硫代杯[6]芳烃衍生物从汽车尾气净化催化剂残渣中选择性识别贵金属离子的研究

以对叔丁基硫代杯[6]芳烃(p-tert-butyl-thiacalix[6]arene, TC6A)为底物, 对其上缘进行脱叔丁基、氯甲基化反应后, 在无水N,N-二甲基甲酰胺(DMF)溶液中将氯甲基化的硫代杯[6]芳烃与硫代乙酸钾进行反应合成了一种新的TC6A衍生物--乙酰硫甲基硫代杯[6]芳烃(TC6A-CH₂SCOCH₃). 对含有铂族金属离子的车用尾气净化催化剂残渣溶液进行萃取研究表明, 在pH为1.5的萃取液中TC6A-CH₂SCOCH₃对其中的钯离子具有最高的选择性萃取能力, 萃取率可达86.2%,在pH为4.0的萃取液中对锆离子具有第二高的选择性萃取能力, 萃取率可达57.3%.     

硫、硒杯[4]芳烃萃取银

以5,11,17,23-四（1,1-二甲基乙基）-25,27-二羟基-26,28-二[（2-乙基硫）乙氧基]杯[4]芳烃（1）和5,11,17,23-四（1,1-二甲基乙基）-25,27-二羟-26,28-二[（2-乙基硒）]乙氧基杯[4]芳烃（2）为萃取剂,研究了在弱酸性条件下杯芳烃衍生物与银的络合行为。杯芳烃衍生物与银形成1：1萃取络合物,在大量碱金属、碱土金属、常见过渡金属离子存在下,对银离子有很高的萃取率和选择性。     

硫(硒)杂多杯[4]芳烃合成及其络合性能研究

合成了下缘硫、硒杂杯[4]芳烃, 然后与杯芳烃片段2,6-二(溴甲基)-4-甲氧基-甲苯在NaH存在条件下缩合得到硫、硒杂多杯[4]芳烃5a和5b. 离子萃取实验表明硫、硒杂多杯[4]芳烃显著增加了对Ag＋和Hg2＋重金属离子的萃取效果.     

硫杂杯[4]芳烃酰胺型氮杂冠醚的合成

硫杂杯[4]芳烃与N,N'-亚乙基双(2-氯乙酰胺)发生分子内"1+1"缩合反应,合成了新型硫杂杯[4]芳烃酰胺型氮杂冠醚--25,27-二羟基-26,28-(1',10'-二氧杂-4',7'-二氮杂-3',8'-二氧代亚癸基)-硫杯[4]芳烃(叔丁基硫杯[4]-1,3-酰胺冠醚)(3),产率68%.1H NMR,ESI-MS和元素分析确证3为1,3-桥联模式且为杯式构象.     

基于对叔丁基杯[8]芳烃的3d-5f核簇化合物(M_xTh_y,M=Co、Ni、Zn)的合成、结构与磁性研究(英文)

本文以对叔丁基杯[8]芳烃(H8C8A)为配体,在溶剂热条件下制得了3个3d-5f化合物,[Co2Th4(HC8A)2O2(OH)2(DMF)6](1)、[Ni2Th5(H2C8A)(C8A)O4(OH)2(DMF)5(CH3OH)2](2)、[Zn2Th6(HC8A)(C8A)O5(CH3O)(C3H6NO2)2(DMF)5(CH3OH)](3)(其中H8C8A=对叔丁基杯[8]芳烃,DMF=N,N-二甲基甲酰胺)。X-射线单晶测试表明,这3个化合物均为2个以尾对尾方式排列的杯[8]芳烃分子中间夹1个3d-5f核簇的三明治型结构。杯[8]芳烃均表现为双锥式构型,且每个锥式空腔下缘结合1个钍离子,双锥的连接处及2个杯芳烃分子之间由过渡金属离子或钍离子连接。不同过渡金属离子不同的配位环境导致3种不同核簇的形成。化合物1的磁性研究表明,该化合物在低温下表现出弱铁磁性相互作用。     

