Preliminary Investigation of Copper(II) Ion Binding or Complex Coordination in Lysozeme Molecules

Hydrophobic Val derivative Schiff base copper(II) complexes and dipeptide (AlaAla, GlyGly) derivative Schiff base copper(II) complexes were introduced into egg white lysozyme. X-ray crystal structure analysis revealed amino acid derivative Schiff base copper(II) complexes were obtained. Herein we discuss primarily on the binding mode of copper(II) of the complexes obtained with egg white lysozyme. The electron density of copper(II) ions was confirmed by X-ray crystal structure analysis. The Val derivative Schiff base copper(II) complex was weakly bound at Arg114 of egg white lysozyme. In other copper(II) complexes, binding of copper(II) ions with dissociated ligands to various residues was observed. The binding sites of copper(II) ions were compared with computational scientific predictions.

Stoichiometry and Stability Constant Values for Copper (II) Chelates with Ethylene Diamine in Deep Eutectic Solvents (DES) (Ethaline) Solutions

In this study we used the deep eutectic solvents (ionic liquids) to investigate the reaction between copper (II) with ethylene diamine (en). Two of the existing methods for analyzing spectrophotometric measurements have been applied for establishing, the stoichiometry and whenever possible, the stability constants of the chelates formed. The method of continuous variations was necessary to determine first whether, the metal ion and the ligand ethylene diamine form one or more than one chelate, when more than one chelate formed, the results obtained depend on the wavelength and for meaningful conclusions the wavelengths were carefully selected. The empirical formulae of the chelates were further substantiated by the molar ratio method. The effect of time and temperature on the formation and stability of these chelates in solution is also studied. The stability constants, K1 and K2 for the copper (II) chelates were calculated, though reliable, and are comparable to literature values.

Role of copper chelating agents: between old applications and new perspectives in neuroscience

The role of copper element has been an increasingly relevant topic in recent years in the fields of human and animal health, for both the study of new drugs and innovative food and feed supplements. This metal plays an important role in the central nervous system, where it is associated with glutamatergic signaling, and it is widely involved in inflammatory processes. Thus, diseases involving copper(Ⅱ) dyshomeostasis often have neurological symptoms, as exemplified by Alzheimer's and other diseases(such as Parkinson's and Wilson's diseases). Moreover, imbalanced copper ion concentrations have also been associated with diabetes and certain types of cancer, including glioma. In this paper, we propose a comprehensive overview of recent results that show the importance of these metal ions in several pathologies, mainly Alzheimer's disease, through the lens of the development and use of copper chelators as research compounds and potential therapeutics if included in multi-target hybrid drugs. Seeing how copper homeostasis is important for the well-being of animals as well as humans, we shortly describe the state of the art regarding the effects of copper and its chelators in agriculture, livestock rearing, and aquaculture, as ingredients for the formulation of feed supplements as well as to prevent the effects of pollution on animal productions.

Role of copper in central nervous system physiology and pathology

Copper is a transition metal and an essential element for the organism,as alterations in its homeostasis leading to metal accumulation or deficiency have pathological effects in several organs,including the central nervous system.Central copper dysregulations have been evidenced in two genetic disorders characterized by mutations in the copper-ATPases ATP7A and ATP7B,Menkes disease and Wilson’s disease,respectively,and also in multifactorial neurological disorders such as Alzheimer’s disease,Parkinson’s disease,amyotrophic lateral sclerosis,and multiple sclerosis.This review summarizes current knowledge about the role of copper in central nervous system physiology and pathology,reports about unbalances in copper levels and/or distribution under disease,describes relevant animal models for human disorders where copper metabolism genes are dysregulated,and discusses relevant therapeutic approaches modulating copper availability.Overall,alterations in copper metabolism may contribute to the etiology of central nervous system disorders and represent relevant therapeutic targets to restore tissue homeostasis.

