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71.
Noeen Malik Wolfgang Voelter Hans-Jürgen Machulla Christoph Solbach 《Journal of Radioanalytical and Nuclear Chemistry》2011,287(1):287-292
In homoaromatic systems, isotopic exchange (18F/19F) was previously (J Label Compd Radiopharm 18(12):1721–1730 [2], J Chem Soc Perkin Trans 1(3):295–298 [3]) proven to be advantageous, yet in general specific activity is thought to be low. For heteroaromatic systems, in particular,
very few examples are published regarding the 18F-labelling of 2-substituted pyridines (J Label Compd Radiopharm 42:975–985 [9]). Therefore, in 2-fluoropyridines, we decided to study the 18F labelling by isotopic exchange (18F/19F). The radiochemical yield for 2-fluoropyridine was 90 ± 2%. Even if 2-fluoropyridine was substituted by an electron-donating
group such as a methyl or a methoxy group, radiochemical yields were 80 ± 1 and 78 ± 1%, respectively. Although in benzenes,
these substituents are known to decrease nucleophilic substitutions by 18F-Fluoride significantly. Moreover, by choosing appropriate concentrations of 2-fluoropyridines, reasonably high specific
activities up to 10 GBq/μmol were obtained. 相似文献
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75.
Knör S Modlinger A Poethko T Schottelius M Wester HJ Kessler H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(21):6082-6090
A convenient synthesis of novel bifunctional poly(amino carboxylate) chelating agents allowing chemoselective attachment to highly functionalized biomolecules is described. Based on the well known chelator 1,4,7,10-tetraazacyclodecane-1,4,7,10-tetraacetic acid (DOTA), we synthesized novel bifunctional chelating agents bearing additional functional groups by alkylating 1,4,7,10-tetraazacyclododecane (cyclen) with one equivalent of para-functionalized alkyl 2-bromophenyl-acetate and three equivalents of tert-butyl 2-bromoacetate. The resulting compounds, which contain an additional carbonyl or alkyne functionality, allow site specific labeling of appropriately functionalized unprotected biomolecules in a rapid manner via click reactions. This was demonstrated by the attachment of our new DOTA derivatives to the somatostatin analogue Tyr3-octreotate by chemoselective oxime ligation and CuI-catalyzed azide-alkyne cycloaddition. Initial biodistribution studies in mice with the radiometalated compound demonstrated the applicability of the described DOTA conjugation. 相似文献
76.
Lomadze N Schneider HJ Albelda MT García-España E Verdejo B 《Organic & biomolecular chemistry》2006,4(9):1755-1759
The affinities of polyamines consisting of ethylenediamine units equipped with either one or two terminal naphthyl-, anthryl-, or acridyl units towards PolyA.PolyU as an RNA model, and Poly(dA).Poly(dT) as a DNA model are screened by measuring the melting point changes (DeltaT(m)) of the double strands, and also partially by a fluorimetric binding assay using ethidium bromide. The larger aromatic moieties with long spacers between them allow bisintercalation; this leads to an increased preference for DNA in comparison to RNA, where ion pairing of the ammonium centers with the major RNA groove phosphates dominates. Allosteric affinity control by metalation is achieved e.g. with Cu(2+) ions, which induce conformational distortions within the chains. With anthryl- in contrast to naphthyl derivatives intercalation can be so strong that distortion of the ethylenediamine chain by metalation is not powerful enough. A particularly high concentration of positive charges is accessible with tripodal derivatives built up from ethylenediamine and propylenediamine units; in the absence of aryl parts, which interfere with the RNA groove preference, one observes the highest affinity difference known until today, reflected in a melting point ratio of DeltaT(m(RNA))/DeltaT(m(DNA)) = 40, whereas other synthetic ligands reach only a DeltaT(m(RNA))/DeltaT(m(DNA)) ratio of about 3. 相似文献
77.
