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81.
The new [2 + 2] Schiff-base macrocyclic ligand L2, containing pyridazine head units and pyridine pendant arms, was synthesised as [Ba(II)2L2(ClO4)4(OH2)] 1 from the barium(II) ion templated condensation reaction of 3,6-diformylpyridazine and N1-(2-aminoethyl)-N1-(methylene-2-pyridyl)-ethane-1,2-diamine. Subsequent transmetallation reactions of 1 with copper(II), iron(II) and manganese(II) perchlorates led to the formation of [Cu(II)2L2](ClO4)4.2MeCN 2, [Fe(II)2L2(MeCN)2](ClO4)4 3 and two manganese complexes, 4 and 5, with the same formula, [Mn(II)2L2(MeCN)(OH2)](ClO4)4, but slightly different crystal structures, respectively. Single-crystal X-ray structural analyses reveal the variety of structures which can be supported by L2 in order to meet the coordination environment preferences of the incorporated metal ions. The barium(II) ions in 1 have an irregular ten-coordinate geometry whereas the copper(II) ions in 2 have a square pyramidal geometry and the iron(II) ions in 3 have an octahedral geometry, while in 4 and 5 every manganese(II) ion is seven-coordinate and the environment can be best described as distorted pentagonal bipyramidal. In 1, 4 and 5 the pyridazine moieties bridge the metal centres [Ba(1)...Ba(2) 4.9557(3)A 1; Mn(1)...Mn(2) 4.520(1)A 4; Mn(1)[dot dot dot]Mn(2) 4.3707(8)A 5] but this is not observed in the copper(II) and iron(II) complexes, 2 and 3, in which the metal ions are well separated [Cu(1)...Cu(2) 5.9378(6)A 2; Fe(1)...Fe(2) 5.7407(12)A 3]. In the cyclic voltammogram of [Cu2(II)L2](ClO4)4.2MeCN 2 in MeCN vs. Ag/AgCl two separate reversible one-electron transfer steps are observed [E(1/2)=0.04 V, DeltaE= 0.12 V and E(1/2)= 0.20 V, DeltaE=0.12 V; K(c)=510; in this system E(1/2)(Fc+/Fc)=0.42 V and DeltaE(Fc+/Fc)=0.08 V]. The other complexes cannot be reversibly reduced/oxidised. 相似文献
82.
83.
Siegfried L Comparone A Neuburger M Kaden TA 《Dalton transactions (Cambridge, England : 2003)》2005,(1):30-36
The metal promoted hydrolysis of nitrile groups in the side chains of tetraazamacrocyclic Cu2+ complexes has been studied by stopped-flow techniques. It is shown that the reaction proceeds by an intramolecular attack of an axially coordinated OH- onto the nitrile group to give the corresponding amide. In alkaline solution the amide then deprotonates and binds to the axial position of the Cu2+ thus preventing further coordination of an OH-. This explains mechanistically that in the Cu2+ complexes of macrocycles carrying two nitrile functions only one is selectively hydrolysed. The nitrile hydrolysis has also been used on a preparative scale to synthesize tetraazamacrocycles with two different side chains. X-Ray diffractions of several products are presented to confirm the structures and the results from the kinetics and equilibria measurements. 相似文献
84.
85.
Thoma G Streiff MB Katopodis AG Duthaler RO Voelcker NH Ehrhardt C Masson C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(1):99-117
Polyvalent carbohydrate-protein interactions occur frequently in biology, particularly in recognition events on cellular membranes. Collectively, they can be much stronger than corresponding monovalent interactions, rendering it difficult to control them with individual small molecules. Artificial macromolecules have been used as polyvalent ligands to inhibit polyvalent processes; however, both reproducible synthesis and appropriate characterization of such complex entities is demanding. Herein, we present an alternative concept avoiding conventional macromolecules. Small glycodendrimers which fulfill single molecule entity criteria self-assemble to form non-covalent nanoparticles. These particles-not the individual molecules-function as polyvalent ligands, efficiently inhibiting polyvalent processes both in vitro and in vivo. The synthesis and characterization of these glycodendrimers is described in detail. Furthermore, we report on the characterization of the non-covalent nanoparticles formed and on their biological evaluation. 相似文献
86.
