杯芳烃化金属卟啉及其苯乙烯环氧化的催化性能

将单功能化四苯基卟啉与对叔丁基杯［４］芳烃通过单链相连，随后插入金属离子，合成了杯芳烃化金属卟啉１－３．在两相条件下对苯乙烯环氧化催化反应研究表明，化合物２的锰络合物中杯芳烃的存在对氧化反应有明显影响．可以根据连接于卟啉分子中憎水杯芳烃造成催化活性中心微环境差异来解释观察到的现象．各杯芳烃化锰卟啉的催化性能按以下次序降低：１ｂ＞２ｂ＞３ｂ－７．     

杯[6]芳烃-双锰卟啉催化苯乙烯环氧化反应的动力学

研究了杯[6]芳烃－双锰卟啉仿P450酶模型化合物对苯乙烯环氧化反应的催化性能，考察了催化剂浓度、底物浓度、氧源浓度及加入方式等对催化反应的影响，结果表明，由于具有较大疏水孔穴的杯[6]芳烃的引入，使金属卟啉的催化性能得以较大的提高，且反应遵从Michaetis-menten规律，在实验基础上，本文提出了一种可能的反应机理。     

杯[6]芳烃－双金属卟啉仿P450酶模型的研究 2: 轴向配体对环己烯 环氧化反 应的影响及反应动力学考察

研究了轴向配体对杯[6]芳烃－双金属卟啉仿P450酶模型催化环己烯环氧化反应的影响,并考察了反应的动力学规律,结合UV-vis监测反应的结果,提出了一种可能的反应机制。     

杯[6]芳烃－双金属卟啉仿P450酶模型的研究 2: 轴向配体对环己烯 环氧化反 应的影响及反应动力学考察

研究了轴向配体对杯[6]芳烃－双金属卟啉仿P450酶模型催化环己烯环氧化反应的影响,并考察了反应的动力学规律,结合UV-vis监测反应的结果,提出了一种可能的反应机制。     

C_(60)键合硅胶液相色谱固定相的合成及其性能评价

 以γ－（乙二胺基）丙基三乙氧基硅烷为偶联剂合成了Ｃ６０键合硅胶固定相；用元素分析法测定得到该固定相的Ｃ６０键合量为５７．５７μｍｏｌ／ｇ。考察了多环芳烃和杯芳烃在Ｃ６０键合硅胶固定相上的分离，多环芳烃在该固定相上的洗脱顺序与ＯＤＳ固定相相似；杯芳烃的洗脱顺序为杯［８］、杯［４］和杯［６］芳烃。     

C_(60)键合硅胶液相色谱固定相的合成及其性能评价

以γ－（乙二胺基）丙基三乙氧基硅烷为偶联剂合成了Ｃ６０键合硅胶固定相；用元素分析法测定得到该固定相的Ｃ６０键合量为５７．５７μｍｏｌ／ｇ。考察了多环芳烃和杯芳烃在Ｃ６０键合硅胶固定相上的分离，多环芳烃在该固定相上的洗脱顺序与ＯＤＳ固定相相似；杯芳烃的洗脱顺序为杯［８］、杯［４］和杯［６］芳烃。     

杯[6]芳烃-双金属卟啉仿P-450酶模型的研究Ⅳ.对异丙苯氧化的催化行为

研究了杯[6]芳烃-双金属卟啉在氧化异丙苯中的催化行为，结果表明杯[6]芳烃-双金属卟啉比之相应的金属卟啉具有更高的催化活性，并表现同样的选择性，生成苯乙酮和醇组份。此一结果同通常酞菁或其它如西弗碱大分子金属络合物催化下生成丙酮和酚不同。还考察了温度、轴向配体、催化剂用量及金属离子种类等对反应的影响，仔细地通过测定反应速度比较了反应的活性。     

杯[6]芳烃-双金属卟啉仿P450酶模型的研究Ⅱ.轴向配体对环己烯环氧化反应的影响及反应动力学考察

研究了轴向配体对杯[6]芳烃-双金属卟啉仿P450酶模型催化环己烯环氧化反应的影响,并考察了反应的动力学规律,结合UV-vis监测反应的结果,提出了一种可能的反应机制.     

