Optimal dietary copper requirements and relative bioavailability for weanling pigs fed either copper proteinate or tribasic copper chloride

Background: The objective of this study was to determine the effects of supplementing Cu on growth performance, Cu metabolism and Cu-related enzyme activities of weanling pigs fed diets with two different Cu sources, and to estimate optimal Cu requirements and relative bioavailability from these two sources for pigs.Methods: Weanling pigs were allocated to 14 treatments arranged factorially, including 6 added Cu levels(5, 10,20, 40, 80, 160 mg/kg), and 2 mineral sources(tribasic Cu chloride, TBCC and copper proteinate, Cu Pro), as well as one negative control(0 mg/kg added Cu level) and one maximum allowed level treatment(200 mg/kg TBCC) for the entire 38-d experiment. Growth performance, mineral status and enzyme activities were measured at the end of this study.Results: Increasing levels of Cu showed linear and quadratic responses(P < 0.01) for final BW, ADG and FCR regardless of the sources. Supplementation with TBCC(> 80 mg/kg) and Cu Pro(> 20 mg/kg) significantly decreased(P < 0.05) diarrhea incidence of weanling pigs. There were linear and quadratic increases(P < 0.01) in bile, hepatic,and intestinal Cu concentrations, fecal Cu contents, and plasma enzyme activities(alkaline phosphatase,ceruloplasmin, Cu, Zn-Superoxide dismutase(Cu/Zn SOD), and glutathione peroxidase), whereas plasma malondialdehyde decreased(P < 0.01) linearly and quadratically as dietary Cu level increased. Similarly, pigs fed Cu Pro absorbed and retained more Cu and excreted less Cu than those fed TBCC when supplemented 80 mg/kg and above. Optimal dietary Cu requirements for pigs from 28 to 66 d of age estimated based on fitted broken-line models(P < 0.05) of bile Cu, plasma Cu/Zn SOD and growth performance were 93–140 mg/kg from TBCC, and 63–98 mg/kg from Cu Pro accordingly. According to slope ratios from multiple linear regression, the bioavailability value of Cu Pro relative to TBCC(100%) was 156–263%(P < 0.01).Conclusion: The findings indicated that Cu recommendation from current NRC(5–6 mg/kg) was not sufficient to meet the high requirement of weanling pigs. Cu from Cu Pro was significantly more bioavailable to weanling pigs than TBCC in stimulating growth and enzyme activities, decreasing diarrhea frequency and fecal Cu contents to the environment.

Dissolution kinetics of low grade complex copper ore in ammonia-ammonium chloride solution

The leaching kinetics of Tang-dan refractory low grade complex copper ore was investigated in ammonia-ammonium chloride solution.The concentration of ammonia and ammonium chloride,the ore particle size,the solid-to-liquid ratio and the temperature were chosen as parameters in the experiments.The results show that temperature,concentration of ammonia and ammonium chloride have favorable influence on the leaching rate of copper oxide ores.But,leaching rate decreases with increasing particle size and solid-to-liquid ratio.The leaching process is controlled by the diffusion of the lixiviant and the activation energy is determined to be 23.279 kJ/mol.An equation was also proposed to describe the leaching kinetics.

Kinetics of the Chlorination of Copper （I） Sulphide by Calcium Chloride in the Presence of Oxygen

The chemism of the chlorination of copper （I） sulphide by calcium chloride in the presence of oxygen has been determined based on the thermodynamic analysis in the Cu2S-CaCl2-O2 system as well as characterization of used raw materials and obtained products. The influence of temperature （from 473 to 773 K）, time （from 2 to 120 min）, oxygen flow （from 20 to 100 L/h） and calcium chloride quantity （from 5 to 40%） on the chlorination degree has been investigated. Kinetic analysis and the activation energy values of 20.89 kJ/mol showed that the chlorination of copper （I） sulphide by calcium chloride in the presence of oxygen is diffusion controlled.

Deprotection of t-Butyldimethylsiloxy (TBDMS) Protecting Group with Catalytic Copper (II) Chloride Dihydrate

t-Butyldimethylsilyl (TBDMS) ether can be cleaved upon refluxing in acetone/H2O (95 : 5) in the presence of a catalytic amount of copper (II) chloride dihydrate (5 mmol %).

Preparation of Pure Copper Powder from Acidic Copper Chloride Waste Etchant

The method for the recycling of copper from copper chloride solution was developed. This process consists of extraction of copper, purification and particle size reduction. In the first step, reductive metal scraps were added to acidic copper chloride waste enchants produced in the PCB industry to obtain copper powder. Composition analysis showed that this powder contained impurities such as Fe, Ni, and water. So, drying and purification were carried out by using microwave and a centrifugal separator. Thereby the copper powder had a purity of higher than 99% and spherical form in morphology. The copper powder size was decreased by ball milling.