通过杯芳烃片段桥联合成杯[4]冠4齐聚物及其络合性能研究

通过杯芳烃片段桥联合成杯[4]冠4齐聚物,并通过两相萃取实验评估其络合性能。络合研究表明,酰胺型杯[4]冠4齐聚物（TCA[4]-III）对软金属银、铅离子和氨基酸具有选择性络合。其对色氨酸和组氨酸的萃取率分别高达87.9% 和 91.5%。     

新型杯[4]芳烃衍生物的合成及其氨基酸萃取性能

杯[4]-1,3-二乙酸乙酯衍生物(1)与水合肼反应生成杯[4]芳烃酰肼衍生物(2),化合物(2)与异硫氰酸苯酯反应得到含酰胺和硫脲单元的新型杯[4]芳烃衍生物(3).总产率达70%.系列氨基酸萃取实验表明化合物(3)对异亮氨酸有较好的选择性萃取能力.     

邻甲氧基羰基苄氧基取代杯[4]芳烃衍生物的合成及其性能研究

杯芳烃是继冠醚、环糊精之后的第三代主体分子[1].据文献[2,3]报道,在杯[4]芳烃下沿酚氧原子上连接乙酸酯得到的四取代衍生物对Na+有很高的选择性,核磁与晶体结构研究均证实这是由于羧酸酯的羰基和酚氧基参与了对Na+的配位,而且配位基团所形成的包络空间大小与钠离子相匹配.一般认为,随着包络空间改变,对金属离子的识别作用会有所变化[4].但目前对这方面的工作并没有给予更多的重视.我们发现,用2-溴甲基苯甲酸甲酯与杯[4]芳烃反应,得到了一种新的四取代杯[4]芳烃衍生物[2]萃取研究结果表明,该化合物对钾离子有较好的选择性.此外,在合成该衍生物的过程中,还得到了另一新的二取代衍生物(3).     

选择性合成三取代乙氧羰基甲氧基硫杂杯[4]芳烃

对叔丁基硫杂杯[4]芳烃与氯乙酸乙酯在K2CO3/丙酮体系中反应,选择性地合成了三取代乙氧羰基甲氧基硫杂杯[4]芳烃,产率78%,其结构经1H NMR,MS和元素分析表征.     

杯芳烃偶氮类衍生物对金属离子的萃取作用

通过杯芳烃的酚羟基的直接烃基化反应,在杯芳烃的下缘引入2,3′-二甲基-4-氨基偶氮苯发色团,得到了一系列杯芳烃偶氮衍生物(n=4,6,8)a-c.研究了它们对碱金属,碱土金属及过渡金属等十种金属离子的萃取作用.结果表明此类杯芳烃偶氮衍生物对过渡金属离子有良好的选择性识别作用,其中空腔较大的杯[8]芳烃偶氮衍生物c的萃取效果尤为显著.     

杯芳烃和柱芳烃桥梁部位的衍生及其功能化

随着大环化学的快速发展,对杯芳烃、柱芳烃及其他类似化合物的桥梁亚甲基部位进行高效修饰的方法日益引起人们的关注.桥梁部位修饰后的大环衍生物,在不改变其原有属性的基础上增加了新的功能,不仅可以引入更多的功能基团,而且可以通过主客体的自组装行为,进一步拓展杯芳烃和柱芳烃等超分子大环在药物递送、化学传感、荧光体系构建等诸多领域...     

杯芳烃与NO2硝化反应的研究

系统地研究了羟基杯[n]芳烃、甲氧基杯[n]芳烃和对特丁基杯[n]芳烃(n＝4, 6, 8)与NO₂气体的硝化反应, 发现可以成功地得到25,26,27,28-四羟基杯[4]芳烃、37,38,39,40,41,42-六羟基杯[6]芳烃以及25,26,27,28-四甲氧基杯[4]芳烃的对位全硝化产物, 产率分别为90%, 70%和40%; 尤其是25,26,27,28-四羟基杯[4]芳烃与NO₂的反应20 min即可完成. 认为共振式酚氧负离子结构是影响该类硝化反应的关键, 并对反应机理进行了探讨.     

