共沉淀法合成铈锆复合氧化物及表征

以共沉淀法制备了Ce0.8Zr0.2O2复合氧化物. 样品经BET法比表面积测定, XRD, SEM和粒度分布等表征, 结果显示500 ℃时(Ce-Zr)O2即形成单一立方相固溶体, SBET可达到135 m2*g-1, D50为7.17 μm, 经900 ℃老化6 h后, 仍保持相结构不变, SBET还大于40 m2*g-1, 显示了较高的热稳定性.     

采用新颖喷墨打印技术制备的薄膜LiCoO2电极及其电化学性能

采用喷墨打印技术制备了LiCoO2薄膜电极. 用X射线衍射、扫描电镜(SEM)、循环伏安和恒电流充放电试验对薄膜电极进行结构表征和电化学性能测试. SEM结果表明, 所制备的薄膜电极表面粒子分布均匀, 厚度约为1.27 μm. 经过轻微热处理(450 ℃, 30 min)的薄膜LiCoO2电极呈现出稳定的充放电循环性能. 当以20 μA/cm2进行充放电时, 第50次循环容量保持率约为首次放电容量(81 mA·h/g)的87%, 10次循环后的充放电过程的充放电效率均接近100％.     

气相色谱-质谱联用法同时测定"电子烟油"中9种吲唑类新型合成大麻素

针对“电子烟油”中的吲唑类新型合成大麻素物质,建立了气相色谱－质谱联用（GC－MS）分析方法。以地西泮为内标物,待测样本经甲醇提取后,采用HP－5MS色谱柱（30 m × 0.25 mm × 0.25 μm）,设置起始温度200 ℃（保持1 min）,以20 ℃/min升至260 ℃（保持1 min）,再以5 ℃/min升至300 ℃（保持10 min）的程序升温条件对9种吲唑类合成大麻素同时进行定性和内标法定量检测,并对目标物的质谱碎片碎裂方式进行解析。结果表明,9种目标物质在20 min内得到有效分离,并在1.0～100.0 μg/mL范围内呈良好的线性关系,相关系数（r2）均大于0.997,检出限和定量下限分别为0.04～0.25 μg/mL和0.15 ~ 0.85 μg/mL;加标回收率为95.1%～104%,日内相对标准偏差（RSD）均小于4.6%,日间RSD均小于8.4%。该方法快速、准确,灵敏度高,适用于实际案件检验。     

气相色谱法测定茄尼醇中有机溶剂残留量

建立了测定茄尼醇中甲醇、正已烷、乙腈残留量的气相色谱法.样品和对照品均以异丙醇为溶剂,四氢呋喃为内标物. 色谱柱HP-5MS石英毛细管柱(5%苯基硅氧烷-95%甲基聚硅氧烷,30 m×0.25 mm×0.25 μm);检测器FID. 程序升温方式:初温80 ℃,保持5 min,以8 ℃/min升温至120 ℃,保持10 min;汽化室温度200 ℃;进样口温度250 ℃;高纯N2气为载气,流速2.0 mL/min;进样量2 μL.     

气相色谱法测定香水中乙醇含量的研究

本文建立了香水中乙醇含量的气相色谱检测方法.选用强极性的Agilent DB-WAXETR毛细管色谱柱(60 m×0.32 mm×0.5 μm),进样口温度180℃,分流比100∶1,进样量1μL,载气为高纯氮气,升温程序:90℃保持14 min,以30℃/min升至180℃,保持3 min,FID温度200℃.结果表明,乙醇含量在2％～20％的范围内有良好的线性(r2=0.99986),回收率为99.33％～101.00％.建立的方法简便、快速、准确,可用于检测香水中的乙醇含量.     

