Synthesis, X-ray crystal structures, and gas sorption properties of pillared square grid nets based on paddle-wheel motifs: implications for hydrogen storage in porous materials

A systematic modulation of organic ligands connecting dinuclear paddle-wheel motifs leads to a series of isomorphous metal-organic porous materials that have a three-dimensional connectivity and interconnected pores. Aromatic dicarboxylates such as 1,4-benzenedicarboxylate (1,4-bdc), tetramethylterephthalate (tmbdc), 1,4-naphthalenedicarboxylate (1,4-ndc), tetrafluoroterephthalate (tfbdc), or 2,6-naphthalenedicarboxylate (2,6-ndc) are linear linkers that form two-dimensional layers, and diamine ligands, 4-diazabicyclo[2.2.2]octane (dabco) or 4,4'-dipyridyl (bpy), coordinate at both sides of Zn(2) paddle-wheel units to bridge the layers vertically. The resulting open frameworks [Zn(2)(1,4-bdc)(2)(dabco)] (1), [Zn(2)(1,4-bdc)(tmbdc)(dabco)] (2), [Zn(2)(tmbdc)(2)(dabco)] (3), [Zn(2)(1,4-ndc)(2)(dabco)] (4), [Zn(2)(tfbdc)(2)(dabco)] (5), and [Zn(2)(tmbdc)(2)(bpy)] (8) possess varying size of pores and free apertures originating from the side groups of the 1,4-bdc derivatives. [Zn(2)(1,4-bdc)(2)(bpy)] (6) and [Zn(2)(2,6-ndc)(2)(bpy)] (7) have two- and threefold interpenetrating structures, respectively. The non-interpenetrating frameworks (1-5 and 8) possess surface areas in the range of 1450-2090 m(2)g(-1) and hydrogen sorption capacities of 1.7-2.1 wt % at 78 K and 1 atm. A detailed analysis of the sorption data in conjunction with structural similarities and differences concludes that porous materials with straight channels and large openings do not perform better than those with wavy channels and small openings in terms of hydrogen storage through physisorption.     

D201×4树脂吸附铬(Ⅵ)的研究

铬 (Ⅵ )的化合物都是有毒的 ,它对农作物、微生物和其它生物有很大的危害作用 ,对人体会引起严重毒害 ,已成为公认的致癌物质。国家规定的Ⅱ类排放标准是铬含量必须小于 0 .0 5毫克 /升[1 ] 。目前处理含铬 (Ⅵ )废水的方法有两大类 :一类是把铬 (Ⅵ )还原为铬 (Ⅲ ) ,然后再使铬 (Ⅲ )转化为沉淀除去。另一类是直接处理铬 (Ⅵ )。第一类方法步骤繁琐 ,第二类方法中离子交换法优势明显 ,不仅治理了含铬 (Ⅵ )的废水 ,同时又回收了铬 (Ⅵ ) ,特别适合治理大量的含铬 (Ⅵ )废水 ;也是高分子配位化学发展的一个重要趋势[2 ,3] 。Ｄ2 0 1× 4树…     

A Facile Synthesis of Ethyl 2,4-Dimethoxy-6-perfluoroalkyl-benzoates via Acyclic Precursors

Introduction Polysubstituted arenes are important intermediates in synthetic medicines and dyestuffs, and the fluorinated analogues are more attractive as a result of their lipo-philicity and the increment of activity.1,2 Therefore, to study the convenient and efficient synthesis of polysub-stituted arenes is valuable in organic synthetic method-ology. We have designed a simple synthesis of fluori-nated polysubstituted arenes through the intramolecular Wittig reaction of a new phosphorous ylid…     

镧掺杂粘土源含铜氧化物催化剂的制备、表征及催化性能

采用共沉淀和水热法合成了不同阴离子粘土前驱型复合氧化物催化材料,样品经XRD,FTIR,TPR,TG-DSC,SEM进行表征.同时考察了铜含量在掺杂和不掺杂稀土时对甲烷催化燃烧的影响,结果发现随含铜量增加催化活性增加;未掺杂La的催化剂在高温下出现失活现象,而掺杂型催化剂稳定性良好.同时,制备方法对催化剂的性能有显著影响,在不同制备前驱物pH的条件下,使用共沉淀和水热法合成的阴离子粘土材料,合成时的pH均对催化剂的活性影响较大;同时焙烧温度对催化活性有不同程度的影响.     

溶胶-凝胶法制备铁酸盐超微粒子催化剂

采用溶胶－凝胶法制备了含Zn,Ni,Co的铁酸盐超微粒子催化剂，运用DTA－TG、IR、XRD以及BET比表面测试等手段对所制备的样品进行了表征。同时，考察了铁酸盐对二氧化碳选择性氧化乙苯制苯乙烯的催化性能。结果表明：制备的铁酸盐均为尖晶石型晶体，粒子的比表面积为31．9－36．3m^2/g，晶粒大小约为30－35nm，在由二氧化碳选择性氧化乙苯制苯乙烯的反应中表现出较好的催化活性。     

Facile synthesis of 9-（N-amino-4-fluoromethyl-3-pyrrolidinyl）-2- fluoro-6-aminopurine from trans-4-hydroxy-L-proline

A novel and simple procedure for synthesis of azanucleoside by Mitsunobu reaction between N-(p-nitrobenzyloxycarbonyl)- trans-4-hydroxy-D-proline methyl ester obtained from trans-4-hydroxy-L-proline after six-step reaction and 2-fluoro-6-azidopurine is described,and azanucleoside is fluorinated by new fluridizer 2,2-difluoro-1,3-dimethylimidazolidine (DFI).All reactions could be carded out under mild condition.     

微铂电极上1-酰基二茂铁动力学参数的测定

本文合成并研究了１－酰基二茂铁在ＣＨ２Ｃｌ２中的伏安行为，测定了它们在ＣＨ２Ｃｌ２中不同支持电解质浓度时的扩散系数，并分明用Ｚ．Ｇａｌｕｓ和Ｋ．Ａｏｋｉ方法计算了两种状态下的电子迁移速率常数。讨论了取代基的诱导效应和共轭效应及其链长对１－酰基二茂铁的动力学性质的影响以及支持电解质及其浓度等因素对伏安曲线的影响。     

TB-curve, a New 2-D Graphical Representation of DNA Sequences

Based on the classifications of the four nucleic acid bases, we introduce a new 2-D method of DNA representation: TB-curve, which avoids loss of information accompanying alternative 2-D representation in which the curve standing for DNA overlaps and intersects itself. The method is illustrated on the coding sequence of the first exon of human beta-globin gene.     

Sequential transition States and the valley-ridge inflection point in the formation of a semibullvalene

[structure: see text] Two sequential transition states are calculated at the B3LYP/6-31G(d,p) level for the deazetization of 3b. The intrinsic reaction coordinate for loss of nitrogen passes through a transition state and then a valley-ridge inflection point and ultimately leads to the transition state for the Cope rearrangement of semibullvalene 4b. The energetic and geometrical consequences are discussed.