Analysis Characterization and Some Properties of Polyacrylamide Copper Complexes

The complexation of polyacrylamide (PAam) with Cu⁺² metal ions was investigated. The metal complexes were characterized by FTIR, UV-Vis and DSC analysis. The Fourier transform infrared spectroscopy was used to study the characteristic shifts in the maximum absorbance bands of N-H amide C=O and N-H₂ absorption bands. UV-Vis spectroscopy was also used to follow the complex formation of PAam-Cu⁺². UV-Vis spectroscopy shows the appearance of a new band that was absent both in the polymer and its salt solutions.

Thermal analysis of PAam-Cu⁺² complexes was studied using DSC. The shifts in Tg values could be attributed to the improvement in the rigidity of PAam in the presence of Cu⁺² associated with the polymer chain. Pure polyacrylamide polymer is electrically insular. The electrical conductivity improved by several orders of magnitude after the complexation process.

AFM was used to image the surface features of PAam and PAam-Cu⁺²complex films. The association of polyacrylamide with Cu⁺² metal ions at 2.5% (w/w) concentration, showed the formation of large grains with roughness 0.5 µm. Increasing the concentration of PAam-Cu⁺² complex up to 25% (w/w), showed different and surprising results: instead of film with large grains, rods 1 µm in diameter were formed.     

Copper(II) Complexes Containing Natural Flavonoid Pomiferin Show Considerable In Vitro Cytotoxicity and Anti-inflammatory Effects

A series of new heteroleptic copper(II) complexes of the composition [Cu(L)(bpy)]NO₃·2MeOH (1), [Cu(L)(dimebpy)]NO₃·2H₂O (2), [Cu(L)(phen)]NO₃·2MeOH (3), [Cu(L)(bphen)]NO₃·MeOH (4), [Cu(L)(dppz)]NO₃·MeOH (5) was prepared, where HL = 3-(3,4-dihydroxyphenyl)-5-hydroxy-8,8-dimethyl-6-(3-methylbut-2-ene-1-yl)-4H,8H-benzo[1,2-b:3,4-b′]dipyran-4-one, (pomiferin) and bpy = 2,2′-bipyridine, dimebpy = 4,4′-dimethyl-2,2′-bipyridine, phen = 1,10-phenanthroline, bphen = 4,7-diphenyl-1,10-phenanthroline, and dppz = dipyrido[3,2-a:2′,3′-c]phenazine. The complexes were characterized using elemental analysis, infrared and UV/Vis spectroscopies, mass spectrometry, thermal analysis and conductivity measurements. The in vitro cytotoxicity, screened against eight human cancer cell lines (breast adenocarcinoma (MCF-7), osteosarcoma (HOS), lung adenocarcinoma (A549), prostate adenocarcinoma (PC-3), ovarian carcinoma (A2780), cisplatin-resistant ovarian carcinoma (A2780R), colorectal adenocarcinoma (Caco-2) and monocytic leukemia (THP-1), revealed the complexes as effective antiproliferative agents, with the IC₅₀ values of 2.2–13.0 μM for the best performing complexes 3 and 5. All the complexes 1–5 showed the best activity against the A2780R cells (IC₅₀ = 2.2–6.6 μM), and moreover, the complexes demonstrated relatively low toxicity on healthy human hepatocytes, with IC₅₀ > 100 μM. The complexes were evaluated by the Annexin V/propidium iodide apoptosis assay, induction of cell cycle modifications in A2780 cells, production of reactive oxygen species (ROS), perturbation of mitochondrial membrane potential, inhibition of apoptosis and inflammation-related signaling pathways (NF-κB/AP-1 activity, NF-κB translocation, TNF-α secretion), and tested for nuclease mimicking activity. The obtained results revealed the corresponding complexes to be effective antiproliferative and anti-inflammatory agents.     

