具有植物激素活性的Schiff碱化合物的研究(Ⅱ)——三氮唑类Schiff碱的合成及其生物活性

合成了11个新的含三氮唑环的Schif碱类化合物,UV、IR、¹HNMR谱和元素分析确定了它们的结构.生物活性测试表明,一些化合物具有明显的植物生长调节活性,其中化合物Ⅱ_e、Ⅰ_b、Ⅰ_c和Ⅰ_e具有良好的细胞分裂素活性,化合物Ⅱ_a、Ⅰ_a、Ⅰ_e、Ⅰ_i和Ⅰ_j具有优异的生根性能.     

具有激素活性的Schiff碱化合物的研究(Ⅰ)──苯氧乙酸类Schiff碱的合成及其生物活性

具有激素活性的Ｓｃｈｉｆｆ碱化合物的研究（Ⅰ）──苯氧乙酸类Ｓｃｈｉｆｆ碱的合成及其生物活性汪焱钢,叶文法,尹大学,黄君珉,陆爱红（华中师范大学化学系,武汉,４３００７０）关键词Ｓｃｈｉｆｆ碱,氨基苯氧乙酸,植物激素活性芳胺的Ｓｃｈｉｆｆ碱类化合物,...     

Synthesis,biological evaluation and SAR studies of benzimidazole derivatives as H1-antihistamine agents

A series of benzimidazole derivatives have been designed,synthesized and evaluated for H₁ antihistamine activity.Six compounds have showed potent antihistamine H₁ activity.The primary SAR analysis indicated that benzyl or benzylidinyl substituted on the exo-nitrogen atom and C2 of the benzimidazole were significant.Further experiments indicated that compound 17d displayed excellent activity to reduce mast cell degranulation,moderate anti-PAF activity and decreased potency on hERG compared to astermizole.Hence compound 17d could serve as anti-allergic agent for further development.     

掺杂WO3的SiO2/TiO2的溶胶热液合成及光催化性能

采用溶胶-热液合成法制备了掺杂WO₃的SiO₂/TiO₂复合光催化剂,用X射线衍射、红外光谱、Zeta电位分析、BET和透射电镜对样品进行了表征,并以甲基橙降解评价了其光催化性能.结果表明:改性后的光催化剂表现出较高的光催化性能,WO₃和SiO₂不仅增加了锐钛矿TiO₂的稳定性,并阻止了TiO₂晶粒的聚集生长.     

稀土氮杂环配合物的合成、 结构及抑菌活性

采用溶液合成法, 在室温下合成了一系列稀土配合[Ln(IAA)₂(phen)₂]·(NO₃)[Ln=Ce(1), Gd(2), Tb(3), Dy(4), Ho(5), HIAA=吲哚乙酸, phen=1,10-菲咯啉], 并通过元素分析、 红外光谱、 热重分析、 X射线单晶衍射、 X射线粉末衍射等方法对配合物进行了表征. 结果表明, 配合物15具有相同的结构, 对配合物2的单晶结构分析表明, 配合物2为超分子网络结构, 通过分子间氢键形成2D网络, 中心金属Gd(Ⅲ)为九配位, 具有单帽四方反棱柱几何构型. 此外, 对该系列配合物进行了抑菌活性的研究, 得到了抑菌活性与配合物组成的构效关系.     

原位限域生长策略制备有序介孔碳负载的超小MoO3纳米颗粒

采用原位限域生长策略制备了一系列有序介孔碳负载的超小MoO₃纳米颗粒复合物(OMC-US-MoO₃). 其中, 有序介孔碳被用作基质来原位限域MoO₃纳米晶的生长. 依此方法制备的MoO₃纳米晶具有超小的晶粒尺寸(<5 nm), 并在介孔碳骨架内具有良好的分散度. 制得的OMC-US-MoO₃复合物具有可调的比表面积(428~796 m²/g)、 孔容(0.27~0.62 cm³/g)、 MoO₃质量分数(4%~27%)和孔径(4.6~5.7 nm). 当MoO₃纳米晶的质量分数为7%时, 所得样品OMC-US-MoO₃-7具有最大的孔径、 最小的孔壁厚度和最规整的介观结构. 该样品作为催化剂时, 表现出优异的环辛烯选择性氧化性能.     

