Novel Substitution Reactions of 5-（4-Nitrophenyl）-10,15,20-TriphenylPorphyrin with Nucleophilic Reagents

Substitution reactions of 5-（4-nitrophenyl）-10, 15,20-triphenylporphyrin （NO2 TPP） and its metal complexes with different nucleophilic reagents were studied for preparing asymmetric porphyrin. The reaction products are different with the nucleophilic reagents changing, and three different products were found. The first obtaining product was diporphyrin when NO2 TPP reacted with sodium phenoxide or diphenoxide in DMF solution; The second was reduced product 5-（4-aminophenyl）-10, 15, 20-triphenylporphrin-M （Ⅱ） when the metal （Ni,Zn） complex of NO2 TPP reacted with above nucleophilic reagents, as well as NO2 TPP reacted with lithium mercaptoethanolate or lithium thiophenolate; The third product CNTPP was achieved with the substitution of nitro group by cyanic anion when NO2 TPP reacted with radium cyanide. Above results were explained with reduction and single electron transfer reaction respectively.     

过渡金属和镧系金属卟啉配合物的合成与表征

合成了新型5, 10, 15, 20-四(对-(4-氟苯甲酰氧基苯基))过渡金属卟啉和新型镧系乙酰丙酮-5, 10, 15, 20-四(对-(4-氟苯甲酰氧基苯基))卟啉配合物，并用元素分析，紫外可见光谱，红外光声光谱，摩尔电导，核磁共振氢谱以及X-射线光电子能谱对其组成和结构进行了表征.     

贵阳市表层土壤重金属污染元素之间的相关分析

主要介绍贵州省贵阳市0~20 cm表层土壤中我国《土壤环境质量标准》中规定含量的8种重金属环境污染元素(汞、镉、铅、铬、砷、锌、铜、镍)含量之间的相关性分析。本文得出达到极相关显著水平(P<0.01)的元素对有:As—Pb、Cd—Cr、N i—Cd、Cu—Cr、Cr—N i、Cr—Zn、Cu—N i、Cu—Pb、Cu—Zn、N i—Zn、Pb—Zn,达到相关显著水平(P<0.05)的元素对有:As—Zn、Cd—Hg、Cd—Zn、Pb—N i。并对相关原因作简单分析。     

Synthesis of novel polymer-bonded water-soluble metal porphyrins

The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru₃(CO)₁₂], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a−2d respectively. Treatment of 2a−2d with Merrifield’s peptide resin obtained 3a−3d. The compounds 3a−3d reacted with methyl iodide respectively gave 4a−4d. New complexes 4a−4d have been identified by IR, UV-visible spectra, and AES. Foundation item: Supported by the Natural Science Foundation of Hubei Province Biography: LI Zao-ying (1949-), female, Associate professor.     

Synthesis and characterization 9-tungstosilicate complexes with transition metal

The title complexes K_aH_b[M(SiW₉O₃₄)₂]·mH₂O(M=Ni,Cu,Zn,Fe or Mn) were synthesized by SiW₉O₃₄ ¹⁰⁻ with transition metal respectively and their structure were characterized by mean of elemental analysis, TG-DTA, IR spectra and, UV spectra. In addition, their redox properties in solution were investigated using polarographic and cyclic voltammographic methods. Experimental results indicated that the complexes have Keggin structure and that the heteropolyanions underwent two-step, two-electron tungsten reduction processes. Biography: Jin Su-rong (1963-), female, Lecturer.     

Study of spectrophotometric method for determination of trace copper after the separation and enrichment with solid phase extractant-microcrystalline phenolphthalein

A new method of using phenolphthalein loaded with 1-(2-pyridylazo)-2-naphthol (PAN) as solid phase extractant to separate and enrich trace copper in diverse water samples has been developed. The ef- fects of different parameters, such as the amounts of PAN and phenolphthalein, stirring time, various salts and metal ions on the enrichment yield of Cu(II) have been investigated to select the experimental conditions. Under the optimum conditions, Cu(II) can be totally adsorbed on the surface of microcrys- talline phenolphthalein. By controlling appropriate acidity (pH=1.0), Cu(II) is completely separated from Cd(II), Pb(II), Mn(II), Co(II), Fe(III), Ni(II), Al(III), Zn(II) and Hg(II) in the solution. The possible reaction mechanism of the enrichment of copper is discussed in detail in this paper. The detection limit of this proposed method is found to be 0.03 μg·L-1 with the enrichment factor of 200. The recovery is in a range of 96.8%―105%. The standard deviation is less than 2.5%. The proposed method has been successfully applied to the determination of trace copper in different water samples with satisfactory results.     

