不除氧条件下喹啉的环糊精诱导室温磷光性质

不除氧条件下，在含２０μＬ二溴乙烷（ＤＢＥ）的１０ｍＬ体系中，喹啉就能产生强而稳定的环糊精诱导室温磷光（ＣＤ－ＲＴＰ）信号，最大λｅｘ／λｅｍ＝２７６／４９６ｎｍ，喹啉浓度在２．０×１０＾－６￣４．０×１０＾－４ｍｏｌ／Ｌ范围内与ＲＴＰ信号呈良好的线性关系，检测限２．０×１０＾－７ｍｏｌ／Ｌ。由于所用重原子微扰剂ＤＢＥ的量很少，本发光体系仅均匀地呈轻微的雾状，而无明显沉淀，使测量精度明显改善。实验     

α-溴代萘的无保护性介质流体室温燐光特性

含α－溴代萘（ａ－ＢｒＮｐ）的水溶液仅以Ｎａ２ＳＯ３作化学除氧剂，在仪器光源的照射下，即能很快触发α－ＢｒＮｐ强而稳定的室温光（ＲＴＰ）信号。体系ＲＴＰ性质和所需光诱导的时间对有机试剂的存在及其种类和用量极为敏感。０．５％（Ｖ／Ｖ）乙腈或丙酮的存在所需光照时间短，ＲＴＰ强度高。α－ＢｒＮｐ浓度分别在 １．０ × １０－６～ ２． ４ × １０－５ ｍｏｌ／Ｌ和 ４． ０ × １０－７～ ２． ０ × １０－５ｍｏｌ／Ｌ范围内与 ＲＴＰ强度呈良好线性关系，检出限分别为 ３，８ × １０－８ ｍｏｌ／Ｌ和 ６．５ × １０－８ ｍｏｌ／Ｌ。     

α—溴代萘的无保护性介质流体室温磷光特性

含α－溴代萘（α－ＢｒＮｐ）的水溶液仅以Ｎａ２ＳＯ３作化学除氧剂，在仪器光源的照射下，即能很快触发α－ＢｒＮｐ或而稳定的室温磷光（ＲＴＰ）信号。体系ＲＴＰ性质和所需光诱导的时间对有机试剂的存在及其种类和用量极为敏感。０．５％（Ｖ／Ｖ）乙腈或丙酮的存在所需光照时间短，ＲＩＰ强度高。α－ＢｒＮｐ浓度分别在１．０×１０＾－６￣２．４×１０＾－５ｍｏｌ／Ｌ和４．０×１０＾－７￣２．０×１０＾－５ｍｏｌ／Ｌ     

β-溴代萘的无保护流体室温磷光性质及介质效应

无任何保护性介质存在下,β－溴代萘（β－ＢｒＮ）水溶液仅以Ｎａ２ＳＯ３作化学除氧剂,经仪器光源适当照射,即能很快产生强而稳定的室温磷光（ＲＴＰ）信号．不同种类和用量的有机溶剂存在时,ＲＴＰ强度和获得稳定ＲＴＰ信号所需光诱导的时间显著不同．含２．５％乙腈的β－ＢｒＮ水溶液仅需极短的光诱导时间就能产生很强的ＲＴＰ发射,β－ＢｒＮ浓度在８．０×１０－８～１．６×１０－５ｍｏｌ／Ｌ范围内与其ＲＴＰ强度呈良好线性关系,检出限４．７×１０－８ｍｏｌ／Ｌ     

β—溴代萘瓣无保护流体室温磷光性质及介质效应

无任何保护性介质存在下,β－溴代奈（β－ＢｒＮ）水溶液仅以Ｎａ２ＳＯ３作化学除氧剂,经仪器光源适当照射,即能很快产生强而稳定的室温磷光（ＲＴＰ）信号,不同种类和用量的有机溶剂存在时,ＲＴＰ强度和获得稳定ＲＴＰ信号所需光诱导的时间显著不同,含２．５％乙腈的β－ＢｒＮ水溶液仅需极短的光诱导时间就能产生很强的ＲＴＰ发射,β－ＢｒＮ浓度在８．０×１０＾－８－１．６×１０＾－５ｍｏｌ／Ｌ范围内与其ＲＴＰ强度     

氨基萘磺酸盐无保护流体室温磷光的取代基位置效应

以ＴＩＮＯ３作重原子微扰剂,Ｎａ２ＳＯ３作化学除氧剂,在无需加入任何保护介质条件下,仅需仪器光源适当照射,１－氨基４－萘磺酸盐、１－氨基５－萘磺酸盐、２－氨基１－萘磺酸盐水溶液均能产生强而稳定的室温磷光信号（ＲＴＰ）。３种氨基萘磺酸盐浓度分别在４．０×１０＾－８￣１．２×１０＾－５ｍｏｌ／Ｌ;１．２×１０＾－６￣１．６×１０＾－５ｍｏｌ／Ｌ;１．６×１０＾－７￣８．０×１０＾－６和８．０×１０＾－     

冠醚存在下稀土络合物荧光体系的荧光增强效应

本详细研究了冠醚对Ｅｕ－ＴＴＡ荧光体系的增敏作用和稀土离子Ｄｙ＾３＾＋或Ｈｏ＾３＾＋对Ｅｕ－ＴＴＡ－冠醚体系的荧光强增效应。对Ｅｕ－ＴＴＡ－冠醚和Ｅｕ－Ｄｙ（或Ｈｏ）－ＴＴＡ－冠醚体系，Ｅｕ的浓度分别在１．０×１０＾－＾８－４．０×１０＾－＾６ｍｏｌ／Ｌ，１．０×１０＾－＾９－１．０×１０＾－＾７ｍｏｌ／Ｌ和１．０×１０＾－＾８－９．０×１０＾－＾６ｍｏｌ／Ｌ范围内与体系的荧光强度呈线性关系，检     

不除氧条件下4-溴联苯的透明环糊精诱导室温燐光体系

利用４－溴联苯内含重原子的特性，通过外加有机溶剂对４－溴联苯的增溶作用和γ－ＣＤ腔的保护性作用，在不除氧条件下首次获得有分析意义的透明ＣＤ－ＲＴＰ体系，该体系对４－溴联苯的检测限为３．０×１０－７ｍｏｌ／Ｌ。     

铕—敌鼠—DL—组氨酸—十六烷基三甲基溴化铵荧光体系及其应用

研究了铕－敌鼠－ＤＬ－组氨酸－ＣＴＭＡＢ荧光体系的荧光特性，测定了体系的影响因素和测定敌鼠的实验方法，体系的激发和发射波长分别为３３０ｎｍ和６１２ｎｍ，各组分的最佳浓度分别为１．０×１０＾－５ｍｏｌ／Ｌ，ＤＬ－组氨酸，１．０×１０＾－４ｍｏｌ／Ｌ，ＣＴＭＡＢ１．０×１０＾－５ｍｏｌ／Ｌ，ｐＨ为９．０，在此条件下，敌鼠浓度在６．０×１０＾－７～９．０×１０＾－５ｍｏｌ／Ｌ范围内同体系的荧光强度成线性     

不除氧条件下4—溴联苯的透明环糊精诱导室温磷光体系

利用４－溴联苯内含重原子的特性，通过外加有机溶剂对４－溴联苯的增容作用和γ－ＣＤ腔的保护性作用，在不除氧条件下首次获得了有分析意义的透明ＣＤ－ＲＴＰ体系，该体系对４－溴联苯的检测限为３．０×１０＾－７ｍｏｌ／Ｌ。     

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.