多苯并咪唑锰( Ⅱ )配合物的合成及对DNA凝聚的促进作用

以多苯并咪唑配体1,1,4,7,7-五(2-苯并咪唑甲基)-二乙基三胺(DTPB)为主配体, 合成了锰(Ⅱ)配合物[Mn(DTPB)Ac]Ac·8H₂O(1)和[Mn₂(DTPB)(NO₃)₂(H₂O)₂][Mn₂(DTPB)(NO₃)₂(H₂O)(CH₃OH)]·(NO₃)₄·5CH₃OH·H₂O(2), 并对其进行了表征. 利用紫外-可见吸收光谱和黏度实验研究了配合物1和2与DNA的相互作用, 发现这2个配合物均能与DNA结合, 并对配合物与DNA作用的机理进行了探讨. 利用琼脂糖凝胶电泳和直角光散射(RALS)技术研究了配合物1和2促进DNA凝聚的性质. 结果表明, 在近中性条件下2个配合物都能促使DNA凝聚. 利用透射电子显微镜(TEM)观察了不同凝聚体的形态.     

Mg-MOF-74对CO2/H2O的吸附性能

以Mg(NO₃)₂·6H₂O和2,5-二羟基对苯二甲酸为原料, 采用溶剂热法制备了金属有机骨架材料Mg-MOF-74. 利用X射线衍射(XRD)、 红外光谱(FTIR)和扫描电子显微镜(SEM)等测试手段对其结构、 形貌和性能进行了分析, 并利用自制穿透实验装置研究了产物吸附CO₂/H₂O的性能. 结果表明: 合成的样品纯度高, 结构完整, 形貌规则有序, 具有较高的CO₂吸附量. 双组分CO₂/H₂O穿透实验结果证实, 在水蒸气存在情况下, 与沸石13X相比, Mg-MOF-74仍具有较高的CO₂吸附能力, 可用于分离高湿烟道气中的CO₂.     

基于柔性四羧酸的三个一维/二维/三维Zn(Ⅱ)/Co(Ⅱ)配合物的晶体结构及荧光性质

通过水热/溶剂热合成的方法制备了3个Zn(Ⅱ)/Co(Ⅱ)配合物{[Zn(H₂L)(H₂O)₃]·H₂O·0.5H₄L}_n(1)、{[Co(L)_0.5(4,4'-bpy)]·0.5H₂O}_n(2)和{[Co(L)_0.5(pbmb)(H₂O)]·H₂O}_n(3)(H₄L=5,5'-(hexane-1,6-diyl)-bis(oxy)diisophthalic acid,4,4'-bpy=4,4'-bipyridine,pbmb=1,1'-(1,3-propane)bis-(2-methylbenzimidazole))。结构分析表明配合物1为一维链结构。2为拓扑符号为(6⁴·7·8)(6·7²)的三重穿插网络结构。3是拓扑符号为(4·6²)(4²·6²·8²)的(3,4)-连接的二维网络结构。配合物1呈现出较好的荧光性质。     

铜配合物修饰的Dawson型钨磷酸盐的合成、晶体结构和催化性能

在水热条件下,Cu(Ⅱ)-H₂biim配合物与Dawson型钨磷酸盐构筑了1个无机-有机杂化化合物[Cu(H₂biim)₂(H₂O)][{Cu(H₂biim)₂}₂(P₂W₁₈O₆₂)]·11H₂O(1)(H₂biim=2,2'-联咪唑)。 通过单晶X射线衍射、红外光谱(IR)、X射线粉末衍射(XRD)、元素分析、电化学分析等技术手段对其进行了表征。 结构分析表明,在化合物1分子中,[P₂W₁₈O₆₂]^6-单元作为双齿配体与2个Cu²⁺离子配位形成双支撑的杂多阴离子[{Cu(H₂biim)₂}₂(P₂W₁₈O₆₂)]^2-,在其外部有1个游离的[Cu(H₂biim)₂(H₂O)]²⁺ 和11个H₂O分子。 H₂biim分子与杂多阴离子/H₂O分子间存在氢键,通过氢键、静电和π-π堆积作用,进一步构成具有3D结构的晶体材料。 该晶体化合物对H₂O₂和NaNO₂的还原具有良好的电催化作用;同时,作为酸催化剂用于合成环己酮乙二醇缩酮反应,催化活性高,可重复使用。     

