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171.
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Li ZR Wang FF Wu D Li Y Chen W Sun XY Gu FL Aoki Y 《Journal of computational chemistry》2006,27(8):986-993
The structure and aromaticity of a royal crown-shaped molecule Li(3)-N(3)-Be are studied at the CCSD(T)/aug-cc-pVDZ level. This molecule is a charge-separated system and can be denoted as Li(3) (2+)N(3) (3-)Be(+). It is found that the Li(3) (2+) ring exhibits aromaticity mainly because the Li(3) (2+) ring can share the pi-electron with the N(3) (-3) ring. The 4n+2 electron counter rule can be satisfied for the Li(3) (2+) subunit if the shared pi valence electron of N(3) (3-) subunit is also taken into account. This new knowledge on aromaticity of a ring from the interactions between subunits is revealed first time in this paper. Li(3)-N(3)-Be can be also regarded as a molecule containing two superatoms (Li(3) and N(3)), which may be named as a "superomolecule." Li(3)-N(3)-Be is a new metal-nonmetal-metal type sandwich complex. The N(3) (3-) trianion in the middle repulses the electron clouds of the two metal subunits (mainly to the Li(3) superatom) to generate an excess electron, and thus Li(3)-N(3)-Be is also an electride. This phenomenon of the repulsion results in: (a) the HOMO energy level increased, (b) the electron cloud in HOMO distended, (c) the area of the negative NICS value extended, and (d) the VIE value lowered. So the superomolecule Li(3)-N(3)-Be is not only a new metal-nonmetal-metal type sandwich complex but also a new type electride, which comes from the interaction between the alkali superatom (Li(3)) and the nonmetal superatom (N(3)). 相似文献
174.
Macrocyclic Gd3+ Complexes with Pendant Crown Ethers Designed for Binding Zwitterionic Neurotransmitters 下载免费PDF全文
Dr. Fatima Oukhatar Hervé Meudal Dr. Céline Landon Prof. Dr. Nikos K. Logothetis Prof. Dr. Carlos Platas‐Iglesias Priv.‐Doz. Dr. Goran Angelovski Dr. Éva Tóth 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11226-11237
A series of Gd3+ complexes exhibiting a relaxometric response to zwitterionic amino acid neurotransmitters was synthesized. The design concept involves ditopic interactions 1) between a positively charged and coordinatively unsaturated Gd3+ chelate and the carboxylate group of the neurotransmitters and 2) between an azacrown ether appended to the chelate and the amino group of the neurotransmitters. The chelates differ in the nature and length of the linker connecting the cyclen‐type macrocycle that binds the Ln3+ ion and the crown ether. The complexes are monohydrated, but they exhibit high proton relaxivities (up to 7.7 mM ?1 s?1 at 60 MHz, 310 K) due to slow molecular tumbling. The formation of ternary complexes with neurotransmitters was monitored by 1H relaxometric titrations of the Gd3+ complexes and by luminescence measurements on the Eu3+ and Tb3+ analogues at pH 7.4. The remarkable relaxivity decrease (≈80 %) observed on neurotransmitter binding is related to the decrease in the hydration number, as evidenced by luminescence lifetime measurements on the Eu3+ complexes. These complexes show affinity for amino acid neurotransmitters in the millimolar range, which can be suited to imaging concentrations of synaptically released neurotransmitters. They display good selectivity over non‐amino acid neurotransmitters (acetylcholine, serotonin, and noradrenaline) and hydrogenphosphate, but selectivity over hydrogencarbonate was not achieved. 相似文献
175.
Thawatchai Tuntulani Praput Thavornyutikarn Sirilux Poompradub Nongnuj Jaiboon Vithaya Ruangpornvisuti Narongsak Chaichit Zouhair Asfari Jacques Vicens 《Tetrahedron》2002,58(52):10277-10285
Tripodal aza crown ether calix[4]arenes, 5a, 5b, 6a and 6b, have been synthesized. The structure of protonated 5a was elucidated by X-ray crystallography to be a self-threaded rotaxane. Complexation studies of 5a and 5b towards anions using Na+ as countercation were carried out by 1H NMR titration in dimethylsulfoxide-d6 and the mixture of chloroform-d and methanol-d4, respectively. Ligands 5a and 5b were able to form 1:1 complexes with Br−, I− and NO3− and the complexation stability varied as follows: NO3−>I−>Br−. The effect of countercation on anion complexation was also investigated. The results showed that the association constants of 5a towards Br− in the presence of various cations varied as K+>Bu4N+>Na+. The enhancement in anion complexation ability of 5a may result from the rearrangement of the tripodal ammonium unit in the presence of K+. The neutral forms, 6a and 6b, were able to form complexes with transition metal ions such as Co2+, Ni2+, Cu2+ and Zn2+. The stability of the complexes followed the sequence: Ni2+2+Cu2+Zn2+. Compounds 6a and 6b may, therefore, potentially be used as either transition metal ion or anion receptors that can be controlled by pH of the solution. 相似文献
176.
