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151.
Adachi K Sugiyama Y Yoneda K Yamada K Nozaki K Fuyuhiro A Kawata S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6616-6628
Novel triply hydrogen bonded suprastructures based on [M(tdpd)2(L)2]2- (H2tdpd=1,4,5,6-tetrahydro-5,6-dioxo-2,3-pyrazinedicarbonitrile, L=solvent) and melamine-analogous cations have been synthesized and characterized. The use of anions containing two AAA sets from [M(tdpd)2(L)2]2- together with cations containing one DDD set (A=hydrogen-bond acceptor, D=hydrogen-bond donor) leads to the formation of complementary triply hydrogen bonded modules in the solid state. In all cases, the building module is further extended via additional hydrogen-bonding interactions to produce a tape, and tapes are assembled into sheets. These results show that a hydrogen-bonded module consisting of different kinds of building blocks, one of which is a metal complex that includes hydrogen-bond acceptor sites and the other is a hydrogen-bond donor molecule, will be attractive for constructing metal-containing supramolecular systems by the self-assembly technique. 相似文献
152.
153.
Koji Nakabayashi Masaki Kawano Prof. Dr. Tatsuhisa Kato Prof. Dr. Ko Furukawa Dr. Shin‐ichi Ohkoshi Prof. Dr. Toshiya Hozumi Dr. Makoto Fujita Prof. Dr. 《化学:亚洲杂志》2007,2(1):164-170
We show a new approach to manipulating the through‐space spin–spin interaction by utilizing the confined cavity of a self‐assembled M6L4 coordination cage. The coordination cage readily encapsulates stable organic radicals in solution, which brings the spin centers of the radicals closer to each other. In sharp contrast to the fact that the radical in solution in the absence of the cage is in a doublet state, in the presence of the cage through‐space spin–spin interaction is induced through cage‐encapsulation effects in solution as well as in the solid state, resulting in the triplet state of the complex. These results were confirmed by ESR spectroscopy and X‐ray crystallography. The quantity of triplet species generated by encapsulation in the cage increases with increasing affinity of the radicals to the cage. We estimated the affinity between several types of guests and the cage in solution by cyclic voltammetry. We also demonstrate that the through‐space interaction of organic radicals within the self‐assembled coordination cage can be controlled by external stimuli such as heat or pH. 相似文献
154.
Jin Y Yoon I Seo J Lee JE Moon ST Kim J Han SW Park KM Lindoy LF Lee SS 《Dalton transactions (Cambridge, England : 2003)》2005,(4):788-796
The NO2S2-donor macrocycle (L1) was synthesised from the ring closure reaction between Boc-N-protected 2,2'-iminobis(ethanethiol) (3) and 2,2'-(ethylenedioxy)bis(benzyl chloride) (4) followed by deprotection of the Boc-group. alpha,alpha'-Dibromo-p-xylene was employed as a dialkylating agent to bridge two L1 to yield the corresponding N-linked product (L2). The X-ray structure of L2 (as its HBr salt) is described. A range of Cd(II) and Hg(II) complexes of L1 (6-9) and L2 (10-12) were prepared and characterised. Reaction of HgX2 (X = Br or I) with L1 afforded [Hg(L1)Br]2[Hg2Br6].2CH2Cl2 6 and [Hg(L1)I(2)] 7, respectively. For 6, the Hg(II) ion in the complex cation has a distorted tetrahedral coordination environment composed of S2N donor atoms from L1 and a bromo ligand. In 7 the coordination geometry is highly distorted tetrahedral, with the macrocycle coordinating in an exodentate manner via one S and one N atom. The remaining two coordination sites are occupied by iodide ions. [Hg(L1)(ClO4)]ClO4 8 was isolated from the reaction of Hg(ClO4)2 and L1. The X-ray structure reveals that all macrocyclic ring donors bind to the central mercury ion in this case, with the latter exhibiting a highly distorted octahedral coordination geometry. The O2S2-donors from the macrocyclic ring define the equatorial plane while the axial positions are occupied by the ring nitrogen as well as by an oxygen from a monodentate perchlorato ion. Reaction of Cd(NO3)(2).4H2O with L1 afforded [Cd(L1)(NO3)2](.)0.5CH2Cl2 9 in which L1 acts as a tridentate ligand, binding exo-fashion via its S2N donors. The remaining coordination positions are filled by two bidentate nitrate ions such that, overall, the cadmium is seven-coordinate. Reactions of HgX2(X = Br or I) with L2 yielded the isostructural 2 : 1 (metal : ligand) complexes, [Hg2(L2)Br4] 10 and [Hg2(L2)I(4)] 11. Each mercury ion has a distorted tetrahedral environment made up of S and N donors from an exodentate L2 and two coordinated halides. Contrasting with this, the reaction of L2 with Cd(NO3)(2).4H2O yielded a 1-D coordination network, {[Cd2(L2)(NO3)4].2CH2Cl2}n 12 in which each ring of L2 is exo-coordinated via two S atoms and one N atom to a cadmium ion which is also bound to one monodentate and one bidentate nitrate anion. The latter also has one of its oxygen atom attached to a neighboring cadmium via a nitroso (mu2-O) bridge such that the overall coordination geometry about each cadmium is seven-coordinate. The [Cd(L2)0.5(NO3)2] units are linked by an inversion to yield the polymeric arrangement. 相似文献
155.
