铁（Ⅲ）催化下的鲁米诺化学发光体系的研究

一些高能化学反应可导致电子激发态产物的产生,这些产物本身若能发射光子或将其能量传递给其它发射物质,便产生化学发光(CL)现象。化学发光的首要条件是反应能提供足够的激发能,通常只有那些反应速度相当快的高能反应,其—ΔG介于170—300kJ/mol之间,才有可能在可见光范围内观察到化学发光现象。而氧化还原反应所释放的能量通常在这个范围内,因此多数化学发光反应是氧化还原反应。     

硅酸盐中Fe（Ⅱ）、Fe（Ⅲ）含量的测定及条件的探讨

硅酸盐经浓盐酸和少量的SnCl2溶液溶解后，用SnCl2-TiCl3还原试液中Fe（Ⅲ），使Fe（Ⅲ）还原为Fe（Ⅱ），再以KzCr2O7滴定，测得铁含量。本方法对实验操作温度，试样溶解酸的选择有一定的要求，宜选用非氧化性强酸在30-60℃溶解矿样。     

负催化光度法测定微量铁──Fe（Ⅲ）──H_2O_2──甲基紫体系

提出了一种褪色光度法测定Ｆｅ３＋的新方法．即在Ｆｅ３＋的催化作用下，Ｈ２Ｏ２在稀Ｈ２ＳＯ２的酸性环境中氧化甲基紫使其褪色．Ｆｅ３＋线性范围０～６μｇ／２５ｍＬ，本法选择性好，用于地面水和地下水的测定，结果满意．     

Al（Ⅲ）—PAN荧光熄灭法测定Cr（Ⅲ）

在对各种Ｍ－ＰＡＮ络合物的荧光作出研究之后,发现Ｃｒ（Ⅲ）－ＰＡＮ不产生荧光,但是,在纯乙醇中,由Ａｌ（Ⅲ）－ＰＡＮ络合物的荧光熄灭,可以测定Ｃｒ（Ⅲ）的含量,检出限达１０－８Ｍ。     

Fe（CN）_6~（3－）／Fe（CN）_6~（4－）体系扩散系数测定方法的比较

本文用循环伏安法、计时电位法、计时电流法、计时电量法和旋转圆盘电极研究了Ｆｅ（ＣＮ）_６~（３－）／Ｆｅ（ＣＮ）_６~（４－）体系的电化学反应过程，用上述几种电化学方法测定了Ｆｅ（ＣＮ）_６~（３－）／Ｆｅ（ＣＮ）_６~（４－）离子的扩散系数，对测定的方法和结果作了全面的分析比较．     

Fe(Ⅲ)-草酸配合物光分解降解苯酚的研究

文章研究了Fe( )-草酸配合物在可见光及太阳光照射下,对苯酚的光解降解作用。结果表明,在pH=5.0、cFe( )=0.040mmol/L、cH2C2O4=1.44mmol/L(草酸分3次加入)及光照3h的条件下,20mg/L的苯酚的降解率为91%。溶液pH值、铁与草酸浓度比和苯酚浓度均对降解效果产生影响。     

水中痕量Fe(Ⅲ)富集方法的研究

本文以环氧氯丙烷为交联剂，与β-环糊精反应，生成一种具有三维网状结构并不溶于水的大分子物质。该物质与显色剂二甲酚橙作用，络合成包结树脂。用该村服富集水中痕量Fe（Ⅲ），结果令人满意。     

以氯磺酚S反相高效液相色谱法分离测定铝（Ⅲ）、铬（Ⅲ）、铌（Ⅴ）、铜（Ⅱ）

用氯磺酚Ｓ作柱前显色剂以反相高效液相色谱法测定铝（Ⅲ）、铬（Ⅲ）、铌（Ⅴ）、铜（Ⅲ）离子，固定相为Ｓｈｉｍ－ｐｏｃｋＯＤＳ柱（１５０ｍｍ×６ｍｍ）．流动相为含有６×１０￣（－２）ｍｏｌ／Ｌ溴化四乙铵，１×１０￣（－２）ｍｏｌ／Ｌ乙酸盐缓冲溶液（ｐＨ３．５）的乙腈（３８％）－四氢呋喃（２％）－水（６０％）溶液。流量１．０ｍｌ／ｍｉｎｎ。用紫外可见分光光度检测器于５７０ｎｍ处进行检测，在此条件下，铝（Ⅲ）、铬（Ⅲ）、铌（Ⅴ）、铜（Ⅱ）得到很好的分离，方法具有高灵敏度和良好的选择性，可用于水、大米、面粉和人发分析。     