The Cytotoxic Effect of Copper (II) Complexes with Halogenated 1,3-Disubstituted Arylthioureas on Cancer and Bacterial Cells

A series of eight copper (II) complexes with 3-(4-chloro-3-nitrophenyl)thiourea were designed and synthesized. The cytotoxic activity of all compounds was assessed in three human cancer cell lines (SW480, SW620, PC3) and human normal keratinocytes (HaCaT). The complexes 1, 3, 5, 7 and 8 were cytotoxic to the studied tumor cells in the low micromolar range, without affecting the normal cells. The complexes 1, 3, 7 and 8 induced lactate dehydrogenase (LDH) release in all cancer cell lines, but not in the HaCaT cells. They provoked early apoptosis in pathological cells, especially in SW480 and PC3 cells. The ability of compounds 1, 3, 7 and 8 to diminish interleukin-6 (IL-6) concentration in a cell was established. For the first time, the influence of the most promising Cu (II) complexes on intensities of detoxifying and reactive oxygen species (ROS) scavenging the enzymes of tumor cells was studied. The cytotoxic effect of all copper (II) conjugates against standard and hospital bacterial strains was also proved.     

添加剂对化学镀铜层机械性能的影响

通过在化学镀铜液中分别添加亚铁氰化钾、２ＭＢＴ及２,２’－联吡啶三种添加剂的实验研究,探讨了添加剂种类及其加入量对镀铜速度和镀铜层延展性产生显著影响的原因。此外,简要讨论了添加剂的加入对镀铜层的耐磨性产生影响的原因     

铜及其合金着色工艺研究进展

总结了目前国内外关于铜及其合金的着色工艺,系统地归纳了化学和电化学着色的配方。着重对目前应用广泛的五种化学着色和四种电化学着色工艺进行比较,并考察了着色机理。最后,对铜及其合金着色工艺的发展趋势进行展望。     

FeIII,CuII and ZnII Complexes of the Rigid 9-Oxido-phenalenone Ligand—Spectroscopy,Electrochemistry, and Cytotoxic Properties

The three complexes [Fe(opo)₃], [Cu(opo)₂], and [Zn(opo)₂] containing the non-innocent anionic ligand opo⁻ (opo⁻ = 9-oxido-phenalenone, Hopo = 9-hydroxyphenalonone) were synthesised from the corresponding acetylacetonates. [Zn(opo)₂] was characterised using ¹H nuclear magnetic resonance (NMR) spectroscopy, the paramagnetic [Fe(opo)₃] and [Cu(opo)₂] by electron paramagnetic resonance (EPR) spectroscopy. While the EPR spectra of [Cu(opo)₂] and [Cu(acac)₂] in dimethylformamide (DMF) solution are very similar, a rather narrow spectrum was observed for [Fe(opo)₃] in tetrahydrofuran (THF) solution in contrast to the very broad spectrum of [Fe(acac)₃] in THF (Hacac = acetylacetone, 2,4-pentanedione; acac⁻ = acetylacetonate). The narrow, completely isotropic signal of [Fe(opo)₃] disagrees with a metal-centred S = 5/2 spin system that is observed in the solid state. We assume spin-delocalisation to the opo ligand in the sense of an opo⁻ to Fe^III electron transfer. All compounds show several electrochemical opo-centred reduction waves in the range of −1 to −3 V vs. the ferrocene/ferrocenium couple. However, for Cu^II and Fe^III the very first one-electron reductions are metal-centred. Electronic absorption in the UV to vis range are due to π–π* transitions in the opo core, giving Hopo and [Zn(opo)₂] a yellow to orange colour. The structured bands ranging from 400 to 500 for all compounds are assigned to the lowest energy π−π* transitions. They show markedly higher intensities and slight shifts for the Cu^II (brown) and Fe^III (red) complexes and we assume admixing metal contributions (MLCT for Cu^II, LMCT for Fe^III). For both complexes long-wavelength absorptions assignable to d–d transitions were detected. Detailed spectroelectrochemical experiments confirm both the electrochemical and the optical assignments. Hopo and the complexes [Cu(opo)₂], [Zn(opo)₂], and [Fe(opo)₃] show antiproliferative activities against HT-29 (colon cancer) and MCF-7 (breast cancer) cell lines in the range of a few µM, comparable to cisplatin under the same conditions.     

