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141.
Simone Zanella Dr. Michele Mingozzi Alberto Dal Corso Dr. Roberto Fanelli Dr. Daniela Arosio Prof. Dr. Marco Cosentino Dr. Laura Schembri Dr. Franca Marino Dr. Marta De Zotti Prof. Dr. Fernando Formaggio Dr. Luca Pignataro Prof. Dr. Laura Belvisi Prof. Dr. Umberto Piarulli Prof. Dr. Cesare Gennari 《ChemistryOpen》2015,4(5):633-641
A dual-action ligand targeting both integrin αVβ3 and vascular endothelial growth factor receptors (VEGFRs), was synthesized via conjugation of a cyclic peptidomimetic αVβ3 Arg-Gly-Asp (RGD) ligand with a decapentapeptide. The latter was obtained from a known VEGFR antagonist by acetylation at the Lys13 side chain. Functionalization of the precursor ligands was carried out in solution and in the solid phase, affording two fragments: an alkyne VEGFR ligand and the azide integrin αVβ3 ligand, which were conjugated by click chemistry. Circular dichroism studies confirmed that both the RGD and VEGFR ligand portions of the dual-action compound substantially adopt the biologically active conformation. In vitro binding assays on isolated integrin αVβ3 and VEGFR-1 showed that the dual-action conjugate retains a good level of affinity for both its target receptors, although with one order of magnitude (10/20 times) decrease in potency. The dual-action ligand strongly inhibited the VEGF-induced morphogenesis in Human Umbilical Vein Endothelial Cells (HUVECs). Remarkably, its efficiency in preventing the formation of new blood vessels was similar to that of the original individual ligands, despite the worse affinity towards integrin αVβ3 and VEGFR-1. 相似文献
142.
143.
Dr. Albert Ferrer‐Ugalde Dr. Arántzazu González‐Campo Prof. Dr. Clara Viñas Dr. Jesús Rodríguez‐Romero Dr. Rosa Santillan Dr. Norberto Farfán Prof. Dr. Reijo Sillanpää Dr. Antonio Sousa‐Pedrares Dr. Rosario Núñez Prof. Dr. Francesc Teixidor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):9940-9951
Two sets of o‐carborane derivatives incorporating fluorene and anthracene fragments as fluorophore groups have been successfully synthesized and characterized, and their photophysical properties studied. The first set, comprising fluorene‐containing carboranes 6 – 9 , was prepared by catalyzed hydrosilylation reactions of ethynylfluorene with appropriate carboranylsilanes. The compound 1‐[(9,9‐dioctyl‐fluorene‐2‐yl)ethynyl]carborane ( 11 ) was synthesized by the reaction of 9,9‐dioctyl‐2‐ethynylfluorene and decaborane (B10H14). Furthermore, reactions of the lithium salt of 11 with 1 equivalent of 4‐(chloromethyl)styrene or 9‐(chloromethyl)anthracene yielded compounds 12 and 13 . Members of the second set of derivatives, comprising anthracene‐containing carboranes, were synthesized by reactions of monolithium or dilithium salts of 1‐Me‐1,2‐C2B10H11, 1‐Ph‐1,2‐C2B10H11, and 1,2‐C2B10H12 with 1 or 2 equivalents of 9‐(chloromethyl)anthracene, respectively, to produce compounds 14 – 16 . In addition, 2 equivalents of the monolithium salts of 1‐Me‐1,2‐C2B10H11 (Me‐o‐carborane) and 1‐Ph‐1,2‐C2B10H11 (Ph‐o‐carborane) were reacted with 9,10‐bis(chloromethyl)anthracene to produce compounds 17 and 18 , respectively. Fluorene derivatives 6 – 9 exhibit moderate fluorescence quantum yields (32–44 %), whereas 11 – 13 , in which the fluorophore is bonded to the Ccluster (Cc), show very low emission intensity (6 %) or complete fluorescence quenching. The anthracenyl derivatives containing the Me‐o‐carborane moiety exhibit notably high fluorescence emissions, with ?F=82 and 94 %, whereas their Ph‐o‐carborane analogues are not fluorescent at all. For these compounds, we have observed a correlation between the Cc?Cc bond length and the fluorescence intensity in CH2Cl2 solution, comparable to that observed for previously reported styrene‐containing carboranes. Thus, our hypothesis is that for systems of this type the fluorescence may be tuned and even predicted by changing the substituent on the adjacent Cc. 相似文献
144.
Dr. Steve Y. Rhieu Dr. Aaron A. Urbas Dr. Daniel W. Bearden Dr. John P. Marino Dr. Katrice A. Lippa Dr. Vytas Reipa 《Angewandte Chemie (International ed. in English)》2014,53(2):447-450
Non‐invasive and real‐time analysis of cellular redox processes has been greatly hampered by lack of suitable measurement techniques. Here we describe an in‐cell nuclear magnetic resonance (NMR) based method for measuring the intracellular glutathione redox potential by direct and quantitative measurement of isotopically labeled glutathione introduced exogenously into living yeast. By using this approach, perturbations in the cellular glutathione redox homeostasis were also monitored as yeast cells were subjected to oxidative stress. 相似文献
145.