基于区间毕达哥拉斯犹豫模糊熵和交叉熵的ELECTRE II决策方法

针对属性权重完全未知或部分已知,属性值为区间毕达哥拉斯犹豫模糊数的多属性决策问题,提出了基于区间毕达哥拉斯犹豫模糊熵和交叉熵的ELECTRE II法。首先给出区间毕达哥拉斯犹豫模糊数的区间形式的得分函数和精度函数,定义新的距离测度。然后基于区间毕达哥拉斯犹豫模糊数的模糊因子、直觉因子和幅度因子,给出熵和交叉熵公式,并证明其性质,提出了基于熵和交叉熵确定属性权重的方法。最后提出了区间毕达哥拉斯犹豫模糊环境下的改进的ELECTRE II法,利用综合优势值对方案进行排序,并通过算例和比较分析验证了该方法的可行性和有效性。

基于改进NSGA-II的轨道交通接驳公交线路优化

为解决接驳公交线路规划不合理和时间安排不完善的问题,提出了基于改进NSGA-II算法的环形接驳公交线路优化方法。首先,结合双层规划理论,以乘客出行时间成本最小化、公交企业运营收益和接驳公交服务率最大化为目标函数,以接驳公交线路站点数、线路长度和发车频率作为约束条件构建上层模型,采用Logit模型构建了下层接驳客流分配模型;其次,运用Floyd算法对NSGA-II算法的初始化种群进行了优化,针对所提出的模型设计了模型求解流程;最后,以哈尔滨市轨道交通1号线医大一院轨道交通站为案例,运用笔者提出的多目标双层规划模型和算法进行求解,并与原NSGA-II算法和基于Logistic混沌映射的NSGA-II算法进行对比。研究结果表明:基于Floyd算法改进的NSGA-II算法在多目标双层规划模型求解时,收敛速度更快效果更好,求解结果可以在Pareto前沿得到多个相互非支配的最优解;不同解集对应目标函数值不同,但可以达到接驳公交网络整体效益最优,采用折衷最优解集表述求解结果。

Synthesis, Structure and Fluorescence of a Copper(II) Complex [Cu_2(bipy)_2(Hpht)_2Cl](Hpht)(bipy=2,2'-Bipyridine,H_2pht=o-Phthalic Acid)

The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.

Synthesis and Crystal Structure of Tri(4-(3-hydroxy2-ethyl-4-pyridinone-1-yl)-aniline Condensation Salicylaldehydato) Monohydratotricopper(II)Dimethylformamide Monohydrate Solvate

The title complex [Cu3L3(H2O)]DMFH2O (H2L = 4-(3-hydroxy-2-ethyl-4- pyridinone-1-yl)-aniline condensation salicylaldehyde) was obtained. The single-crystal X-ray study shows that it is a trinuclear compound [Cu3(C20H15N2O3)3(H2O)]DMFH2O. The coordi- nation sphere about each copper ion in the complex consists of two oxygen atoms from hydroxylpyridinone moiety of one ligand and one oxygen and one nitrogen atoms from salicyladehyde Schiff-base moiety of another ligand arranged in a slightly distorted square planar geometry. Among the three copper ions, one (Cu(2)) is coordinated by the other oxygen atom of water molecule on the fifth coordinate position to form a distorted square pyramid geometry. The crystal is of monoclinic, space group P21/c with a = 12.9202(5), b = 27.197(1), c = 17.0116(7) ? b = 100.588(1), V = 5875.9(4) 3, Z = 4, C63H57N7O12Cu3, Mr = 1294.78, Dc = 1.464 g/cm3, m = 1.146 mm-1, F(000) = 2668, R = 0.0784 and wR = 0.1546 for 6926 observed reflections with I > 2s(I). The differences of coordinate bond lengths are observed between anhydrous and hydrous units: in the former unit, the average bond lengths are 1.978 ?for CuN (azomethine), 1.883 ?for CuO (phenolic) in Schiff-base moiety, 1.959 ?for CuO (keto), and 1.919 ?for CuO (hydroxy) in hydroxypyridinone moiety; while those in the latter are longer with the following corresponding values: 1.985(5), 1.908(5), 1.993(5) and 1.919(4) ? respectively. The Cu(2)O (water) bond length is 2.375(6) ?

