PTFE—乙醚柱反相萃取层析连续分离和测定镓（Ⅲ）铟（Ⅲ）的研究

研究了在抗坏血酸存在下的６ｍｏｌ／Ｌ ＨＢｒ介质作流动相，以ＰＴＦＥ（聚四氟乙烯）负载的乙醚作固定相，反相萃取层析使微量Ｇａ（Ⅲ），Ｉｎ（Ⅲ）与Ｆｅ＾３＋、Ｔｌ＾３＋、Ｍｏ＾６＋、Ａｕ＾３＋、Ｔｉ＾４＋、Ｂｉ＾３＋、Ａｌ＾３＋、Ｍｇ＾２＋、Ｃａ＾２＋、Ｎｉ＾２＋、Ｃｏ＾２＋、Ｃｄ＾２＋、Ｚｎ＾２＋、Ｐｂ＾２＋、Ｃｕ＾２＋等多种离子分离。留于柱上的铟、镓分别用ＨＣｌ（４ｍｏｌ／Ｌ）－Ｈ２Ｏ２（３％）     

Eu^3＋,Bi^3＋Me2Y8（SiO4）6O2中的发光特性与取代格位

在紫外光激发下，Ｅｕ＾３＋和Ｂｉ＾３＋在Ｍｅ２Ｙ８（ＳｉＯ４）６Ｏ２基质（Ｍｅ＝Ｍｇ，Ｚｎ，Ｃａ，Ｓｒ）中分别发射红光（＾５Ｄ０－＾７Ｆ２）和蓝光（＾３Ｐ１－＾１Ｓ０）．Ｅｕ＾３＋发光的红橙比随着激发波长和Ｍｅ＾２＋的不同而变化。荧光拉曼光谱表明，Ｅｕ＾３＋在四种基质中同时占据了４ｆ格位和６ｈ格位。依据Ｂｉ＾３＋发光的Ｓｔｏｋｅｓ位移推断，当Ｍｅ＝Ｃａ，Ｚｎ时，Ｂｉ＾３＋主要占据４ｆ格位，而当Ｍｅ     

溶胶—凝胶合成（Mg,Ca）O—SiO2：Eu^3＋,Bi^3＋发光体及其发光行为

以Ｍｇ（ＮＯ３）２，Ｃａ（ＮＯ３）２，Ｅｕ（ＮＯ３）３，Ｂｉ（ＮＯ３）３和Ｓｉ（ＯＣ２Ｈ５）４为反应物，采用溶胶－凝胶法，在比较低的温度，首次合成０．７０１ｍｏｌＭｇＯ－０．１７５ｍｏｌＣａＯ－１．２５ｍｏｌＳｉＯ２：０．０６ｍｏｌＥｕ＾３＋，０．００２ｍｏｌＢｉ＾３＋（加入Ｌｉ＾＋作为电荷补偿剂）发光体，得到了最佳合成条件，研究了由溶胶向凝胶转变和凝胶向发光晶体的转变过程，探讨了发光体在不同激光     

β—型过渡元素三取代钨锗杂多配合物的合成,表征和催化活性

报道Ａ－β－Ｍ＇ｘＨｙ－［ＧｅＷＯＭ３（Ｈ２Ｏ）３Ｏ３７］．ｎＨ２Ｏ（Ｍ＝Ｃｒ＾３＾＋，Ｃｏ＾２＾＋，Ｎｉ＾２＾＋，Ｃｕ＾２＾＋；Ｍ＇＝Ｂｕ４Ｎ＾＋，Ｋ＾＋）的立体有择合成法制备及红外和远红外光谱，紫外和可见光谱和循环伏安，磁化率和磁矩，ＸＰＳ，ＥＳＲ以及催化活性等研究结果。     

（四甲基二硅撑）双（3—三甲硅基环戊二烯基）—四羰基二铁…

标题化合物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２〕２／（μ－ＣＯ）２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ２Ｃｌ、ＣｌＣＨ２ＣＯＯＣ２Ｈ５和Ｐｈ３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２Ｒ〕２（Ｒ：Ｍ     

以磷酸三丁脂为载体的乳状液膜迁移,分离稀土元素的研究：Sm（Ⅲ）与常…

用磷酸三丁酯Ｓｐａｎ８０－二甲苯乳状液膜体系迁移Ｓｍ（Ⅲ）的研究表明，在确定的条件下，可以快速并完全迁移Ｓｍ（Ⅲ）。许多常见离子不能在此条件下通过液膜迁移，故可从含有Ｆｅ＾２＋，Ｃｏ＾２＋，Ｎｉ＾２＋，Ｃｕ＾２＋，Ｚｎ＾２＋，Ｃｄ＾２＋，Ｍｎ＾２＋等离子混合液中分离出Ｓｍ（Ⅲ）分离效率高。     