Tortosa-Estorach C Ruiz N Masdeu-Bultó AM 《Chemical communications (Cambridge, England)》2006,(26):2789-2791
High selectivity in acids is obtained in the first example of hydrocarboxylation of 1-octene in supercritical carbon dioxide using a Pd/P(4-C6H4-CF3)3 catalyst system and a perfluorinated surfactant. 相似文献
146.
Grald Lelais Dieter Seebach Bernhard Jaun RaveendraI. Mathad Oliver Flgel Francesco Rossi Marino Campo Arno Wortmann 《Helvetica chimica acta》2006,89(3):361-403
The correlation between β2‐, β3‐, and β2,3‐amino acid‐residue configuration and stability of helix and hairpin‐turn secondary structures of peptides consisting of homologated proteinogenic amino acids is analyzed (Figs. 1–3). To test the power of Zn2+ ions in fortifying and/or enforcing secondary structures of β‐peptides, a β‐decapeptide, 1 , four β‐octapeptides, 2 – 5 , and a β‐hexadecapeptide, 10 , have been devised and synthesized. The design was such that the peptides would a) fold to a 14‐helix ( 1 and 3 ) or a hairpin turn ( 2 and 4 ), or form neither of these two secondary structures (i.e., 5 ), and b) carry the side chains of cysteine and histidine in positions, which will allow Zn2+ ions to use their extraordinary affinity for RS? and the imidazole N‐atoms for stabilizing or destabilizing the intrinsic secondary structures of the peptides. The β‐hexadecapeptide 10 was designed to a) fold to a turn, to which a 14‐helical structure is attached through a β‐dipeptide spacer, and b) contain two cysteine and two histidine side chains for Zn complexation, in order to possibly mimic a Zn‐finger motif. While CD spectra (Figs. 6–8 and 17) and ESI mass spectra (Figs. 9 and 18) are compatible with the expected effects of Zn2+ ions in all cases, it was shown by detailed NMR analyses of three of the peptides, i.e., 2, 3, 5 , in the absence and presence of ZnCl2, that i) β‐peptide 2 forms a hairpin turn in H2O, even without Zn complexation to the terminal β3hHis and β3hCys side chains (Fig. 11), ii) β‐peptide 3 , which is present as a 14‐helix in MeOH, is forced to a hairpin‐turn structure by Zn complexation in H2O (Fig. 12), and iii) β‐peptide 5 is poorly ordered in CD3OH (Fig. 13) and in H2O (Fig. 14), with far‐remote β3hCys and β3hHis residues, and has a distorted turn structure in the presence of Zn2+ ions in H2O, with proximate terminal Cys and His side chains (Fig. 15). 相似文献
147.
148.
Dr. Jordi Poater Prof. Dr. Miquel Solà Prof. Dr. Clara Viñas Prof. Dr. Francesc Teixidor 《Angewandte Chemie (International ed. in English)》2014,53(45):12191-12195
A bridge between classical organic polycyclic aromatic hydrocarbons (PAH) and closo borohydride clusters is established by showing that they share a common origin regulated by the number of valence electrons in an electronic confined space. Application of the proposed electronic confined space analogy (ECSA) method to archetypal PAHs leads to the conclusion that the 4n+2 Wade–Mingos rule for three‐dimensional closo boranes is equivalent to the (4n+2)π Hückel rule for two‐dimensional PAHs. More importantly, use of ECSA allows design of new interesting fused closo boranes which can be a source of inspiration for synthetic chemists. 相似文献
149.
Prof. Dr. Francesc Teixidor Dr. Ariadna Pepiol Prof. Dr. Clara Viñas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(30):10650-10653
A new class of globular polybranched macromolecules that contain multiple anionic metallacarborane clusters at the o‐carborane periphery is reported. The water soluble high boron rich containing molecules could be of interest for boron neutron capture therapy (BNCT) as well as for drug delivery. The reinforced electrostatic noncovalent interactions between anionic polyethylene glycol cobaltabisdicarbollide (PEG‐COSAN) branches and the ammonium cation have been shown using ESI‐MS. 相似文献
150.
Gabriella Leo Laura Cartechini Piero Pucci Antonio Sgamellotti Gennaro Marino Leila Birolo 《Analytical and bioanalytical chemistry》2009,395(7):2269-2280
The identification of proteinaceous components in paintings remains a challenging task for several reasons. In addition to
the minute amount of sample available, complex and variable chemical composition of the paints themselves, possible simultaneous
presence of several binders and contaminants, and degradation of the original materials due to aging and pollution are complicating
factors. We proposed proteomic strategies for the identification of proteins in binders of paintings that can be adapted to
overcome the requirements and difficulties presented by specific samples. In particular, we worked on (1) the development
of a minimally invasive method based on the direct tryptic cleavage of the sample without protein extraction; (2) the use
of microwave to enhance the enzymatic digestion yield, followed by the analysis of the peptide mixtures by nanoLC-MS/MS with
electrospray ionization (ESI). Moreover, as an additional tool to tackle the problem of contaminating proteins, we exploited
the possibility of generating an exclusion list of the mass signals that in a first run had been fragmented and that the mass
spectrometer had to ignore for fragmentation in a subsequent run. The methods, tested on model samples, allowed the identification
of milk proteins in a sample from paintings attributed to Cimabue and Giotto, thirteenth-century Italian masters, decorating
the vaults of the upper church in the Basilica of St. Francis in Assisi, Italy. 相似文献