磷酸铁锂废料中FePO4·2H2O提取及其杂质形成机理

采用化学共沉淀方法从磷酸铁锂废料中提取FePO₄·2H₂O,并研究了回收过程中杂质形成的机理。在热力学计算基础上绘制了298和363 K时Fe-P-Li-H₂O体系的电势(φ)-pH图,结果表明当pH≤5.0时,Fe(OH)₃相可以自发地转成FePO₄·2H₂O相,从而得到高纯的FePO₄·2H₂O。但实验结果发现当溶液中铁、磷的物质的量之比(n_Fe∶n_P)为1∶1,合成pH为1.5～2.2时得到的FePO₄·2H₂O中存在Fe(OH)₃杂质,这是因为在共沉淀过程中少量Fe³⁺以Fe(OH)₃快速沉淀,而陈化时Fe(OH)₃相转化速率慢,因此FePO₄·2H₂O中含有Fe(OH)₃     

稀土冠醚类配合物的研究(Ⅺ)——硝酸钪、钇与二苯并-24-冠-8的固态配合物的合成及性质

以无水乙腈为反应介质,合成了硝酸钪及硝酸钇与DB24C8的固态配合物,确定其组成为Sc(NO₃)₃·DB24C8·2H₂O和[Y(NO₃)₃]₄·(DB24C8)₃·8H₂O,并对冠醚及其配合物的某些性质进行了对比研究。     

过渡金属-联咪唑-Dawson型钨磷酸盐杂化化合物的酶固定化性能

利用水热法和直接沉淀法, 设计合成了5例由过渡金属(TM)-联咪唑配阳离子与Dawson型钨磷酸阴离子构成的多金属氧酸盐(POM)基有机-无机杂化化合物[Ni(H₂biim)₃]₄[Ni(H₂biim)₂(P₂W₁₈O₆₂)₂]·2H₂O(1), [Co^III(H₂biim)₃]₂[P₂W₁₈O₆₂]·8H₂O(2), [Cu(H₂biim)₂]₃[P₂W₁₈O₆₂]·4H₂O(3), [Co^II(H₂biim)₃]₂H₂[P₂W₁₈O₆₂]·9H₂O(4)和 [Ni(H₂biim)₃]₃[P₂W₁₈O₆₂]·2H₂O(5); 并利用X射线单晶衍射分析(SC-XRD)、 红外光谱(IR)和热重-差热分析 (TG-DTA)等对其进行了表征. 化合物1~5作为载体用于固定辣根过氧化物酶(HRP)时, 显示出了较高的酶固定化能力. 另外, 利用圆二色光谱(CD)和激光扫描共聚焦显微镜(LSCM)等方法评价了固定化酶HRP/1~HRP/5的重复使用性、 储存稳定性和检测过氧化氢(H₂O₂)的性能. 由于该类POMs与HRP间存在强的相互作用, 利用简单的物理吸附法即可实现POMs对HRP的固载. POMs对酶的固定不但提高了HRP对使用及储存环境的耐受性, 同时也拓展了POMs在酶固定化领域的应用.     

高氯酸铕的双亚砜配合物研究

本文报告了高氯酸铕的高、低熔点双(正-辛基亚砜)乙烷和双(苯基亚砜)乙烷的四个配合物:Eu(ClO₄)₃(α-BOSE)₃·2H₂O(Ⅰ)、Eu(ClO₄)₃(β-BOSE)₄·2H₂O(Ⅱ)、Eu(ClO₄)₃(α-BPhSE)₃(Ⅲ)和Eu(ClO₄)₃(β-BPhSE)₄·2H₂O(Ⅳ)的合成及性质。     

A Novel 3D CdⅡ-CP Based on a Bi-functional（N-/O-Sites） Triazole-modified Carboxyl Ligand: Structure,Topology and Photoluminescence

