Thermochemical properties of the coordination complex of 8-hydroxyquinolinato-bis-(salicylato) praseodymium (III)

The product, [Pr(C₇H₅O₃)₂(C₉H₆NO)], which was formed by praseodymium nitrate hexahydrate, salicylic acid (C₇H₆O₃), and 8-hydroxyquinoline (C₉H₇NO), was synthesized and characterized by elemental analysis, UV spectra, IR spectra, molar conductance, and thermogravimetric analysis. In an optimalizing calorimetric solvent, the dissolution enthalpies of [Pr(NO₃)₃·6H₂O(s)], [2 C₇H₆O₃(s) + C₉H₇NO(s)], [Pr(C₇H₅O₃)₂(C₉H₆NO)(s)], and [solution D (aq)] were measured to be, by means of a solution-reaction isoperibol microcalorimeter, $ \begin{gathered}\Updelta_{\text{s}} H_{\text{m}}^{\theta}\left[ {{ \Pr }\left( {{\text{NO}}_{ 3} } \right)_{ 3} \cdot 6{\text{H}}_{ 2} {\text{O}}\left( {\text{s}} \right), 2 9 8. 1 5{\text{ K}}} \right] \, = - ( 20. 6 6 { } \pm \, 0. 29)\,{\text{kJ}}\,{\text{mol}}^{ - 1} , \\\Updelta_{\text{s}} H_{\text{m}}^{\theta } \left[ { 2 {\text{C}}_{7} {\text{H}}_{ 6} {\text{O}}_{ 3} \left( {\text{s}} \right) +{\text{ C}}_{ 9} {\text{H}}_{ 7} {\text{NO}}\left( {\text{s}}\right),{ 298}. 1 5 {\text{ K}}} \right] \, = \, ( 4 2. 2 7 { }\pm \, 0. 3 1)\,{\text{kJ}}\,{\text{mol}}^{ - 1} , \\\Updelta_{\text{s}} H_{\text{m}}^{\theta } \left[ {{\text{solutionD }}\left( {\text{aq}} \right), 2 9 8. 1 5 {\text{ K}}} \right] \,= - \left( { 8 9. 1 5 { } \pm \, 0. 4 3}\right)\,{\text{kJ}}\,{\text{mol}}^{ - 1} , \\\end{gathered} $ Δ s H m θ [ Pr ( NO 3 ) 3 · 6 H 2 O ( s ) , 2 9 8.1 5 K ] = ? ( 20.6 6 ± 0.2 9 ) kJ mol ? 1 , Δ s H m θ [ 2 C 7 H 6 O 3 ( s ) + C 9 H 7 NO ( s ) , 298.1 5 K ] = ( 4 2.2 7 ± 0.3 1 ) kJ mol ? 1 , Δ s H m θ [ solution D ( aq ) , 2 9 8.1 5 K ] = ? ( 8 9.1 5 ± 0.4 3 ) kJ mol ? 1 , and $ \Updelta_{\text{s}} H_{\text{m}}^{\theta } \left\{ {\left[ {{\Pr }\left( {{\text{C}}_{ 7} {\text{H}}_{ 5} {\text{O}}_{ 3} }\right)_{ 2} \left( {{\text{C}}_{ 9} {\text{H}}_{ 6} {\text{NO}}}\right)} \right]\left( {\text{s}} \right),{ 298}. 1 5 {\text{ K}}}\right\} \, = - \left( { 4 1.0 4 { } \pm \, 0. 3 3}\right)\,{\text{kJ}}\,{\text{mol}}^{ - 1} $ Δ s H m θ { [ Pr ( C 7 H 5 O 3 ) 2 ( C 9 H 6 NO ) ] ( s ) , 298.1 5 K } = ? ( 4 1.0 4 ± 0.3 3 ) kJ mol ? 1 , respectively. Through an improved thermochemical cycle, the enthalpy change of the designed coordination reaction was calculated to be $\Updelta_{\text{r}} H_{\text{m}}^{\theta} = \, ( 2 1 3. 1 8\pm0. 6 9)\,{\text{kJ}}\,{\text{mol}}^{ - 1} $ Δ r H m θ = ( 2 1 3.1 8 ± 0.6 9 ) kJ mol ? 1 , the standard molar enthalpy of the formation was determined as $ \Updelta_{\text{f}} H_{\text{m}}^{\theta} \left\{ {\left[ {{\Pr }\left( {{\text{C}}_{ 7} {\text{H}}_{ 5} {\text{O}}_{ 3} }\right)_{ 2} \left( {{\text{C}}_{ 9} {\text{H}}_{ 6} {\text{NO}}}\right)} \right]\left( {\text{s}} \right), 2 9 8. 1 5 {\text{K}}}\right\} \, = \, - \, ( 1 8 7 5. 4\pm 3.1)\,{\text{kJ}}\,{\text{mol}}^{ - 1} $ Δ f H m θ { [ Pr ( C 7 H 5 O 3 ) 2 ( C 9 H 6 NO ) ] ( s ) , 2 9 8.1 5 K } = ? ( 1 8 7 5.4 ± 3.1 ) kJ mol ? 1 .     

新试剂联苯基双荧光酮分光光度法测定微量钼

研究了非离子表面活性剂Triton X-100存在下,新试剂联苯基双荧光酮与钼的显色反应条件,结果表明:在pH为5.1的HAc-NaAc缓冲溶液中,试剂与钼形成1∶1的红色配合物,配合物的最大吸收波长为530nm处;表观摩尔吸光系数为e=1.41×105L·mol-1·cm-1;钼含量在0-15μg/25mL范围内符合比耳定律;多数常见离子不干扰测定,方法灵敏度高,选择性好.拟定方法用于合金钢中微量钼的测定,结果满意.     

