定向合成高效捕获CO2的新型多孔芳香材料

通过简单的离子热法,以四（4-氰基联苯基）硅烷作为四面体基块,将其与无水氯化锌在充满氩气气氛的手套箱中充分研磨后密封,分别以400和550 ℃的反应温度合成了新型多孔芳香骨架材料（PAF-51）,得到PAF-51-1（400 ℃条件下）与PAF-51-2（550 ℃条件下）的比表面积分别为720和557 m²·g^-1 （BET）.与CH₄和N₂对比,该材料对CO₂具有极好的选择性吸附能力. 273 K条件下,CO₂/N₂分离指数最高可达52.2,CO₂/CH₄分离指数也达到10.3,这一性质极有可能使得PAF-51成为捕获CO₂理想材料,并对再生能源具有潜在的应用.     

四苯基乙烯基共轭微孔聚合物的制备及其气体吸附

共轭微孔聚合物由于其在气体吸附与分离、非均相催化和光电子等领域的巨大应用前景而广受关注. 本文以四苯基乙烯为基本构筑单元, 通过Sonogashira-Hagihara偶联反应制备了3种共轭微孔聚合物新材料, 研究了结构组成和构建模块对制备聚合物孔性能和气体吸附性能的影响. 氮气吸附测试结果表明, 由1,1,2,2-四炔四苯基乙烯自聚合制备的TPE-CMP1具有较大的比表面积, 为1096 m²·g^-1. 在1.13 bar/273 K条件下, TPE-CMP1的CO₂吸附能力为2.36 mmol·g^-1; 在1.13 bar/77.3 K条件下, TPE-CMP1对H₂的吸附能力为1.35 wt%. 另外, 制备的共轭微孔聚合物展示出较高的CO₂/N₂选择性吸附值. 由于这类多孔聚合物材料具有合成方法简单、优良的物理化学及热稳定性、高的比表面积和CO₂吸附性能, 因此将在气体吸附与分离方面具有潜在的应用前景.     

富氮多级孔炭材料的制备及其吸附分离CO2的性能

使用新型含氮聚合物席夫碱为炭源, SBA-15为模板,通过纳米铸型法原位合成微孔-中孔-大孔串联的多级孔富氮炭材料.材料的比表面积为752 m²·g^-1,孔容0.79 cm³·g^-1; X光电子能谱分析表明炭材料中的氮含量高达7.85%(w).将所制备的多孔炭材料应用于CO₂的吸附分离,发现炭材料的微孔发挥主导作用,表面氮掺杂发挥辅助作用.在两者的协同作用下, CO₂吸附量在常压、273 K下可达97 cm³·g^-1, CO₂/N₂和CO₂/CH₄的分离比(摩尔比)分别为7.0和3.2,低压亨利吸附选择性分别为23.3和4.2.采用Toth模型对单组分平衡吸附进行拟合,并根据理想溶液吸附理论(IAST)预测双组分CO₂/N₂和CO₂/CH₄混合气体的分离选择性分别为40和18.     

氨基硫脲修饰卟啉基聚合物的制备及对CO2和Hg2+的吸附

利用四苯基卟啉和三种酰基化交联剂(草酰氯、对苯二甲酰氯和均苯三甲酰氯)经Friedel-Crafts酰基化反应,制备了卟啉基聚合物中间体,进一步用氨基硫脲与之发生席夫碱反应,得到了氨基硫脲修饰卟啉基聚合物.结果发现,聚合物的交联结构使其具有高比表面积和丰富的超微孔,显示出优异的CO₂吸附(138 mg/g,273 K,10⁵ Pa)及CO₂/N₂选择性.同时,聚合物表面氨基和硫脲的引入使得其对Hg²⁺的吸附量可达311.0 mg/g,吸附机理也证实了N和S对Hg²⁺的配位作用.     

