A novel one-dimensional manganese phosphomolybdate with rectangular cavities: [H3N(CH2)(4)NH3] (H3O)(2){[Mn(phen)(2)](4) [(MnMo12O30)-O-v(HPO4)(6)(H2PO4)2} center dot 4H(2)O

A novel manganese phosphomolybdate, [H3N(CH2)(4)NH3](H3O)(2){[Mn(phen)(2)](4)[(MnMovO30)-O-12(HPO4)(6)(H2PO4)(2)]} . 4H(2)O 1, has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. The crystal data: triclinic, P (1) over bar, a = 14.172(7) Angstrom, b = 16.547(2) Angstrom, c = 16.679(3) Angstrom, alpha = 62.881(12)degrees, beta = 73.83(3)degrees, gamma = 88.81(3)degrees. X-ray crystallography shows that the [Mn(phen)(2)] fragments are covalently bonded to the [Mn(Mo6P4)(2)] dimers leading to a one-dimensional chain with rectangular cavities occupied by tetramethylene-diamine cations and water molecules. (C) 2002 Elsevier Science B.V. All rights reserved.

A chromic molybdenum phosphate with a tunnel structure: hydrothermal synthesis and structure of (NH3CH2CH2NH3)(2) center dot (NH3CH2CH2NH2)(3)center dot[NaCr2Mo12O30(PO4)(HPO4)(4)(H2PO4)(3)]center dot 6H(2)O

A chromic molybdenum phosphate, (NH3CH2CH2NH3)(2).(NH3CH2CH2NH2)(3).[NaCr2Mo12O30(PO4)(HPO4)(3)]. 6H(2)O, involving molybdenum present in V oxidation, has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction and IR spectrum. Deep brown-red crystals are formed in the triclinic system, space group P (1) over bar, a = 12.067(2), b = 14.677(3), c = 21.290(2) Angstrom, alpha = 80.940(10)degrees, beta = 82.960(10)degrees, gamma = 76.61(2)degrees. The structure of the title compound may be considered to be two [Mo6O15(HPO4)(H2PO4)(3)](5-) units bonded to a chromic atom, although several P-O groups are not protonated on account of coordination with a Na+ cation. The one-dimensional tunnels were formed in the solid of the title compound. (C) 2000 Elsevier Science B.V. All rights reserved.

A nickel molybdenum phosphate with tunnel: Hydrothermal synthesis and structure of (NH3CH2CH2NH3)(4)center dot(NH3CH2CH2NH2)center dot Na center dot[Ni2Mo12O30(PO4)(HPO4)(4)(H2PO4)(3)]center dot 6H(2)O

A nickel molybdenum phosphate, (NH3CH2CH2NH3)(4).(NH3CH2CH2NH2). Na .[Ni2Mo12O30(PO4)(HPO4)(4)(H2PO4)(3)]. 6H(2)O, invoicing molybdenum present in V oxidation, has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Deep brown-red crystals are formed in the triclinic system, space group P (1) over bar, a = 12,011(2), b = 14,612(3), c = 21.252(4) Angstrom, alpha = 80.54(2)degrees, beta = 83.10(2)degrees, gamma = 76.29(2)degrees, V = 3561.4(12) Angstrom(3), Z = 2, lambda(MoK alpha) = 0.71073 Angstrom (R(F) = 0.0529 for 9880 reflections), Data mere collected on a Siemens P4 diffractometer at 20 degrees C in the range of 1.75 degrees < theta < 23.02 degrees using the omega-scan technique. The structure was solved by direct methods using the program SHELXTL-93 and refined with the method of fun-matrix least-squares on F-2. The structure of the title compound may be considered to be two [Mo6O15(HPO4)(H2PO4)(3)](5-) units bonded together with a nickel atom, although several P-O groups are not protonated on account of coordination with a Na+ cation, The one-dimensional tunnels were formed in the solid of the title compound. A probe reaction of the oxidation of acetaldehyde with H2O2 using the title compound as catalyst was carried out in a liquid- solid system, showing that the title compound had high catalytic activity in the reaction, (C) 1999 Academic Press.

A ferric molybdenum phosphate with a tunnel: hydrothermal synthesis and structure of (NH3CH2CH2NH3)(2)center dot(NH3CH2CH2NH2)(3)center dot Na center dot[Fe2Mo12O30(PO4)(HPO4)(4)(H2PO4)(3)]center dot 7H(2)O

A new ferric molybdenum phosphate containing a tunnel structure and crystallographically different clusters has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. A probe reaction of the oxidation of acetaldehyde with H2O2 using the tide compound as catalyst was carried out in a liquid-solid system, showing that the title compound had high catalytic activity in the reaction. (C) 1998 Elsevier Science S.A. All rights reserved.