With triazole-modified derivative as link,one new framework[Cd₅(μ₅-HL^2-)₂(μ₄-L^3-)₂（H₂O）₁₀]·2H₂O(1,H₃L=2-（1,2,4-triazol-1-yl）benzene-1,3,5-tricarboxylic acid) has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction,powder X-ray diffraction and elemental analysis.Complex 1exhibits a 3D （3,4,6）-connected net cross-linked by binuclear[Cd₂     

八面体纳米笼构筑的金属-有机框架化合物

利用半刚性的三足羧酸配体1,3,5-tris[3-(carboxyphenyl)oxamethyl]-2,4,6-trimethylbenzene acid (H₃TBTC)与金属离子自组装成功合成了两例八面体纳米笼构建的金属-有机框架化合物: {[Zn₃TBTC₂(DMA)(H₂O)]·3DMA·3H₂O}_n (1), {[Cd₃TBTC₂(DMA)₂(H₂O)₂]·2DMA·2H₂O}_n (2). TBTC^3-配体在化合物中呈现出cis,cis,cis-和cis,trans,trans-两种构型. cis,cis,cis-构型的TBTC^3-配体与Zn₃(COO)₆次级结构基元(secondary building units, SBUs)构筑了畸变的八面体金属-有机纳米笼, 因而化合物的结构可以看成是八面体金属-有机纳米笼作为超分子构建单元(supramolecular building blocks, SBBs), 在空间上与cis,trans,trans-构型的配体相连, 最终形成具有(3,18)-连接的三维无限网络. 荧光测试结果表明, 化合物1～2的荧光都是基于配体的发射. 相对于配体的发射光谱, 化合物1～2的发射光谱展现出蓝移的现象. 气体吸附测试结果表明, 化合物1～2具有选择性吸附二氧化碳的能力.     

铜掺氧化锌多孔纳米棒的水热合成及其光催化性能

通过两步法合成铜掺杂的氧化锌纳米棒,通过X射线衍射（XRD）、扫描电子显微镜（FESEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）和紫外-可见（UV-Vis）分光光谱等技术对系列样品进行了表征,研究并探索了铜掺杂的氧化锌纳米棒光降解染料罗丹明B（RhB）和气体乙醛的催化活性。通过对多孔Cu掺杂ZnO纳米棒光催化分解乙醛进行了评价。多孔Cu掺杂ZnO纳米棒（CZ-5）光催化剂具有最高的催化分解乙醛的能力,比其它多孔Cu掺杂ZnO纳米棒具有很高的催化活性。多孔Cu掺杂ZnO纳米棒光催化剂在室温下在可见光（435 nm）下照射16 h,5.50×10^-4（φ,体积分数）的乙醛气体完全降解为二氧化碳（CO₂）。多孔铜掺杂的氧化锌纳米棒光催化剂的光催化性能的改善主要归因于铜和氧化锌纳米棒之间的协同作用。这种改进的光催化协同作用归因于Cu掺杂ZnO的可见光吸收的延伸和光生电子空穴对的抗重组。     

Isolation of hemoglobin with metal–organic frameworks Y(BTC)(H_2O)_6

The hierarchical metal-organic frameworks(MOFs),such as Y(BTC)(H_2O)_6,are prepared with yttrium nitrate and benzene-1,3,5-tricarboxylic acid at room temperature.The product is characterized by Fourier transform infrared(FT-IR),X-ray diffraction(XRD),scanning electron microscopy(SEM)and thermogravimetric analysis(TGA).The Y(BTC)(H_2O)_6 particles are sufficiently rigid for performing solid phase extraction and they exhibit favorable selectivity toward the adsorption of hemoglobin.The adsorption behavior of hemoglobin onto the Y(BTC)(H_2O)_6 fits the Langmuir adsorption model with a theoretical adsorption capacity of 555.6 mg g 1.An adsorption efficiency of 87.7%for 100μg mL 1hemoglobin in 1 mL sample solution(at pH 6.0)is achieved with 0.40 mg Y(BTC)(H20)6.77.3%of the retained hemoglobin is readily recovered using a 0.5%(m/v)SDS solution as the stripping reagent.Circular dichroism spectra indicated that the conformation of hemoglobin is maintained during the adsorption-desorption process.The MOFs material is applied for the isolation of hemoglobin from human blood and the purity of the obtained hemoglobin is further verified by sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE).     

