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1.
Pyrene-azacrown ether hybrid: cation-π interaction   总被引:1,自引:0,他引:1  
A pyrene-modified lariat ether was synthesized in order to observe the cation-π interaction in solution.  相似文献   
2.
Adsorption of two alkylated N,N′-diaza-18-crown-6 ethers (decyl- and hexadecyl-derivatives, ACE-10 and ACE-16, respectively) on solid surfaces was studied by using contact angle and neutron reflectivity measurements. The solid substrates used were (a) Si covered with a native oxide layer (Si/SiO2) and (b) Si with sputtered Pt layer (Si/Pt). The sensitivity of neutron reflectivity was drastically improved by applying the intermediate Pt layer of 150 Å, which gave rise to several Kiessig fringes in the experimentally accessible q-range. The position of the fringes is very sensitive to slight changes of the interfacial composition induced by adsorption of a thin monolayer, otherwise very difficult to detect. Unfortunately, in the studied case this sensitivity is immediately lost due to undesired adsorption of a protonated material on the Pt surface exposed to the lab air. A decrease of surface energy (increase of contact angle) of both Si/SiO2 and Si/Pt upon exposure to toluene solutions of ACEs suggests that the latter are attached to the surface via the hydrophilic azacrown ether head with alkyl chains standing upright towards the liquid phase.  相似文献   
3.
Four new achiral and four new chiral monoazacrown ethers containing an acridinone or an N-methylacridinone fluorescent signalling unit were prepared by reacting chloromethyl-substituted acridinone derivatives with achiral monoazacrown ethers with different cavity sizes and enantiopure monoaza-18-crown-6 ethers having two methyl and two isobutyl groups on their chiral centres, respectively. The operation of these chemosensors is based on the photoinduced electron transfer (PET) process, thus they show fluorescence enhancement in the presence of cationic guests. Their fluorescent behaviour as well as their complexation properties towards selected metal ions and the enantiomers of α-(1-naphthyl)ethylammonium perchlorate and potassium mandelate were examined.  相似文献   
4.
张进琪  谈证 《合成化学》1993,1(4):326-332
在高度稀释条件下芳香族二胺与相应的二酰氯起环化缩合反应,合成了5种大环酰胺型氮杂冠醚,接着用 LiAlH_4-THF 还原生成大环仲胺型氮杂冠醚;这两类冠醚的结构均经元素分析、IR、~1HNMR 和 MS 所证实。  相似文献   
5.
经环氧活化的棉杆纤维素醚分别与3-羟基-1,5-二氯杂环庚烷和3-羟基-1,5-二氮杂环辛烷反应,制备了二种氮杂冠醚化棉杆纤维衍生物,测定了它们对金属离子的吸附性能及溶液pH值的影响。结果表明二者对Hg2 ,Cd2 有较好的吸附性能,对Cu2 的吸附-解吸-再吸附实验表明,二种氮杂冠醚化棉杆纤维衍生物具有重复使用的性能。  相似文献   
6.
1,10-N,N′-bis-(β-d-ureidoglucopyranosyl)-4,7,13-trioxa-1,10-diazacyclopentadecane is a new, recently synthesized compound, which exhibits complexation ability towards drugs. In the present study various theoretical methods, including molecular mechanics, computer simulations, semiempirical and DFT calculations, are applied to find the lowest energy conformers of this molecule in vacuo and in aqueous solution. For the most stable structures the vibrational frequencies as well as the C and H chemical shifts were computed. Along with the theoretical investigation the IR in the KBr discs and the NMR spectra in water and in pyridine were experimentally recorded. It is shown that in the lowest energy structures the two glucosyl units are placed on the same side of the diazacrown ring with their mutual orientations favoring formation of hydrogen bonds. The “open” structure, in which no such hydrogen bonds can be formed, is found to have much higher energy. The computed and measured IR spectra and NMR chemical shifts are compared and discussed in detail. The most stable structures are analyzed with respect to the possible mechanism of complexation of drugs.  相似文献   
7.
Ligands derived from 4,4′-dinitrobiphenyl containing azacrown cavities in the 2,2′ position have been used in extraction and transport experiments. Control experiments with a system containing only one complexing cavity have demonstrated that the capability of forming a sandwich-type complex in the aforementioned ligand not only increases extraction but also the transport across a liquid membrane. Extraction studies have also shown that the complex present in the membrane has a 1:1 stoichiometry with regard to both ligands. Electrochemical studies have also been carried out. The ligand containing two complexing cavities is capable of giving rise to a 2:1 complex under electrochemical conditions.  相似文献   
8.
The influence of Li+, Na+, K+, Cs+, Mg2+, Ca2+, Sr2+, Ba2+, Co2+, Ni2+, Cu2+, Zn2+, Pb2+ and Al3+ ions on the spectroscopic properties of the dansyl group covalently linked to crown ether or diazacrown ethers was investigated by means of absorption and emission spectrophotometry. Interaction of the alkali metal ions with all fluoroionophores studied is weak, while alkaline earth metal ions interact strongly causing about 50% quenching of dansyl fluorescence of A21C5-Dns and A218C6-Dns. The Cu2+, Pb2+ and Al3+ cations interact very strongly with dansyl chromophore regardless the crown ether type, causing a major change in absorption spectrum of the chromophore and forming non-fluorescent complexes. The Co2+, Ni2+, Zn2, Mg2+ and Ag+ cations interact moderately with all fluoroionophores studied causing about 20% of fluorescence quenching of dansyl, except for a strong dansyl fluorescence quenching of 15C5-Dns by Co2+ ion. The quenching efficiency of didansylated fluoroionophores by the alkali metal ions and alkaline earth metal ions is weaker than monodansylated ones.  相似文献   
9.
Three sodium complexes (bromide, iodide and thiocyanate) of 4,13-diaza-18-crown-6 were studied using Raman and IR spectroscopy and normal coordinate calculations to probe the stoichiometry of the complexes and the variation in the conformation of azacrown moiety on complex formation. complex formation is accompanied by characteristic shifts of the bands, especially of those in the 800–900 cm–1 region. Complexes of both 11 and 21 stoichiometry were observed. Normal coordinate calculations showed the reduction of symmetry of azacrown moiety toC i , in contrast to theC 2h symmetry known for the parent azacrown and potassium thiocyanate complex.  相似文献   
10.
Reaction of pernosylated diethylenetriamine and 2-substituted propane-1,3-diols in dry THF in the presence of triphenylphosphine and diisopropyl azodicarboxylate gives the corresponding protected 9-substituted 1,4,7-triazacyclodecanes. The Mitsunobu reaction was also used in the preparation of 3-substituted 1,5,9-triazacyclododecanes and macrocyclic pyridine derivatives.  相似文献   
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