共轭微孔聚合物多孔硬炭的KOH活化碳化与储锂性能

以1,3,5-三乙炔基苯为单体自聚合成了共轭微孔聚合物（CMP）,经直接碳化、KOH活化碳化分别制备了多孔硬炭（PHC）和KOH活化多孔硬炭（K-PHC）。用SEM、N₂吸附-脱附测试对K-PHC和PHC形貌结构进行了分析。K-PHC具有丰富的孔结构和较大的比表面积（1234.5 m²·g^-1）。恒流充放电测试表明：K-PHC的首次充放电比容量为972.1和2438.2 mAh·g^-1; 0.6 A·g^-1电流密度下循环300次,仍可达到627.2 mAh·g^-1的高比容量。      

碳化多孔有机骨架制备氮掺杂多孔碳及其气体吸附研究

通过简单的一步碳化方法, 以含氮的多孔有机骨架JUC-Z2为碳前驱物制备出氮掺杂多孔碳材料. 与原始JUC-Z2材料相比, 制备的多孔碳材料显示出明显提高的气体吸附量和增强的吸附焓. 其中JUC-Z2-900的CO₂吸附量高达113 cm³·g^-1, H₂吸附量也达到246 cm³·g^-1, 超过了大部分报道的多孔材料. 尤其是JUC-Z2-900的CH₄吸附量在273 K, 1 bar下高达60 cm³·g^-1, 据我们所知, 这一值为目前报道材料的最高值. 除此之外, 样品还显示出选择性吸附CO₂的能力, 273 K下, JUC-Z2-900的CO₂/N₂的选择性高达10, CO₂/H₂的选择性也高达66. 另外, 样品具有很高的热稳定性, 有望应用在碳捕获和清洁能源储存等领域.     

MIL-101(Cr)/GO复合吸附剂的O2/N2分离性能研究

变压吸附（PSA）制取O₂的核心是吸附剂.近年来,金属有机骨架（MOFs）被认为是一种具有广阔应用前景的新型吸附剂.通过水热法制备了MIL-101（Cr）/氧化石墨烯（GO）.结果表明,MIL-101（Cr）/GO-15具有更高的比表面积（3486 m²·g^-1）和更大的孔体积（2.39 cm³·g^-1）,因此也表现出更高的O₂吸附量（0.54 mmol·g^-1）.进一步根据理想吸附溶液理论（IAST）预测了其在O₂/N₂体积比为1：4混合气体中的O₂/N₂选择性为1.2,相比MIL-101（Cr）提高了17.65%.同时,MIL-101（Cr）/GO-15的循环利用性能更佳,经过三次O₂吸脱附循环后,依然拥有高达80%的O₂吸附量,具有较好的循环再生性能.     

一个基于5-(3-氨基-吡啶-4-基)-间苯二羧酸和桨轮状[Cu2(COO)4]簇的rtl-金属有机骨架材料的合成及其CO2选择性吸附性质

利用新配体5-（3-氨基-吡啶-4-基）-间苯二羧酸（NH₂-H₂L₁）,我们成功设计、合成了一例氨基功能化的柱-层型rtl-MOF,SNNU-Bai65。与原型MOF（SYSU）对比,极性官能团氨基对孔表面的功能性修饰和对孔道的分割使得SNNU-Bai65经活化后展现出更好的CO₂/N₂和CO₂/CH₄的选择性CO₂吸附性能。     

芴基共价三嗪骨架聚合物的室温合成和取代基效应研究

高效合成和功能性基团的引入是当前有机微孔聚合物材料研究的热点. 采用强质子酸催化的腈基三聚环化反应, 室温合成制备了一系列带有不同取代基的芴基共价三嗪骨架聚合物(FCTF1～FCTF3), 系统研究了取代基的变化对所得材料光学性能、多孔性能及CO₂吸附能力的影响. 其中乙基取代的聚合物FCTF2具有最高的BET比表面积(621 m²/g)和CO₂吸附能力(1.8 mmol/g, 273 K/1.1 bar). 该研究有助于加深对有机微孔聚合物结构与性能关系的理解, 对该类材料的分子设计有借鉴意义.     

基于磁性共轭微孔聚合物的超高效液相色谱-串联质谱法测定果蔬中7种有机磷杀虫剂

建立了基于磁性共轭微孔聚合物的磁固相萃取-超高效液相色谱-串联质谱（UPLC-MS/MS）测定果蔬中7种有机磷杀虫剂的方法。将亚苯基亚乙炔基修饰的Fe₃O₄与1,3,5-三溴苯、1,3,5-三乙炔苯反应,制备磁性共轭微孔聚合物,材料能有效吸附共轭结构的有机磷杀虫剂,并在外磁场中实现便捷磁分离。方法的检出限（LOD）为0.12~5.0 ng/kg,加标回收率为80.8%~125%,相对标准偏差（RSD）小于6%（n=5）。方法应用于分析市场上果蔬样品中7种有机磷杀虫剂,检出含量为1.1~500.0 ng/kg。该方法灵敏度高,准确可靠,对果蔬中有机磷杀虫剂的检测具有良好的应用潜力。     

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.