高分子负载Mn（Ⅲ）卟啉／PhIO体系催化烯烃环氧化反应研究

研究了负载化金属卟啉催化烯烃环氧化反应的催化活性，探索了催化反应体系中轴向配体、溶剂、锰卟啉在高分子上的担载量及反应温度等对催化反应的影响．结果表明，金属卟啉负载化后，增大了催化剂的稳定性．本文还考察了负载化催化剂对苯乙烯催化环氧化反应的动力学行为，根据Ｍｉｃｈａｅｌｉｓ－Ｍｅｎｔｅｎ方程，求得了相关的动力学参数     

杯芳烃-金属卟啉仿酶模型化合物的合成及其电子光谱研究(英文)

本文首次报道杯芳烃-金属卟啉键联化合物作为仿细胞色素P-450酶模型的合成。对紫外-可见光谱进行了较详细的研究,将模型化合物与相应未键联杯芳烃的卟啉化合物的光谱比较,发现兰移现象,从而说明杯芳烃卟啉键联物中,杯环与卟啉环之间存在相互影响。金属离子插入后其相互作用加强。     

杯芳烃接枝超细SiO2的制备及其对Cu2+、Ag+萃取性能的研究

通过对杯[4]芳烃以及杯[6]芳烃上缘进行烯丙基化和硅氢加成2步衍生化反应得到硅氢化杯[4]芳烃以及硅氢化杯[6]芳烃,再将这2种硅氢化杯芳烃衍生物分别接枝到超细SiO₂上。在不同的pH值条件下,就2种杯芳烃接枝超细SiO₂衍生物对水合Cu²⁺及Ag⁺的萃取性能进行了研究。结果表明,与对叔丁基杯芳烃相比较,杯芳烃接枝超细SiO₂衍生物对Cu²⁺和Ag⁺的萃取率都有所提高,其中杯[4]芳烃接枝超细SiO₂对Ag⁺的最高萃取率达到98.78%,杯[6]芳烃接枝超细SiO₂对Cu²⁺的最高萃取率达到67.74%。     

Calixarene ionic liquids: excellent phase transfer catalysts for nucleophilic substitution reaction in water

The first examples of calixarene ionic liquids 3 and 6 with 3D-shaped cavities were obtained in high yields by reacting calix[4]arene or thiacalix[4]arene with 1,6-dibromohexane and then refluxing in 1-methylimidazole. The experiments of phase transfer catalysis in water suggested that they possessed excellent catalytic properties of aromatic nucleophilic substitution reaction and benzyl nucleophilic substitution. The optimized yields of product in catalytic reaction were as high as approximate 97% under mild reaction conditions. The cavities of calixarene skeleton played the crucial roles in catalysis and the stable cone conformation was favorable for catalysis.     

Extraction of Catecholamines by Calixarene Carboxylic Acid Derivatives

Extraction behaviors of catecholamines with a series of calixarene carboxylic acid derivatives were investigated. Relatively large calix[6]arene and calix[8]arene extract catecholamines into the organic solution, while smaller calix[4]arene and the monomer analog do not. The calix[6]arene, which has a cavity that fits a protonated amino group well, selectively extracts a primary amino compound dopamine over other catecholamines. Slope analysis and Job’s method confirmed formation of a 1:1 complex between the calix[6]arene and dopamine. On the other hand, the calix[8]arene extracts both dopamine and adrenaline, due to the large cavity for induced-fit recognition. Dopamine extracted with the calixarene is quantitatively stripped by contacting the organic solution with a fresh acidic solution.     

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.     

Polycyclic aromatic hydrocarbons as test probes to investigate the retention behavior of 1,3‐alternate calix[4]arene silica‐bonded stationary phases

A series of polycyclic aromatic hydrocarbons (PAHs) of different size and shape has been used to characterize the chromatographic behavior of five calix[4]arene stationary phases in 1,3‐alternate conformation synthesized in our laboratory. The selection of linear, four‐ring nonlinear, and five‐ring PAHs gave data on selectivity changes across range of the calix[4]arene columns. Retention of the 12 aromatic solutes has been evaluated at various methanol contents in the mobile phase (70–100% v/v) and column temperatures (20–45°C). The thermodynamic parameters underlying the retention mechanisms revealed that each of the five calix[4]arene columns exhibited variation in selectivity and retention of PAHs caused by enthalpy and entropy effects. The calixarene stationary phases substituted with electron‐withdrawing groups exhibit enhanced selectivity toward PAHs in comparison to the rest of the investigated columns. The observed divergences are due to differences in solute–stationary phase interactions and originate in π–π and π‐electron transfer specific to the analytes and the type of calix[4]arene functionalization at the upper rim, as well as steric and sorption phenomena.     

