三齿配体杂环五配位有机锡化合物的合成与生物活性

邻氨基苯酚与邻羟基芳香醛(酮)反应,合成了4个三齿Schiff碱配体(2a,2d,2g和2j),2分别与二苄基二氯化锡,二苯基二氯化锡,二正丁基二氯化锡反应合成了12个未见文献报道的三齿配体杂环五配位有机锡配合物(3a~3l),其结构经1HNMR,IR和元素分析确证。体外抗菌和抗癌活性测试结果表明,3b,3c,3f,3i和3k具有较强的抑菌活性;3c和3l具有较好的抗癌活性。     

YbCl3·3H2O-18-C-6-CH3COCH3体系(25℃)的相化学研究与 固态配合物的合成与 性质

采用半微量相平衡方法研究了YbCl3·3H2O-18-C-6-CH3COCH3三元体系(25℃)的溶度,测定了各饱和溶液的折光率,绘制了体系的溶度图与饱和溶液折光率曲线,考察了相平衡过程中水的行为。体系中形成两种化学计量的新配合物：2YbCl3·18-C-6·6H2O·CH3COCH3(1)与YbCl3·18-C-6·3H2O·0.5CH3COCH3(2),两者均为固液异成分溶解的配合物。比较讨论了盐的阴离子与溶剂对形成配合物的影响。在相平衡结果指导下,制备了固态配合物,用化学分析、元素分析、IR,DTG,TG与DSC研究了固态配合物的组成与性质,预示了固态配合物YbCl3·18-C-6·3H2O与YbCl3·18-C-6的配位结构。     

新型取代吲哚-3-甲醇类衍生物的合成

以取代吲哚为原料,经维尔斯迈尔-哈克反应制得取代吲哚-3-甲醛,再通过DMSO/NaOH体系制得N-取代吲哚-3-甲醛(3a~3g);3a~3g经Na BH4还原合成了7个未见文献报道的取代吲哚-3-甲醇类衍生物(4a~4g),其结构经~1H NMR,~(13)C NMR和MS表征。     

α-羰基二硫缩烯酮的吲哚化反应

研究了BINOL酸催化α-羰基二硫缩烯酮的吲哚化反应,合成了12个β-吲哚基-β-乙硫基缩烯酮类化合物(3a~3l),其中3a,3d~3e,3g~3k为新化合物,其结构经~1H NMR,~(13)C NMR,IR和HR-MS表征。对反应条件进行了优化。结果表明:20 mol%BINOL酸为催化剂,3,3-二乙硫基苯丙烯酮与吲哚于85℃反应2.5 h,3-吲哚基-3-乙硫基苯丙烯酮收率85%。     

Spectroscopic Studies on Charge Transfer from Ce^3＋ to Yb^3＋ in KMgF3 ： Ce, Yb Nanocrystals

Nanocrystals of KMgF3 single-doped and codoped with Ce^3＋ or/and Yb^3＋ were synthesized separately by the mi-croemulsion method. The X-ray diffraction（XRD） patterns were indexed to show that the KMgF3 crystal system was unchanged. The fluorescent spectra of KMgF3： Ce, Yb polycrystal powders were studied and compared with those of the Ce,Yb doped KMgF3 crystals produced using the high-temperature solid phase method. The diffuse reflection spectra and infrared emission of KMgF3： Ce, Yb were investigated. From the results, the authors could confirm that there were charge transfer processes from Ce^3＋ to Yb^3＋ in both KMgF3： Ce,Yb nanocrystals and polycrystal powders.     

Upconversion Luminescence of SrTiO3:Er3+ Ultrafine Powders Produced by 785 nm Laser

Er3+ doped SrTiO3 ultrafine powders were prepared by solid state reaction in a molten NaCl flux. The structural properties were characterized by X-ray diffraction, field emission scanning electron microscopy, and Fourier transform infrared spectroscopy. The Stokes emission spectra of Er3+ in SrTiO3:Er3+ ranging from green to near infrared region were investigated under 514.5 nm laser excitation. The green and redupconverted luminescence spectra of Er3+ were measured under excitation into the 4I9=2 level by 785 nm laser. The upconversion mechanisms were studied in detail through laser power dependence and Er3+ ion concentration dependence of upconverted emissions, and results show that excited state absorption and energy transfer process are the possible mechanisms for the upconversion. The upconversion properties indicate that SrTiO3:Er3+ may be used in upconversion phosphors.     