化学法制备电极用超细铜粉

以CuSO4溶液为原料,采用NaOH沉淀-葡萄糖预还原-水合肼还原工艺（简称两步液相还原法）制得了粒度均匀可控、分散性好、适用于陶瓷电容器电极的球形超细铜粉。实验研究了葡萄糖预还原、水合肼的添加方式以及添加剂聚乙烯吡咯烷酮（PVP）和NH4Cl对超细铜粉粒度和形貌的影响。结果表明,葡萄糖预还原和水合肼的分步添加均有利于超细铜粒子的均匀生长,适量PVP的加入有助于超细铜粉粒径均匀并使其形貌趋于一致,NH4Cl可使铜粉的粒径变小,当Cu与NH4Cl的摩尔比为1∶1时铜粉的形貌会由类球形向正多面体转变。     

Isoxazole-Derived Aroylhydrazones and Their Dinuclear Copper(II) Complexes Show Antiproliferative Activity on Breast Cancer Cells with a Potentially Alternative Mechanism Of Action

This paper reports the design, synthesis and cytotoxicity studies of two new isoxazole-derived aroylhydrazone ligands and their dinuclear copper(II) complexes. Compounds were fully characterized by various spectroscopic and analytical techniques. The molecular structures of four derivatives were confirmed by X-ray crystallography. The stability of the ligands and the complexes in aqueous medium was monitored spectroscopically. Both the ligands and the complexes were shown to interact with calf thymus DNA (ct-DNA). Additionally, structures containing a phenol pendant arm were significantly more cytotoxic than those carrying a pendant pyridine substituent, reaching sub-micromolar IC₅₀ values on the triple-negative human breast cancer cell line MDA-MB-231. The metal chelation and transchelation ability of the compounds towards Fe^II, Fe^III and Zn^II ions was explored as a possible mechanism of action of these compounds.     

熔融铜渣回收铜及铜铁合金工艺研究

本文根据某炼铜熔融炉渣的矿物特性和选矿工艺特点,提出了一种"两步法"新工艺分别回收铜和铜铁合金,即低温阶段回收铜,高温阶段回收铜铁合金。该工艺对铜和铜铁合金提取比较充分,回收率均在90%以上。回收铜的品位可达99%,可直接送去火法精炼;产出的铜铁合金有害杂质少,可作为耐候钢的理想原料,其价值比纯铁高。此工艺用粉状或粒状非焦煤代替焦炭作还原剂,不用烧结,可以充分利用铜厂现有的设备,节省投资成本。该工艺简单易行,操作方便,有效实现了铜渣的资源化利用,具有良好的经济、社会和环境效益,是一种应用前景广阔的铜渣再利用工艺。     

Development of Gene-Targeted Polypyridyl Triplex-Forming Oligonucleotide Hybrids

In the field of nucleic acid therapy there is major interest in the development of libraries of DNA-reactive small molecules which are tethered to vectors that recognize and bind specific genes. This approach mimics enzymatic gene editors, such as ZFNs, TALENs and CRISPR-Cas, but overcomes the limitations imposed by the delivery of a large protein endonuclease which is required for DNA cleavage. Here, we introduce a chemistry-based DNA-cleavage system comprising an artificial metallo-nuclease (AMN) that oxidatively cuts DNA, and a triplex-forming oligonucleotide (TFO) that sequence-specifically recognises duplex DNA. The AMN-TFO hybrids coordinate Cu^II ions to form chimeric catalytic complexes that are programmable – based on the TFO sequence employed – to bind and cut specific DNA sequences. Use of the alkyne-azide cycloaddition click reaction allows scalable and high-throughput generation of hybrid libraries that can be tuned for specific reactivity and gene-of-interest knockout. As a first approach, we demonstrate targeted cleavage of purine-rich sequences, optimisation of the hybrid system to enhance stability, and discrimination between target and off-target sequences. Our results highlight the potential of this approach where the cutting unit, which mimics the endonuclease cleavage machinery, is directly bound to a TFO guide by click chemistry.     