Adsorption of Lead(II),Copper(II) on tourmaline from Altai mine in China's Sinkiang

Tourmaline from Altai mine in China＇s Sinkiang was used to remove lead （II）, copper （II） from aqueous solution. The results demonstrate that tourmaline contains Na（Mg,V）3AI6（BO3）3Si6Ols （OH）4, NaFe3AI6（BO3）3Si6Ols（OH）4. The data show that Tourmaline from Altai mine in China＇s Sinkiang can be used natural adsorbent for lead （II）, copper （II）.It is observed that the adsorption data fitted to the Langmuir isotherm. Furthermore, both Pb （II） and Cu （II） absorbed by tourmaline and tourmaline were characterized by X-ray diffraction, Laser Raman Spectrum, Fourier transform infrared spectroscopy, X-ray energy dispersive spectrometer, Transmission electron microscopy and Zeta potential.

Synthesis and Structure of bis(μ-2-aminopyridine N-oxide)-bis[dichlorocopper(II)]

The complex [Cu2（apo）4Cl4]·2H2O （apo=2-aminopyridine N-oxide） was obtained. A single- crystal X-ray study shows that the complex is a binuclear compound （Cu2C20H28Cl4N8O6）. The coordination geometry about each copper atom is best described as a distorted square pyramid. The compound [Cu2（apo）4Cl4]·2H2O belongs to the triclinic system with space group P, lattice constants: a = 7.8550（7）, b = 8.5378（7）, c = 12.082（1） ?, α = 72.807（1）, β = 77.641（1）, γ = 70.800（1）(, V =724.85（11） ?3, Z=1, Mr =745.38, Dc=1.708 g/cm3, μ =1.886mm-1, F（000） =378, R=0.0359, wR2=0.0884 for 2220 reflections with I >2σ（I）. The distances between Cu（II） and O atoms are in the range from 1.934（2） to 2.042（2）?. The distance between two copper atoms Cu-Cu（A） is 3.2978（8） ?. The distances of Cu-Cl（1） and Cu-Cl（2） are 2.2322（9）, 2.5095（10） ?, respectively. There is no evident hydrogen bond between N and Cl.

Synthesis, Structure and Spectral Characterization of a Discrete Binuclear Copper (II) Complex

A discrete binuclear copper (II) complex containing Cu 2O 2 unit has been synthesized by the reaction of Cu (ClO 4) 2·6H 2O with 2 aminopyridine in the CH 3OH solution and characterized by X ray diffraction study and IR spectroscopy. The crystal is monoclinic, space group: P2 1/n, with unit cell parameters: a=8.2952(2), b=18.4633(3), c=10.5049(2) . β=108.965(1)°, V=1521.56(5) 3, Z=2, C 22 H 30 N 8O 10 Cl 2Cu 2, M r =764.52, D c =1.669 Mg/m 3, F(000)=780, μ (Mo Kα )=8.60, T =293(2)K, final R=0.0623, wR =0.1536 for 2660 observed reflections with I>2.0σ(I ). The centrosymmetric complex Cu 2(CH 3O) 2(C 5H 6N 2) 4(ClO 4) 2 comprises a pair of Cu(II) atoms bridged by two methanoxo and N coordination 2 aminopyridine. The Cu(II)…Cu(II) distance is 3\^002(1).

Relationship between Coordination Structure and Biological Activity of Copper(II) Nicotinate

The copper（Ⅱ） complexes of pyridine-3-carboxylic acid （nicotinic acid） and pyridine-2-carboxylic acid （isonicotinic acid） were synthesized, and their structures were characterized by elemental analysis, infrared spectrum, powder X-ray diffraction and so on. The results show that under experimental conditions, the ligands of synthesized copper nicotinate and copper isonicotinate are coordinated simultaneity with copper（Ⅱ） via the nitrogen of pyridine group and an oxygen of carboxylic acid group to form bidentate chelates. The crystal of copper nicotinate with two six-membered chelate rings belongs to monoclinic system, while that of copper isonicotinate having two five-membered chelate rings is of triclinic system. The tests show that the biological activities, such as the improvement of feed utilization, growth, anti-oxidation ability of organism and disease-resistant power, are different when copper nicotinate, copper inicotinate, copper-lysine chelate, copper-methionine chelate and copper sulphate are added in pig＇s feed, respectively. Due to its higher biological activity, less pollution and lower toxicity, copper nicotinate has wide potential applications as a feed additive.

