Y2O2S：Eu,Mg,Ti,Tb红色长时发光材料的研究

利用高温固相反应法合成了一种新型的红色长时发光材料－Y2O2S：Eu,Mg,Ti,Tb.材料的XRD测试结果表明Eu掺杂引起Y2O2S，Eu,Mg,Ti,Tb晶胞增大，激发光谱，发射光谱和发光衰减曲线表明该材料是一种适合紫外线和可见光激发，并具有很好的长时发光性能的红色长时发光材料，热释光谱测试结果表明该材料可能具有两个较深的陷阱能级，研究了Eu,Mg,Ti,Tb的加入量对材料发光特性的影响。结果表明：Eu,Mg,Ti,Tb影响材料的初始亮度和发光时间，Eu决定材料的红色比。     

掺杂表面活性剂及金属离子对纳米Y2O3:Eu3+粉体的发光性能的影响

采用草酸沉淀法,通过填加表面活性剂四丁基溴化铵、十六烷基三甲基溴化铵和金属离子K+,Mg2+,Ba2+,制备出稀土发光材料Y2O3Eu3+,利用XRD与激发和发射光谱等测试手段对样品的结构与光学性能进行了表征,考察了同时加入不同表面活性剂和金属离子对Y2O3Eu3+的结构和发光性质的影响.结果表明加入表面活性剂和金属离子对发光材料Y2O3Eu3+的发光性能有较大的影响,其中以同时加入四丁基溴化铵和Ba2+以及加入十六烷基三甲基溴化铵和Mg2+对Y2O3Eu3+粉体的发光性能影响最大.     

利用热释光和光激励技术研究合成工艺对BaFBr∶Eu2+,Al3+发光性质的影响

利用热释发光谱和光激励发光谱表征了不同合成工艺条件对合成BaFBr: Eu2+, Al3+发光性质的影响. 利用理论分析找出了热释发光衰减与光激励衰减的异同, 理论上计算了不同的合成工艺对BaFBr:Eu2+, Al3+色心能级的影响, 其热释发光谱和光激励发光谱的理论计算值能较好的吻合, 并且能够很好的表征实验结果.     

(Y,Gd)BO3:Eu的真空紫外光谱特性

近年来由于等离子体平板显示(PDP)技术的需要,对真空紫外(VUV)光激发的荧光粉的研究成为发光材料领域中的一个新方向[1～3]. 由于技术和实验仪器等方面的原因[4], 以往人们对稀土发光材料VUV区的研究很少, 缺乏对其光谱和能级的完整认识. 另外, 稀土离子Gd3+在荧光粉的能量传递中具有特殊作用, 一些含Gd3+的发光材料在VUV区发光效率很高, 例如, (Y,Gd)BO3:Eu在VUV区的发光效率比YBO3:Eu提高了20%, 比Y2O3:Eu提高了1.8倍, 与其它红粉相比更具有实际应用价值[4,5]. 但目前对于(Y,Gd)BO3:Eu的研究主要集中在紫外可见区[6], 因此, 深入研究(Y,Gd)BO3:Eu的真空紫外光谱特性, 对于发展PDP技术具有重要意义.     

GdPO_4∶Eu~(3 )和GdBO_3∶Eu~(3 )中“Gd-Eu”间的能量传递

利用同步辐射光源(德国HASYLAB实验室的SUPERLUMI实验站)对高温固相法制备的GdPO4∶Eu3 和GdBO3∶Eu3 的发射谱与激发谱进行了研究,并从量子剪裁的角度对“Gd3 -Eu3 ”之间的能量传递作了讨论。在两种样品监测Eu3 红光发射的激发谱上,都显著观察到了对应Gd3 离子4f-4f跃迁的谱线,说明从基质中Gd3 离子向掺杂的Eu3 离子之间存在非常有效的能量传递,这有利于量子剪裁的发生。在激发谱上还观察到了对应Eu3 -O2-电荷迁移态的宽激发带(180~270nm),而对应Gd3 离子8S7/2→6GJ跃迁的谱线(196nm,203nm)叠加在这个宽带之上,微弱可辨,这不利于Gd3 -Eu3 间交叉弛豫的能量传递过程,从而不利于量子剪裁的发生。结合Eu3 -O2-电荷迁移态位置变化的规律,提出了如何避开其干扰以增强量子剪裁效应的材料设计方案。     