液相色谱-串联质谱分析盐胁迫下植物激素的含量变化

建立了高效液相色谱．离子阱串联质谱高灵敏、快速测定多种内源植物激素的新方法。在最佳条件下,吲哚乙酸（IAA）、脱落酸（ABA）和赤霉酸（GA3）在5min内实现完全分离,最低检测限为8．0ng．mL-1．借助串联质谱技术,解释了三种激素的结构碎裂过程．探讨了盐胁迫下,上述内源激素含量的变化趋势．研究表明,随着NaCl浓度增大,IAA和GA3含量降低,ABA含量明显升高．初步揭示了内源激素和植物抗盐性之间的相互关系．     

三种不同碳桥联双核茂钛配合物的合成及催化乙烯聚合研究

合成了3种不同结构的CnH₂n桥联双核茂钛配合物(CH₃)₂C[(C₅H₄)TiCl₂(C₅H₅)]₂(3),(CH₂)_n[(C₅H₄)TiCl₂(C₅H₅)]₂(6,n=3;7,n=4),并用1HNMR进行了表征.发现以甲苯为溶剂时,不仅提高了产率,而且有效地避免了副产物Cp₂TiCl₂的生成.研究了化合物7/MAO(甲基铝氧烷)催化乙烯聚合的反应,考察了反应条件对催化体系的影响.结果表明,催化活性随着n(Al)/n(Cat.)比的增大而提高,聚乙烯的分子量在n(Al)/n(Cat.)=500和50℃时达到最高值9.0102×10⁴;随着聚合时间的延长,催化活性下降,而产物分子量不断升高;随着温度的上升,50℃时催化活性和聚乙烯的分子量最高,分别为2.4074×10⁵gPE/(molTi·h)和6.8679×10⁴.随着桥联双核茂钛配合物碳桥的增长,催化活性增加,所得聚乙烯的分子量降低.     

Synthesis of titania and titanate nanomaterials and their application in environmental analytical chemistry

TiO₂ nanoparticles and H₂Ti₂O₅·H₂O, Na₂Ti₂O₄(OH)₂ nanotubes were synthesized by solvothermal method and their applications in the degradation of active Brilliant-blue (KN-R) solution were investigated. The experimental results revealed that the synthesized TiO₂ nanoparticles had a good crystallinity and a narrow size distribution (about 4–5 nm); the obtained H₂Ti₂O₅·H₂O, Na₂Ti₂O₄(OH)₂ were tubelike products with an average diameter of 20–30 and 200–300 nm length. The three catalysts we synthesized had some hydroxyl groups and the maximum absorption boundaries of the samples were all red-shifted, which indicated the samples had a promising prospect in photocatalysis.

The results of the photocatalytic experiments indicated that the photocatalytic activity of the samples was: TiO₂ > H₂Ti₂O₅·H₂O > Na₂Ti₂O₄(OH)₂, which was in good accordance with the fact of FTIR and UV–vis absorption spectra. The formation mechanism of these nanostructures was also discussed.     

Synthesis of Cu^Ⅱ/ZIF-8 Metal-organic Framework Catalyst and Its Application in the Aerobic Oxidation of Alcohols

The tliree-dimensional copper-doped zeolitic imidazolate framework ZIF-8(Cu^Ⅱ/ZIF-8) was prepared by a metal ion exchange process, using reaction of three different copper salts, zinc nitrate hexahydrate[Zn(NO)3·6H2O] and 2?methylimidazole(2-MelM) under nitrogen atmosphere at the room temperature. The TEM and PXRD results indicated that the morphology of Cu^Ⅱ/ZIF-8 was rhombic dodecahedron and the structure was intact after copper was doped into the porous ZIF-8. The synthesized Cu(NO3)2/ZIF-8 heterogeneous catalyst showed an excellent activity for tlie aerobic oxidation of primary alcohols employing molecular oxygen as oxidant. Moreover, tlie Cu(NO3)2/ZIF-8 heterogeneous catalyst can cycled 15 times without leaching of copper.     

β-MnO2和α-Mn2O3纳米棒的自牺牲模板法制备、 表征和应用

在150 ℃下, 仅以高锰酸钾溶液和无水乙醇为原料, 通过水热反应合成前驱体γ-MnOOH纳米棒. 以γ-MnOOH纳米棒为自牺牲模板, 分别在350和600 ℃下煅烧90 min, 制备出高纯度的β-MnO₂和α-Mn₂O₃纳米棒. 采用X射线粉末衍射(XRD)、 扫描电子显微镜(SEM)及热重分析(TGA)等对所制备的样品进行表征. 结果表明, 前驱物γ-MnOOH为高纯度的纳米棒状晶体, 直径约100~300 nm, 长度可达数微米, 且终产物β-MnO₂和α-Mn₂O₃均具有较高的纯度, 也很好地保持了前驱物的纳米棒状结构. 以二者为锰源, 通过固相反应合成出尖晶石LiMn₂O₄正极材料. 当充放电倍率为0.5 C时, 其首次放电比容量分别可达到120.4和123.9 mA·h/g, 而且表现出良好的循环性能和倍率性能.     