融合NSGA-II和CSA的多目标车间调度

针对在灵活车间系统中调度作业和自动引导车(automated guide vehicle,AGV)的同时调度问题,考虑在有限多个AGV和加工机台的情况下,以最小化最大完工时间、单个AGV搬运消耗时间及所有AGV搬运总消耗时间为目标函数,设计融合NSGA-II(non-dominated sorting genetic algorithms)和克隆选择(clonal selection algorithm,CSA)的改进算法INGCSA来解决此类问题。采用工件、加工机台和AGV三部分编码;引入非支配排序和目标函数值大小排序后总得分进行种群分层,从而有效地保留优秀个体;针对克隆后的种群,对不同等级的种群采取不同的变异概率,并对染色体进行内部交换与均匀交叉混合交换的基因重组,有效地提高了种群的多样性与防止陷入局部最优。通过三组对比实验,验证了该算法在探索最优解时,具有运行时间短、稳定性高和收敛性好等优点。

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.

Hydrothermal Synthesis and Crystal Structure of a Square Grid Coordination Copper(II) Polymer from 1,4-Bis(imidazole-1-ylmethyl)benzene

The title compound [Cu（bix）2（NO3）z·H2P]n 1 （bix = 1,4-bis（imidazole-1-ylme-thyl） benzene） has been synthesized by hydrothermal method. Its crystal structure is of monoclinic, space group P1^- with a = 8.3075（13）, b = 9.4725（13）, c = 10.0192（13） A, α = 91.088（4）, β = 104.063（6）, γ = 101.88（1）, V = 746.5（3） A^3, Z = 1, C28H30N10O7Cu1, Mr = 682.16, Dc = 1.518 g/cm^3, μ = 0.796 mm^-1, F（000） = 353, the final R = 0.0535 and wR = 0.0996 for 2921 observed reflections with I 〉 2σ（I）. Each bix ligand binds two Cu（Ⅱ） ions to form a 2-D（4,4） square grid layer, which is connected by hydrogen bonds showing large channels occupied by solvated water molecules and nitrate anions.

Synthesis and Crystal Structure of Tetraaquacopper(II) Bis(5-fluorouracil-1-acetate) Tetrahydrate

The title compound, [Cu（C6H4N2O4F）2（H2O）4].4（H2O） I, has been hydrothermally synthesized and structurally determined by single-crystal X-ray diffraction method. It crystallizes in monoclinic, space group P21/c with a = 8.3041（17）, b = 12.045（2）, c = 11.077（2） A, β = 92.567（3）°, V= 1106.8（4） A^3, Mr = 581.89, Z= 2, Dc = 1.746 g/cm^3, F（000） = 598,μ（MoKa） = 1.090 mm^-1, the final R = 0.0296 and wR = 0.0806 for 3195 observed reflections with Ⅰ 〉 2σ（Ⅰ）. In the centrosymmetric compound I, each Cu（Ⅱ） ion is coordinated by six O atoms from two 5-fluorouracil-1-acetate anions and four water molecules, forming a six-coordinated octahedral environment. N-H…O and O-H…O hydrogen-bonding interactions are observed in the structure, leading to the formation of a three-dimensional network.

