8-羟基喹啉两亲配合物的LB膜及其电致发光器件研究

制备了两亲配体N-十六烷基-8-羟基-2-喹啉甲酰胺(HL)十个配合物的LB膜。采用π-A等温线和小角X射线衍射等方法研究了这些LB膜的性质和结构。两亲配合物的单分子占有面积为(1.25±0.06)nm^2和(0.75±0.06)nm^2,分别对应于两亲分子中两个喹啉环平躺和环与环之间以一定的角度倾斜于气/水界面。LB膜内分子排列是二维有序的超晶格结构,双层高度(5.0±0.1)nm;LB膜具有导电各向异性,其平面和垂直直流电导率分别为10^-^5S.m^-^1和10^-^9S.m^-^1;LB膜的高荧光性质使之可以用作为电致发光器件的发光材料。以LaL~2(H~2O)~4Cl的LB膜为发光层的单层电致发光器件的驱动电压为9V,发光亮度330cd/m^2,为黄绿色发光。     

8-羟基喹啉镧两亲性配合物LB膜的双层电致发光器件

以具有不同层数的两亲配合物二[2-(N-十六烷基氨基甲酰基)-8-羟基喹啉]合镧[La(HQ)₂Cl]的LB膜为发光层,PBD为电子传输层,制备了双层结构的电致发光(EL)器件:ITO/LB膜/PBD/Al.器件产生黄绿色注入式发光.LB膜的层数和沉积压对器件的性能具有重要影响.在16V激发电压下,5,11和21层LB膜双层EL器件的电流密度分别为48,29和16.4mA/cm²,启亮电压阀值为7.5,8.5和9.5V.器件的亮度随电流密度和驱动电压的增加而增加.在相同偏压下,21层LB膜EL器件的亮度大于5和11层LB膜的器件.在25mN/m沉积的LB膜制备的EL器件具有较高的亮度(1219cd/m₂)和击穿电压.     

胆红素及其两亲衍生物的Langmuir-Blodgett膜研究

研究了亚相酸度和金属离子对胆红素(1)及其两个两亲衍生物胆红素二(十八烷基)酯(2)和胆红素二(十八烷基)酰胺(3)的单分子膜和LB膜性能的影响.通过π-A等温线、X射线光电子能谱、紫外-可见光谱等方法,研究了它们在有序分子膜中的分子伸展及与金属离子的配位方式.胆红素及其两亲衍生物与金属离子在有序分子膜中的配位(生成1:1型配合物)明显不同于其在本体溶液中的配位(1:1,1:2或2:1型配合物).小角X射线衍射表明1,2和3形成双层膜间距分别为2.15,5.55和5.65nm的Y型LB膜.     

亚相酸度及金属离子对2-十六氨基甲酰基-8-羟基喹啉成膜性能的影响

合成了两亲配体2-十六氨基甲酰基-8-羟基喹啉(简称HHQ),研究了亚相酸度及金属离子对HHQ成膜性能的影响。金属离子的半径、电荷及核外价电子层结构不同是影响HHQLang-muir单分子层膜性能的本质原因。从含有Ni²⁺、Cu²⁺离子的亚相表面所制备的多层LB膜的吸收光谱中产生了一个新的吸收峰。     

酸度对2-十八胺基甲酰基-8-羟基喹啉成膜性能的影响

两亲分子的成膜性能的研究主要集中在以羧基、磺酸基、磷酸基和第四铵盐等为亲水头基的化合物[1 ,2 ] ,而对亲水头基中兼有酸、碱性基团的两亲配体研究很少 ,本文报道了我们合成的一种新型两亲配体 2 -十八胺基甲酰基 - 8-羟基喹啉 (以下简写为 HL)在不同 p H的亚相溶液中单分子膜的形成。结果表明 ,HL在酸性亚相中不易成膜 ,而在碱性亚相中成膜性能较好 ,单分子膜由膨胀型向压缩型转变。并且讨论了亚相 p H对 HL单分子膜崩溃压的影响 ,以及 8-羟基喹啉头基在气 /液界面上的离解 -缔合情况。实　验　部　分一 .试剂与仪器2 -十八胺基甲…     