黄海北部CDOM近紫外区吸收光谱特性研究

有色溶解性有机物(CDOM)近紫外区吸收光谱包含CDOM分子结构、组成等重要理化信息。利用2009年3月黄海北部海域CDOM吸收系数的实测数据,分析了该海域CDOM近紫外区的吸收光谱特性,结果表明:由于近岸陆源输入的影响,黄海北部海域CDOM构成差异较大,属于典型的二类水体;特定拟合波段范围的光谱斜率及特定波段处的吸收系数对CDOM分子量相对大小均具有一定的指示作用,250~275,350~400,300~350,275~300 nm波段的光谱斜率Sg,250~275,Sg,350~400,Sg,300~350,Sg,275~300与CDOM分子量相对大小指示参数M值的相关性依次递增,最高可达0.95,吸收系数ag(λ)与M值的相关性随波长增大逐渐变大,400 nm波段处相关性可达0.92;光谱斜率与吸收系数存在相关性与否由光谱斜率拟合波段范围及吸收系数获取波长共同决定,Sg,275~300与ag(400)的相关性最大,可达0.87。     

混合工业污泥热解及动力学特性实验研究

工业污泥中一般都含有大量的病原菌、寄生虫、致病微生物,以及砷、铜、铬、汞等重金属和二恶英、放射性元素等难以降解的有毒有害物质,工业污泥处理与处置已成为我国突出的环境问题之一.文中针对三种典型工业污泥(制药、造纸、啤酒的工业污泥)及其不同的质量混合比,采用热重法研究了其单一及混合物的热解及动力学机理与特性,研究了其不同热解温度阶段的动力学参数,并得到不同条件下的热解特征温度和特征指数.研究结果表明,制药、造纸、啤酒工业污泥在低温区、中温区、高温区的热解反应级数分别为1.、2、1.     

Fabrication and characterization of core-shell photonic crystals via a dipping process

High-quality polystyrene (PS) colloidal photonic crystals in large area were fabricated in 24 h via a capillary-enhanced process. Then, the photonic crystals with core-shell structure were obtained by incorporating silica nanoparticles into the interstitial space of opal template via a dipping process. The filling ratio (V_silica) of interstitial space could be manipulated by dipping colloidal crystals into suspensions with different concentrations of silica nanoparticles, which in turn renders the obtained core-shell photonic crystals. The absorptive peak of opal without dipping process is at 445 nm as measured by UV–vis spectrometry. The filling ratios of 0.130, 0.167 and 0.253 can be calculated according to the modified Bragg's Law, which corresponds to the absorptive peaks for core-shell opals at 453, 463 and 469 nm obtained from suspensions with silica nanoparticles of 0.017, 0.122, and 0.244 wt%, respectively. Therefore, by using this dipping process, the characteristic absorption wavelength for photonic crystal will be varied easily, efficiently and cost effectively than that by traditional methods for constructing opal from monodispersed colloids of different diameters.     

钌(Ⅱ)多吡啶配合物光断裂DNA的实验研究

研究了一系列钌(Ⅱ)多吡啶配合物对pBR 322DNA的光断裂作用,并与光谱法和粘度法的研究结果进行了对比．实验结果表明,钌(Ⅱ)多吡啶配合物光断裂DNA的能力不仅与配合物与DNA相互作用的结合模式和结合强度有关,还与配合物自身的电子结构有关;钌(Ⅱ)多吡啶配合物对DNA的光断裂存在立体选择性;其断裂机理是激发态的配合物与溶液中的氧分子发生能量转移生成单线态氧活性氧化物种,将鸟嘌呤碱基氧化而导致DNA断裂．本研究对于遗传工程中的化学核酸酶以及以DNA为靶标的药物设计有重要的意义．     

Facile and One-Pot Synthesis of 1,2-Dihydroquinazolin-4(3H)-ones via Tandem Intramolecular Pinner/Dimroth Rearrangement

An efficient synthetic method for the preparation of quinazolin-4-one derivatives was designed. The facile condensation of aromatic o-aminonitriles with aromatic aldehydes catalyzed by Lewis acid give 1,2-dihydroquinazolin-4(3H)-ones in moderate to good yields under refluxing dimethylformamide.     

A Sulfide (Selenide)-Centered Nonanuclear Silver Cluster: A Distorted and Flexible Tricapped Trigonal Prismatic Ag<Subscript>9</Subscript> Framework

Two luminescent, monoanionic chalcogenide-centered nonanuclear silver clusters stabilized by dichalcogenophosphates were synthesized and fully characterized by various spectroscopies including multinuclear NMR and ESI-mass. Single crystal X-ray diffraction studies on both cluster anions, [Ag₉(S){S₂P(OEt)₂}₈]^?, 1, and [Ag₉(Se){Se₂P(OEt)₂}₈]^?, 2, reveal that the nine silver atoms form an extremely distorted tricapped trigonal prism, which has an encapsulating chalcogenide. The coordination geometry of the central chalcogenide appears to be monocapped trigonal prismatic, which was analyzed by DFT calculations. The origin of the yellow emission is assigned by TDDFT calculations to originate from a chalcogen (ligand + encapsulated) → silver charge transfer.     

A μ9-iodide in a tricapped trigonal-prismatic geometry

Two luminescent, undecanuclear silver complexes [Ag(11)(μ(9)-I)(μ(3)-I)(3){E(2)P(O(i)Pr)(2)}(6)](PF(6)) [E = S (yellow), 1; Se (orange), 2], containing the first μ(9)-iodine inscribed at the center of a pentacapped trigonal-prismatic silver skeleton, were reported.