Recovery of Copper（II） and Nickel（II） from Plating Wastewater by Solvent Extraction

The solvent extraction technology, was applied to recover Cu^2＋ and Ni^2＋ from plating wastewater.Lix984N was chosen as the extractant due to-its gooff extraction performance. The influence parame-ters were examlned. The results show that the separation of Cu^2＋ and Ni＂ from sulphate medium can be realized by adjusting pH value with the help of Lix984N. For extracting Cu^2＋ and Ni^2＋, the optimal pH values are 4 and 10.5, and the maximal extraction percentages are 92.9% and 93.0%, respectively .With recovered Cu^2＋ and Ni^2＋ stripped in 170g.L^ -1 and 200 g.L^-1 H2SO4 medium, the stripping percentages of Cu^2＋ and Ni^2＋ are 92.9% and 93.0%, respectively. This method is simple and can be used to recover Cu^2＋ and Ni^2＋ from plating wastewater. And a flow sheet for separation of Cu^2＋ and Ni^2＋ is presented.

Hydrothermal Synthesis and Structure of a Copper(II) Complex, [Cu(4,4'bpy)(H_2O)_3]SO_42H_2O

The title complex [Cu(4,4?bpy)(H2O)3]SO42H2O (Mr = 405.86) was synthesized under hydrothermal conditions and its crystal structure has been determined by X-ray diffraction. It crystallizes in the hexagonal system, space group P61 with a = 11.1870(4), c = 21.578(1) ? V = 2338.6(2) ?, Dc = 1.729 g/cm3, Z = 6, m(MoKa) = 1.583 mm-1 and F(000) = 1254. The final R and wR are 0.0253 and 0.0416 for 1458 observed reflections with I≥2s(I), respectively. It was revealed that the square pyramidal Cu(II) sites are linked through 4,4?bipyridine groups, forming infinite one-dimensional chains, with the sulfate anions and lattice water molecules occupying the inter-chain positions. During the electrostatic interactions, there exist O…O hydrogen bonds and p-p stacking interactions between the parallel aromatic bipy rings in the structure.

Synthesis, structure, DNA binding and cleavage activity of a new copper(II) complex of bispyridylpyrrolide

A copper-bispyridylpyrrolide complex [Cu(PDPH)Cl](PDPH = 2,5-bis(2′-pyridyl)pyrrole) was synthesized and characterized. The complex crystallizes in the orthorhombic system with space group Pccn, a = 0.9016(3) nm, b = 1.0931(4) nm, c =2.5319(8) nm, and V = 2.4951(15) nm3. The copper center is situated in a square planar geometry. The interaction of the copper(II)complex with calf thymus DNA(CT-DNA) was investigated by electronic absorption, circular dichroism(CD) and fluorescence spectra. It is proposed that the complex binds to CT-DNA through groove binding mode. Nuclease activity of the complex was also studied by gel electrophoresis method. The complex can efficiently cleave supercoiled p BR322 DNA in the presence of ascorbate(H2A) via oxidative pathway. The preliminary mechanism of DNA cleavage by the complex with different inhibiting reagents indicates that the hydroxyl radicals were involved as the active species in the DNA cleavage process.

Novel Screen-Printed All-Solid-State Copper(II)-Selective Electrode for Mobile Environmental Analysis

Based on poly(vinyl chloride) membranes, a novel miniaturized screen-printed all-solid-state copper(II)-selective electrode has been developed for applications in environmental monitoring. Performance and applicability of the ion-selective electrode (ISE) have been proved by potentiometric investigations. Conducting polymers were used as intermediate layers and as solid contacts between the ion-selective membrane and the graphite transducer. The ion-complexing reagent 2-mercapto-benzoxazole was incorporated into poly(vinyl chloride) membranes. In the concentration range 10-6 - 10-2 mol/L, the ISE exhibited a linear Nernstian potential response to copper(II) with an average slope value of 28 mV/decade. The detection limit was 3 × 10-7 mol/L. The electrode exhibits a short response time (<10 s) and can be used in the range of pH = 3 - 7. Selectivity coefficents against certain interfering ions are investigated. The life time of the electrode under laboratory conditions was approximately 12-month. The electrode was applied in the investigation of different aqueous environmental samples and the electrode characteristics were described. The copper(II) ASS electrode has also successfully been used in potentiometric, complexometric titrations with ethylenediaminetetraacetic acid.