g-C_3N_4/BiOBr异质结光催化剂的制备与可见光催化活性

以三聚氰胺作为合成g-C_3N_4纳米片的前躯体,以Bi(NO3)3·5H2O和KBr作为合成BiOBr的原料,采用水热法构建g-C_3N_4/Bi OBr二维异质结可见光催化剂,有效的晶面复合和合适的能带组合有助于增强g-C_3N_4和BiOBr的可见光催化活性。利用X射线衍射(XRD)、透射电镜(TEM)、X射线光电子能谱(XPS)、光致发光光谱(PL)和紫外-可见漫反射光谱(UVvis DRS)等方法表征其结构、光学性质以及组成结构。在可见光(λ420 nm)下以光催化降解RhB来评价合成催化剂的光催化活性,结果表明,g-C_3N_4/BiOBr光催化降解罗丹明B(Rh B)的效率高于单体g-C_3N_4和BiOBr,并对g-C_3N_4/BiOBr增强可见光催化RhB机理进行解释。     

低温合成超导体Ba1-xKxBiO3

先以BaCO3和Bi2O3为原料由传统的固相反应制备纯BaBiO3,然后在低温下将用KOH-KF熔盐处理这样的拓扑反应合成了Ba1-xKxBiO3超导体.所有样品均进行了粉末X射线衍射(XRD)和磁性表征.XRD结果表明,所得Ba1-xKxBiO3样品均为纯相,且均可用赝立方晶胞指标化.磁性测量表明所有样品具有超导电性,最高超导转变温度(Tc)为30.6 K.讨论了反应时间、前驱体与熔盐质量比对超导转变温度的影响.最佳的反应条件为:反应温度450°C,反应时间4 h,BaBiO3:KOH:KF质量比1:5:2.5.     

Laterally substituted naphthalene-2,7-diol-based bent-shaped liquid crystals

Novel series of laterally 1-substitued (H, Cl, CH₃, CN, NO₂) naphthalene-2,7-diol based liquid crystals were synthesized and their mesomorphic properties identified using DSC studies, texture observation, X-ray investigations and electro-optical measurements. Depending on the chain length and type of lateral substitution, the compounds exhibit a variety of mesophases. In materials with short alkyl chains, the rectangular columnar B₁ phase was found. Increasing the alkyl chain length for the non-substituted core causes the appearance of the so-called B_N phase. In CH₃- and Cl-substituted compounds, the antiferroelectric B₂ phase (SmC_AP_A) was found. Introduction of the CN and NO₂ substituents led to the formation of the B₇ phase.     

三元正极材料前驱体Ni1/3Co1/3Mn1/3(OH)2的连续合成与条件探究

以硫酸锰、硫酸镍、硫酸钴为原材料、NaOH和氨水分别为沉淀剂和络合剂,采用共沉淀法制备三元正极材料前驱体Ni_1/3Co_1/3Mn_1/3(OH)₂. 探究了搅拌速度对造核颗粒形貌和晶核流量、氨水流量、浆料返流、搅拌桨对晶体结构、前驱体形貌、粒度及其粒度分布的影响. 物理表征结果表明,搅拌速度300 r•min^-1时,生成的晶核聚集成球形或类球形,分散性好,颗粒粒径4~5 μm;在造核金属液流量0.4L•h^-1,生长金属液流量1.72 L•h^-1,搅拌桨为推进式时,产物为单一相的β-Ni(OH)₂层状结构,粒度D₅₀为6~7 μm,振实密度≥2.0 g•cm^-3,比表面积6~10 m²•g^-1;电化学测试结果表明,在3.0~4.25 V电压范围内,0.2 C时,其首次放电容量为149.7 mAh•g^-1,循环100次后,容量保持率为94.09 %;产物满足高端三元正极材料厂家需求. 多釜串联工艺简单有效,具有可行性,有望用于三元正极材料前驱体的规模生产.     