Lucia?MutihacEmail author Hans-Jürgen?Buschmann Radu-Cristian?Mutihac Eckhard?Schollmeyer 《Journal of inclusion phenomena and macrocyclic chemistry》2005,51(1-2):1-10
The ability of calix[n]arenes to form complexes, to act as extractants in liquid–liquid extraction, and run as carriers in transport through liquid membranes of different biological amine compounds (e.g., ammonium ion, amines, amino acids, and peptides) has been the central topics of many reports. These features recommend the calix[n]arenes as competitive candidates for studying the interactions involved in host–guest recognition as well as useful receptors in separation processes. Some specific aspects of their applications in binding and separation of various amine compounds by extraction, and in transport through liquid membranes have therefore been considered. The effect of the factors that might influence the separation of above compounds by extraction, and the transport through liquid membranes using the calix [n]arenes has been presented.This revised version was published online in July 2005 with a corrected issue number. 相似文献
78.
Hans-Jürgen?BuschmannEmail author Lucia?Mutihac Eckhard?Schollmeyer 《Journal of inclusion phenomena and macrocyclic chemistry》2005,51(1-2):53-57
The formation of complexes between α-cyclodextrin and n-alkylamines and their hydrochlorides has been studied in aqueous solution using calorimetric titrations. All alkylamines form stronger complexes than the corresponding hydrochlorides. The values of the reaction enthalpies are smaller for the alkylamine hydrochlorides compared with the alkylamines. By increasing the number of methylene groups, these differences become smaller. In addition, the reaction enthalpies for protonation of the alkylamines and their complexes with α-cyclodextrin have been measured. The heat of protonation of these complexes is always smaller compared with the alkylamines. Due to the protonation and the formation of a strong solvation shell around the ammonium group the interactions with α-cyclodextrins are weakened. From a thermodynamic cycle using all measured reactions, it can be concluded that the aggregation of the alkylamines with long alkyl chains (heptyl-, octyl-, and nonylamine) has an influence on the values of the reaction enthalpies and entropies for the protonated form only.This revised version was published online in July 2005 with a corrected issue number. 相似文献
79.
This work is part of an effort to develop chelating agents for stable binding and easy conjugation of Re-188 to biologically interesting structures. Starting from the well-known in vivo stability of [(188)ReO(DMSA)(2)](-), we want to exploit this coordination system for the design of (188)ReO(V) chelates, which are stable toward reoxidation to perrhenate and toward ligand exchange under all conditions of radiopharmaceutical development. Therefore, a new type of tetradentate ligand has been synthesized by bridging two molecules of N,N'-diisobutyl-2,3-dimercaptosuccinamide with N-(3-aminopropyl)propane-1,3-diamine. The resulting stereoisomeric tetrathiolato S(4) ligand of composition ((i)()Bu)(2)N(O)C-C(SH)-C(SH)-C(O)NH-(CH(2))(3)-NH-(CH(2))(3)-NHC(O)-C(SH)-C(SH)-C(O)N((i)Bu)(2) forms anionic five-coordinate oxorhenium(V) complexes by a ligand-exchange reaction of NBu(4)[ReOCl(4)] in methanol. In the absence of a base, the compounds were isolated as "betaine", [ReO(S(4))], with the protonated nitrogen of the bridge serving as an internal "counterion". Two representatives have been fully characterized in both the solid and solution states and found to adopt the expected square-pyramidal coordination geometry. The equatorial plane is formed by four thiolate sulfur atoms, whereas the oxygen occupies the apical position. The orientation of the metal oxo group is exo in relation to the carbamido groups in both isomers. Both complexes are stereoisomeric regarding the junction of the triamine chain. 相似文献
80.
Konstantin Runovski Hans-Jürgen Schmeisser 《Journal of Fourier Analysis and Applications》2008,14(1):16-38
Means and families of operators generated by Bochner-Riesz kernels are studied. Some sharp results on their convergence are
achieved. The equivalence of the approximation errors of these methods to smoothness quantities related to the Laplacian is
proved.
相似文献