Kinetics of the thermal dehydrations and decompositions of some mixed metal oxalates

Both isothermal and programmed temperature experiments have been used to obtain kinetic parameters for the dehydrations and the decompositions in nitrogen of the mixed metal oxalates: FeCu(ox)₂·3H₂O, CoCu(ox)₂·3H₂O and NiCu(ox)₂·3.5H₂O, [ox=C₂O₄]. Results are compared with those reported for the thermal decompositions of the individual metal oxalates, Cuox, Coox·2H₂O, Niox·2H₂O and Feox·2H₂O. X-ray photoelectron spectroscopy (XPS) was also used to examinee the individual and the mixed oxalates. Dehydrations of the mixed oxalates were mainly deceleratory processes with activation energies (80 to 90 kJ·mol⁻¹), similar to those reported for the individual hydrated oxalates. Temperature ranges for dehydration were broadly similar for all the hydrates studied here (130 to 180°C). Decompositions of the mixed oxalates were all complex endothermic processes with no obvious resemblance to the exothermic reaction of Cuox, or the reactions of physical mixtures of the corresponding individual oxalates. The order of decreasing stability, as indicated by the temperature ranges giving comparable decomposition rates, was NiCu(ox)₂>CoCu(ox)₂>FeCu(ox)₂, which also corresponds to the order of increasing covalency of the Cu−O bonds as shown by XPS. In celebration of the 60^th birthday of Dr. Andrew K. Galwey     

5－（4－乙酰氧基苯基），10，15，20－三苯基卟啉金属配合物修饰的铂支撑双层脂膜的IV性质

合成并表征了５－（４－乙酰氧基苯基），１０，１５，２０－三苯基卟啉及其金属配合物，将它们作为修饰物，制得铂支撑的双层脂膜，用循环伏安法研究了抗坏血酸的氧化还原反应，并对其机理作了探讨。     

单一稀土Ce, La和混合稀土在工业纯铝中的作用

通过对比实验的方法，研究了稀土Ce，La和混合稀土对工业纯铝组织、电性能和机械性能的影响。结果表明：单一稀土La，Ce可降低工业纯铝的电阻率，提高工业纯铝的导电性，其中La的效果优于Ce．而混合稀土对电阻率几乎无影响；La，Ce和混合稀土均能减小工业纯铝的晶粒度，在其加入量为0．1％后细化效果明显，当其含量大于0．5％后细化效果趋于平缓，其中Ce的效果最佳，La次之，混合稀土最弱；单一稀土La，Ce在一定含量时可提高工业纯铝的σb6和δ，Ce的作用强于La，混合稀土对σb和δ的影响不明显。     

Spin-transition behaviour of transition metal complexes with 2,6-bis-(benzimidazol-2′-yl)-pyridine induced by deprotonation of the complex

Summary 2,6-bis-(Benzimidazol-2-yl)-pyridine (bzimpy = H₂ L) acts as a bidentate ligand when combining with transition metal ions. The complexes [M(bzimpy)₂](ClO₄)₂ (M = Fe²⁺, Mn²⁺, Zn²⁺, Co²⁺, and Ni²⁺) were obtained as solids. The protonation constants (logK) for the ligand and the complexes were evaluated in 30:70 (v/v) H₂O:EtOH at 293 K and at constant ionic strength of 0.12M KCl. Coordination of the ligand to the metal ions leads to an increase of acidity of the imino-hydrogen of the benzimidazole group of the ligand as a function of the complex stability. Deprotonation leads to a spin-state transition (intermediate spin-state low-spin) of the iron(II)-complex, followed by a shift of the metal-to-ligandcharge transfer band (MLCT) to lower energies (_max=563 to 580 nm). The d-d absorption bands are found to shift to higher energies and the low-spin isomer is favoured at room temperature. An opposite shift of theMLCT band (_max=563 to 557 nm) is observed when HClO₄ is added to the complex solution, rendering the high-spin state of the complex more favourable.On leave from the Chemistry Department, Jahangirnagar University, Dhaka, Bangladesh     

以硫醚为主链的螯合树脂研究Ⅰ.4-氨基安替吡啉树脂和乙基原磺酸基树脂的合成及吸附性能

聚环硫氯丙烷或环硫氯丙烷与环氧氯丙烷共聚物，在少量二乙烯三胺存在下制得交联预聚物，将交联预聚物与4－氨基安替吡啉（4AAP）或乙基原磺酸钾（PEA）反应，制得四种侧链带氨基安替吡啉，乙基原碘酸基的新型螯合树脂。它们对贵金属具有优良的吸附性能和高的吸附选择性。并通过X－射线光电子能谱初步探讨了树脂对金属离子的螯合作用。     

金属配合物-寡聚核苷酸定位断裂剂研究进展

核酸切割试剂与寡聚核苷酸(ODN)偶联制得的人工核酸酶能在特定位点断裂DNA或RNA,为人工核酸酶的分子设计提供了一种新方法.本文综述了金属配合物-ODN识别切割试剂的偶联方式及其与靶分子的作用机制,并指出了今后的研究方向.     