NMR studies of the interaction betweenBacillis subtilis neutral proteinase and inorganic metal compounds

The interaction betweenBacillis subtilis neutral proteinase (B.S.NP) and inorganic metal compounds (CoCl₂, NiCl₂) was investigated by¹H NMR spectroscopy. It has been shown that the Zn(II) ion in the active center of the native enzyme may directly interact with external CoCl₂ and NiCl₂, producing Co(II)- and Ni(II)-substituted derivatives, and their¹H NMR spectra were obtained for the first time. From the¹H NMR spectra, the coordinated structure of the active center in the native enzyme was described.     

过渡金属离子协同紫外活化过硫酸盐

为研究不同过渡金属离子协同紫外(UV)活化过一硫酸盐(PMS)的能力,以Co~(2+)为基准进行Cu~(2+)、Mn~(2+)、Ni~(2+)、Zn~(2+)和Fe~(3+)协同紫外活化PMS的对比实验。结果显示:Cu~(2+)、Mn~(2+)、Ni~(2+)、Zn~(2+)和Fe~(3+)与单独紫外和单独PMS联合均不能有效降解目标物;与Co~(2+)/PMS/UV体系相比,Cu~(2+)、Mn~(2+)、Ni~(2+)、Zn~(2+)和Fe~(3+)协同紫外活化PMS的能力高于Co~(2+),其中Cu~(2+)、Mn~(2+)和Fe~(3+)的协同能力高于Ni~(2+)和Zn~(2+);投加叔丁醇(TBA)和乙醇(EA)的实验发现,Cu~(2+)/PMS/UV、Mn~(2+)/PMS/UV和Fe~(3+)/PMS/UV体系中的主要氧化物是硫酸根自由基(SO_4~-·)和少量的羟基自由基(HO·)。Cu~(2+)/PMS/UV、Mn~(2+)/PMS/UV和Fe~(3+)/PMS/UV体系中AO7的降解过程均符合假一级动力学。紫外可见光谱图分析结果表明,Cu~(2+)/PMS/UV、Mn~(2+)/PMS/UV和Fe~(3+)/PMS/UV体系中AO7均被有效降解。M/PMS/UV对于染料类物质具有广泛的应用范围。     

邻香兰素-D,L-苏氨酸过渡金属配合物的合成、表征及热稳定性研究

采用分步合成法合成了以邻香兰素－D，L－苏氨酸席夫碱为配体的铜、锌、钴、镍配合物，并进行了元素分析和红外光谱表征。同时，利用差热分析对配合物的热稳定性进行了研究，得出其热稳定性次序为：钴配合物＞锌配合物＞镍配合物＞铜配合物。     

基于地统计学方法的城市灰尘重金属污染的空间变异特征

运用ArcGIS的地统计学组件,分析了金华市城市地表灰尘中重金属Ph、Cr、Cu、Zn、Ni、Mn的空间分布特征．结果表明：上述重金属具有复合污染或一定的同源性特征,其中Pb、Cr、Cu、Mn可能主要受金华市城市产业布局和功能分区等结构性因素的影响,而Zn则受非结构性因素影响更大,来源比较复杂．Ph、Cr、Cu、Zn、Ni等重金属的空间分布比较相似．     

Synthesis of Schiff bases of naphtha[1,2-d]thiazol-2-amine and metal complexes of 2-(2′-hydroxy)benzylideneaminonaphthothiazole as potential antimicrobial agents

Objective: A series of 2-benzylideneaminonaphthothiazoles were designed and synthesized incorporating the lipophilic naphthalene ring to render them more capable of penetrating various biomembranes. Methods: Schiff bases were synthesized by the reaction of naphtha[1,2-d]thiazol-2-amine with various substituted aromatic aldehydes. 2-(2′-Hydroxy)benzylideneaminonaphthothiazole was converted to its Co(II), Ni(II) and Cu(II) metal complexes upon treatment with metal salts in ethanol. All the compounds were evaluated for their antibacterial activities by paper disc diffusion method with Gram positive Staphylococcus aureus and Staphylococcus epidermidis and Gram negative Escherichia coli and Pseudomonas aeruginosa bacteria. The minimum inhibitory concentrations of all the Schiff bases and metal complexes were determined by agar streak dilution method. Results: All the compounds moderately inhibited the growth of Gram positive and Gram negative bacteria. In the present study among all Schiff bases 2-(2′-hydroxy)benzylideneaminonaphthothiazole showed maximum inhibitory activity and among metal complexes Cu(II) metal complex was found to be most potent. Conclusion: The results obtained validate the hypothesis that Schiff bases having substitution with halogens, hydroxyl group and nitro group at phenyl ring are required for the antibacterial activity while methoxy group at different positions in the aromatic ring has minimal role in the inhibitory activity. The results also indicated that the metal complexes are better antibacterial agents as compared to the Schiff bases.     