This paper reports on studies on the reaction of InCl with SnCl2 to form ternary halides. The reaction route is investigated by x‐ray investigations at different temperatures. Depending on the modification of InCl as educt and on the temperature conditions the reaction follows different pathways which may include intermediate redox reactions of the type In+ + Sn2+ → In3+ + Sn0. 相似文献
87.
E. Anklam Maria Rosa Bassani Thomas Eiberger Stefan Kriebel Markus Lipp Reinhard Matissek 《Analytical and bioanalytical chemistry》1997,357(7):981-984
Pyrolysis Mass Spectrometry (Py-MS) was used for the discrimination of cocoa butters from other vegetable fats. Mass spectra
ranging from 50 amu to 250 amu were analyzed by principal component analysis (PCA) and with neural nets. The application of
neural nets leads to a good discrimination between the two classes. Detailed analysis of the nets revealed that only the first
60 masses were used within the net. The use of PCA requires a careful selection of the number of masses included in the calculation.
Canonical variance analysis was applied to determine the significant masses. Optimal performance of PCA was observed only
using the first 22 significant masses. Most of these masses were different from the ones used by the neural net. It seems
that the mass spectra obtained by Py-MS contain sufficient information for the discrimination of pure cocoa butter from other
vegetable fats, but none of the methods seems to be able to extract all information available. Neural net provides a very
robust method for this task and no prior data selection was necessary.
Received: 13 May 1996 / Revised: 7 August 1996 / Accepted: 7 August 1996 相似文献
88.
A series of enantiomerically pure 8-oxabicyclo[3.2.1]oct-6-en-3-ones functionalized in the unsaturated two-carbon bridge has been prepared by the title reaction. Carbocation reactivity has been fined-tuned at -95 degrees C and adjusted to diene nucleophilicity. Conventional electrophilic substitution of 3-silylated and 3-stannylated furan is suppressed in favor of the rapid 4 + 3 cycloaddition mode. In the case of cycloadduct 13A, stereoselectivity (17:1) is perfectly matched to regioselectivity (17:1). High stereoselection as well as unprecedented regioselection and chemoselection is attributed to the low-temperature cycloaddition protocol and the design of chiral auxiliary and tether. 相似文献
89.
90.
Martin Sukopp Luciana Marinelli Markus Heller Trixi Brandl SimonL. Goodman ReinhardW. Hoffmann Horst Kessler 《Helvetica chimica acta》2002,85(12):4442-4452
The (3R,5S,6E,8S,10R)‐11‐amino‐3,5,8,10‐tetramethylundec‐6‐enoic acid (ATUA; 1 ), which was designed as a βII′‐turn mimic according to the concepts of allylic strain and 2,4‐dimethylpentane units, was incorporated into a cyclic RGD peptide. The three‐dimensional structure of cyclo(‐RGD‐ATUA‐) (=cyclo(‐Arg‐Gly‐Asp‐ATUA‐)) 4 in H2O was determined by NMR techniques, distance geometry calculations and molecular‐dynamics simulations. The RGD sequence of 4 shows high conformational flexibility but some preference for an extended conformation. The structural features of the RGD sequence of 4 were compared with the RGD moiety of cyclo(‐RGDfV‐) (=cyclo(‐Arg‐Gly‐Asp‐D ‐Phe‐Val‐)). In contrast to cyclo(‐RGDfV‐), which is a highly active αvβ3 antagonist and selective against αIIbβ3, cyclo(‐RGD‐ATUA‐) shows a lower activity and selectivity. The structure of the ATUA residue in the cyclic peptide resembles a βII′‐turn‐like conformation. Its middle part, adjacent to the C?C bond, strongly prefers the designed and desired structure. 相似文献