Macrocyclic compound as ionophores in lead（Ⅱ） ion-selective electrodes with excellent response characteristics

Macrocyclic compounds, such as crown ethers, azacrown ethers, thiacrown ethers, calixarenes and porphyrins, which act as ionophores in lead（Ⅱ） ion-selective electrodes, are systematically summarized based on the latest literatures. The molecular structure characteristics of the ionophores are generalized. The modification regulations for the substituted ionophores are elaborated with the purpose of improving the response features of the lead（Ⅱ） ion-selective electrodes assembled by them. It is pointed out that the introduction of pendant moieties which contain soft base coordination centers like N, S and P atoms is in favor of adjusting the cavity size and conformation of the macrocyclic com- pounds. Furthermore, there is synergic effect between the cavity and the donor sites of the ligand and thus the selective complexation of lead ions is easily realized, resulting in significant avoidance of the interference from other metal ions. The macrocyclic ionophore having the best response characteristics thus far was found to be N,N＇-dimethylcyanodiaza-18-crown-6 with the detection limit of 7.0×10^8 （14.5 μg/L）, which is one of the uncommon ionophores that can really eliminate the interference from silver and mercury ions. The selectivity coefficients of the ionophore for lead ions over other metal ions, such as alkali, alkaline earth and transition metal ions are in the order of 10^-4 or smaller, where the selectivity coefficient of lead（Ⅱ） over mercury（Ⅱ） ions is much lower, down to 8.9×10^4, The structure design idea for high-performance ionophore is proposed according to present results. The incorporation of nitrogen atom, especially cyano group or thiocyano group or amino/imino groups, rather than thio atom alone could result in new excellent lead ionophores. The aborative design for metacyclophanes containing aromatic nitrogen atoms with the aim of creating excellent ionophores would also become a potential research trend. The lead（Ⅱ） ion-selective electrodes have shown wid     

Macrocyclic compound as ionophores in lead(Ⅱ) ion-selective electrodes with excellent response characteristics

Macrocyclic compounds,such as crown ethers,azacrown ethers,thiacrown ethers,calixarenes and porphyrins,which act as ionophores in lead(Ⅱ) ion-selective electrodes,are systematically summarized based on the latest literatures.The molecular structure characteristics of the ionophores are general-ized.The modification regulations for the substituted ionophores are elaborated with the purpose of improving the response features of the lead(Ⅱ) ion-selective electrodes assembled by them.It is pointed out that the introduction of pendant moieties which contain soft base coordination centers like N,S and P atoms is in favor of adjusting the cavity size and conformation of the macrocyclic com-pounds.Furthermore,there is synergic effect between the cavity and the donor sites of the ligand and thus the selective complexation of lead ions is easily realized,resulting in significant avoidance of the interference from other metal ions.The macrocyclic ionophore having the best response characteris-tics thus far was found to be N,N'-dimethylcyanodiaza-18-crown-6 with the detection limit of 7.0×10-8(14.5 μg/L),which is one of the uncommon ionophores that can really eliminate the interference from silver and mercury ions.The selectivity coefficients of the ionophore for lead ions over other metal ions,such as alkali,alkaline earth and transition metal ions are in the order of 10-4 or smaller,where the se-lectivity coefficient of lead(Ⅱ) over mercury(Ⅱ) ions is much lower,down to 8.9×10-4.The structure de-sign idea for high-performance ionophore is proposed according to present results.The incorporation of nitrogen atom,especially cyano group or thiocyano group or amino/imino groups,rather than thio atom alone could result in new excellent lead ionophores.The aborative design for metacyclophanes containing aromatic nitrogen atoms with the aim of creating excellent ionophores would also become a potential research trend.The lead(Ⅱ) ion-selective electrodes have shown widely potential applications in the potentiometric titration,and flow injection potentiometry,and in the direct determination of lead in stack emissions of lead smelters,and assay of lead in rocks,particularly in the direct measurements of trace amount of lead(Ⅱ) in human hair,blood,edible oil,food,water,and air.     