Electrochemical Studies of Calixarene-[60]Fullerene Inclusion Processes

[60]Fullerene (C₆₀)-calix[n]areneinteractions were studied in toluene:MeCN = 10:1 (v/v)using an electrochemical method. In the presence ofhomooxacalix[3]arenes and calix[5]arenes, bothE_pc and _pa shifted to the negativepotential, whereas they were scarcely affected by theaddition of calix[4]arenes. The₂values electrochemically determined forthe association with C₆₀ ^- are generallysmaller than the ₁ valuesspectroscopically determined for the association withC₆₀. The tendency indicates that thecharge-transfer-type interaction is one of thedriving forces for C₆₀ inclusion.thanks|Author for correspondence     

Cucurbit[n]uril-calix[n]arene-based supramolecular frameworks assembled using the outer surface interactions of cucurbit[n]urils

Based on the crystal structures of two cucurbit[6]uril/calix[n]arene-based supramolecular frameworks reported by Long and co-workers,we further investigated the interactions of cucurbit[6]uril with 4-sulfocalix[4]arene and 4-sulfocalix[6]arene using ¹H NMR spectroscopy and isothermal titration calorimetry(ITC),respectively.Moreover,solid fluorescent materials were prepared via the adsorption of fluorescent dyes by these porous supramolecular frameworks,which exhibit a selective response to certain volatile organic compounds.     

An Interesting Approach to Bis-calix[5]arene Analogue from Calix[6]arene

Calix [n] arenas {n = 4, 6 or 8} are easily prepared from formaldehyde and para-substituted phenols via cyclic condensation under alkaline conditions in one step. It is not surprising that the calyx [n] arene (n = 4, 6, 8) chemistry has been developing very rapidly during the latest 20 years1. However, it is not the case for calixarenes with odd benzene rings (for example, n = 5). The yield of p-tert-butylcalix [5] arene synthesized in one-step from p-tert-butylphenol and formaldehyde was a…     

Synthesis of Ag nanoparticles for the electrochemical detection of anticancer drug flutamide

Ag nanoparticles were synthesized on the surface of a glassy carbon electrode modified with p‐tert‐butylcalix[4]arene and p‐tert‐butylcalix[6]arene by the deposition of Ag+at an open circuit potential ...     

银纳米颗粒的合成及用于抗癌药氟他胺的电化学检测（英文）

Ag nanoparticles were synthesized on the surface of a glassy carbon electrode modified with p‐tert‐butylcalix[4]arene and p‐tert‐butylcalix[6]arene by the deposition of Ag+ at an open circuit potential followed by the electrochemical reduction of the Ag+.The presence of the calixarene layer on the electrode surface controlled the particle size and prevented agglomeration.Cyclic voltam‐metry showed that the Ag nanoparticles on the modified glassy carbon electrode had good catalytic ability for the reduction of flutamide.The effects of calixarene concentration,potential applied for the reduction of Ag+,number of calixarene layers,and p H value on the electrocatalytic activity of the Ag nanoparticles were investigated.The modified electrode had a linear range in differential pulse voltammetry of 10-1000 μmol/L with a detection limit of 9.33 μmol/L for flutamide at an S/N = 3.The method was applied to the detection of flutamide in practical samples.     

The Synthesis of Ester and Ketone Derivatives of Azocalix[4]arene Containing Chromogenic Groups

Azocalix[4]arenes were prepared by linking 4-ethylaniline, 4-n-butylaniline, 4-acetamide aniline and 2-aminothiazol to calix[4]arene through a diazo-coupling reaction. A new family of azocalix[4]arenes, L1–L12, have been prepared by the incorporation of acetyl, benzoyl, and methyl ketone units to azocalix[4]arene. Characterization of the synthesized compounds was carried using elemental analyses, UV–Vis, IR and ¹H NMR spectroscopic studies.     

Synthesis and binding studies of novel bisthiacalix[4]arenes with diimime linkages

A series of novel bisthiacalix[4]arenes with diimine linkages of different aromatic or heteroaromatic dialdehydes have been synthesized. The structure of one of the bisthiacalixarene has been analyzed by X-ray crystallography. These molecules quantitatively extract silver ion from aqueous into organic phase under neutral conditions.