D−A型有机近红外材料的设计、合成及表征

近年来，随着近红外领域研究的深入，特别是光通讯工业的发展，迫切需要一大批具有良好发光性质的近红外材料。有机材料由于成本低、工艺简单和结构易调控等优点而备受关注。目前，对近红外有机发光材料的研究主要集中在两大类：一是稀土元素配合物；二是有机离子染料。但由于稀土元素的4f-4f跃迁是宇称禁阻的，其分子的激发需通过配体与中心离子的能量转移，发光效率低。同时有机离子染料由于静电相互作用，分子容易因聚集而导致发光萃灭，其器件结构主要采用主客体掺杂技术，存在着较强的主体材料发光和器件发光效率低等缺点。传统有机非离子型材料则不受上述因素的限制，可得到聚集态下高效的发光效率。本论文通过将电子给体与受体共轭连接，设计并合成了系列非离子型的窄带隙有机小分子，研究了它们在近红外电致发光等器件中的应用，主要工作内容和结果如下： (1)在分子内同时引入电子给体和受体，将它们共轭连接，设计并合成了系列D-π-A-π-D型的有机小分子，利用分子内电荷转移，实现近红外区域的吸收和发射。我们选择三苯胺和芴为电子给体，苯并双噻二唑及其衍生物为电子受体，苯、噻吩和吡咯为连接基团，得到的系列化合物的光谱及电化学性质能在很大的范围内进行调节。化合物的吸收光谱可从600nm至1400nm，发射光谱从900nm至1600nm范围内调节。化合物的带宽可从1.19eV减小到0.56eV。由于分子间的强相互作用，化合物在混合溶剂中可自组装成带状结构。同时该系列化合物在隔绝氧气的环境中有良好的光化学稳定性，可应用于电致发光或光伏器件中。 (2)多层器件结构是提高有机电致发光效率的有效方法，但前提是发光材料最好是可真空蒸镀。我们在前部分工作的基础上，合成了系列热稳定的可蒸镀型有机小分子。通过改变受体及给体结构可调节发光波长及效率。利用“掺杂剂/主体材料的思想”制备的电致发光器件，发光波长覆盖700nm到1500nm的范围，最长中心波长为1115nm。发光波长752nm时，器件最高外量子效率为1.12%。基于化合物IV-5制备的非掺杂器件，发光波长为1080nm，外量子效率为0.28%。该效率比基于有机离子染料的器件提高了近10倍。基于化合物IV-7的器件最大发射波长为1220nm，为迄今为止非掺杂有机电致发光器件中的最长发射波长。以上结果证明，该系列分子是良好的近红外电致发光材料。 (3)我们研究了含苯并双噻二唑分子与常见阴离子的相互作用关系，发现其只对CN-离子和F-离子有响应，而对其它阴离子如Cl , Br , I , AcO , H2PO4 , HSO4 , 和NO3 等则没有任何响应。并且通过将其中噻二唑环换成硝基，可实现对CN-离子和F-离子的区分。化合物V-2可高选择性的检测氰离子，其它离子的存在不会干扰检测信号，包括氟离子。检测信号为外观颜色的改变，可作为显色传感器。化合物V-3可定量检测CN-离子，检测极限为1μM。并且检测信号包括近红外发射的萃灭、可见发射的增强和吸收光谱的改变，多重检测信号可增加检测的可靠性。由于响应信号处于近红外区的生物波段，可应用于生物领域