一种新型紫外正型光刻胶成膜树脂的制备及光刻性能研究

本文合成了N-(p-羧基苯基)甲基丙烯酰胺单体,并将其与N-苯基马来酰亚胺共聚得到共聚物聚N-(p-羧基苯基)甲基丙烯酰胺共N-苯基马来酰亚胺(poly(NCMA-co-NPMI)).将此共聚物作为成膜树脂,与感光剂、溶剂等复配得到一种新型耐高温紫外正型光刻胶.本文探讨了该光刻胶的最佳配方组成和最佳光刻工艺.最佳配方组成为:15%—20%成膜树脂,4.5%—6%感光剂和70%—80%溶剂;最佳光刻工艺为:匀胶30 s(4000 rpm),前烘4 min(90℃),感度为30—35mJ/cm²,在0.2%TMAH溶液显影10 s和后烘2 min(90℃).     

硅球多层模板溶胶浸渍法制备有序多孔TiO2薄膜

采用垂直沉积法组装了平均球径为188 nm的三维有序二氧化硅微球阵列。以该阵列为模板，通过在TiO₂前驱体溶胶中多次浸渍热处理循环，随后采用超声辅助的NaOH溶液腐蚀去除硅球模板，制备了>20层厚的反转结构的二氧化钛多孔膜。该二氧化钛薄膜在550 ℃下热处理20 h其多孔结构保持不变，表明采用此方法制备的二氧化钛多孔膜具有较好的热稳定性。X射线衍射图表明550 ℃下热处理得到的是具有锐钛矿结构的二氧化钛多孔膜。透光光谱显示了光子带隙出现在～400 nm。通过SEM观察，二氧化钛多孔膜     

新型锂离子电池三维结构泡沫NiO电极的制备及电化学性能

通过固相氧化方法,以三维结构泡沫镍为基体和金属镍源,制备了三维结构泡沫氧化镍负极。XRD和SEM结果表明,经500℃氧化处理,泡沫镍基体上形成了NiO微米级的致密活性氧化层。通过充放电测试和循环伏安测试研究了电极的电化学性能,结果表明,三维结构泡沫氧化镍在放电电位区间0.05～3.2VvsLi/Li+,0.2C倍率下充放电,初始容量损失为20%,且经40次循环后,质量比容量为950mAh·g-1,三维泡沫氧化镍电极具有优异的循环容量保持性能。三维泡沫氧化镍具有的大的活性表面积,降低了界面反应的极化,从而提高了NiO电极的倍率放电性能。     

裂解酞菁铁和乙烯制备取向碳纳米管阵列

采用热化学气相沉积(TCVD)法裂解酞菁铁(FePc)和乙烯(C2H4)制备出高210 μm的取向碳纳米管阵列(ACNTA). 用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、拉曼光谱和X射线光电子能谱(XPS)对制备的样品进行了表征, 系统研究了反应温度、反应时间、C2H4流量对ACNTA生长的影响. 结果表明, 样品具有高取向性且纯度高. 800 ℃是裂解FePc和C2H4制备ACNTA的最优温度, 催化剂的活性可以保持较长时间(60 min), 通入C2H4促进了ACNTA的快速生长, 最适合流量为50 cm3/min.     

图案化锥形氧化锌纳米带的原位热氧化法制备与发光性质

采用光刻技术制备出图案的锌膜,所得锌膜与纯氧在700℃氧化反应10 min,在锌膜的表面上原位生长出具有图案的锥形ZnO纳米带阵列,实现了ZnO纳米带生长位置的可控生长。锌膜上得到的锥形ZnO纳米带为单晶六方纤锌矿结构,长度在1～4μm,纳米带根部和顶部的宽度分别在300～700 nm和100～300 nm。提出了锥形ZnO纳米带的可能生长机理。在波长为300nm光的激发下,发现了锌膜上锥形ZnO纳米带具有发光峰位于395 nm弱的紫外光发光和510 nm强的蓝绿光发光,它们分别起源于ZnO宽带隙的激子发射以及表面上离子化氧空位中的电子与价带中光激发的空穴之间的复合。     

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.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

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.     

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.     

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.     

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.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.