六元瓜环修饰的铜催化剂活性对比

采用液相化学还原法,将不同摩尔比的五水硫酸铜和修饰剂六元瓜环(Q[6])溶液混合后,经抗坏血酸还原获得系列六元瓜环修饰的铜。采用X射线粉末衍射、扫描电镜和紫外-可见光谱对产物进行结构和形貌表征以及催化性能评价。结果表明,修饰剂用量对产物形貌和性质有较大影响,Q[6]用量为0.4 mmol时,获得的产物为直径2.0μm花团状铜,其催化性能最佳,反应速率较快,0.08 g/L花团状铜在100 min内对染料罗丹明B和次甲基蓝的脱色率超过86%。     

六元瓜环修饰的花团状铜的催化活性

采用水热法,将六元瓜环(Q[6])分散的五水硫酸铜用抗坏血酸还原后获得了六元瓜环修饰的超微花团状铜(Q[6]-Cu花团).利用X射线粉末衍射(XRD)和扫描电子显微镜(SEM)对产物进行了结构和形貌表征,通过催化氧化染料罗丹明B(Rh B)、结晶紫(CV)、茜素红(AR)和次甲基蓝(MB)考察了产物的催化性能.结果表明,Q[6]-Cu花团直径约为2.0μm.在Q[6]-Cu/H_2O_2体系中,0.08 g/L的Q[6]-Cu在300 min内对染料脱色效率均超过87%.     

复合光催化材料H3PW122O40/Ta2O5光催化降解染料的研究

采用溶胶-凝胶法制备了半导体型金属氧化物Ta2O5,并通过浸渍法与杂多酸H,PW12O40复合,获得了纳米复合光催化材料H3PW12O40/Ta2O5.通过1CP-AES、FT-lR、N2吸附、Tc等手段对其组成、结构及其表面物理化学性质进行了表征,并在可见光下考察了该复合材料对可溶性染料罗丹明B和亚甲基蓝的光催化活性.实验结果表明,该复合材料存可见光下有较好的光催化活性,其中,H3PW12O40/Ta2O5在180min内对亚甲基蓝的光催化降解转化率达到78%.     

铜纳米粒子的制备及其对环境污染物的催化降解

本文以CuCl_2·2H_2O为铜源,在室温下合成了新的铜纳米粒子,并用X射线衍射仪(XRD)、X射线光电子能谱(XPS)、场发射扫描电镜(FESEM)以及透射电子显微镜(TEM)对合成的产物进行分析和表征。研究发现在合成的过程中氨水和苯酚的加入对铜纳米粒子的形成具有一定的保护作用,使合成的铜纳米粒子不易被氧化;同时探究了铜纳米粒子作为催化剂降解环境中的有机污染物,如对硝基苯酚(4-NP)、罗丹明B(Rh B)、亚甲基蓝(MB)和甲基橙(MO),和不同反应温度下催化剂对降解环境污染物的影响。运用朗伯比尔定律和准一级动力学公式计算不同温度下的降解速率及反应速率常数,结果显示合成的铜纳米粒子具有很好的催化性能。     

不同供氢底物用于测定H2O2的酶催化动力学研究

研究了牛血红蛋白(hemoglobin,Hb)作为过氧化物模拟酶,以酸性铬蓝K、罗丹明B、亚甲基蓝不同供氢底物测定H2O2的酶催化反应体系的催化特性和反应条件。探讨了采用不同底物测定时的催化反应机理。用于雨水中H2O2含量的测定,结果满意。     

Sb2O3／TiO2纳米复合物的合成及性质研究

以改进的溶胶-凝胶法制备了Sb2O3／TiO2纳米复合物,用扫描电镜、X射线粉末衍射、傅立叶红外光谱、紫外-可见光谱以及荧光等测试技术对产物进行了分析和表征．结果表明：所得纳米复合物颗粒分散均匀,具有锐钛矿相结构,平均粒径约为10nm．还研究了所得产物的光催化性质、电化学性质及电化学发光行为．结果表明：Sb2O3的掺入可以提高TiO2的光催化效果,当反应物中m（Sb2O3）／m（TiO2）=10％时,所得纳米复合物对亚甲基蓝和罗丹明B的光催化效果最好．     

