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81.
Interaction of PiB‐Derivative Metal Complexes with Beta‐Amyloid Peptides: Selective Recognition of the Aggregated Forms 下载免费PDF全文
Dr. André F. Martins David M. Dias Dr. Jean‐François Morfin Dr. Sara Lacerda Dr. Douglas V. Laurents Dr. Éva Tóth Prof. Carlos F. G. C. Geraldes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5413-5422
Metal complexes are increasingly explored as imaging probes in amyloid peptide related pathologies. We report the first detailed study on the mechanism of interaction between a metal complex and both the monomer and the aggregated form of Aβ1–40 peptide. We have studied lanthanide(III) chelates of two PiB‐derivative ligands (PiB=Pittsburgh compound B), L1 and L2, differing in the length of the spacer between the metal‐complexing DO3A macrocycle (DO3A= 1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acid) and the peptide‐recognition PiB moiety. Surface plasmon resonance (SPR) and saturation transfer difference (STD) NMR spectroscopy revealed that they both bind to aggregated Aβ1–40 (KD=67–160 μM ), primarily through the benzothiazole unit. HSQC NMR spectroscopy on the 15N‐labeled, monomer Aβ1–40 peptide indicates nonsignificant interaction with monomeric Aβ. Time‐dependent circular dichroism (CD), dynamic light scattering (DLS), and TEM investigations of the secondary structure and of the aggregation of Aβ1–40 in the presence of increasing amounts of the metal complexes provide coherent data showing that, despite their structural similarity, the two complexes affect Aβ fibril formation distinctly. Whereas GdL1, at higher concentrations, stabilizes β‐sheets, GdL2 prevents aggregation by promoting α‐helical structures. These results give insight into the behavior of amyloid‐targeted metal complexes in general and contribute to a more rational design of metal‐based diagnostic and therapeutic agents for amyloid‐ associated pathologies. 相似文献
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Ren Y Acuña UM Jiménez F García R Mejía M Chai H Gallucci JC Farnsworth NR Soejarto DD Carcache de Blanco EJ Kinghorn AD 《Tetrahedron》2012,68(12):2671-2678
Six new (1-6) and eight known germacranolide-type sesquiterpene lactones, along with several known phenylpropanol coumarates and methylated flavonoids, were isolated from the leaves of Piptocoma rufescens, collected in the Dominican Republic. The new compounds were identified by analysis of their spectroscopic data, with the molecular structure of 3 being established by single-crystal X-ray diffraction. The absolute configurations of the sesquiterpene lactones isolated were determined from their CD and NOESY NMR spectra, together with the analysis of Mosher ester reactions. Bioassay screening results showed the majority of the sesquiterpene lactones isolated (1-13) to be highly cytotoxic toward the HT-29 human colon cancer cell line, with the most potent compound being 15-deoxygoyazensolide (10, IC(50), 0.26 μM). In addition, several of the sesquiterpene lactones exhibited NF-κB (p65) inhibitory activity. 相似文献
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The hydroxyalkylation reaction has been used to condense benzocrown ethers with various aldehydes and ketones. The condensation reactions are catalyzed by triflic or sulfuric acid. The products from the reactions are bis(benzocrown ethers) and they are formed in good yields (42-98%, 13 examples). 相似文献
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Dr. Lingui Zhu Dr. Shasha Liu Dr. Justin T. Douglas Prof. Dr. Ryan A. Altman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(38):12800-12805
The conversion of an alcohol‐based functional group, into a trifluoromethyl analogue is a desirable transformation. However, few methods are capable of converting O‐based electrophiles into trifluoromethanes. The copper‐mediated trifluoromethylation of benzylic xanthates using Umemoto’s reagent as the source of CF3 to form C? CF3 bonds is described. The method is compatible with an array of benzylic xanthates bearing useful functional groups. A preliminary mechanistic investigation suggests that the C? CF3 bond forms by reaction of the substrate with in situ generated CuCF3 and CuOTf. Further evidence suggests that the reaction could proceed via a radical cation intermediate. 相似文献
87.
Yulin Ren Francisco Jiménez Ricardo García Milciades Mejía Heebyung Chai Norman R. Farnsworth Djaja D. Soejarto A. Douglas Kinghorn 《Tetrahedron letters》2013
A new sesquiterpene lactone, rufescenolide C (1), the first furanoheliangolide dimer, was isolated from the leaves of Piptocoma rufescens, collected in the Dominican Republic. Its structure was determined by interpretation of its spectroscopic data, with the absolute configuration being established by analysis of the CD spectrum. A plausible biogenesis of this dimer is proposed. This compound showed potent cytotoxicity with an IC50 value of 150 nM, when tested against HT-29 human colon cancer cells. 相似文献
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Nadia Balucani Laura Cartechini Zahra Homayoon Joel M. Bowman 《Molecular physics》2015,113(15-16):2296-2301
Following a recent investigation on the N(2D) + H2O reaction [Homayoon et al., J. Phys. Chem. Lett. 5, 3508 (2014)], we report on an experimental and theoretical study of the isotopologue N(2D) + D2O reaction. Crossed molecular beam (CMB) experiments were conducted at a collision energy of 10.3 kcal mol–1. Quasiclassical trajectory calculations were performed on a recent potential energy surface to derive the centre-of-mass functions necessary to simulate the CMB laboratory distributions. Excellent agreement was found. The importance of the channel leading to HON/DON was confirmed. The inclusion of this channel, in addition to that leading to the isomer HNO/DNO, can affect the models considering the coupling between nitrogen and oxygen chemistry in the upper atmosphere of Titan. 相似文献