载体对负载PdO催化剂的CO氧化活性的影响

由于催化燃烧比传统的热力燃烧法有反应温度低和能量消耗低的优点，因而广泛用于挥发性有机物和CO的消除．把和铂是最常用的催化剂，但是载体对催化性能的影响很大【‘’‘］．本文制备了系列负载把催化剂，发现载体的性质对催化剂的CO氧化活性影响很大．本文所用载体为CeO。，TIO。，SnO。，AI。O。，ZAI。，ZSM－5和SIO。催化剂制备采用浸渍法，把负载量为5％（质量分数）．催化剂经120C烘干后，于650’C空气气氛焙烧4h制成．在常压固定床流动反应装置上考察催化剂的CO氧化活性，反应气组成为CO2．4％，O。1．2％，N。96．4…     

A new class of functionalized polyoxometalates: synthesis, structure and preliminary antitumor activity studies of three arylimido substituted hexamolybdates bearing a strong electron-withdrawing nitro group, (Bu4N)2[Mo6O18([triple bond]NAr)] (Ar = 3-NO2-C6H4, 2-CH3-4-NO2-C6H3, 2-CH3-5-NO2-C6H3)

Three novel mono-functionalized arylimido derivatives of hexamolybdate bearing the strongest electron-withdrawing nitro group, (Bu(4)N)(2)[Mo(6)O(18)([triple bond, length as m-dash]NAr)] (, and ), have been synthesized for the first time by an improved reaction of octamolybdate ion and 3-nitroaniline hydrochloride, 2-methyl-4-nitroaniline hydrochloride and 2-methyl-5-nitroaniline hydrochloride respectively with DCC (N,N'-dicyclohexylcarbodiimide) as a dehydrating agent. Complete assignments were achieved for the title compounds by elemental analysis, IR, (1)H NMR, UV/visible and single-crystal X-ray diffraction analyses. The preliminary antitumor activity test indicated that the title compounds have some effects on the cellular growth inhibition of K562 cells.     

Synthesis of dihydroxyurea and its application to the U/Pu split in the PUREX process

Dihydroxyurea (DHU) was synthesized using tri-associated solid phosgene [bis(trichloromethyl) carbonate] dissolved in dioxane and hydroxylamine hydrochloride dissolved in potassium acetate solution. The reduction of Pu(IV) by DHU was investigated using UV-Vis spectrophotometry. The reduction back-extraction behavior of Pu(IV) in 30% tri-butyl phosphate/kerosene was firstly investigated under conditions of various temperature, various DHU and HNO₃ concentrations and various phase contact times. The results showed that Pu(IV) in the organic phase can be stripped rapidly to the aqueous phase by DHU. Simulating the 1B contactor of the PUREX process using a 0.1 M DHU in 0.36M nitric acid solution as the stripping agent, the separation factors of uranium/plutonium can reach 2.1·10⁴. This indicates that DHU is a promising salt free agent for uranium/plutonium separation.     

Nonperipherally Octa(butyloxy)‐Substituted Phthalocyanine Derivatives with Good Crystallinity: Effects of Metal–Ligand Coordination on the Molecular Structure,Internal Structure,and Dimensions of Self‐Assembled Nanostructures

To investigate the effects of metal–ligand coordination on the molecular structure, internal structure, dimensions, and morphology of self‐assembled nanostructures, two nonperipherally octa(alkoxyl)‐substituted phthalocyanine compounds with good crystallinity, namely, metal‐free 1,4,8,11,15,18,22,25‐octa(butyloxy)phthalocyanine H₂Pc(α‐OC₄H₉)₈ ( 1 ) and its lead complex Pb[Pc(α‐OC₄H₉)₈] ( 2 ), were synthesized. Single‐crystal X‐ray diffraction analysis revealed the distorted molecular structure of metal‐free phthalocyanine with a saddle conformation. In the crystal of 2 , two monomeric molecules are linked by coordination of the Pb atom of one molecule with an aza‐nitrogen atom and its two neighboring oxygen atoms from the butyloxy substituents of another molecule, thereby forming a Pb‐connected pseudo‐double‐decker supramolecular structure with a domed conformation for the phthalocyanine ligand. The self‐assembling properties of 1 and 2 in the absence and presence of sodium ions were comparatively investigated by scanning electronic microscopy (SEM), spectroscopy, and X‐ray diffraction techniques. Intermolecular π–π interactions between metal‐free phthalocyanine molecules led to the formation of nanoribbons several micrometers in length and with an average width of approximately 100 nm, whereas the phthalocyaninato lead complex self‐assembles into nanostructures also with the ribbon morphology and micrometer length but with a different average width of approximately 150 nm depending on the π–π interactions between neighboring Pb‐connected pseudo‐double‐decker building blocks. This revealed the effect of the molecular structure (conformation) associated with metal–ligand (Pb? N_isoindole, Pb? N_aza, and Pb? O_butyloxy) coordination on the dimensions of the nanostructures. In the presence of Na⁺, additional metal–ligand (Na? N_aza and Na? O_butyloxy) coordination bonds formed between sodium atoms and aza‐nitrogen atoms and the neighboring butyloxy oxygen atoms of two metal‐free phthalocyanine molecules cooperate with the intrinsic intermolecular π–π interactions, thereby resulting in an Na‐connected pseudo‐double‐decker building block with a twisted structure for the phthalocyanine ligand, which self‐assembles into twisted nanoribbons with an average width of approximately 50 nm depending on the intertetrapyrrole π–π interaction. This is evidenced by the X‐ray diffraction analysis results for the resulting aggregates. Twisted nanoribbons with an average width of approximately 100 nm were also formed from the lead coordination compound 2 in the presence of Na⁺ with a Pb‐connected pseudo‐double‐decker as the building block due to the formation of metal–ligand (Na? N_aza and Na? O_butyloxy) coordination bonds between additionally introduced sodium ions and two phthalocyanine ligands of neighboring pseudo‐double‐decker building blocks.     