非对称取代卟啉锌、镉的生成反应动力学及动力学盐效应研究

本文报道应用停流方法对非对称取代卟啉［5-(4-乙酰氨基苯基)-10,15,20-三(4-甲基苯基)卟啉］(H₂T(p-CH₃)₃(p-NHCOCH₃)PP)与Zn(Ⅱ)、Cd(Ⅱ)在丙酮中的生成反应动力学进行了研究,提出了反应机理,并用非线性拟合和线性拟合的方法求得了生成反应各基元步骤的动力学参数,同时还探讨了温度,溶剂效应、动力学盐效应对反应体系的影响,并对锌、镉两种卟啉在生成机理及生成反应速率上的差异给予了解释。     

程序升温脱附法研究超细Mo/Al2O3催化剂

程序升温脱附法研究超细Ｍｏ／Ａｌ_２Ｏ_３催化剂张智敏，郝建刚，李耀龙（山西大学化学系，太原０３０００６）关键词超细粒子，氧化钼，氧化铝，负载型催化剂，程序升温脱附在催化领域中，对以ｙ－ＡＩ。Ｏ。为载体的Ｃｏ，Ｍｏ，Ｎｉ，Ｆｅ，Ｐｄ和Ａｇ等负载型催化剂...     

新型5-取代吲哚-3-甲酰胺化合物的合成

以5-取代吲哚为原料,经维尔斯迈尔-哈克反应制得5-取代吲哚-3-甲醛(2a~2e); 2a~2e在DMF催化下,与盐酸羟胺反应制得5-取代吲哚-3-甲腈（3a~3e）; 3a~3e在H₂O₂和NaOH溶液中水解合成了5-取代吲哚-3-甲酰胺（4a~4e, 4b~4e为新化合物）,产率62.0%~75.0%,其结构经¹H NMR, ¹³C NMR和ESI-MS表征。     

HO3+ 杂Ge-In-Sb-S玻璃陶瓷光谱特性

采用熔融淬冷法和热处理工艺制备了系列掺Ho3+的透明G eS2-In2S3-Sb2S3硫系玻璃陶瓷.测试了Ho3掺杂的基质玻璃和玻璃陶瓷样品的密度、显微硬度、红外光谱以及在900 nm激光泵浦下的近红外及中红外荧光光谱.结果表明:热处理后样品析出的晶相为In2S3和Sb2S3颗粒的混合体,晶粒尺寸限制在～100 nm以...     

从污水微生物合成聚羟基烷酸酯

聚羟基烷酸酯(PHA)是一类具有生物相容性、光学活性、热塑性和完全生物降解性等的生物高分子,具有巨大的应用前景.PHA是一些微生物在不平衡生长条件下胞内能量和碳源储藏物质,可通过微生物发酵合成[1,2].目前大幅度降低PHA的成本一直是国内外研究者关注的难题.通常处理有机废水的活性污泥中含有多种可积累PHA的天然微生物[3],故可以利用污水中的有机物和混合菌种群合成PHA,降低PHA的成本[4,5].本工作以某纺织厂的工业废水和城市生活污水为原料,采用微嗜气-好气过程驯化活性污泥,研究了供氧量、碳源调节物浓度、培养时间、温度等因素…     

新型烟酰胺腺嘌呤二核苷酸(NAD)类似物的合成及其辅酶活性

尝试4种形成焦磷酸键的方法合成了5种结构新颖的新型烟酰胺腺嘌呤二核苷酸(NAD)类似物.初步考察了类似物的生物活性,发现苹果酸酶和醇脱氢酶以类似物3b和3d为辅酶时,活性只有以NAD为辅酶时的13%～30%;而以类似物3a,3c和3e为辅酶时,这些酶的活性均极低.     

Preparation of 3-Aryl-4-(5-ARYL-Δ2-1,2,4-Oxadiazolin-3-YL)Sydnones and their Conversion into 3-ARYL-4-(5-ARYL-1,2,4-Oxadiazol-3-YL)Sydnones

3-Aryl-4-(5-aryl-Δ²-1,2,4-oxadiazolin-3-yl)sydnones (5) were synthesized in high yields by the reaction of 3-arylsydnone-4-carboxamide oximes (prepared from the corresponding 3-arylsydnone-4-carbonitriles) with aromatic aldehydes in the presence of acid catalysts. No reaction occurred when aliphatic aldehydes were used. The oxadiazolin-3-ylsydnones (5) were easily converted into the corresponding 3-aryl-4-(5-aryl-1,2,4-oxadiazol-3-yl)sydnones by N-bromosuccinimide oxidation. The 3-arylsydnone-4-carbonitrile oxides were synthesized in good yields by N-bromosuccinimide oxidation of the corresponding 3-arylsydnone-4-carboxaldehyde oximes.     

Chemically Modified Ordered Mesoporous Carbon/Polyaniline Composites for Electrochemical Capacitors

Chemically modified ordered mesoporous carbon CMK-3 materials were prepared by means of an easy wet-oxidative method in 2 mol/L nitric acid aqueous solution. A large amount of oxygen-containing functional groups were introduced onto the CMK-3 surface. Modified CMK-3(m-CMK-3) and aniline monomer were polymerized via an in situ chemical oxidative polymerization method. Morphological characterizations of m-CMK-3/PANI (polyaniline) composites were carried out via field emission scanning electron microscopy(SEM)...     