Selective extraction of catecholamines by packed fiber solid‐phase using composite nanofibers composing of polymeric crown ether with polystyrene 下载免费PDF全文
Li‐Qin Chen Yu Wang Jian‐Song Qu Jian‐Jun Deng Xue‐Jun Kang 《Biomedical chromatography : BMC》2015,29(1):103-109
For the first time, electrospun composite nanofibers comprising polymeric crown ether with polystyrene (PCE‐PS) have been used for the selective extraction of catecholamines – dopamine (DA), norepinephrine (NE) and epinephrine (E) – prior to their analysis by high‐performance liquid chromatography–electrochemical detection. Using a minicartridge packed with PCE‐PS composite nanofibers, the target compounds were extracted effectively from urine samples to which diphenylborinic acid 2‐aminoethyl ester was added as a complexing reagent. The extracted catecholamines could be liberated from the fiber by the addition of acetic acid. A good linearity was observed for catecholamines in the range of 2.0–200 ng mL?1 (NE, E and DA). The detection limits of catecholamines (signal‐to‐noise ratio = 3) were 0.5 ng mL?1 (NE), 0.2 ng mL?1 (E) and 0.2 ng mL?1 (DA), respectively. Under the optimized conditions, the absolute recoveries of the above three catecholamines were 90.6% (NE), 88.5% (E) and 94.5% (DA). The repeatability of extraction performance was from 5.4 to 9.2% (expressed as relative standard deviation). Our results indicate that the proposed method could be used for the determination of NE, E and DA in urine. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
177.
Xiao Hua WANG Han Zhi WANG Hui LIU Yuan KOU 《中国化学快报》2006,17(12):1531-1533
Recent years, crown ethers have been used in many fields, including phase transfer catalysis, chromatography stationary phase, ionselective electrode, and concentration of metal ions, etc1.. However, the toxicity of free crown ethers makes them unsuitable for industrial use2. Introduction of a crown ether as a functional group to functionalized ionic liquids has been reported3. These functionalized ionic liquids will combine the excellent properties of crown ether and ionic liquids without los… 相似文献
178.
Jerzy Lisowski Marta Paluch Tadeusz Lis 《Journal of inclusion phenomena and macrocyclic chemistry》2006,55(1-2):123-129
The template condensation of (R)-2,2′-diamino-1,1′-binaphthyl and 2,6-diformylpyridine leads to lanthanide(III) complexes of the new chiral hexaaza macrocycle L that adopts highly twisted conformation in [LnL](NO3)3 complexes. The complexes have been characterised by ESI MS spectrometry and NMR spectroscopy. The analogous N2O4 chiral crown ether L2 that has the same carbon skeleton as L does not exhibit tendency to bind lanthanide(III) ions. The X-ray crystal structure of L2 exhibit squeezed conformation of the macrocycle and spatial disposition of donor atoms that does not predispose it for coordination of lanthanide(III) ions. 相似文献
179.
Reed M. Izatt Gypzy C. Lindh Peter Huszthy Glen A. Clark R. L. Bruening Jerald S. Bradshaw James J. Christensen 《Journal of inclusion phenomena and macrocyclic chemistry》1989,7(5):501-509
The macrocycle-mediated fluxes of alkali, alkaline earth, and several transition metal cations have been determined and compared in a H2O-CH2Cl2-H2O liquid membrane system using four water-insoluble macrocycles containing a dialkylhydrogenphosphate moiety. Transport of alkali metal cations by these ligands was greatest from a source phase pH = 12 or above into an acid receiving phase (pH = 1.5). Very low fluxes were observed for the transport of the alkaline earth cations and all transition metal ions studied except Ag+ and Pb2+ which were transported reasonably well by these new macrocycles.Deceased: September 5, 1987. 相似文献
180.