造纸污泥焚烧中Zn/Cu/Ni/Mn的热力学平衡分布

采用化学热力学平衡分析方法,应用造纸污泥实测数据预测了其焚烧中重金属(Ni、Mn、Zn和Cu)的迁移和转化规律.研究结果表明,考虑矿物质存且在低温条件下,造纸污泥焚烧中重金属Ni和Zn易与Fe2O3结合形成稳定的固体化合物,从而抑制了Ni和Zn的挥发性,而对Mn和Cu没有影响.焚烧温度为400—1800K范围内有矿物质存在条件下,Mn未出现其气体产物,而其他三种金属在高温条件下则以其气态单质或气态氧化物挥发进入大气环境.焚烧过程中只有小部分气态CuCl生成,未见其它气态金属氯化物;在焚烧温度为400—1800K条件下未发现金属硫化物或者硫酸盐生成,表明在有矿物质存在条件下S对金属的挥发性影响很小.在未考虑矿物质存在条件下,S在低温条件下易与重金属结合形成金属硫酸盐固体从而拟制了金属的挥发;随着温度的升高,Cl和重金属易形成金属氯化物气体,促进了金属的挥发特性,并且Cl对Cu的挥发影响较大,其次为Zn和Mn,影响较小的金属是Ni.从而根据污泥在不同焚烧温度下不同的产物形态进行重金属的污染控制.     

Bioaccumulation of heavy metal in wild growing mushrooms from Liangshan Yi nationality autonomous prefecture,China

The heavy metal bioaccumulation levels of 13 species of mushrooms were studied. 13 different species of wild mushrooms growing in China were analyzed for Cu, Zn, Pb, Cd, and As. Contents of Cu, Zn, Cd and Pb in mushroom and Cu, Zn in Soil were tested by atomic absorption spectrometer （AAS）, and As in samples by atomic fluorescent light （AFL）. Contents of Cd and Pb in soil were analyzed by graphite furnace AAS. The results showed that contents of Cu, Pb, Cd, and As in Termitomyces microcarpus were the highest in the tested mushroom samples, which were 135.00, 13.28, 65.30, and 1.60 mg·kg^-1 （dry biomass） respectively, and the corresponding bioconcentration factor （BCF） for Cu and Cd was 57 and 1 674 separately, which was the highest data in 13 mushroom species. The capability ofBoletus griseus for Cd accumulation was very strong with BCF of 300. when people consume the wild edible mushrooms, contents of Cd and Pb should be greatly considered.     

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）.     

垃圾焚烧飞灰中重金属的传统与生物电沉积联用技术研究

为了探究深圳市城市生活垃圾焚烧飞灰中主要重金属含量和浸出浓度, 选择浸出浓度超标的Cu(II) (100 mg/L), Pb(II) (200 mg/L) 和Zn(II) (300 mg/L)作为研究对象, 联合生物电化学系统(BES)和传统电沉积反应器(ER), 验证从飞灰浸出溶液中分离回收Cu, Pb和 Zn的可行性和经济性。研究结果表明, BES能有效地将混合溶液中的Cu(II)还原为单质, 去除效率大于98%。分步施加1.5 V和2.5 V 外加电压, ER可以分别将Pb(II)和Zn(II)浓度由200和300 mg/L降至23.5±1.1和4.3±0.2 mg/L。系统能耗分析结果显示, BES系统每还原1 kg Cu(II), 可以产生16.55 kWh的额外电能, ER系统每处理1 kg Pb(II)和Zn(II), 分别消耗60.91和114.27 kWh的电能, 溶解性重金属离子被转化为固态单质、氧化物和含重金属盐等。BES和ER联用技术表现出回收重金属和节约电能的双重优势。     

Visible-light photocatalytic H2 evolution over a series of transition metal substituted Keggin-structure heteropoly blues

The visible light photocatalytic H 2 evolution activities of a series of transition-metal substituted Keggin-structure heteropoly blues K 6 SiW 11 O 39 M(H 2 O)·nH 2 O (M=Co,Ni,Cu and Zn) were systematically studied with Pt nanoparticles as co-catalyst.The H 2 evolution rates were 150,98,65 and 48 mol h-1g-1 for SiW 11 Cu,SiW 11 Ni,SiW 11 Co and SiW 11 Zn,respectively,meaning that the order of photocatalytic activity of these heteropoly blues from transition-metal substituted polyoxometalates was:SiW 11 Cu > SiW 11 Ni > SiW 11 Co > SiW 11 Zn.The catalysts could be efficiently reused for at least 5 cycles.     