催化动力学荧光光度法测定痕量铜

在氨性介质中,铜对H2O2氧化次甲基蓝褪色反应有强烈催化作用。研究发现,次甲基蓝的氧化产物在紫外线照射下发出强荧光,据此建立一种测定痕量铜的催化动力学荧光光度法。本法检出限达0．02ng／mL,铜的质量浓度在0～6ng／mL范围内与相对荧光强度（△F）有良好线性关系。     

二氧化硅/氧化锌复合体系的制备及其去除亚甲基蓝和罗丹明B研究

利用溶剂热法,以正硅酸乙酯为硅源,硝酸锌为锌源一次性合成了二氧化硅/氧化锌(SiO₂/ZnO)复合材料,利用傅里叶红外光谱和X射线衍射对其结构进行了表征分析,研究了该复合材料对亚甲基蓝和罗丹明B的吸附性能。结果表明,SiO₂/ZnO可快速去除水中的亚甲基蓝和罗丹明B,并在20 min内达到吸附平衡,SiO₂/ZnO对亚甲基蓝的吸附速率和吸附量均高于罗丹明B。吸附动力学研究表明,SiO₂/ZnO对亚甲基蓝和罗丹明B的吸附动力学均符合准二级动力学方程。等温吸附数据分析表明,Langmuir比Freundlich模型能更好地拟合亚甲基蓝和罗丹明B的吸附过程,由Langmuir计算得到亚甲基蓝和罗丹明B的单层饱和吸附量分别为235.3 mg/g和100.1 mg/g。此外,SiO₂/ZnO具有良好的重复使用性能,经过5次吸附-脱附循环后,其对亚甲基蓝的吸附能力仍保持在80%以上。     

H_6P_2Mo_(18)O_(62)/Zn(BDC)(Bipy)_(0.5)复合材料的合成、表征及对亚甲基蓝的吸附

在溶剂热条件下,以H6P2Mo18O62、对苯二甲酸(H2BDC)、4,4'-联吡啶(Bipy)和硝酸锌为原料构筑了1个三维金属有机骨架复合材料H_6P_2Mo_(18)O_(62)/Zn(BDC)(Bipy)_(0.5),并采用红外光谱(IR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、热重分析(TG)、N2吸附-脱附等手段对产物进行了表征.同时,研究了产物对水溶液中亚甲基蓝(MB)的吸附性能,并探讨了MB初始p H值、初始浓度和温度对吸附量的影响.结果表明,产物的等温吸附模型符合Langmuir等温吸附模型,动力学符合拟二级动力学.H_6P_2Mo_(18)O_(62)/Zn(BDC)(Bipy)_(0.5)对亚甲基蓝的吸附是自发和放热的,此外,产物对甲基紫、罗丹明B、孔雀石绿等阳离子染料也具有良好的吸附性能.     

碳酸氢钠溶液中微量 Mn2+离子催化氧化降解有机污染物

 考察了微量 Mn2+离子在 NaHCO3 溶液中催化 H2O2 氧化降解有机污染物的性能. 结果表明, NaHCO3, MnCl2 和 H2O2 浓度分别为 25, 0.1 和 100 mmol/L 时, 在 25 oC 下反应 180 min 后亚甲基蓝可完全脱色, 化学耗氧量和总有机碳去除率分别达到 44.0% 和 13.8%. 该催化体系对甲基橙、罗丹明 B 以及垃圾渗滤液等都有较好去除效果. 紫外-可见光谱分析及反应动力学测试表明, MnIV=O 是该催化体系主要活性物种.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.