Synthesis of Mg5(CO3)4(OH)2·4H2O with Flower-like Microstructure and Its Catalytic Activity for Transesterification of Dimethyl Carbonate with Phenol

A novel flower-like hydrated magnesium carbonate hydroxide,Mg_5(CO_3)_4(OH)_2·4H_2O,with micro-structure composed of individual thin nano-sheets was synthesized using a facile solution route without the use of template or organic surfactant.Reaction time has an important effect on the final morphology of the product.The micro-structure and morphology of Mg_5(CO_3)_4(OH)_2·4H_2O were characterized by means of X-ray diffractometry(XRD),field-emission scanning electron microscopy(FE-SEM).Brunauer-Emmett-Teller(BET)surface areas of the samples were also measured.The probable formation mechanism of flower-like micro-structure was discussed.It was found that Mg_5(CO_3)_4(OH)_2·4H_2O with flower-like micro-structure was a novel and efficient catalyst for the synthesis of diphenyl carbonate(DPC)by transesterification of dimethyl carbonate(DMC)with phenol.     

The ternary system H2O–Fe(NO3)3–Co(NO3)2 isotherms 0 and 15 °C

The solid–liquid equilibria of the ternary system H₂O–Fe(NO₃)₃–Co(NO₃)₂ were studied by using a synthetic method based on conductivity measurements.

Two isotherms were established at 0 and 15 °C, and the stable solid phases which appear are the iron nitrate nonahydrate (Fe(NO₃)₃·9H₂O), the iron nitrate hexahydrate (Fe(NO₃)₃·6H₂O), the cobalt nitrate hexahydrate (Co(NO₃)₂·6H₂O) and the cobalt nitrate trihydrate (Co(NO₃)₂·3H₂O).     

铈源对甲醇水蒸气重整制氢CuO/CeO2催化剂的影响

采用沉淀法合成了CeO_2载体,再经浸渍法负载活性组分得到CuO/CeO_2催化材料,探究了铈源(Ce(NO_3)_3·6H_2O、Ce Cl_3·6H_2O、Ce(NH_4)_2(NO_3)_6、Ce(SO_4)_2·4H_2O)对CuO/CeO_2催化性能的影响。通过采用XRD、SEM、N_2O滴定、BET和H_2-TPR等表征手段对催化材料的结构和性质研究发现,四种铈源合成的CuO/CeO_2催化材料在Cu比表面积、还原性能以及活性组分和载体间的相互作用方面存在着明显差别。其中,由Ce(NO_3)_3·6H_2O合成的CuO/CeO_2催化材料的Cu比表面积较大,CuO还原温度较低,CeO_2载体与CuO之间相互作用较强,在甲醇水蒸气重整反应过程中,表现出较佳的催化活性,在反应温度为553 K,水醇比n(H_2O)/n(MeOH)为1.2,甲醇水蒸气气体空速(GHSV)为1760 h~(-1)时,甲醇的转化率为100%,重整气中CO摩尔含量为0.84%。     

Hydrothermal synthesis, crystal structure and characterization of [Zn(H2O)4]2 [H2As6V15O42(H2O)]·2H2O

The compound [Zn(H₂O)₄]₂[H₂As₆V₁₅O₄₂(H₂O)]·2H₂O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) Å, c=33.970(7) Å, γ=120°, V=4278.8(12) Å³, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H₂As₆V₁₅O₄₂(H₂O)]⁴⁻ anions and [Zn(H₂O)₄]²⁺ cations linked through hydrogen bonds into a network. The [H₂As₆V₁₅O₄₂(H₂O)]⁶⁻ cluster consists of 15 VO₅ square pyramids linked by three As₂O₅ handle-like units.     