柴油机尾气碳黑氧化催化剂钛酸钾的制备与表征

以TiO₂和K₂CO₃为原料,采用固相法合成K/Ti比不同的钛酸钾催化剂。利用XRD和SEM对催化剂结构进行表征,并通过程序升温反应（TPR）对催化剂活性进行评估。结果表明,K₂Ti₂O₅在850℃达到较好的结晶度,分别以CH₃COOK、KNO₃及K₂CO₃作为K前驱体时,制备出的K₂Ti₂O₅结晶程度基本一致;K/Ti比较高的K₂Ti₂O₅可明显降低碳黑颗粒氧化温度,最低起燃温度为280℃,且K₂Ti₂O₅比担载贵金属Pt催化剂的碳黑氧化催化活性更高。     

Soot deep oxidation catalyzed by molybdena and molybdates: a thermogravimetric investigation

Molybdena (MoO₃) and molybdates of bismuth (Bi₂Mo₃O₁₂), chromium (Cr₂Mo₃O₁₂), barium (BaMoO₄), manganese (MnMoO₄) and copper (Cu₃Mo₂O₉) were synthesized and characterized by X-ray powder diffractometry and infrared spectroscopy. They were then assessed as ‘loose contact' catalysts for soot deep oxidation (combustion) in air by thermogravimetry. A similar assessment was carried out on commercial chromia (Cr₂O₃) and tungsta (WO₃). Observed high oxidation activity of MoO₃, as compared to both Cr₂O₃ and WO₃, is attributed to the higher volatility (mobility) of MoO_x species. On similar grounds, observed high activity of MoO₃ and Cu₃Mo₂O₉, as compared to the other test molybdates, is explained. Relatively speaking, however, a higher activity was observed for Cu₃Mo₂O₉ than MoO₃, whereby soot ignition temperature decreased from 571°C (uncatalyzed oxidation) to 430°C, to occur within the temperature range of diesel exhaust (200–450°C). This observation is ascribed to copper-promoted redox conduct of Mo(VI) in the oxidation reaction of soot. Kinetics of the reaction was studied non-isothermally, and the kinetic parameters (A, k, ΔE and the reaction order) were calculated.     

Bi2Sn2o7的不同水热法制备及其可见光光催化除As(Ⅲ)性能分析

利用微波和普通水热法合成出了具有可见光响应的Bi₂Sn₂o₇纳米光催化剂,并用X射线衍射(XRD)、氮气吸脱附、紫外-可见漫反射光谱(UV-Vis DRS)、扫描电镜(SEM)、透射电镜(TEM)、电子顺磁共振谱(ESR)、X射线光电子能谱(XPS)等技术对样品的晶相、比表面积、光吸收性能、形貌、光催化活性物种等结构与性质进行了系统表征,比较微波水热Bi₂Sn₂o₇(MH-BSo)与普通水热Bi₂Sn₂o₇(TH-BSo)形貌和微结构,并考察两者在可见光光照下光催化氧化As(Ⅲ)的性能差别。实验结果表明, MH-BSo具有更细小的粒径和更大的比表面积,而在可见光照射下, MH-BSo样品比TH-BSo样品具有更好的As(Ⅲ)的光催化氧化能力(可达98.7%)。此外,对Bi₂Sn₂o₇纳米光催化剂氧化去除As(Ⅲ)的光催化机理进行初步探索,结果表明超氧自由基(o₂^-•)和空穴(hVB+)是主要起作用的中间反应活性物种。     

B-TS-1分子筛的合成及其催化氧化性能

通过将杂原子B引入钛硅-1（TS-1）分子筛对其进行改性,并研究其催化氧化性能。结果发现,B-TS-1明显延长了环己酮氨肟化反应运行寿命。结合氨肟化体系催化剂失活主要原因以及反应体系H₂O₂反应路径,分析表明,H₂O₂是控制TS-1/H₂O₂氨肟化体系副反应发生的关键,并且有机副产物是导致催化剂堵孔失活的重要原因。本文提出B-TS-1能有效控制体系H₂O₂残留,从而进一步抑制副反应发生与积碳生成以延长催化剂寿命。结合Al-TS-1的催化特性,发现同时引入适量B、Al的B/Al-TS-1具有进一步提高环己酮肟化反应稳定性的作用。     

钨含量对W/SiO2/Al2O3催化剂上1-丁烯自歧化反应的影响

采用浸渍法制备了一系列钨负载量不同的W/SiO₂/Al₂O₃ 催化剂. 采用X 射线衍射(XRD)、激光拉曼(Raman)光谱、紫外-可见(UV-Vis)光谱、氢气程序升温还原(H₂-TPR)和氨程序升温脱附(NH₃-TPD)等技术对催化剂进行了表征. 实验结果表明: 钨的负载量对催化剂上氧化钨物种的分散程度、还原性以及催化剂的酸性有非常重要的影响. 对该类催化剂上1-丁烯自歧化反应进行了详细考察, 结果表明: 当钨的质量分数为6.0%时,W/SiO₂/Al₂O₃催化剂表现出最佳的歧化活性和稳定性. 原因在于6.0%的钨负载量可以使催化剂上氧化钨物种具有中等程度的分散性、合适的还原性, 并且使催化剂具有一定程度的酸性, 这些因素有利于在催化剂上形成烯烃歧化活性位.