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Aragoni MC Arca M Bencini A Biagini S Blake AJ Caltagirone C Demartin F De Filippo G Devillanova FA Garau A Gloe K Isaia F Lippolis V Valtancoli B Wenzel M 《Inorganic chemistry》2008,47(18):8391-8404
Two new mixed aza-thia crowns 5-aza-2,8-dithia[9]-(2,9)-1,10-phenanthrolinophane (L(4)) and 2,8-diaza-5-thia[9]-(2,9)-1,10-phenanthrolinophane (L(7)) have been synthesized and characterized. The coordination behavior of L(4) and L(7) toward the metal ions Cu(II), Zn(II), Pb(II), Cd(II), Hg(II), and Ag(I) was studied in aqueous solution by potentiometric methods, in CD3CN/D2O 4:1 (v/v) by (1)H NMR titrations and in the solid state. The data obtained were compared with those available for the coordination behavior toward the same metal ions of structurally analogous mixed donor macrocyclic ligands L(1)-L(3), L(5), L(6): all these contain a phenanthroline subunit but have only S/O/N(aromatic) donor groups in the remaining portion of the ring and are, therefore, less water-soluble than L(4) and L(7). The complexes [Cd(NO3)2(L(5))], [Pb(L(7))](ClO4)2 x 1/2MeCN, [Pb(L(4))](ClO4)2 x MeCN, and [Cu(L(7))](ClO4)2 x 3/2MeNO2 were characterized by X-ray crystallography. The efficacy of L(1)-L(7) in competitive liquid-liquid metal ion extraction of Cu(II), Zn(II), Cd(II), Pb(II), Ag(I), and Hg(II) was assessed. In the absence of Hg(II), a clear extraction selectivity for Ag(I) was observed in all systems investigated. 相似文献
94.
Srinivas N Moehle K Abou-Hadeed K Obrecht D Robinson JA 《Organic & biomolecular chemistry》2007,5(19):3100-3105
The turn-forming D-Pro-L-Pro template has been frequently used to promote regular beta-hairpin conformations in cyclic protein epitope mimetics. Here the use of three isomeric biaryl templates has been studied as alternatives to D-Pro-L-Pro in the preparation of beta-hairpin peptidomimetics. The o,o'- o,m'- and m,m'-isomers of carboxymethyl- and aminomethyl-substituted biaryl templates have been incorporated into novel macrocyclic mimics of the naturally occurring cationic antimicrobial peptide protegrin I. The presence of the o-carboxymethyl-o'-aminomethyl-biaryl template within the macrocyclic peptide resulted in the appearance of slowly interconverting atropisomers. Although none of the resulting mimetics adopted stable beta-hairpin structures in aqueous solution, they all nevertheless retained a significant antimicrobial activity against Gram positive and Gram negative bacteria. These mimetics provide interesting starting points for an optimization program in the search for potent and novel antimicrobial compounds. 相似文献
95.
Structure-activity-based design of a synthetic malaria peptide eliciting sporozoite inhibitory antibodies in a virosomal formulation 总被引:1,自引:0,他引:1
Okitsu SL Kienzl U Moehle K Silvie O Peduzzi E Mueller MS Sauerwein RW Matile H Zurbriggen R Mazier D Robinson JA Pluschke G 《Chemistry & biology》2007,14(5):577-587
The circumsporozoite protein (CSP) of Plasmodium falciparum is a leading candidate antigen for inclusion in a malaria subunit vaccine. We describe here the design of a conformationally constrained synthetic peptide, designated UK-39, which has structural and antigenic similarity to the NPNA-repeat region of native CSP. NMR studies on the antigen support the presence of helical turn-like structures within consecutive NPNA motifs in aqueous solution. Intramuscular delivery of UK-39 to mice and rabbits on the surface of reconstituted influenza virosomes elicited high titers of sporozoite crossreactive antibodies. Influenza virus proteins were crucially important for the immunostimulatory activity of the virosome-based antigen delivery system, as a liposomal formulation of UK-39 was not immunogenic. IgG antibodies elicited by UK-39 inhibited invasion of hepatocytes by P. falciparum sporozoites, but not by antigenically distinct P. yoelii sporozoites. Our approach to optimized virosome-formulated synthetic peptide vaccines should be generally applicable for other infectious and noninfectious diseases. 相似文献
96.
The structure and dynamics of hydration of ammonia/ammonium and methylamine/methylammonium systems have been studied by Car-Parrinello molecular dynamics simulation. While methylamine interacts weakly with the aqueous environment, the interaction of ammonia is found to be much stronger than expected. Both protonated species show a highly structured first solvation sphere. The solvent exchange mechanisms for all species were also investigated, along with the geometry of the hydration spheres. Comparison of these exchange mechanisms with that published for the ammonium ion shows only a minor difference. Analysis of the respective distribution functions has allowed insight into the thermodynamics of solvation for both systems. The calculated pKa values (9.23/10.65) correspond very closely with the published experimental values of 9.25 and 10.65. 相似文献
97.
In a medical procedure to comminute kidney stones the patient is subjected to hypersonic waves focused at the stone. Unfortunately such shock waves also damage the surrounding kidney tissue. We present here a model for the mechanical response of the soft tissue to such a high speed loading regime. The material model combines shear induced plasticity with irreversible volumetric expansion as induced, e.g., by cavitating bubbles. The theory is based on a multiplicative decomposition of the deformation gradient and on an internal variable formulation of continuum thermodynamics. By the use of logarithmic and exponential mappings the stress update algorithms are extended from small‐strain to the finite deformation range. In that way the time‐discretized version of the porous‐viscoplastic constitutive updates is described in a fully variational manner. By numerical experiments we study the shock‐wave propagation into the tissue and analyze the resulting stress states. A first finite element simulation shows localized damage in the human kidney. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
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Equilibrium Pressure Measurements in the System Se/O/Br The saturation pressure or saturation decomposition pressure of SeOBr2,l, Se2Br2,l and SeBr4,s were determined in a membran zero manometer. The decomposition behaviour follows from pressure measurements outside of saturation. From the equilibrium data are derived the Enthalpies of formation: Data see Inhaltsübersicht. Informations about the melting diagrams obtained via the barograms of the condensed compositions SeO2/SeBr4 and Se/Br. 相似文献
100.