杯芳烃的配位化学（XI）：4种杯[4]芳烃萃取铁（Ⅲ）的研究

合成了杯［４］芳烃、四对叔丁基杯［４］芳烃、四乙氧基羰基甲氧基四对叔丁基杯［４］芳烃、四乙酰基甲氧基四对叔丁基杯［４］芳烃等４种杯芳烃,研究了这些杯芳烃对铁（Ⅲ）的萃取化学,讨论了这些体系的萃取机理,并求出了它们的萃取平衡常数。     

Sb（Ⅲ）-HCl-H_2O体系中Sb（Ⅲ）浓度分布的理论计算

针对Sb（Ⅲ）-HCl-H2O体系,应用热力学计算方法,根据同时平衡原理,建立了数学模型,以Sb（Ⅲ）的总浓度5×10-5 mol/L为例,计算了不同pH时Sb（Ⅲ）的各种存在形式的浓度分布.计算结果表明,pH=1.3～4.0时,SbO＋是主要存在形式,且n（SbO＋）/n（Sb总）〉99.8%.     

Availability and toxicity of Fe(II) and Fe(III) in Caco-2 cells

The objective of the present study was to compare the toxicity and availability of Fe(II) and Fe(III) to Caco-2 cells. Cellular damage was studied by measuring cell proliferation and lactate dehydrogenase (LDH) release. The activities of two major antioxidative enzymes [superoxide dismutase (SOD) and glutathione peroxidase (GPx)] and differentiation marker (alkaline phosphatase) were determined after the cells were exposed to different levels of iron salts. The cellular iron concentration was investigated to evaluate iron bioavailability. The results show that iron uptake of the cells treated with Fe(II) is significantly higher than that of the cells treated with Fe(III) (P<0.05). Fe(II) at a concentration >1.5 mmol/L was found to be more effective in reducing cellular viability than Fe(III). LDH release investigation suggests that Fe(II) can reduce stability of the cell membrane. The activities of SOD and GPx of the cells treated with Fe(II) were higher than those of the cells treated with Fe(III), although both of them increased with raising iron supply levels. The results indicate that both Fe(II) and Fe(III) could reduce the cellular antioxidase gene expression at high levels.     

氧氟沙星荧光光度法测定痕量铁

研究了在HAc-NaAc缓冲溶液中氧氟沙星与Fe(Ⅲ)的络合反应，结果表明：在pH=4．0的缓冲溶液中，氧氟沙星有稳定而较强的荧光；与Fe(Ⅲ)络合后，荧光强度减弱．最大激发及发射波长为324nm和498．6nm，Fe(Ⅲ)的质量浓度在0．56～3．08mg／L范围内，荧光强度与浓度呈良好的线性关系．检出限为0，076mg／L，常见的共存离子不干扰其测定．本方法用于水中痕量铁的测定，得到了满意的结果。     

Investigation of performances and mechanism of fluoride removal by Fe (III)-loaded ligand exchange cotton cellulose adsorbent

Novel adsorbent, Fe(III)-loaded ligand exchange cotton cellulose adsorbent [Fe(III)LECCA], was used to investigate the adsorption performances and mechanism of fluoride removal from aqueous solutions. The adsorbent was found to adsorb fluoride rapidly and effectively. The fluoride removal was influenced by pH. Adsorption model followed first-order reaction at different temperature, theapparent adsorption activated energyE, was 6.37 kJ·mol⁻¹, and adsorption enthalpy ΔH was 5.35 kJ·mol⁻¹. The adsorption capacity of fluoride on adsorbent was 3.2 mmol·g⁻¹ (dry weight). The maximal integer coordination ratio of fluoride with Fe(III) LECCA was 3∶1. The ligand exchange mechanism of adsorption was elucidated through chemical methods and IR spectral analysis. Foundation item: Supported by the National Natural Science Foundation of China (29977010) and Shanghai Priority Academic Discipline Biography: ZHAO Ya-ping (1974-), female, Ph.D., research direction: water and wastewater treatment.     

Geobacter metallireducens accesses insoluble Fe(III) oxide by chemotaxis

Microorganisms that use insoluble Fe(III) oxide as an electron acceptor can have an important function in the carbon and nutrient cycles of aquatic sediments and in the bioremediation of organic and metal contaminants in groundwater. Although Fe(III) oxides are often abundant, Fe(III)-reducing microbes are faced with the problem of how to access effectively an electron acceptor that can not diffuse to the cell. Fe(III)-reducing microorganisms in the genus Shewanella have resolved this problem by releasing soluble quinones that can carry electrons from the cell surface to Fe(III) oxide that is at a distance from the cell. Here we report that another Fe(III)-reducer, Geobacter metallireducens, has an alternative strategy for accessing Fe(III) oxides. Geobacter metallireducens specifically expresses flagella and pili only when grown on insoluble Fe(III) or Mn(IV) oxide, and is chemotactic towards Fe(II) and Mn(II) under these conditions. These results suggest that G. metallireducens senses when soluble electron acceptors are depleted and then synthesizes the appropriate appendages to permit it to search for, and establish contact with, insoluble Fe(III) or Mn(IV) oxide. This approach to the use of an insoluble electron acceptor may explain why Geobacter species predominate over other Fe(III) oxide-reducing microorganisms in a wide variety of sedimentary environments.     