过渡金属对分子筛担载Pd催化剂上CO氧化性能影响

分别采用共浸和连续浸渍法制备了一系列添加过渡金属的Pd-M-Ox-NaZSM-5(M=Cr，Mn，Fe，Co，Ni，Cu，Zn，Mo，Zr等)负载型催化剂．以CO氧化为探针反应，考察了不同制备方法对CO氧化性能影响，结果表明共浸法制备的各催化剂其活性明显优于连续浸渍法．详细考察了反应温度、Fe含量、氢气预还原、空速以及水蒸气等对共浸Pd-Fe-Ox-NaZSM-5催化剂上CO氧化行为影响，并应用XRD和XPS等手段对催化剂体相结构和表面状态进行了表征．结果表明：加入Fe2O3可明显提高Pd/NaZSM-5催化剂活性，且催化CO氧化的转化率随反应温度及Fe含量增加而增加；空速增加以及H2预还原作用导致Pd-Fe-Ox-NaZSM-5活性有所降低；催化剂对水蒸气较为敏感．XRD测试结果表明催化剂中Pd组分处于较高分散状态，以红铁矿形式存在的Fe2O3的引入，促进了Pd物种在NaZSM-5载体上的分散．表面XPS分析证实Fe2O3与Pd物种间存在较强的相互协同作用，且催化剂表面Pd物种处于较高氧化状态．Pd的高分散及其与Fe2O3的相互协同作用是共浸催化剂具有高活性的关键因素．     

Theoretical study on interaction of different coordination modes of BH4 ligand with transition metal in [TM(BH4)(CO)4] (TM = Cr, Mo)

Density functional calculations were performed on bonding and structural features of [(ηⁿ-BH₄)TM(CO)₄]⁻ (n = 1, 2, 3; TM = Cr, Mo) complexes. Calculations show that the ground state is bidentate which is in good agreement with experimental results. It has been found that the bridge and terminal hydrogen atoms will interchange by two pathways: (i) twist of BH₄ about one of the bridge B-H and (ii) twist of BH₄ about one of the terminal B-H. The molecular orbital calculations and natural bond orbital methodologies for different isomers of these complexes have been evaluated. The final results indicate that case (i) is more preferable relative to another case.     

Design of Supramolecular Cyclodextrin Complex Sensors for Ion and Molecule Recognition in Water

The design and function of novel supramolecular fluoroionophore/cyclodextrin (CyD) complex sensors for ion and molecule recognition in water are reviewed. For the crown ether fluoroionophore/-CyD complex, the dimerization of the fluoroionophore inside the -CyD is found to be selectively promoted by alkali metal ion binding, thereby resulting in metal-ion-selective pyrene dimer emission in water. This supramolecular function is successfully utilized in the design of a podand fluoroionophore/-CyD complex for sensing toxic lead ion in water. The boronic acid fluoroionophore/-CyD complex binds sugars and produces increased fluorescence emission in water. The response mechanism appears to be due to the suppression of the photoinduced electron transfer (PET) from pyrene donor to trigonal phenylboronic acid acceptor. This is a novel emission function provided by the boronic acid fluoroionophore/-CyD complex sensors in water.     

担体对Fe—MnO催化剂CO＋H2反应性能的影响

考察氧化物担体对Fe-MnO催化剂反应性能影响的结果表明,担体的类型对Fe-MnO催化剂CO加氢反应性能影响很大,其低碳烯烃选择性相差悬殊,Al_2O_3、SiO_2和MgO担载的Fe-MnO催化剂都不利于低碳烯烃的生成,而TiO_2担载的Fe-MnO催化剂则具有较高的烯烃选择性和催化活性。从担体-金属相互作用本质的差异,研究了担体对金属活性组分化学状态的影响及催化活性相与F-T合成烯烃的关系,发现担体-金属间的电子效应有利于催化剂活性和选择性的提高,其它物理化学效应引起的相互作用则不利于改善催化剂性能;还表明Fe_(?)C是催化活性相,Fe~(2+)物种的存在不利于提高烯烃的选择性。