Real-solution stability diagrams for copper-ammonia-chloride-water system

A comprehensive thermodynamic model, which combined the Helgeson Kirkham-Flowers （HKF） equation of state for standard-state thermodynamic properties of all species with realistic activity coefficient model developed by BROMLEY, was used to calculate the thermodynamic equilibrium, and a graphical method was developed to construct predominance existence diagrams （PED） for copper-ammonia-chloride in the presence of realistically modeled aqueous solutions. The existence of the different predominant chemical species for Cu（lI） predicted by the diagrams was corroborated by spectrophotometrical studies and X-ray diffractometry. The simulated and experimental results indicate that the predominance of a given species in solution strongly depends on the pH value in this system. More quantitative information on real copper hydrometallurgy in the presence of ammonia and chloride can be obtained from these diagrams compared with the conventional predominance existence diagrams.

Oxidation of 2,2'-Dihydroxy-3,3'-di-tert-buty-5,5'-dimethoxyl-biphenyl to 3,3'-Di-tert-butylbiphenyl-2,5,2',5'-diquinone with Copper(Ⅱ)Chloride as Catalyst:Synthesis,Structure and Spectral Properties of Diquinone

Use of free air as oxidant and copper（II）chloride as catalyst,3,3＇-di-tert-butylbi-phenyl-2,5,2＇,5＇-diquinone（BBDQ）was prepared via catalytic oxidation of 2,2＇-dihydroxy-3,3＇-di-tert-butyl-5,5＇-dimethoxy-biphenyl（di-BHA）.The yield of reaction attained 95% and the selectivity for BBDQ was 100%.The single-crystal X-ray diffraction analysis reveals that the dihedral angle between two rings（benzene rings for di-BHA and quinone rings for BBDQ）changes from 89.8 to 45.3o,indicating the steric hindrance effects of methyl disappear in the oxidation process.The crystal structures of di-BHA and BBDQ are further confirmed by their spectral characterizations.The probable mechanism for this oxidation process is also discussed.

铜(Ⅰ)催化氧化无溶剂合成苯并吖啶二酮衍生物

建立了一种苯并吖啶二酮衍生物的绿色合成方法,以2-(苯基氨基)萘-1,4-二酮类化合物与氰乙酸乙酯为原料,在铜(Ⅰ)与绿色氧化剂过氧叔丁醇的催化氧化体系下,通过无溶剂的自由基串联反应合成9个苯并吖啶二酮衍生物3a~3i,收率72%~79%.该合成策略绿色环保、操作简单(萃取和洗涤,无柱色谱分离)、原料简单易得,为高效合成具有潜在生物活性的苯并吖啶二酮衍生物提供了新的途径.

Synthesis,Crystal Structure and Luminescent Property of a New Copper(Ⅰ) Iodide Complex Based on 3,5-Dimethyl-4-amino-triazole

The title compound,[Cu4I4（C4H8N4）4],has been synthesized and characterized by single-crystal X-ray diffraction analysis.It crystallizes in monoclinic,space group Pbca,with a=18.1851（10）,b=9.3697（5）,c=19.8034（10）A,V=3374.3（3）A^3,C16H32Cu4I4N16,Mr=1210.34,Z=4,Dc=2.383 g/cm^3,μ=6.183 mm^-1,F（000）=2272,S=1.032,the final R=0.0309 and wR=0.1180 for 3854 observer reflections（I〉2σ（I））.The structure of the title compound consists of tetranuclear copper cluster units bridged by the halogen atoms with the 3,5-dimethyl-4-aminotriazole ligands coordinated to the metal ions through the triazole nitrogen atoms.The luminescent property of 1 was also studied.

CATHODIC REDUCTION OF METAL-CHLORIDE COORDINATION IONS

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Synthesis,Structure and Luminescence of a 1-D Chain of Copper(Ⅰ) Cyanide Decorated by Triphenylphosphine

A new wave-like infinite chain coordination polymer [Cu3（CN）3（PPh3）4]n（1,PPh3=triphenylphosphine） has been synthesized by solution reaction and characterized by X-ray single-crystal structure diffraction analysis.The complex crystallizes in space group P1 with a=13.343（6）,b=13.429（7）,c=20.694（10）A,α=103.163（4）,β=96.704（5）,γ=101.981（6）o,V=3479（3）A^3,Z=2,C75H60Cu3N3P4,Mr=1317.76,Dc=1.258 g/cm^3,F（000）=1356,μ=1.043 mm^-1,the final R=0.0680 and wR=0.1305 for 9232 observed reflections with I〉2σ（I）.The infinite chain is linked by C-H…π H bonding interactions to form a 2-D supramolecular network.Luminescent study reveals that the complex has green-light emission.

