Antioxidant vs. Prooxidant Properties of the Flavonoid,Kaempferol, in the Presence of Cu(II) Ions: A ROS-Scavenging Activity,Fenton Reaction and DNA Damage Study

Kaempferol is a flavonoid that occurs in tea and in many vegetables and fruits, including broccoli, cabbage, beans, grapes, apples, and strawberries. The efficacy of Kaempferol has been demonstrated in the treatment of breast, esophageal, cervical, ovarian, and liver cancers and leukemia, which very likely arises from its prooxidant properties and the activation of pro-apoptotic pathways. Indeed, this matter has already been the focus of a number of published studies and reviews. The aim of the present study was to elucidate the antioxidant vs. prooxidant properties of flavonoids in the presence of the redox-active metal, copper (II) ion, by means of the Fenton reaction. The specific motivation of this work is that, since an increased level of Cu(II) ions is known to be associated with many disease states such as neurological conditions (Alzheimer’s disease) and cancer, any interaction between these ions and flavonoids might affect the outcome of therapeutic uses of the latter. The structure of the Cu-kaempferol complex in DMSO was investigated by means of low temperature EPR spectroscopy, which confirmed the existence of at least two distinct coordination environments around the copper (II) ion. UV vis-spectra of kaempferol and its Cu(II) complex in DMSO revealed an interaction between the 5-OH (A ring) group and the 4-CO (C ring) group of kaempferol with Cu(II) ions. An ABTS assay confirmed that kaempferol acted as an effective radical scavenger, and that this effect was further enhanced in the form of the Cu(II)-kaempferol complex. Quantitative EPR spin trapping experiments, using DMPO as the spin trap, confirmed suppression of the formation of a mixture of hydroxyl, superoxide, and methyl radicals, in a Fenton reaction system, upon coordination of kaempferol to the redox-active Cu(II) ions, by 80% with respect to the free Cu(II) ions. A viscometric study revealed a better DNA-intercalating ability of the Cu-kaempferol complex than for free kaempferol, essential for conferring anticancer activity of these substances. The results of the viscometric measurements were compared with those from a DNA damage study of Cu-kaempferol complexes in a Fenton reaction system, using gel electrophoresis. At low concentrations of kaempferol (Cu–kaempferol ratios of 1:1 and 1:2), a very weak protective effect on DNA was noted, whereas when kaempferol was present in excess, a significant DNA-protective effect was found. This can be explained if the weakly intercalated kaempferol molecules present at the surface of DNA provide protection against attack by ROS that originate from the Fenton reaction involving intercalated Cu(II)-kaempferol complexes. Following the application of ROS scavengers, L-histidine, DMSO, and SOD, gel electrophoresis confirmed the formation of singlet oxygen, hydroxyl radicals, and superoxide radical anions, respectively. We propose that the prooxidant properties of Cu-kaempferol complexes may provide anticancer activity of these substances. When present in excess, kaempferol displays antioxidant properties under Cu-Fenton conditions. This suggests that kaempferol might prove a suitable candidate for the prevention or treatment of oxidative stress related medical conditions that involve a disturbed metabolism of redox metals such as copper, for example, Menkes disease, and neurological disorders, including Alzheimer’s disease. For the potential use of kaempferol in clinical practice, it will be necessary to optimize the dose size and critical age of the patient so that this flavonoid may be beneficial as a preventive drug against cancer and neurological disorders.     

一种新型生物絮凝剂来提高水中铜离子的去除

从吉林污水处理厂活性污泥中筛选出一株高效絮凝铜离子的菌株,通过16S rDNA扩增和菌株鉴定。鉴定其为植生乌拉尔菌(Raoultella planticola),研究了生物絮凝剂对铜离子(0.2ppm)的絮凝条件。结果表明,絮凝效率达到80%以上。影响絮凝效率的主要因素和变量为pH、絮凝时间。在pH=5、1.62h 、氧化石墨烯Graphene Oxide（GO）助凝诱导剂13.11mg/L时,絮凝效率达到86.01%,达到最高的絮凝效率。     

基于遗传算法的铜闪速熔炼过程控制优化

基于已建立的铜闪速熔炼神经网络模型,以能耗费用最低为目标,在工艺指标控制范围内,采用遗传算法对铜闪速熔炼过程的工艺参数进行了仿真优化计算。结果表明,当空气、分配风、工艺氧和中央氧的市场价格折合比值分别为0.05、0.1、0.4和0.45,精矿量为128 t,其成分(质量分数)为Cu 20.61%、S 27.59%、Fe 24.72%、SiO2 11.64%和MgO 1.39%时,铜闪速熔炼工艺参数的遗传优化值为空气15 011 m3、分配风1 302 m3、工艺氧17 359 m3、中央氧1 000 m3、熔剂13.6 t;与实践平均值相比,若采用优化工艺参数控制,熔炼能耗费用可降低4.6%。     

基于核偏最小二乘法的动态预测模型在铜转炉吹炼中的应用

为实现铜转炉吹炼过程中的关键操作参数的准确预测,构造一种基于核偏最小二乘法的动态预测模型,并提出一种适用于动态建模的在线式异常样本剔除方法。该动态预测模型使用滑动窗方法不断更新建模数据,再利用核偏最小二乘法对动态模型的参数进行辨识,最后根据反馈的前次计算误差对本次预测值进行修正。仿真研究结果表明：该动态预估模型具有较好的泛化能力和较强的鲁棒性,并具有较好预测精度（风量预测的相对均方根误差小于10%,氧量预测的相对均方根误差小于19%）。目前,该预测模型被用于某转炉的吹炼辅助决策系统中。     

铜合金模具材料在不锈钢中厚板冲压成形中的应用

分析了不锈钢板材冲压成形性能特点以及工件产生擦伤的原因,概述了铜合金模具材料的特性及应用范围.最后以实例方式介绍了模具镶块的结构优化设计,解决了工件表面擦伤和模具寿命急剧下降的技术瓶颈.     