New structure model of oxygen-evolving center and mechanism for oxygen evolution in photosynthesis

So far, many important questions and problems concerning the structure and mechanism of photosynthetic oxygen evolution are still unsolved. On the basis of recent achievements in this field, a new structure model is proposed whereby two H2O molecules bind asymmetrically to two manganese ions (Mn1Ⅱ and Mn4Ⅲ) at the open end of "C" shaped cluster and keep rather large distance. Two histidine residues coordinate to the other two manganese ions in higher oxidation state (Mn2Ⅳ and Mn3Ⅳ ) through their nitrogen atoms of the imidazole. Cl bound as terminal ligand to Mn4Ⅲl is connected to Ca, and the latter is needed to maintain the special configuration of two Mn2O2 units by bridged-oxo and bridged-carboxylate ligands. The whole structure of oxygen evolution center is asymmetry. A new mechanism for oxygen evolution invokes predictions of asymmetric oxidation of two H2O molecules, dynamic structural changes of oxygen e-volving center and indirect proton transport, etc. Only in S2 state, could Mn1Ⅳ = O. intermediate with high oxidation potential be formed. The S2→S3 process occurs with significant structural changes, as well as intramolecular and intermolecular hydrogen transfer. The S3 state corresponds to intermediate of Mn1Ⅳ-O… H… O-Mn4Ⅳ . During S3→ [S4] →S0, the O-O bond is formed only in S4 state. The change of nucleophilic interaction between Cl and manganese ions different oxidation states has consequence for the significant structural changes in H2O oxidation process.     

Discussion of an Enrichment Mechanism of Precious Metals by Base Metals and Mattes in Pyrometallurgical Processes

The enrichment mechanisms of precious metals by base metals or their mattes in pyrometallurgical processes are discussed at the atomic level in this paper. The reasons brought forward for a trace amount of precious metals to be trapped into base metals or mattes are that the melted slag phases possess different chemical structures and properties from that of the melted base metal or matte phases. As for the melted slag phase, its formation is thought to depend on the covalent bonds and the ionic bonds between Si, O atoms and Ca2+, Mg2+, Fe2+ ions to tie up each other. Because the bridging electrons in the slag phase are all thought as the localized electrons, the precious metal atoms are not stable among them. However, as for the metal phase, its formation is thought depend on the metal bonds to bind up the metal atoms. Because the electrons in the metal phases can move freely among the atoms, the precious metal atoms that enter the metal phase can cause the system’s free energy to decrease. For the melted mattes phase,because it has high electrical conductivities (between 103～104 s·cm-1) at higher temperatures, and its temperature coefficients presents the negative values, its conductance mechanism belongs with the electronic conduction. The property of the mattes is in fact similar to that of the metal at their melted state, so the precious metal atoms will enter the matte phase instead of the slag phase in a mattesmelting process.     

Study on the electronic structure of nickel hydroxide by quantum chemical DV-Xα calculation

The electronic structures of atom clusters NiTO12H12^2＋ and NiTO12H9^- of β-Ni（OH）2 were calculated by quantum chemical DV-Xα method. By analyzing the state densities, orbital populations, net charges and electric charge density differences of the selected clusters, it was indicated that β-Ni（OH）2was not typical ionic crystal, and the bonds between Ni and O atoms had obvious covalent characteristics. The bonds between H atom and other atoms in the crystal structure were weaker, which ensured that H atoms can easily deintercalate and intercalate into β-Ni（OH）2. The structure of β-Ni（OH）2 was not changed by moderate de-intercalation of H atoms. However, with the excessive de-intercalation of H atoms, the structure of β-Ni（OH）2 changed and the electrochemical active properties were reduced.     

Synthesis, structure and superoxide dismutase activity of two self-assembly transition metal complexes containing a tridentate amino-Schiff base deviating from salicylaldehyde with glycine

Two new transition metal （Cu, Ni） complexes with amino-Schiff base ligand, （CgH7NO3）Cu（C14H12N2）.H2O （1） and （C9HTNO3）Ni（C3H4N2）3.H2O （2）, have been designed and synthesized in ethanol solution at room temperature. Both of the complexes have been characterized by elemental analysis, IR spectra, UV-vis spectroscopy and X-ray single crystal diffraction. For complex 1, the coordination environment of the central copper atom is a distorted square pyramid, and one-dimensional chain is formed through the inter-molecular hydrogen bonds （O4-H2W…O3, O4…H2W…O3#1 （#1： -x＋1, y, -z＋3/2）） and weak interactions （∏-∏ stacking interaction） between the phenyl rings. For complex 2, the nickel atom is 6-coordinated and in a distorted octahedral environment, and a discrete hydrogen-bond cluster （four molecules are connected by hydrogen bonds into a group） is formed via two types of intra-molecular hydrogen bonds （O-H...O, N-H...O） and inter-molecular hydrogen bonds （O-H...O, N-H...O）.     