有机-无机杂化铜(Ⅰ)基卤化物闪烁体研究进展

近年来,有机-无机杂化金属卤化物材料由于其优异的光电性质引起了研究人员的广泛关注。其中低维铜(Ⅰ)基卤化物作为高效发光材料的代表,在照明与显示、辐射探测等领域表现出良好的应用前景。有机无机杂化铜(Ⅰ)基卤化物的组成和结构丰富多变,给研究人员提供了巨大的研究空间。本文综述了有机-无机杂化铜(Ⅰ)基卤化物作为发光材料的研究进展,并以[CuX_(n)](X=Cl,Br,I)结构单元及其连接方式为依据,对离子型有机-无机杂化铜(Ⅰ)基卤化物进行了系统的分类,总结了其组成-结构-性质之间的构效关系。讨论了有机-无机杂化铜(Ⅰ)基卤化物的发光机制和光物理过程,并重点归纳了用于X射线探测的有机-无机杂化铜(Ⅰ)基卤化物闪烁体的最新进展。最后,对这一新兴的研究领域做出了展望。

Disposal of cuprous chloride waste water

The waste water system generated in the process of production of cuprous chloride was studied.The existing forms of copper in the system and the influence of temperature and pH on the existing forms of copper ion were analyzed and determined through calculating the coefficients of copper complex distribution.In the waste water system,the main forms of copper are CuSO4, Cu2 +,CuCl + ,CuCl, 2-and2- 3 CuCl.Temperature has little influence on the distribution coefficient of Cu(Ⅱ),but has significant influence on distribution coefficient of Cu(Ⅰ).With the increase of temperature,the distribution coefficient ofCuCl, 2-increases significantly while the distribution coefficient of2- 3 CuCl decreases.The pH has nearly no influence on the distribution coefficients of various Cu(Ⅰ)-compounds,but has sizable influence on the distribution coefficients of Cu(Ⅱ)-compounds.With the increase of pH,the distribution coefficient of CuSO4(aq)increases while the distribution coefficients of Cu 2+ and CuCl + decrease.According to these results,the anion resin of 201×7 OH-and the cation resin of 732 Na were chosen to dispose the waste water solution of cuprous chloride.Finally,97.9%copper in the waste water is recovered.

Synthesis,Structure and Luminescent Properties of Polymeric Copper(Ⅰ) Halide Complexes Bearing Phosphine and N-donor Bridging Ligands

Three polymeric copper（Ⅰ） halide complexes beating phosphine and N-donor bridging ligands, [（PPh3）2Cu2（μ-Br）2（μ-4,4＇-bipy）]∞ 1 （bipy = bipyridine）, [（PPh3）2Cu2（μ-Br）2（μ- bpe）]∞ 2 （bpe = trans-1,2-bis（4-pyridyl）ethene） and [（PPh3）2Cu2（μ-Cl）2（μ-bpe）]∞ 3, were synthesized by the multilayer diffusion method, and the structures were refined by single-crystal X-ray diffraction. Complex 1 crystallizes in triclinic, space group P1^- with a = 9.122（3）, b = 9.322（3）, c = 13.201（4） A, α = 106.440（4）, β= 105.965（5）, γ= 94.167（5）°, V = 1021.3（6） A^3, Mr= 967.62, Z = 1, De= 1.573 g/cm^3, F（000） = 486, μ = 3.111 mm^-1, the final R = 0.0383 and ωR = 0.0960 for 2792 observed reflections （I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1^- with a = 9.420（3）, b = 10.209（4）, c = 12.407（4） A, α = 104.136（6）, β = 108.132（5）, γ= 95.338（6）°, V = 1081.0（7） A^3, Mr= 496.83, Z = 2, Dc= 1.526 g/cm^3, F（000） = 500, μ = 2.941 mm^-1, the final R = 0.0445 and ωR = 0.1117 for 3251 observed reflections （I 〉 2σ（I））. Complex 3 crystallizes in triclinic, space group P1^- with a = 8.32（1）, b = 11.53（2）, c = 13.94（3） A, α = 109.57（3）, β= 93.85（3）, γ= 97.28（3）°, V= 1242（4） A^3, Mr= 1074.59, Z = 1, Dc = 1.436 g/cm^3, F（000） = 548, μ = 1.279 mm^-1, the final R = 0.0786 and ωR = 0.1586 for 2266 observed reflections （I 〉 2σ（I））. The complexes exhibit intensive solid-state photoluminescence tentatively assigned to an admixture of triplet intraligand （IL） and metal-to-ligand charge-transfer （MLCT） excited state.