白光LED用荧光材料Ba3Gd（BO3）3∶Eu^（3＋）的发光性能研究

用高温固相反应法制备了稀土离子Eu^3＋掺杂的三元稀土硼酸盐Ba3Gd（BO3）3发光材料,通过X射线衍射（XRD）、荧光光谱和扫描电镜（SEM）等测试手段对Ba3Gd（BO3）3∶Eu^3＋荧光粉的制备条件、发光性能以及形貌进行了研究。XRD结果表明,在1000℃时可得到Ba3Gd（BO3）3纯相。扫描电镜照片显示颗粒基本为球形,粒径约为200-400 nm。发光光谱测试表明,Ba3Gd（BO3）3∶Eu^3＋荧光粉在近紫外区（UV）（396 nm）和蓝光区（466 nm）可以被有效地激发,分别用255和396 nm的紫外光激发样品时,以Eu3＋的5D0-7F2（611和616 nm）超灵敏跃迁为主要发射峰。当Eu3＋的掺杂浓度为10%（摩尔分数）时,Ba3Gd（BO3）3∶Eu3＋在611和616 nm处的发光强度最大。因此,这种荧光粉是一种可能应用在白光LED上的红色荧光材料。     

微乳液法制备MAl2O4：Eu^2＋，Dy^3＋（M=Ca，Sr，Ba）发光材料及其发光性能

采用微乳液法合成了MAl2O4：Eu^2＋，Dy^3＋（M=Ca，Sr，Ba）长余辉发光材料，并对其晶体结构和发光性能进行了比较与讨论。XRD分析表明，所合成的Ca2O4：Eu^2＋，Dy^3＋，SrAl2O4：Eu^2＋，Dy^3＋粉体为单斜晶系结构，BaAl2O4：Eu^2＋，Dy^3＋粉体为六方晶体结构。MAl2O4：Eu^2＋，Dy^3＋（M=Ca，Sr，Ba）发光材料的激发光谱都为一宽带连续谱，表明从紫外至可见光均可有效的激发该材料。发射光谱的发射波长峰值分别为440nm（M=Ca），520nm（M=Sr）和496nm（M=Ba）。对应的发光颜色分别为蓝色、黄绿色和蓝紫色。余辉衰减曲线分为快衰减、中间过渡衰减和随后极长的慢衰减过程，符合双曲线方程I=At^-n，余辉亮度与时间顺序为Sr〉Ca〉Ba。     

Y2O2S∶Eu,Mg,Ti,Tb红色长时发光材料的研究

利用高温固相反应法合成了一种新型的红色长时发光材料--Y2O2S∶Eu, Mg, Ti, Tb. 材料的XRD测试结果表明Eu掺杂引起Y2O2S∶Eu, Mg, Ti, Tb晶胞增大. 激发光谱、发射光谱和发光衰减曲线表明该材料是一种适合紫外线和可见光激发, 并具有很好的长时发光性能的红色长时发光材料. 热释光谱测试结果表明该材料可能具有两个较深的陷阱能级. 研究了Eu, Mg, Ti, Tb的加入量对材料发光特性的影响, 结果表明: Eu, Mg, Ti, Tb影响材料的初始亮度和发光时间, Eu决定材料的红色比.     

GdPO4:Eu3+和GdBO3:Eu3+中"Gd-Eu"间的能量传递

利用同步辐射光源(德国HASYLAB实验室的SUPERLUMI实验站)对高温固相法制备的GdPO4 Eu3+和GdBO3Eu3+的发射谱与激发谱进行了研究, 并从量子剪裁的角度对"Gd3+-Eu3+"之间的能量传递作了讨论. 在两种样品监测Eu3+红光发射的激发谱上, 都显著观察到了对应Gd3+离子4f-4f跃迁的谱线, 说明从基质中Gd3+离子向掺杂的Eu3+离子之间存在非常有效的能量传递, 这有利于量子剪裁的发生. 在激发谱上还观察到了对应Eu3+-O2-电荷迁移态的宽激发带(180～270 nm), 而对应Gd3+离子8S7/2→6GJ跃迁的谱线(196 nm, 203 nm)叠加在这个宽带之上, 微弱可辨, 这不利于Gd3+-Eu3+间交叉弛豫的能量传递过程, 从而不利于量子剪裁的发生. 结合Eu3+-O2-电荷迁移态位置变化的规律, 提出了如何避开其干扰以增强量子剪裁效应的材料设计方案.     

Y2O2S:Eu,Ti,Mg的光谱性质和长时发光特性

研究了Ti, Mg, Eu等离子掺杂的Y2O2S材料的光谱性质和长时发光特性, 并发现了光致激发下Y2O2S∶Ti中峰值为594nm的宽带发射及长时发光现象. 根据发射光谱和衰减曲线的分析, 认为Ti掺杂后在Y2O2S晶体中形成施主能级, 有效地捕获离化的电子, 造成长时发光现象. 共掺入Mg进行电荷补偿可增强初始发光亮度和发光时间. 在红色长时发光材料Y2O2S∶Eu, Ti, Mg中, Eu3 作为发光中心, 接受被俘获的电子和空穴重新复合后释放的能量, 发射Eu3 的626和616 nm等特征光谱.     

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.     

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.     

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.     

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.