 × 10-5 cm· s^-1） to caco-2 monolayer. Conclusion These results suggested that mercury polysulfide complexes might be potential bioactive species in the interaction with cysteine proteases and other- SH-content proteins, providing a new clue to understand the mechanism of the toxicological and pharmacological actions of cinnabar and other insoluble mercury compounds.

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.

离子印迹磁性碳纳米球基电化学传感器用于铜(II)的选择性检测

本文报道一种基于Cu(II)离子印迹聚合物为识别元件的电化学传感器。通过耦合表面离子印迹和电化学沉积的制备方法,制备了由磁性碳纳米球组成的离子印迹聚合物电极。所组装的传感器表现出对Cu(II)检测的特异识别性和高灵敏特性。通过场发射扫描电子显微镜和透射电子显微镜对印迹聚合物的微观形貌进行表征,采用傅里叶变换红外光谱对其官能团和化学结构进行表征。传感器电化学性能表明,与非印迹电极和裸电极相比,印迹电极对Cu(II)具有更强的选择性和更高的灵敏度。传感器对浓度为10^(-6)至10^(-10) mol L^(-1)的Cu(II)表现出良好的线性相应电流,其检测限提升至5.138×10^(-16) mol L^(-1)(S/N=3)。此外,该传感器具有良好的抗干扰性、重现性和稳定性,为金属离子的检测提供了新的策略。

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).

Adsorption characteristics of Pb(Ⅱ)ions on sulfidized hemimorphite surface under ammonium sulfate system

In this work,the effect of ammonium sulfate on the adsorption characteristics of low-concentration Pb(Ⅱ)ions on the sulfidized hemimorphite surface was comprehensively investigated.The results showed that ammonium sulfate could increase the maximum recovery of hemimorphite from 69.42%to 88.24%under a low concentration of Pb(Ⅱ)ions.On the hemimorphite surface pretreated with ammonium sulfate,the adsorption of Pb(Ⅱ)ions was enhanced and the main species of Pb adsorbed was changed from Pb―O/OH to PbS.This was due to the larger amount of ZnS providing more effective adsorption sites for Pb components to generate Pb S.Meanwhile,the intensity of ZnS decreased with the formation of PbS,demonstrating that ZnS was covered by PbS which formed later on the mineral surface.It was beneficial for the adsorption of butyl xanthate on the hemimorphite surface to form more hydrophobic substances.As a result,ammonium sulfate played a crucial role in realizing the efficient recovery of hemimorphite.