Co(Ⅱ)-Zn(Ⅱ)掺杂配位聚合物的 合成及物理性能

采用均苯三甲酸配体、 硝酸锌与硝酸钴反应, 一步合成了钴掺杂的锌配位聚合物Zn_1-xCo_x(BTC)·(OH)(H₂O)₃(NMP)(DMF)(H₂O)_1.5(H₃BTC为1,3,5-均苯三酸, NMP为1-甲基-2-吡咯烷酮, DMF为N,N'-二甲基甲酰胺, x=0~0.8). 该化合物结构经X射线单晶衍射确定, 属于立方晶系, 空间群P2₁3, 晶胞参数a=1.43863(20) nm. 利用元素分析、 能量散色光谱(EDS)、 UV-Vis光谱、 X射线粉末衍射(XRD)、 热重分析(TGA)、 氮气吸附和磁性分析等表征手段对样品的物理性质进行了表征. 氮气吸附实验结果表明, 该配位聚合物具有良好的微孔吸附特性, Langmiur比面积为832 m ²/g, 孔径为0.84 nm; 元素分析结果表明, 钴/锌摩尔比为1∶1时, 在37~300 K温度范围内其磁性表现为反铁磁性, 并满足Curie-Weiss定律.     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

Hydrothermal synthesis, crystal structures and luminescent properties of two new Ln(III)–succinate (Ln=Eu, Tb) complexes exhibiting three dimensional networks

Two new coordination polymers, [Eu₂(L)₃(H₂O)₂]_n 1 and {[Tb₂(L)₃(H₂O)₂]·H₂O}_n 2, (H₂L=succinic acid) have been synthesized by the reaction of H₂L with nitrate salts of Eu(III) or Tb(III) under hydrothermal conditions. The X-ray diffraction analysis reveals that the two complexes are constructed by L bridging the chains of edge-sharing EuO₈(H₂O) or TbO₈(H₂O) polyhedra to form 3D network structure. 1 and 2 possess different topological structures due to the difference in the conformations of L. The solid photoluminescence of 1 and 2 was also investigated in room temperature.     

The electrolyte NRTL model and speciation approach as applied to multicomponent aqueous solutions of H2SO4, Fe2(SO4)3, MgSO4 and Al2(SO4)3 at 230–270 °C

This work presents chemical modeling of solubilities of metal sulfates in aqueous solutions of sulfuric acid at high temperatures. Calculations were compared with experimental solubility measurements of hematite (Fe₂O₃) in aqueous ternary and quaternary systems of H₂SO₄, MgSO₄ and Al₂(SO₄)₃ at high temperatures. A hybrid model of ion-association and electrolyte non-random two liquid (ENRTL) theory was employed to fit solubility data in three ternary systems H₂SO₄–MgSO₄–H₂O, H₂SO₄–Al₂(SO₄)₃–H₂O at 235–270 °C and H₂SO₄–Fe₂(SO₄)₃–H₂O at 150–270 °C. Employing the Aspen Plus™ property program, the electrolyte NRTL local composition model was used for calculating activity coefficients of the ions Al³⁺, Mg²⁺ Fe³⁺ and SO₄²⁻, HSO₄⁻, OH⁻, H₃O⁺, respectively, as well as molecular species. The solid phases were hydronium alunite (H₃O)Al₃(SO₄)₂(OH)₆, hematite Fe₂O₃ and magnesium sulfate monohydrate (MgSO₄)·H₂O which were employed as constraint precipitation solids in calculating the metal sulfate solubilities. A correlation for the equilibrium constants of the association reactions of complex species versus temperature was implemented. Based on the maximum-likelihood principle, the binary interaction energy parameters for the ionic species as well as the coefficients for equilibrium constants of the reactions were obtained simultaneously using the solubility data of the ternary systems. Following that, the solubilities of metal sulfates in the quaternary systems H₂SO₄–Fe₂(SO₄)₃–MgSO₄–H₂O, H₂SO₄–Fe₂(SO₄)₃–Al₂(SO₄)₃–H₂O at 250 °C and H₂SO₄–Al₂(SO₄)₃–MgSO₄–H₂O at 230–270 °C were predicted. The calculated results were in excellent agreement with the experimental data.