Structure and ~(57)Fe conversion electron Mssbauer spectroscopy study of Mn-Zn ferrite nanocrystal thin films by electroless plating in aqueous solution

Mn1-xZnxFe2O4 thin films with various Zn contents and of different thickness were synthesized on glass substrates directly by electroless plating in aqueous solution at 90℃ without heat treatment.The Mn-Zn ferrite films have a single spinel phase structure and well-crystallized columnar grains growing perpendicularly to the substrates.The results of conversion electron 57Fe M?ssbauer spectroscopy(CEMS)indicate that the cation distribution of Mn1-xZnxFe2O4 ferrite nanocrystal thin films fabricated by electroless plating is different from the bulk materials' and a great quantity of Fe3 ions are still present on A sites for x>0.5.When the Zn content of the films increases,Fe3 ions in the films transfer from A sites to B sites and the hyperfine magnetic field reduces,suggesting that Zn2 has strong chemical affinity towards the A sites.On the other side,with the increase of the thickness of the films,Fe3 ions,at B sites in the spinel structure,increase and the array of magnetic moments no longer lies in the thin film plane completely.At x = 0.5,Hc and Ms of Mn1-xZnxFe2O4 thin films show a minimum of 3.7 kA/m and a maximum of 419.6 kA/m,respectively.     

Review on aggregation of acid extractants in solvent extraction of metal ions: remark on the general model

The aggregation behavior of various acid extractants in the solvent extraction systems of metal ions is re-examined and explained according to knowledge obtained in recent work. The conclusions are as follows. (1) Complexes formed by the extractants and metal ions can form reversed micelles in organic diluents, depending on the microstructures of the complexes. The dimers of the acid extractant cannot percolate to the metal-extractant aggregates, and the acid-salt complexes are always formed in the aggregates. The reversed micelles or the W/O microemulsions formed by different species cannot be associated with each other to form a unified aggregate. (2) In solvent extraction systems, hydration of the extractants and metal ions can be considered as the driving force of forming reversed micelles. (3) Information of the first approach to the insight of the bicontinuous microemulsion of NaDEHP shows that various components in the aqueous phase behave confined and very similar to the typical AOT/n-heptane W/O microemulsions. (4) In the extraction of lanthanide ions by the W/O microemulsion of sodium naphthenate, the saponification is a process of forming reversed micelle or W/O microemulsion, while the extraction step is a process of destroying reversed micelles or W/O microemulsion droplets.     

Structure-property relationship of potassium titanyl (KTP) isomorphous substituted crystal

KTiOPO-4(KTP) crystal is a nonlinear optical material with superior properties. The KTP structure, point group mm2, is typified by the chemical form {K++}〔Ti 4+〕O(P 5+)O-4, where the curly brackets indicate nine or eightfold coordination, the square brackets sixfold octahedral coordination and the parentheses fourfold tetrahedral coordination. Different isovalent and aliovalent substitutions in a given structure is quite interesting. The KTP-type structure is extremely accommodating with respect to partial or complete isomorphous substitution which may be especially significant in optical devices such as waveguides. A monographic review of the structure-property relationship of KTP isomorphous substitution is briefly and precisely presented. It is shown that the properties of KTP are very sensitive to its structure. Among the composition, structure and properties of KTP-type crystal, the structure is the core because it is a link between the composition and properties.     

Synthesis and crystal structure of tetranuclear zinc benzoate

A tetranuclear zinc benzoate Zr4O(C6H5CO2)6 was synthesized and characterized by X-ray single crystal determination. It crystallizes in cubic, space group Ia-3d. Its crystal cell is very large, α=4.10063(18)nm, V=68.953(5)nm^3 and Z=48. The structure is composed of discrete Zr4O(C6H5CO2)6 molecules. In each molecule, four zinc atoms are held together by a central oxygen atom, which results in the formation of a regular tetrahedron. All benzoate ligands coordinate to zinc atoms in a bidentate bridging mode. Each zinc atom is in a slightly distorted tetrahedral geometry, coordinated by three benzoate oxygen atoms and the central oxygen atom. The intermolecular interactions result in the formation of a three-dimensional supramolecular framework, with non-intersecting parallel channels.     

Effects of electric pulse on microstructure of Al-Si alloy in liquid and solid states

In order to investigate the change in liquid microstructure of Al-Si alloy treated by electric pulse (EP), X-ray diffraction tests with liquid Al-Si alloy and ZL109 alloy treated or not by EP were carried out. The results show that the number of Al-Si atomic clusters decreases and that of Al-Al and Si-Si atomic clusters increases for the treated samples. The tests with ZL109 alloy indicate that a large amount of primary crystal Si appears in the solidified microstructure after treated by EP. It is found that EP canchange the microstructure of liquid metal by affecting the probability of electrons appearing in different atoms (Al and Si) in the liquid metal.The combining force of different atoms decreases relatively, and that of the same atoms increases, which is the main reason of reducing the atomic cluster with different atoms (Al-Si) and increasing the atomic cluster with the same atoms (Al-Al, Si-Si). The increasing of the atomic cluster with the same atom cluster resulted in the increasing of Si activity and the higher point of eutectics in the phase diagram. It makes a lot of primary silicon appeared in ZL109 alloy.     