化学镀铜废液的综合利用和处理

探讨了利用原化学镀铜废液中的甲醛将铜还原，后酸化回收EDTA的新工艺。实验证明，该工艺铜的去除率可达99％，甲醛去除率为68．9％，同时EDTA的回收率为96．6％。用这种方法回收的EDTA纯度大于97％，可直接回用于化学镀铜工业。     

Immunogenic Cell Death of Breast Cancer Stem Cells Induced by an Endoplasmic Reticulum-Targeting Copper(II) Complex

Immunogenic cell death (ICD) offers a method of stimulating the immune system to attack and remove cancer cells. We report a copper(II) complex containing a Schiff base ligand and a polypyridyl ligand, 4 , capable of inducing ICD in breast cancer stem cells (CSCs). Complex 4 kills both bulk breast cancer cells and breast CSCs at sub-micromolar concentrations. Notably, 4 exhibits greater potency (one order of magnitude) towards breast CSCs than salinomycin (an established breast CSC-potent agent) and cisplatin (a clinically approved anticancer drug). Epithelial spheroid studies show that 4 is able to selectively inhibit breast CSC-enriched HMLER-shEcad spheroid formation and viability over non-tumorigenic breast MCF10 A spheroids. Mechanistic studies show that 4 operates as a Type II ICD inducer. Specifically, 4 readily enters the endoplasmic reticulum (ER) of breast CSCs, elevates intracellular reactive oxygen species (ROS) levels, induces ER stress, evokes damage-associated molecular patterns (DAMPs), and promotes breast CSC phagocytosis by macrophages. As far as we are aware, 4 is the first metal complex to induce ICD in breast CSCs and promote their engulfment by immune cells.     

选择性螯合滴定法测定酸铜镀液中的CuSO4

本文提出一种测定ＣｕＳＯ４含量的螯合滴定方法。该方法是在酸铜镀液中，加入过量的ＥＤＴＡ络合全部的金属离子，再用硫脲、抗坏血酸和１，１０－二氮杂菲选择性地分解Ｃｕ－ＥＤＴＡ．该方法有效地消除了镀液中Ｆｅ＾３＋、Ｚｎ＾２＋、Ａｌ＾３＋等杂质金属离子对测定结果的干扰。方法简便，结果准确，已被成功用于镀铜生产中ＣｕＳＯ４的测定。     

铜酞菁磺酸苯酯的光谱性质研究

将铜酞菁氯磺化,与苯酚酯化,合成了标题化合物。在不同的溶剂中测试其电子光谱:Q带吸收峰为:664.6nm～672.4nm,强度为0.363～1.477;B带吸收峰336.8nm～348.4nm,强度为:0.181～0.708。产物的荧光光谱随溶剂的极性减弱而强度降低:DMF>THF>CH_2Cl_2>DMSO>丙酮>吡啶>CHCl_3;其波长随溶剂的极性减弱而发生蓝移:DMSO>THF>DMF>丙酮>CH_2Cl_2>吡啶>CHCl_3。     

Practical Methods for the Synthesis of Trifluoromethylated Alkynes: Oxidative Trifluoromethylation of Copper Acetylides and Alkynes

Two practical and complementary methods are reported for the synthesis of trifluoromethylated alkynes. The first one, a mix‐and‐stir process, is based on the oxidative trifluoromethylation of readily available and bench‐stable copper acetylides while the second one, which displays a broad substrate scope and has several advantages over existing procedures, is based on the oxidative copper‐catalyzed direct trifluoromethylation of terminal alkynes. Both reactions provide user‐friendly processes for the synthesis of trifluoromethylated acetylenes which can be easily obtained from readily available starting materials.