Studies on A Novel Mixed-Valence Complex of Copper(Ⅰ,Ⅱ)α-Methacrylate with Imidazole and Aqua

A novel mixed-valence copper (Ⅰ,Ⅱ) complex Cu3 [CH2=C(CH3) COO]5 (imH)3 (H2O)has been synthesized and characterized by XPS spectra and single crystal X-ray structural analysis.The title complex crystallized in monoclinic space group P21/c, with α=11 .225 (3), b=13.9023 (12),c=24.559 (2), β=92.372 (10)°and Z=4. Final R=0.0495 for 5546 reflections [I＞2σ (Ⅰ)].

Crystal Structure of Di[bis(diphenylphosphino)propane]Copper(Ⅰ) Perchlorate Complex

The complex [Cu (dppp)2] (ClO4) was prepared by the reaction ofcopper (Ⅱ) perchlorate wlth bis(diphenylphosphino) propane (dppp) in methanol, andits crystal structure was determlned by X-ray crystallography. The crystal is monoclin-ic, space group P1, M. = 1019. 90 with cell parameters a = 11. 951 (6), b = 12. 178(4), c=18. 413(5) A, α=70. 52(3), β=83. 56(4), γ=77. 61 (4), V=2465. 2 A3,Z = 2, Dc = 1. 371 g/cm3. The structure was solved by direct methods and refined byblock-diagonal and full-matrix least-squares methods to a final R of 0. 043 for 4085 in-dependent reflections of I>3σ(I). In this complex [Cu (dppp)2] (ClO4), dppp func-tions as a bidentate chelate ligand. The four P atoms from two dppp are coordinated tothe tetrahedral copper (P4).

A New Tetranuclear Copper(Ⅰ) Complex of Dithiolate Ligand Fused with TTF Moiety

A tetranuclear copper (I) complex of the ditholate ligand fused with a TTF moiety hasbeen synthesized and characterized crystallographically. This is the first example of a metaJ clustercoordinated with the new type ligand. The complex shows interesting redox and radical properties.

Investigation of Intermolecular C-H···Halogen Hydrogen Bonded Supramolecular Assemblies in Three Copper(Ⅰ) Complexes Formed by 3,3'-Dimethoxy-6,6'-dimethyl-2,2'-bipyridine Ligand

Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3＇-dimethoxy-6,6＇-dimethyl-2,2＇-bipyridine ligand（dmbp） with the corresponding Cu（Ⅰ） salts.Crystal data for 1：orthorhombic Pbca,a = 18.5858（12）,b = 8.1821（5）,c = 20.6066（13） ,V = 3133.7（3） 3,Z = 8,Dc = 1.843 g/cm3,F（000） = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2：Orthorhombic Pbca,a = 18.7883（16）,b = 8.3249（7）,c = 19.0294（17） ,V = 2976.4（4） 3,Z = 8,Dc = 1.731 g/cm3,F（000） = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3：monoclinic P21/c,a = 13.812（10）,b = 9.910（7）,c = 23.444（17） ,β = 104.3350（10）°,V = 3090（4） 3,Z = 4,Dc = 1.476 g/cm3,F（000） = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2（1） and C14H16BrCuN2O2（2） are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional（3D） supramolecular network in 1 and a two-dimensional（2D） sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4（3） is ionic.In 3,the [Cu（dmbp）2]＋ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional（1D） chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated.

Synthesis, Structure and Fluorescence of Olefin-Copper(Ⅰ) Coordination Polymers

The organic olefin ligand 2,5-dimethyl-1-(4-vinyl-benzyl)-piperazine reacts with CuX(X = Cl, Br) to obtain two novel olefin-copper(I) coordination polymers [C_(15)H_(22)N_2Cu_2Cl_3]n(1) and [C_(15)H_(20)N_2Cu_2Br_2]n(2). There are two types of CuX warp structures that have never been seen before in the presence of methanol under solvothermal conditions. The new olefin-copper(I) coordination complex crystallizes in the monoclinic space group P21/c to obtain compounds 1 and 2. Its unique green fluorescence effect can be applied to the LED field.