2-(N-十六烷基氨基甲酰基)-8-羟基喹啉镉配合物的电致发光

本文首次报道了采用2-(N-十六烷基氨基甲酰基)-8-羟基喹啉镉配合物作为一种新型发光材料，通过LB膜技术来制备发光层所制得的电致发光器件。在室温下，当直流正向偏压为6.5 V时，可于暗室中用肉眼观察到发光。当电流密度为35 mA/cm²时，可得稳定的发光，其电致发光图谱峰值在490 nm处。     

铜盐与二甲氧基嘧啶胺配合物的合成及其结构表征

利用氯化苄基三乙基胺（TEBA）为催化剂，改进文献方法提高2－氨基－4，6 －二甲氧基嘧啶（AMP）的产率。无水乙醇中回流制得水合氯化铜和硝酸铜与AMP的 物质的量比为1：2的固态配合物，用化学分析和元素分析确定它们的组成为Cu (AMP)2Cl2(1)和Cu(AMP)2(NO3)2(2)；用IR，XPS和^1H NMR等手段研究了它们的成 键情况；配合物中配体通过氨基N原子和嘧啶环上一个N原子与Cu^2+双齿配位，配 合物2中NO3^-未参与配位，中心离子Cu^2+分别为sp^3d^2和sp^3杂化，配位数为6 和4。据此，推测了它们的可能结构。     

7-{2-[1-(8-羟基喹啉-7-亚甲基)]苯并咪唑基}-8-羟基喹啉及其金属配合物的合成与荧光性能

以7-甲酰基-8-羟基喹啉和邻苯二胺为原料,经缩合反应合成了一种新型的配体——7-{2-[1-(8-羟基喹啉-7-亚甲基)]苯并咪唑基}-8-羟基喹啉(H2L);H2L分别与醋酸锌和三氯化铝经配位反应合成了两种新型的金属配合物Zn L·H2O(1)和Al_2L_3·3H_2O(2),其结构和性能经UV-Vis,1H NMR,IR,元素分析及FL表征。1和2的λem分别为514 nm(λex=400 nm)和525 nm(λex=401 nm)。     

3-[2-(8-羟基喹啉基)-乙烯基]-N-芳基咔唑及其金属配合物的合成和光电性能研究

设计合成了3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲苯基咔唑(8)和3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲氧苯基咔唑(9)及其金属锌配合物(10和11), 用UV-Vis, FTIR, ESI-MS, FAB-MS, ¹H NMR和元素分析确认了化合物的结构. 热重分析实验结果表明, 金属锌配合物(10和11)有很好的热稳定性, 这对真空蒸镀制电致发光器件是有益的. 金属锌配合物组装成有机单层发光器件的结构为ITO/Organ layer(50 nm)/Al(100 nm), 其荧光发射峰分别位于592和583 nm, 为稳定的黄色光. 这两个发光器件的最大亮度分别为489和402 cd/m², 最大电流效率分别为0.41和1.81 cd/A. 电致发光研究表明, 通过化学修饰8-羟基喹啉的2-位取代基可以改变这两个金属锌配合物的电致发光性能.     

新荧光试剂5-(4-氟苯偶氮)-8-水杨醛缩氨基喹啉荧光法测定痕量铜

合成了新荧光试剂5-(4-)氟苯偶氮)-8-水杨醛缩氨基喹啉(p-FPSAQ)，探讨了与Cu^2 反应的荧光性质。在pH8．5的缓冲体系中，p-FPSAQ与Cu^2 形成2：1络合物；线性范围5．0～90．0ng／L，检出限为2．43ng／L，可用于自来水中铜的测定。     

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%.     

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.     

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.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

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.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.