东北黑土重金属污染发生机理及健康动力学研究

东北黑土高有机质含量和巨大而连续的耕作带使它成为中国重要的粮食生产基地。随着人类开发和利用程度的加剧，其直接后果是导致黑土健康质量逐渐下降。土壤重金属污染是导致黑土健康质量下降的重要因素之一。本研究通过对东北黑土重金属污染初步调查，确定黑土分布地区重金属污染的主要类型、来源、污染趋势和分布状况，分析污染黑土中重金属形态、迁移和生物有效性等特点。结果表明：黑土环境中，镉、铅、锌的含量呈明显上升趋势，镉是对土壤健康危害最大的重金属；污染较为严重的区域主要分布在城区和城乡结合部，重金属在这些区域中生物有效性高，工业排放和污水灌溉是其重要来源；而在农区耕作土壤中磷肥的长期施用是造成土壤中镉含量上升的主要原因。 根据调查结果，选择黑土中主要重金属污染类型—镉，对其在土壤中导致污染发生的主要机理进行了深入研究。从形态、生物有效性和吸附-解吸过程等方面阐述了镉在土壤环境中的主要化学行为，以及这些行为对有机农药交互作用的响应。研究表明，外源镉离子进入土壤后能很快被吸附，由于这种吸附作用，使交换态镉容易向结合态和残渣态转化，被土壤吸附的镉离子有一部分被解吸下来，这也使形态转化呈一个互为可逆的过程。由于黑土特殊的土壤理化性质，镉离子在黑土中的吸附和转化趋势明显强于棕壤。乙草胺的加入能加强这种吸附作用和转化趋势，而敌敌畏的作用则增加了吸附态镉离子释放的风险。镉和乙草胺复合污染条件下对生物的毒性呈拮抗作用。 最后，采用化学固定修复的方法，对镉污染黑土进行健康调控研究。通过重金属溶出、形态转化、生物毒性和微观构像等实验评估的结果表明，一种富含H2PO4-、HCO3-和CO32-等配位体的人工合成固定剂对镉污染黑土具有一定的修复潜力。对污染程度较低的重金属面源污染耕作土壤的调控，化学固定化修复在时间和成本等方面显示其修复的优越性。

Novel highly selective anion chemosensors based on 2,5-bis(2-hydroxyphenyl)-1,3,4-oxadiazole

2-(2-Hydroxyphenyl)-5-phenyl-1,3,4-oxadiazole 1 and 2,5-bis(2-hydroxyphenyl)-1,3,4-oxadiazole 2 were used as anion fluorescent and colorimetric chemosensors with high selectivity for H2PO4- and F- over Cl-, while 2 can even distinguish H2PO4- from F-. (C) 2002 Elsevier Science Ltd. All rights reserved.

Synthesis and structure of a novel open-framework zincophosphate with intersecting three-dimensional helical channels

A new open-framework zincophosphate, Zn-0.5(H2PO4).0.5H(2)O (denoted as FJ-13), possessing intersecting three-dimensional helical channels, has been synthesized under solvothermal conditions.

Hydrothermal synthesis and crystal structure of sandwich-like heteropolymolybdophosphates

Sandwich-like heteropoly molybdochromophosphates of supermolecular compound [NH3(CH2)(6)NH3](2)H-3{Cr[Mo6O15(HPO4)(H2PO4)(3)](2)}. 4H(2)O has been hydrothermally synthesized and the single crystal structure has been determined by X-ray diffraction. The crystal data are has follows: triclinic, space group P (1) over bar a=12.156(2), b=12.809(3), c=13.530(3) Angstrom, alpha=102.46(3)degrees, beta=93.67(3)degrees, gamma=93.46(3)degrees, V=2046.9(7) Angstrom(3), Z=1, M-r=2768.69, D-c=2.246 g/cm(-3), F(000)=1337, mu=2.162 mm(-1). The structure has been refined to R=0.0666 and wR=0.1745 by full-matrix least-squares method. The title compound is composed of 1, 6-diaminohexane, water molecules, and {Cr[Mo6O15(HPO4)(H2PO4)(3)](2)}(7-) anion which consists of six oxygen atoms from two [Mo6P4] units with a sandwich-like transition metal atom Cr located at the center of symmetry.

Suitability of extractants for predicting available sulfur in natural grassland in the Inner Mongolia steppe of China

It was the objective of this study to compare the suitability of different extractants for predicting the availability of sulfur (S) in natural grassland in a sulfur response trial on three different soil types in the Inner Mongolia steppe of China. For soil analysis, seven different extractants have been employed. The inorganic SO4-S concentration was determined by ion chromatography. Additionally, in the Ca(H-2-PO4)(2) extract the total soluble S was determined employing turbidimetry. Weak salt solutions (0.15% CaCl2, Ca(H2PO4)(2), and KH2PO4) extracted similar amounts Of SO4-S. Extraction with 0.025 M KCl provided the lowest SO4-S values. Deionized water dissolved significantly more SO4-S in the control plots than most weak salt extractants. The concentration of soluble organic S decreased in the control plots after 100 days of plant growth, indicating that the organic S pool contributed significantly to the S nutrition of the forage crops. Significant relationships among the SO4-S in the soil determined in different extracts and crop yield, sulfur content in the forage, and total sulfur uptake were only found for the Ca(H2PO4)(2) extract. In general, the correlation coefficients proved to be unsatisfactory for field experimentation.