Synthesis and structures of an unusual germanium(II) calix[4]arene complex and the first germanium(II) calix[8]arene complex and their reactivity with diiron nonacarbonyl

The protonolysis reaction of the germanium(II) amide Ge[N(SiMe3)2]2 with calix[4]arene and calix[8]arene furnishes the two germanium(II) calixarene complexes {calix[4]}Ge2 and {calix[8]}Ge4, respectively, which have been crystallographically characterized. The calix[4]arene complex contains a Ge2O2 rhombus at the center of the molecule and is one of the only four germanium(II) calix[4]arenes that have been structurally characterized. The calix[8]arene species is the first reported germanium calix[8]arene complex, and it exhibits an overall bowl-shaped structure which contains two Ge2O2 fragments. The latter complex reacts with Fe2(CO)9 to yield an octairon compound, which has also been structurally characterized and contains four GeFe2 triangles arranged around the macrocyclic ring. The germanium(II) centers are oxidized to germanium(IV) in this process, with concomitant reduction of the neutral diiron species to Fe2(CO)(8)2- anions.     

Multiple proton ionizable calixarene derivatives with different ring sizes and complexation ability as efficient ionophores for complexation and solvent extraction of trivalent indium

The solvent extraction behavior of multiple proton ionizable p-tert-butylcalix[4]arene and [6]arene carboxylic acid derivatives towards indium has been investigated along with an acyclic monomeric analogue from weakly acidic media into chloroform. The extraction mechanism is ion exchange and carboxylic acid groups are adequate ligating sites for extraction. The cyclic structure of calixarene ligands to accommodate the potential guest species and the cooperativity effect of multifunctional groups significantly affect the complexation behavior and calixarene derivatives are found to be excellent extractants over the monomeric analogue. The composition of the extracted complex depends on the solution pH and attempts to determine the composition of the extracted complex for the extraction of indium have been stymied by complications arising from the formation of polynuclear species of indium and bridged polymeric species of calixarene carboxylic acid derivatives. One mole of calix[4]arene derivative extracts 2.5 moles of indium whereas the calix[6]arene derivative tends to extract 4.0 moles of indium. The loaded indium is back extracted with 1 mol dm(-3) hydrochloric acid solution. Though quantitative back extraction of indium was achieved from the fully loaded calix[6]arene derivative, it was only achieved up to 85% in the case of the calix[4]arene derivative.     

The first versatile synthetic approach to cofacial bis-porphyrins with calixarene spacers

[structure: see text] A versatile stepwise synthetic approach to cofacial bis-porphyrin species with calix[4]arene spacers has been designed. The three examples described demonstrate that the method allows selection, in a tailor-made fashion, of the calix[4]arene conformation, the type of functionalization of the calixarene rims, and the anchoring point of the chromophores on the calix[4]arene spacer.     

New organized systems based on amphiphilic oxyethylated calix[4]arene

The aggregation of amphiphilic oxyethylated calix[4]arene is studied in the absence and presence of polyethyleneimine. At low calixarene concentrations, large ensembles with a hydrodynamic diameter of about 100 nm are formed and coexist with small (smaller than 10 nm) aggregates, which are observed in the entire concentration range. It is established that calixarene-based systems catalyze the neutral hydrolysis of bis(chloromethyl)phosphinic acid p-nitrophenyl ester, with the catalytic effect being as high as two orders of magnitude in the presence of La(III) ions. The rate of hydrolysis of phosphonates depends on the composition of the supramolecular system. The maximum acceleration exceeds three orders of magnitude in comparison with alkaline hydrolysis of the substrates.