金属卟啉－甲基紫精二连体配合物的合成及其光化学行为

本文合成了四（对－氯代甲基）苯基－甲基紫精卟啉及其Ｚｎ，Ｃｏ，Ｍｎ配合物，用元素分析、红外光谱和紫外可见光谱进行了表征。研究了它们的光化学性质。结果表明，在ＴＥＯＡ中光照使Ｍ。ＴＣＭＰＰ－ｍｖ＾２＋发生了分子内从卟啉到甲基紫精的电子迁移反应。在ＺｎＴＣＭＰＰ－ｍｖ＾２＋／ＴＥＯＡ／ＤＭＳＯ－Ｈ２Ｏ体系中可发生光敏化还原ｍｖ＾２＋反应，生成较稳定的ｍｖ＾＋。在Ｍｎ（Ⅲ）ＴＣＭＰＰ－ＭＶ＾２＋／ＣＨ３     

应用CS2在Ag—S键中的插入反应生成新型Ag原子簇化合物研…

应用ＣＳ２在Ａｇ－Ｓ键中的单核插入物（ＰＰｈ３）２Ａｇ（Ｓ２ＣＳＰｒ３＾ｉＣ６Ｈ２）与ＣＨ２Ｃｌ２－Ｐｒ＾ｉＯＨ混合溶剂反应，生成了一个中性的三核银簇合物，并用Ｘ射线单晶衍射法测定了其晶体结构。     

杂元素冠醚研究（Ⅻ）——氧,硫,硒和碲杂冠醚的液膜迁移性能…

报道了碲杂冠醚（ＴｅＢ１５Ｃ５）对Ｎａ＾＋、Ｋ＾＋、Ａｇ＾＋和Ｐｂ＾２＋的液膜迁移能力，并与相应的全氧冠醚（Ｂ１５Ｃ５）、硫杂冠醚（ＳＢ１５Ｃ５）和硒杂冠醚（ＳｅＢ１５Ｃ５）作了比较；同时以ＳｅＢ１５Ｃ５对Ｋ＾＋的迁移为例考察了冠醚浓度和盐浓度对迁移速率的影响。     

非过滤法共沉淀富集—火焰原子吸收测定饮水中镉铜铅

在中性或弱碱性条件下，向被没水样中加入适量Ｂｉ＾３＋和硫化钠，使水样中Ｃｄ＾２＋，Ｃｕ＾２＋，Ｐｂ＾２＋与Ｂｉ＾３＋一起硫化物（ＣｄＳ，ＣｕＳ，ＰｂＳ）和Ｂｉ２Ｓ３的共沉淀，加入明矾加速硫化物的沉淀，凝结，然后用虹吸法吸去上层清液（无须过滤），将沉淀物用热稀硝酸溶液，以火焰原子吸收法测定这三个元素的含量。方法简便，实用，且具有较高的准确率和精密度，尤其适于对大体积水样的沉淀富集。     

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.     

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.     

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.     

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.     

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.     

Microwave-assisted copper-catalyzed stereoselective ring expansion of three-membered heterocycles with α-diazo-β-dicarbonyl compounds

Microwave-assisted copper-catalyzed ring expansions of three-membered heterocycles with α-diazo-β-dicarbonyl compounds were investigated. Thiiranes generated 3-acyl-5,6-dihydro-1,4-oxathiines in the presence of copper sulfate and trans-3-acyl-5,6-dihydro-1,4-oxathiines as stereospecific products for 1,2-disubstituted cis-thiiranes through an intramolecular S_N2 process. Oxiranes gave rise to 2-acyl-5,6-dihydro-1,4-dioxines under the catalysis of copper hexafluoroacetylacetonate and cis-3-acyl-5,6-dihydro-1,4-dioxines as stereospecific products for 1,2-disubstituted cis-oxiranes via an intimate ion-pair mechanism. The current method provides a direct and simple strategy in efficient preparation of 3-acyl-5,6-dihydro-1,4-oxathiines and 2-acyl-5,6-dihydro-1,4-dioxines, important agents in medicinal and agricultural chemistry, from readily available thiiranes and oxiranes, respectively.     

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.