     

Investigation of the Characteristics and Antibacterial Activity of Polymer-Modified Copper Oxide Nanoparticles

The proliferation of drug-resistant pathogens continues to increase, giving rise to serious public health concerns. Many researchers have formulated metal oxide nanoparticles for use as novel antibacterial agents. In the present study, copper oxide (CuO) was synthesized by simple hydrothermal synthesis, and doping was performed to introduce different polymers onto the NP surface for bacteriostasis optimization. The polymer-modified CuO NPs were analyzed further with XRD, FTIR, TEM, DLS and zeta potential to study their morphology, size, and the charge of the substrate. The results indicate that polymer-modified CuO NPs had a significantly higher bacteriostatic rate than unmodified CuO NPs. In particular, polydopamine (PDA)-modified CuO (CuO-PDA) NPs, which carry a weakly negative surface charge, exhibited excellent antibacterial effects, with a bacteriostatic rate of up to 85.8 ± 0.2% within 3 h. When compared to other polymer-modified CuO NPs, CuO-PDA NPs exhibited superior bacteriostatic activity due to their smaller size, surface charge, and favorable van der Waals interactions. This may be attributed to the fact that the CuO-PDA NPs had relatively lipophilic structures at pH 7.4, which increased their affinity for the lipopolysaccharide-containing outer membrane of the Gram-negative bacterium Escherichia coli.     

Kinetics Study of the Hydrodechlorination of Chlorobenzene Catalyzed by Immobilized Copper Complexes

The hydrodechlorination of chlorobenzene to benzene and biphenyl was studied using poly(4-vinylpyridine)-immobilized Cu catalysts under CO in basic (NaOH, N(C₂H₅)₃ or Na(CH₃CO₂)) aqueous 2-ethoxyethanol medium. This Cu system also catalyzed the water gas shift reaction. The catalytic activities for hydrodechlorination of chlorobenzene to benzene were studied as functions of the reaction parameters (nature of the base, reaction time, [Cu], P(CO), T, and S/C). Among the different base studied activity is maximum for NaOH. The rate of benzene formation displays a first-order dependence on [Cu] over the range 1.25–12.50 wt%. This observation was interpreted in terms of the presence of active species having the same nuclearity. The catalytic activity towards benzene formation proved to be first order dependence on P(CO) over the range 5–35 atm. The kinetics behavior with respect to P(CO) leads to the proposal that CO addition to the catalytic species precedes the rate-limiting step. The catalytic activity proved to be non-linear in chlorobenzene/Cu content, over the range 50–400 molar ratio. The results suggest that the rate-limiting step is preceded by reversible oxidative addition of chlorobenzene to Cu immobilized species.     

铜合金化学抛光技术研究进展

综述了铜合金化学抛光的应用现状,硝酸及硝酸盐体系、过氧化氢体系抛光液中各组分的作用,存在的问题及其解决方案。指出目前铜合金化学抛光工艺存在的溶液稳定性和环境污染问题,通过对铜合金不同化学抛光工艺的分析,探讨了绿色环保型铜合金化学抛光工艺是今后的发展方向。     

聚苯胺修饰铜网聚酯导电薄膜的性能

首先通过化学氧化法制备了聚苯胺(PANI),并用樟脑磺酸对PANI进行掺杂,在铜网聚酯膜上通过旋涂法制备了PANI修饰导电薄膜;采用傅里叶变换红外光谱仪进行了合成PANI的官能团分析,采用扫描电子显微镜观察了合成PANI及PANI修饰铜网聚酯膜的外貌,采用X射线衍射仪分析了PANI的衍射谱图,最后对PANI在铜网和聚酯膜上的成膜生长机理进行了讨论。     

废杂铜的回收与利用

介绍了我禺铜的需求及资源状况,提出了我国废杂铜回收利用的必要性。总结了国惠废杂铜的分类方法和废杂铜回收利用的现状以及废杂铜的回收处理方法,并针对国内废杂铜的回收利用情况提出了意见与建议,希望能够为我国废杂铜的回收利用提供参考。