碳苷研究 V: 用Grignard试剂合成取代苯酚中酚羟基的保护及脱保护

本文报道了一些取代苯酚的合成, 并探讨了用Grignard试剂合成取代苯酚中酚羟基的保护及脱保护的问题. 利用苄基和甲基作为酚羟基的保护基, 对文献报道的切断醚键脱保护方法进行了评价. 找到了两种新体系能在更温和条件下切断醚键的方法, 指出了它们的适用条件. 实验结果符合硬软酸碱理论.     

Electronic transition and energy transfer processes in LaPO4-Ce3+/Tb3+ nanowires

Ce3+ and Tb3+ coactivated LaPO4 nanowires and micrometer rods were synthesized by hydrothermal methods. Their fluorescent spectra and dynamics were systematically studied and compared. The results indicated that the extinction coefficients of Ce3+ and Tb3+ in nanowires were higher than those in micrometer rods. The electronic transition rates of Ce3+ and Tb3+ in nanowires had little variation in contrast to those in micrometer rods, and the energy transfer rate and efficiency of Ce3+ --> Tb3+ in nanowires were reduced greatly. It is important to observe that the brightness for the 5D4-7F5 green emissions of Tb3+ via energy transfer of Ce3+ --> Tb3+ in nanowires increased several times that in micrometer rods. This was attributed to the decreased energy loss in the excited states, being higher than 5D4 due to the hindrance of the boundary.     

不同浓度KCl和NH4Cl溶液中H3BO3介稳区的性质

测定了H3BO3在0~25 ℃内于不同浓度KCl和NH4Cl溶液中的溶解度和超溶解度, 得到了H3BO3的介稳区宽度, 并推算出表观成核级数m, 给出了成核速率方程. 研究了KCl和NH4Cl对H3BO3介稳区性质的影响, 并对影响的机理进行了探讨. 结果表明, KCl使H3BO3介稳区向低温方向移动; NH4Cl使H3BO3介稳区向高温方向移动; 根据所得结论分析了KCl和NH4Cl在柴达木西部油田水析硼过程中的影响, 认为KCl和NH4Cl在蒸发过程中浓度的变化是造成硼分散析出而不能富集的因素之一.     

Synthesis of (thia)Calixarene-based exTTF Derivatives and Their Electron Transfers Towards p-Chloranil and C60

Two novel (thia)calixarene-based exTTF derivatives(3a and 3b) were prepared by Mitsunobu reactions in toluene using diethyl azodicarboxylate(DEAD) and triphenylphosphine(PPh₃) system. The cyclic voltammograms of compounds 3a and 3b were provided, and two electron-irreversible waves with redox potentials were observed. Meanwhile, the intermolecular electron transfer(ET) properties of both compounds 3a and 3b towards p-chloranil(Q) and C₆₀ were investigated via UV-Vis and fluorescent spectroscopies, respectively. The results indicated that the introduced nonoxidable metal ions(Al³⁺, Pb²⁺, Sc³⁺) might promote the intermolecular ET from compounds 3a and 3b towards Q ensembles, whereas the effects of Sc³⁺ were the most impressive. Furthermore, the effects of the same metal ions(Al³⁺, Pb²⁺, Sc³⁺) added for compound 3b were greater than those for compound 3a. Additionally, the photoinduced intermolecular ET from compounds 3a and 3b towards C₆₀ was observed.     

Electronic property and molecule design for luminescent metal complexes of tris(8-hydroxyquinoline) gallium

By means of ab initio HF and DFT B3LYP methods, the structure of Gaq3 (q = 8-hydroxyquinoline) was optimized. The frontier molecular orbital characteristics and energy levels of Gaq3 have been analyzed systematically in order to study the electronic transition mechanism in Gaq3. Three derivatives of Gaq3 and their polymers were designed and the possibilities that they were employed as luminescent materials were discussed. The regularities and characteristic of energy bands of Gaq3 and its derivatives were also investigated. The results show that the electronic π-π* transitions in Gaq3 are localized on the quinolate ligands. The emission of Gaq3 is due to the electron transitions from a phenoxide donor to a pyridyl acceptor. Two possible electron transfer pathways are presented, one by carbon atoms, and the other via metal cation Ga3 . The derivatives of Gaq3 may possess high luminescence efficiency.     

新型（E）-1-取代苯基-3-（3P-取代吲哚基）-2-丙烯酮类化合物的合成和抗炎活性研究

设计合成了一系列新的内烯酮化合物3a～3p，其结构经^1H NMR，IR，LC／MS确证，用化合物对小鼠耳部巴豆油炎症影响的炎症模型测定化合物3a～3i的生物活性，结果表明，化合物3d，3f，3g可明显抑制巴豆油致小鼠耳部炎症．其抑制率分别为19．5％，27．6％，16．1％．