Influence of PPCA inhibitor on CaCO3 scale surface deposition and bulk precipitation at elevated temperature

Scale formation is a serious and costly problem encountered in the oil and gas industry. Polyphosphinocarboxylic acid (PPCA) is a common commercial organic scale inhibitor used in the oil and gas industry which is normally referred to a nucleation inhibitor. In this paper, the effect of PPCA on calcium carbonate scale is studied systematically and some new insights into the mechanisms of PPCA inhibition are given. Traditionally, the studies of scale formation and inhibition have focused on bulk precipitation or surface deposition. Few studies have focused on the difference between surface deposition and bulk precipitation processes. In this paper, the effect of PPCA inhibitor on calcium carbonate scale formation is studied both in the bulk solution and on the metal surface in supersaturated scale formation solutions which represent typical waters encountered in oil and gas production. It is clear that PPCA inhibits both bulk precipitation and surface deposition but to a different degree. At 4 ppm PPCA, the inhibition efficiency of surface deposition is greater than the inhibition efficiency of bulk precipitation. It is assumed that the inhibitor film formed on the metal surface at the highest concentration of PPCA (4 ppm) prevent the adsorption of scale crystals on the metal surface. In addition, PPCA suppresses aragonite and calcite crystal formation and results in the least stable vaterite crystal dominating the scale.     

Palladium（ Ⅱ ） and Platinum（ Ⅱ ） Compounds Derived From Potentially Terdentate Ligands

Transition metal complexes derived from potentially terdentate ligands have attracted great interest in the late years. Among all the examples described so far, those containing palladium（ Ⅱ ） or platinum（ Ⅱ ） and ligands holding three heteroatoms with different donor abilities are particularly relevant. In compounds of this kind, the potential hemilability of one of the terminal σ（M-donor atom） bonds, plays an important role in the view of their applications in homogeneous catalysis. On the other hand, it is well-known that in dimetallic complexes the presence of two different metals in a close vicinity may influence their mutual cooperation in a wide variety of processes. Besides that, some examples of the utility of chiral palladium（ Ⅱ ） as well as platinum（ Ⅱ ） complexes as precursors for organic and/or organometallic synthesis, as chiral recognitors or discriminators, or even in Bio-Medicine have also been reported. However, chiral heterodimetallic compounds holding ferrocenyl units and potentially terdentate ligands are scarce.     

Structures and stability of (HAlNH)n (n=1－15)

The geometries, electronic states, vibrational spectra and thermodynamic properties for (HAlNH)_n clusters with n=1－15 have been investigated using the ab initio DFT/B3LYP method with basis sets 6-31G* and their ground state structures obtained. Comparison of the (HAlNH)_nwith (AlN)_n clusters shows that the skeletons of (HAlNH)_nconsist of four-membered and six-membered rings made of Al-N bonds, and either Al or N atom forms four bonds in which three ones are Al-N bonds and the rest is Al-H or N-H bond. The number of Al-N bonds of (HAlNH)_n is equal to that of (AlN)_n. The magic number regularity of (HAlNH)_n is n =2, 4, 6, 8, etc., all of which are even numbers.     

New crystal structure of molecular complex 1-piperidine carboxylate-piperidinium-H<Subscript>2</Subscript>O studied by X-ray single crystal diffraction

Piperidine absorbs CO2 and H2O in air to form a molecular complex： piperidium-l-piperidinecarboxylate-H2O. The structure of the complex was characterized by X-ray single crystal diffraction. The crystal structure was determined to be triclinic, space group P1^-with a=0.648 6（8） nm, b=0.809 200） nm, c= 1.357 1（16） nm, a=96.96706）°, β =102.506（15）°,γ=104.202 05）°, Z=2. The complex is stabilized via five hydrogen bonds between the three components, N-O electrostatic interaction and O-O interaction （electron transfer） betweenl-piperidinecarboxylate and H2O. Due to electron transference of carbamate ion, the oxygen atom in water molecule is strongly negatively charged and the O-H bond is considerably shorter than that of the free molecule of water. The formation of the molecular complex is a reversible process and will decompose upon heating. The mechanism of formation and stabilization is further investigated herein.     

