硒功能化杯[4]芳烃对金属离子的识别及在PVC基质支撑液膜的传输作用

提出以PVC为基质的支撑液膜传输体系，研究了以新研制的硒功能化杯[4]芳烃 为活性载体，邻苯二甲酸二辛酯（DOP）为膜溶剂的PVC基质支撑液膜对金属离子的 传输性能。采用双层夹心膜电位法测定了活动载体-金属离子在膜中的配合物生成 常数，对离子在膜中的传输速率、选择性系数以及生成常数之间的相关性作了研究 。使用该体系发现，在8种金属离子中汞具有最快的传输速率；进一步讨论了硒功 能化杯[4]芳烃对金属离子的识别作用和支撑液膜传输机理。     

杯芳烃衍生物液－液萃取和液膜传输银的对比研究及机理探讨

以4类含硫、硒、氮等杂原子基团二取代的杯[4]芳烃五衍生物（1－14）为中 性载体，在H2O-CHCl3-苦味酸体系萃取银和H2O-CHCl3-H2O液膜体系中传输银进行 了对比研究。萃取和传输结果具有一致性，除了苯并噻唑取代的杯[4]芳烃衍生物 （3－6）外，其它10个含硫、硒、氮的杯[4]芳烃衍生物1－14均对软重金属银和汞 有很高的选择性，而吡啶取代的杯[4]芳烃衍生物7－10对铅有一定的萃取选择性， 其中羟基硫醚取代的杯[4]芳烃衍生物11－14对银的萃取率和传输速率最大。并且 就杯[4]芳烃衍生物对银的传输机理进行了探讨，发现传输速率随源相中金属离子 浓度和有机相中载体浓度的增加而增大，因此推论这是由金属离子浓度梯度推动下 的传输。     

杯芳烃的超分子化学研究（IV）：对-叔丁基杯[4]芳烃对ATP的分子识别及液膜传输作用

采用气泡式准乳化液膜法 ,研究了对 -叔丁基杯 [4 ]芳烃对ATP分子的液膜传输作用 ,讨论了源相与吸收相的组成、酸度、源相中的ATP的起始浓度及吸收相中NH3 ·H2 O浓度等因素对传输结果的影响 ;进而讨论了对 -叔丁基杯 [4 ]芳烃对ATP的分子识别作用和液膜传输机理     

杯芳烃的超分子化学研究（IV）：对-叔丁基杯[4]芳烃对ATP的分子识别及液膜传输作用

采用气泡式准乳化液膜法,研究了对-叔丁基杯[4]芳烃对ATP分子的液膜传输 作用,讨论了源相与吸收相的组成、酸度、源相中的ATP的起始浓度及吸收相中 NH_3·H_2O浓度等因素对传输结果的影响;进而讨论了对-叔丁基杯[4]芳烃对ATP 的分子识别作用和液膜传输机理。     

杯[4]芳烃衍生物对Pb2＋的液膜传输动力学

以3类含不同基团的杯[4]芳烃衍生物作为离子载体在H2O-CHCl3-H2O液膜传输体系下分别对Pb2＋进行液膜传输实验. 简要讨论了以杯[4]芳烃衍生物作为离子载体对Pb2＋液膜传输的动力学机理. 重点研究了不同载体种类, 载体浓度, 搅拌速度, 传输时间等因素对Pb2＋传输的影响. 实验结果表明: 以含Br原子的杯[4]芳烃衍生物和含S原子的杯[4]芳烃衍生物作为离子载体对Pb2＋有明显的传输效果. 可以用本文的动力学模型来描述整个传输体系的动力学特性.     

含酰胺基和酯基的新型杯[4]冠醚的合成及其对金属离子的识别能力

利用杯[4]芳烃与含酰胺基和酯基的丙二酸酯衍生物的"1+1"分子间缩合合成了一例新型结构的杯[4]-1,3-冠醚;利用核磁共振、红外光谱、质谱及元素分析表征了其结构,并测定了其对金属离子的识别能力.结果表明,合成的新型杯[4]冠醚对金属阳离子和阴离子均有较好的识别能力.     

环氧丙基杯[6]-1,4-冠-4聚合物的合成与吸附性能

通过具有稳定锥式构象的杯[6]-1,4-冠-4与环氧氯丙烷反应,再与多乙烯多胺开环聚合,合成了一系列具有稳定构象的新型含氮杯[6]芳烃冠醚聚合物(3a-3c)。并研究了它们对阳离子的吸附性能,结果表明,其吸附选择性较没有稳定构象的类似杯[6]芳烃聚合物好,聚合物3b和3c对Cu^2 表现较好的选择性吸附能力。     

一类新型四酰胺杯[4]氮杂冠醚的合成及阴离子识别研究

合成了一类新型四酰胺杯[4]氮杂冠醚（4a，4b），其结构经~1H NMR、质谱及 元素分析证实。用紫外可见光谱研究了主体与阴离子之间的相互作用，并计算出其 配合常数。结果表明，四酰胺杯[4]氮杂冠醚（4a，4b）对四面体型阴离子（p - O_2GC_6OPO_3~2_4）没有识别性能，而对平面型阴离子（p - O_2NC_6H_4O）有较 好地选择性识别性能，且主客体间形成1：1配合物。     

对叔丁基杯[6]-1,4-2,5-双冠醚的合成、构象及其对阳离子的识别性能研究

采用分步法高产率地合成了系列新型对叔丁基杯[6]双冠醚，并得到了除杯式与1，2，3－交替式构象之外的第3种稳定构象的杯[6]衍生物：1，4－交替式杯[6]-1,4-2,5-双冠醚。研究了它们对碱金属及脂肪胺离子的两相萃取性能，发现杯[6]双冠醚具有与杯[6]单冠醚不同的识别能力。     

冠醚改性聚甲基硅氧烷液膜离子传输性能

合成了两种新型的冠醚改性聚甲基硅氧烷，研究了它们作为液膜离子传输载体对离子的传输性能，并考察了膜的稳定性。     

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%.     

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.     

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.     

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.     

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.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

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.