绿色水处理缓蚀剂聚天冬氨酸的研究进展

聚天冬氨酸具有高生物可降解性,是一种公认的环境友好型水处理药剂.综述了近年来聚天冬氨酸作为水处理缓蚀剂的研究进展;探索了其对碳钢、铜及铜合金在不同体系中的缓蚀效果;指出了复配聚天冬氨酸具有较好的缓蚀协同效应.复配聚天冬氨酸可作为今后绿色水处理缓蚀剂的发展方向.     

N,N−二甲基−二硫代甲酰胺丙磺酸钠对THPED体系化学镀铜的影响

研究了N,N?二甲基?二硫代甲酰胺丙磺酸钠(DPS)作为添加剂对以四羟丙基乙二胺(THPED)为单一配位剂的化学镀铜体系的沉积速率、镀层形貌和晶体结构的影响。结果发现,当DPS的质量浓度从0 mg/L增大到1.0 mg/L时,沉积速率从2.91μm/h提高到6.73μm/h,所得镀层结晶均匀、细致。线性扫描伏安测量结果表明,DPS是通过促进甲醛的阳极氧化来加速化学镀过程。本体系的Cu镀层主要呈面心立方多晶取向,DPS的添加会令晶面取向从(220)转变为(111)。     

HEDP镀铜废水的组合处理方法

提出了一种HEDP镀铜废水的组合处理方法:用石灰乳液调节废水的pH至10~12后,加入氯化钙沉淀HEDP和酒石酸钾钠配位剂,从配合物中释放出的铜离子生成氢氧化铜沉淀;然后加入二甲基二硫代氨基甲酸钠沉淀残留的配合物中的铜离子,所释放出的HEDP及酒石酸根进一步与钙离子生成沉淀物。该方法简单、成本低,出水能满足排放要求。     

Differential Cytotoxicity Mechanisms of Copper Complexed with Disulfiram in Oral Cancer Cells

Disulfiram (DSF), an irreversible aldehyde dehydrogenase inhibitor, is being used in anticancer therapy, as its effects in humans are known and less adverse than conventional chemotherapy. We explored the potential mechanism behind the cytotoxicity of DSF-Cu⁺/Cu²⁺ complexes in oral epidermoid carcinoma meng-1 (OECM-1) and human gingival epithelial Smulow-Glickman (SG) cells. Exposure to CuCl₂ or CuCl slightly but concentration-dependently decreased cell viability, while DSF-Cu⁺/Cu²⁺ induced cell death in OECM-1 cells, but not SG cells. DSF-Cu⁺/Cu²⁺ also increased the subG1 population and decreased the G1, S, and G2/M populations in OECM-1 cells, but not SG cells, and suppressed cell proliferation in both OECM-1 and SG cells. ALDH enzyme activity was inhibited by CuCl and DSF-Cu⁺/Cu²⁺ in SG cells, but not OECM-1 cells. ROS levels and cellular senescence were increased in DSF-Cu⁺/Cu²⁺-treated OECM-1 cells, whereas they were suppressed in SG cells. DSF-Cu⁺/Cu²⁺ induced mitochondrial fission in OECM-1 cells and reduced mitochondrial membrane potential. CuCl₂ increased but DSF- Cu²⁺ impaired oxygen consumption rates and extracellular acidification rates in OECM-1 cells. CuCl₂ stabilized HIF-1α expression under normoxia in OECM-1 cells, and complex with DSF enhanced that effect. Levels of c-Myc protein and its phosphorylation at Tyr58 and Ser62 were increased, while levels of the N-terminal truncated form (Myc-nick) were decreased in DSF-Cu⁺/Cu²-treated OECM-1 cells. These effects were all suppressed by pretreatment with the ROS scavenger NAC. Overexpression of c-Myc failed to induce HIF-1α expression. These findings provide novel insight into the potential application of DSF-CuCl₂ complex as a repurposed agent for OSCC cancer therapy.     

铜-铈/ZSM-5分子筛催化剂制备及脱硝性能研究

氮氧化物是大气主要污染源之一,危害人体健康,并引发酸雨。随着环保法规的升级,氮氧化物排放浓度的限值要求越来越高。这要求脱硝工艺尤其是脱硝催化剂必须进一步提高脱硝性能。以ZSM-5分子筛为载体,以铜、铈为活性组分,制备脱硝催化剂活性组分;用铝胶将脱硝催化剂活性组分附着在蜂窝状陶瓷上,得到脱硝催化剂。与ZSM-5分子筛相比,脱硝催化剂活性组分增加了4.73%的铜（以CuO质量分数计）和5.40%的铈（以CeO₂质量分数计）,比表面积由287.04 m²/g降到275.05 m²/g,孔容、孔径未发生变化,酸性增强,晶型基本保持不变。脱硝催化剂最佳反应条件：反应时间≥60 min,反应温度≥250 ℃,空速≤10 200 h^-1。脱硝催化剂在最佳反应条件下的脱硝效率约为85%。脱硝催化剂能适应较低的反应温度,并且具有较高的脱硝效率。