Synthesis of Novel Covalent-linked Linear Porphyrin-Thiophene Copolymers

0　IntroductionTheconstructionofmacro molecularsystemcontainingmul tipleredoxcentersorphotosensitizersisanimportantsub jectinthedesignofmolecularelectronicdevices[1 ,2 ] .Forsuchobjectives,systematizationofdonor (redoxcenter) acceptortriadmoleculesintolargemolecularsystemsisoneofthemostfeasibleapproaches,becausetheexquisiteincorporationofthephotosensi tizersandsuitableelectrondonorsand /oracceptorsintoapoly mericchainisusefulforvariousmolecularsystembasedonphoto inducedelectrontransfer[3 ,4] …     

上海某化工区土壤重金属污染情况的调查与评价

以上海某化工区周边土壤为研究对象, 研究了土壤重金属污染特征, 对土壤样品中Ag, As, Be, Cd, Cr, Cu, Ni, Pb, Se, Sb, Tl, Zn 和Hg 共13 种金属的空间分异结构进行了分析, 并利用单因子指数法和内梅罗综合指数法评价了土壤重金属的污染程度. 结果表明, 土壤样品中Ag, As, Be, Cd, Cr, Cu, Ni, Pb, Se, Sb, Tl, Zn和Hg的平均含量分别为0.10, 10.20, 2.50, 0.60, 93.00, 78.00, 33.80, 14.90, 1.00, 3.45, 0.40, 124.00, 0.19 mg/kg. 以展览会用地A 级标准为评价标准, 土壤样品中Cu, Zn, Cd 的超标率较高, 分别占样品总数的12.20%, 8.16% 和8.16%; Cr, Ni, Sb, Hg的超标率在4.08%~6.12% 之间. 采用立体分层方式采集样品, 分析结果表明, 表层和中层土壤受到的金属污染比较严重, 但随着采样深度的增加, 土壤重金属浓度有不断降低的趋势. 对土壤重金属元素间的相关性进行了研究, 表明重金属污染来源具有同源性, 或者区域土壤中存在复合污染.     

峰峰煤矿塌陷区典型农田土壤剖面重金素元素化学风化规律

采集峰峰煤矿塌陷区典型农田剖面土壤,通过测定分析不同埋深土壤重金属元素(As、Cu、Ni、Pb、Cr、Cd、Zn和Hg)分布特征,利用质量平衡理论进行化学风化规律研究,探究塌陷驱动下剖面土壤重金属元素化学风化过程.结果 表明:峰峰煤矿塌陷区典型农田剖面土壤重金属元素Pb、Cd和As的含量超过国家农用地土壤污染风险管控标准,最大超标倍数分别为3.86、59.77、3.82;元素Cu、Ni、Zn、Cr和Hg未超标.重金属元素Cd和As可能在塌陷驱动下,受地表径流和雨水淋滤下渗影响,使得其含量自表层向下逐渐增加.表层土壤元素Cu、Pb、Cr、Hg迁入富集,元素Ni、As、Zn和Cd迁出淋滤;犁底层元素Cu、Ni、Zn和Pb迁出淋滤,Hg迁入富集,其余元素规律变化不明显.累积元素存在潜在风险,需要监控;淋滤元素存在直接风险,需要高度管控.实验结论为全面评估煤矿开采对土壤化学性能的影响,防治流域水土流失和保护区域生态环境提供科学依据.     

广东东莞地区土壤-蔬菜系统重金属分布与富集特性分析

 对东莞地区常见的7种叶菜类蔬菜及其相应的土壤样品中Cu、Zn、Cr、Ni、Pb等重金属元素的全量和稀盐酸可提取态进行了分析。结果表明,蔬菜存在明显的有毒金属元素Pb、Ni超标和有益金属元素Cu、Zn缺乏问题。蔬菜重金属含量与土壤重金属总量和可提取态重金属含量均无显著的相关性,但基于可提取态含量的富集系数与蔬菜重金属含量具有显著相关性。因此,在评价土壤重金属污染对作物的影响时,仅仅用土壤重金属可提取态含量仍不足以有效反应土壤污染的生态危害性。不同品种蔬菜对同一重金属元素的富集不尽相同,总体而言,叶菜类蔬菜对金属元素的富集具有较强的选择性,对Cr的富集能力最强,其次为Zn、Cu、Ni,Pb最弱。但因土壤中Cr、Zn、Cu的可提取态含量及可提取态系数均较低,故作物未出现超标,蔬菜中Pb含量超标的成因较为复杂,以大气污染为主要来源。