Boron-based Drug Design for Cancer Therapy

1 Results Selective inhibition of protein tyrosine kinases is gaining importance as an effective therapeutic approach for the treatment of a wide range of human cancers.The epidermal growth factor receptor (EGFR) protein tyrosine kinase is one of the important kinases that play a fundamental role in cell growth signal pathways.We focused on the 4-anilinoquinazoline framework,which is observed in both compounds as a common structure.A boron atom has a vacant orbital and interconverts with ease between the neutral sp2 and the anionic sp3 hybridization states.This generates a new stable interaction between the boron atom and a donor molecule through a covalent bond.Therefore,it is expected that the boron atoms introduced into quinazoline framework would interact with a target protein not only through hydrogen bonds but also through covalent bonds,which would produce potent biological activity We introduced a boronic acid moiety into R1 and R3 groups as shown in Scheme 1.     

Mechanism of diamond-to-graphite transformation at diamond-stable conditions

The diamond-to-graphite transformation at diamond-stable conditions is studied by temperature gradient method （TGM） under high pressure and high temperature （HPHT）, although it is unreasonable from the view of thermodynamic considerations. It is found that, at diamond-stable conditions, for example, at 5.5 GPa and 1550 K, with fine diamond grits as carbon source and NiMnCo alloy as metal solvent assisted, not only large diamond crystals, but metastable regrown graphite crystals would be grown by layer growth mechanism, and the abundance of carbon source in the higher temperature region is indispensable for the presence of metastable regrown graphite crystals. From this transformation, it is concluded that, with metal solvent assisted, although the mechanism of crystal growth could be understood by the macro-mechanism of solubility difference between diamond and graphite in metal solvents, from the point of micro-mechanism, the minimum growth units for diamond or graphite crystals should be at atomic level and unrelated to the kinds of carbon source （diamond or graphite）, which could be accumulated free-selectively on the graphite with Sp2Tr or diamond crystals with sp3 bond structure.     

Molecular orbital study on antiferromagnetic coupling mechanism in a silver (I) complex

Typically, magnetic interactions between paramagnetic centers through diamagnetic metal ions are negligibly small or weakly antiferromagnetic[1]. However, it has been proven that some metal complexes with organic radical ligands, in which the metal ions are diamagnetic, mediate substantial magnetic interactions. For example, metal complexes with semiquinones[2―4] show that a variety of magnetic interactions depend on metal ions and coordina-tion geometries, and the magnitude of the magnetic i…     

Granite landform characteristics, distribution and evolution patterns in Huangshan Mt.

The various types of granite landforms in the Huangshan Mt. are distributed in a concentric pattern. The remaining parts of the planation surface are in the center; domical peaks, castle peaks, pointed peaks, and ridges are arranged from the center to the periphery accordingly. This reveals that knick points are still near the center and the center area is the common divide of the radial water system. It is inferred that the granite bodies in the Huangshan Mt. were exposed to erosion in Miocene and Pliocene, and the planation surface was also formed then. After the slight uplift in late Pliocene, a light-incised surface was formed. Then, in early Quaternary, there were intense uplifts and incisions so that deep incised surface was formed. The above process is still in progress, and results in high peaks and deep gorges outside of the center area. However, due to the limited catchment area in the center, headward erosion is mild, and the current landforms in the Huangshan Mt. can be maintained for a long time.     

Structure of aqueous sodium sulfate solutions derived from X-ray diffraction

A rapid liquid X-ray diffractometer was used to study the time-averaged and space-averaged structure of aqueous sodium sulfate solutions at 298 and 323 K. Difference radial distribution functions of the solutions were obtained from accurate diffraction data. The interaction distances of Na^＋-OH2 and S-H2O in solutions were found to be 0.235 and 0.385 nm, respectively, after deconvolution of superposition peaks by Gaussian multi-peak fitting program. The characteristic distance of the NaSO; contact ion pairs in higher concentration solutions was determined to be 0.345 nm, suggesting that the Na^＋ ions coordinated with SO4^2- ions in the mono-dentate form. Effects of concentration and temperature on the hydration structure of the solutions were discussed in the present paper. With a decrease in concentration, the contributions of the H2O to the diffraction pattern increase, the average coordination number of the Na^＋ ions hardly changes, while the hydration number of SO4^2- ions increases slightly. The formation of NaSO; contact ion pairs becomes easier at higher temperature. The structure of hydrogen bond in dilute solutions is broken to a considerable extent with rising temperature, and the peak at 0.290 nm splits into two peaks at 0.275 and 0.305 nm, respectively.