Enantioselective total synthesis of (-)-kibdelone C

The kibdelones are aromatic polyketide natural products featuring isoquinolinone and tetrahydroxanthone ring systems. They display potent cytotoxicity toward a range of human cancer cell lines. Here, we present an enantioselective total synthesis of kibdelone C that utilizes a Shi epoxidation to establish the absolute and relative stereochemistry, an acid-catalyzed cyclization to form the tetrahydroxanthone, and a C-H arylation to complete the hexacyclic skeleton.     

共线量子散射方法研究D+CID体系

用共线量子散射方法计算D+CID体系的反应几率和传能几率。发现存在很强的振荡现象。体系的碰撞中间态的寿命的计算结果为fs-ps数量级。当某一反应通道打开时,在能量阈值附近通常都伴随着一些长寿命的碰撞中间态。这一点该体系中表现很比较明显。     

Ultralong Phosphorescence from Organic Ionic Crystals under Ambient Conditions

A new type of materials, organic salts in the crystal state, have ultralong organic phosphorescence (UOP) under ambient conditions. The change of cations (NH₄⁺, Na⁺, or K⁺) in these phosphors gives access to tunable UOP colors ranging from sky blue to yellow green, along with ultralong emission lifetimes of over 504 ms. Single‐crystal analysis reveals that unique ionic bonding can promote an ordered arrangement of organic salts in crystal state, which then can facilitate molecular aggregation for UOP generation. Additionally, reversible ultralong phosphorescence can be realized through the alternative employment of fuming gases (ammonia and hydrogen chloride), demonstrating its potential as a candidate for visual ammonic or hydrogen chloride gas sensing. The results provide an environmental responsible and practicable synthetic approach to expanding the scope of ultralong organic phosphorescent materials as well as their applications.     

5-二乙胺基-2-(吡啶-2’-亚氨甲基)苯酚的合成及其对Zn2+的识别

本文利用2-氨基吡啶与4-二乙胺基水杨醛反应合成了5-二乙胺基-2-(吡啶-2’-亚氨甲基)苯酚(探针L),对其结构进行了表征。在DMSO/Tris(6:4, v/v, pH =7.4)溶液中,探针L高选择性荧光“关-开”识别Zn₂₊,在365 nm紫外灯照射下,由无荧光变成蓝色荧光。实验表明,探针L与Zn₂₊的结合比为1:1,结合常数为2.6×10₃ L. mol_-1,检测限为 9.39×10_-7mol/L,pH适用范围为7-11,并可检测水样中的Zn₂₊。     

遥爪型液体聚合物及其多相共聚物——Ⅷ.端羧基乙烯基四氢呋喃-环氧丙烷液体聚合物与甲基丙烯酸缩水甘油酯的交联

本文研究了端羧基乙烯基四氢呋喃-环氧丙烷液体共聚物(TVC-PTP)与甲基丙烯酸缩水甘油酯(GMA)的反应。观察了组成比,催化剂等对反应产物力学性能的影响。用红外光谱跟踪了这一反应过程,观察了乙烯基和环氧基的消失速度。用平衡溶胀法测定了交联聚合物单位体积内有效交联链的数目和交联点间平均分子量,观察了它们对交联聚合物力学性能的影响。