Fe(III)掺杂对TiO2光催化活性的影响机理

采用平面波赝势(PWPP)方法进行密度泛函(DFT)总能量计算,优化了TiO2超晶胞构型参数,模拟计算了Fe(III)掺杂锐钛矿TiO2对能隙、Fermi能级、态密度的影响.Fe(III)掺杂锐钛矿TiO2晶体后禁带(Eg)变小,TiO2的Fermi能级降低,使TiO2 的吸收带红移,同时电子-空穴在表面的复合几率降低,从而增强了光催化的活性.     

铁催化烯基环丙烷类化合物的三氟甲基化反应

对铁催化的烯基环丙烷类化合物的自由基三氟甲基化反应进行了研究.以中等到良好的收率获得了含三氟甲基的二氢萘衍生物.方法具有反应条件温和,催化剂廉价易得,反应时间短等优点.同时对反应机理进行了初步研究.     

Crystal structure and photoelectricity property of Fe(II/III) coordination supermolecules

Three new mixed-ligand Fe(II/III) complexes [Fe₂(μ₂–btec)(μ₂–H2btec)(phen)₂(H₂O)₂]_n (1), [Fe2(btec) (phen)₂(H₂O)₄] (2), and {[Fe(o-pha)(phen)(H₂O)]•H₂O}_n (3) (phen=1,10-phenanthroline, o-H₂pha=o-phthalic acid, H₄btec=1,2,4,5-benzenetetracarboxylic acid) have been hydrothermally synthesized and detected by single crystal X-ray diffraction, showing that complexes (1) and (2) are both bridged by the betc⁴⁻ ligands to form 1D chain and dinuclear structure and complex (3) is bridged by the o-pha groups to form 1D chain structure. The coordinated modes of the carboxyl groups adopt μ₂-η¹η¹ηη¹η¹ and μ₂-η²η¹ respectively in com-plexes (2) and (3). The betc groups in complex (1) show two different coordinated modes: μ₂-η¹η¹η¹η¹ and μ₂-η¹η¹. In addition, the hydrogen bonds and π…π type interactions make the complex molecule further connect to three-dimensional and two-dimensional networks respectively. These complexes are detected by IR, UV-Vis-NIR and surface photovoltage spectrum (SPS). The SPS of complexes (1)–(3) indicate that there are positive SPV responses in the range of 300–600 nm and show p-type semiconductor characteristic. Because the structure, the valence and the coordinative environment of the Fe ions are all different in the three complexes, the intensity, position and the number of the response bands are different obviously. The results of SPS are corresponding with UV-Vis-NIR spectra.     

Cu~(2+)-catalyzed mechanism in oxygen-pressure acid leaching of artificial sphalerite

The potential autoclave was used to study the catalytic mechanism of Cu~(2+) during the oxygen pressure leaching process of artificial sphalerite. By studying the potential change of the system at different temperatures and the SEM–EDS difference of the leaching residues, it was found that in the temperature range of 363–423 K, the internal Cu~(2+) formed a Cu S deposit on the surface of sphalerite, which hindered the leaching reaction, resulting in a zinc leaching rate of only 51.04%. When the temperature exceeds 463 K, the system potential increases steadily. The increase in temperature leads to the dissolution of the CuS, which is beneficial to the circulation catalysis of Cu~(2+). At this time, the leaching rate of Zn exceeds 95%. In addition, the leaching kinetics equations at 363–423 and 423–483 K were established. The activation energy of zinc leaching at 363–423 and 423–483 K is 38.66 and 36.25 kJ/mol, respectively, and the leaching process is controlled by surface chemical reactions.     

Fe/MCM-41催化臭氧氧化水中对氯苯甲酸

利用水热法合成介孔材料MCM-41及Fe负载的MCM-41（Fe/MCM-41）,并通过催化臭氧氧化水中对氯苯甲酸（p-CBA）考察其催化性能.经过X射线粉末衍射（XRD）、紫外可见漫反射光谱（DR UV-Vis）、傅立叶红外光谱（FT-IR）及比表面（BET）表征,表明所合成的MCM-41及Fe/MCM-41具有较规则的六方孔道结构及较大的比表面积.MCM-41与Fe/MCM-41的加入有利于p-CBA和TOC的去除,其中Fe/MCM-41与O3具有协同效应,表现出较好的催化活性.     

卫星导航定位系统（三）

介绍了欧盟与其他国家的合作和中国加入伽利略计划的情况，分析了印度加紧发展空间技术的情况。