Young Gun Ko Ung Su Choi Yong Sung Park Je Wan Woo 《Journal of polymer science. Part A, Polymer chemistry》2004,42(8):2010-2018
The role of hydrogen bonding in the chemistry of transition‐metal complexes remains a topic of intense scientific and technological interest. Poly(acrylo‐amidino diethylenediamine) was synthesized to study the effects of hydrogen bonding on complexes at different pHs. The polymer was synthesized through the coupling of diethylene triamine with polyacrylonitrile fiber in the presence of AlCl3 · 6H2O addition. The adsorption capacity of this polymer was 11.4 mequiv/g. The ions used for the adsorption test were CrO, PO, Cu2+, Ni2+, Fe2+, and Ag+. All experiments were confirmed with Fourier transform infrared. In the study of anion adsorption, at low pHs, only ionic bonds existed, whereas at high pHs, no bonds existed. However, in the middle pH region, both ionic bonds and hydrogen bonds formed between poly(acrylo‐amidino diethylenediamine) and the chromate ion or phosphate ion. When poly(acrylo‐amidino diethylenediamine) and metal ions (Cu2+, Ni2+, Fe2+, and Ag+) formed complexes, a hydrogen‐bonding effect was not observed with Fourier transform infrared. The quantity of metal ions adsorbed onto poly(acrylo‐amidino diethylenediamine) followed the order Ag+ > Cu2+ > Fe2+ > Ni2+. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2010–2018, 2004 相似文献
156.
Reversed-phase liquid chromatographic retention and membrane activity relationships of local anesthetics 总被引:1,自引:0,他引:1
The chromatographic retention and membrane activity relationships of local anesthetics were studied to address the possible mechanisms for structure specificity and inflammation-associated decrease of their effects. Five representative drugs (3 mM for each) were reacted with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine liposomes in 25 mM potassium phosphate buffer (pH 5.9-7.9, containing 100 mM NaCl and 0.1 mM EDTA) for 10 min at 37 degrees C and the membrane fluidity changes were analyzed by measuring fluorescence polarization with 1,6-diphenyl-1,3,5-hexatriene. Their capacity factors were determined on octadecyl-, octyl- and phenyl-bonded silica columns with a mobile phase consisting of 25 mM potassium phosphate buffer (pH 5.9-7.9, containing 100 mM NaCl and 0.1 mM EDTA)-methanol (30:70, v/v) at a flow rate of 1.0 ml/min and at a column temperature of 37 degrees C and diode-array detection. Mepivacaine, prilocaine, lidocaine, ropivacaine and bupivacaine fluidized membranes in increasing order of intensity, which agreed with their clinical potency. The relative degree of membrane fluidization correlated with that of retention on an octadecyl stationary phase more significantly than the other phases. Both membrane-fluidizing effects and capacity factors decreased by lowering the reaction and mobile phase pH, being consistent with the hypothesis that anesthetic potency is reduced in inflammation because of tissue acidity. Reversed-phase liquid chromatography appears to be useful for estimating the structure-specific and pH-dependent membrane-fluidizing effects of local anesthetics. 相似文献
157.
No K Bok JH Suh IH Kang SO Ko J Nam KC Kim JS 《The Journal of organic chemistry》2004,69(20):6938-6941
A series of novel tetrahomodioxacalix[4]biscrowns with crown-2, crown-3, crown-4, crown-5, and crown-6 units were synthesized. Conformations of each product are dependent on the base used and their conformation stabilities. All conformations were proven by NMR spectra and/or X-ray crystal structures. The 1,3-alternate homodioxacalix[4]biscrown-4 (4b) shows the best selectivity for K+, whereas the 1,3-alternate homodioxacalix[4]crown-5 (5) does for Cs+. Those selectivities are attributable to electrostatic interaction between the metal ion and the crown ring, as well as a pi-metal complexation. However, the C-1,2-alternate conformation does not take the metal ions regardless of the crown species as a result of steric hindrance from the methylene bridge of an ArCH2Ar unit. 相似文献
158.
159.
A polyacrylonitrile (PAN) fiber was adopted for the backbone of a chelate polymer and poly(acrylo‐amidino ethylene amine) (PAEA) was prepared through a one‐step reaction between the PAN fiber and ethylenediamine (EDA). The maximum removal capacity and degree of substitution were 7.8 meq per gram of dried PAEA and 98%, respectively. The PAEA was tested as an adsorbent in single and two‐component metal aqueous solutions under changing pH. The Cu2+ ion accomplished maximum adsorption amount at pH 3 and the order of maximum adsorbed amounts on PAEA is Cu2+ > Ag+ > Zn2+ > Ni2+ > Pb2+ in molar basis. FT‐IR spectroscopy was employed to characterize the chemical bonding in metal aqueous solutions and surface morphology was examined using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
160.
A. N. Kravchenko A. S. Sigachev E. Yu. Maksareva G. A. Gazieva N. S. Trunova B. V. Lozhkin T. S. Pivina M. M. Il’in K. A. Lyssenko Yu. V. Nelyubina V. A. Davankov O. V. Lebedev N. N. Makhova V. A. Tartakovsky 《Russian Chemical Bulletin》2005,54(3):691-704
Two general procedures were developed for the synthesis of chiral N-mono-, N, N′-di-, N, N′ N″-tri-, and N, N′, N″, N′″-tetraalkylglycolurils based on the reactions of 4,5-dihydroxy-imidazolidin-2-ones or glyoxal with one or two moles of alkylureas, respectively, by acid catalysis. The reactions of N-monoalkyl- and N, N′-dialkylureas with glyoxal proceed regioselectively. The mechanism of these reactions was suggested and partly confirmed by quantum-chemical calculations and experimental data. The enantiomeric separation of some chiral glycolurils by chiral-phase HPLC was carried out for the first time.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 680–692, March, 2005. 相似文献