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71.
72.
Pierre Garcia Dr. Yannick Evanno Dr. Pascal George Dr. Mireille Sevrin Dr. Gino Ricci Prof. Dr. Max Malacria Dr. Corinne Aubert Prof. Dr. Vincent Gandon 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(14):4337-4344
An in‐depth study of the cobalt‐catalyzed [2+2+2] cycloaddition between yne‐ynamides and nitriles to afford aminopyridines has been carried out. About 30 nitriles exhibiting a broad range of steric demand and electronic properties have been evaluated, some of which open new perspectives in metal‐catalyzed arene formation. In particular, the use of [CpCo(CO)(dmfu)] (dmfu=dimethyl fumarate) as a precatalyst made possible the incorporation of electron‐deficient nitriles into the pyridine core. Modification of the substitution pattern at the yne‐ynamide allows the regioselectivity to be switched toward 3‐ or 4‐aminopyridines. Application of this synthetic methodology to the construction of the aminopyridone framework using a yne‐ynamide and an isocyanate was also briefly examined. DFT computations suggest that 3‐aminopyridines are formed by formal [4+2] cycloaddition between the nitrile and the intermediate cobaltacyclopentadiene, whereas 4‐aminopyridines arise from an insertion pathway. 相似文献
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Simon Giret Christophe Théron Audrey Gallud Dr. Marie Maynadier Dr. Magali Gary‐Bobo Dr. Marcel Garcia Dr. Michel Wong Chi Man Dr. Carole Carcel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(38):12806-12814
Two new prodrugs, bearing two and three 5‐fluorouracil (5‐FU) units, respectively, have been synthesized and were shown to efficiently treat human breast cancer cells. In addition to 5‐FU, they were intended to form complexes through H‐bonds to an organo‐bridged silane prior to hydrolysis‐condensation through sol–gel processes to construct acid‐responsive bridged silsesquioxanes (BS). Whereas 5‐FU itself and the prodrug bearing two 5‐FU units completely leached out from the corresponding materials, the prodrug bearing three 5‐FU units was successfully maintained in the resulting BS. Solid‐state NMR (29Si and 13C) spectroscopy show that the organic fragments of the organo‐bridged silane are retained in the hybrid through covalent bonding and the 1H NMR spectroscopic analysis provides evidence for the hydrogen‐bonding interactions between the prodrug bearing three 5‐FU units and the triazine‐based hybrid matrix. The complex in the BS is not affected under neutral medium and operates under acidic conditions even under pH as high as 5 to deliver the drug as demonstrated by HPLC analysis and confirmed by FTIR and 13C NMR spectroscopic studies. Such functional BS are promising materials as carriers to avoid the side effects of the anticancer drug 5‐FU thanks to a controlled and targeted drug delivery. 相似文献
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Carbazole‐based liquid single‐crystal elastomers (LSCEs) are valuable fluorescent flexible materials to perform optical mechanotransduction under ambient conditions. Indeed, the covalent incorporation of carbazole derivatives into nematic LSCEs allows to tune their luminescence on demand under mechanical control in a quick and reversible fashion. Specifically, the fluorescence intensity for these materials can be switched back and forth in less than a second. Moreover, such a process can be performed several times without detecting any sign of fatigue in the system. In addition, these materials show excellent resistance to aging; 2 years after their preparation they exhibit the very same mechanofluorescent behavior as when freshly prepared. In fact, the here reported fluorescent systems are highly sensitive; the application of a force of 70 mN decreases the fluorescence in the elastomeric material by 7%. Thus, mechanical forces are attractive external stimuli to modulate the fluorescence of nematic elastomers rapidly and reversibly enabling thereby mechanotransduction.
78.
Jochen C. Lauer Dr. Avinash S. Bhat Chantal Barwig Nathalie Fritz Tobias Kirschbaum Dr. Frank Rominger Prof. Dr. Michael Mastalerz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(51):e202201527
The pollution of groundwater with nitrate is a serious issue because nitrate can cause several diseases such as methemoglobinemia or cancer. Therefore, selective removal of nitrate by efficient binding to supramolecular hosts is highly desired. Here we describe how to make [2+3] amide cages in very high to quantitative yields by applying an optimized Pinnick oxidation protocol for the conversion of corresponding imine cages. By NMR titration experiments of the eight different [2+3] amide cages with nitrate, chloride and hydrogen sulfate we identified one cage with an unprecedented high selectivity towards nitrate binding vs. chloride (S=705) or hydrogensulfate (S>13500) in CD2Cl2/CD3CN (1 : 3). NMR experiments as well as single-crystal structure comparison of host-guest complexes give insight into structure-property-relationships. 相似文献
79.
Leonardo Dalseno Antonino Júlia Rocha Gouveia Rogrio Ramos de Sousa Júnior Guilherme Elias Saltarelli Garcia Luara Carneiro Gobbo Lara Basílio Tavares Demetrio Jackson dos Santos 《Molecules (Basel, Switzerland)》2021,26(8)
Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. 31P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers. 相似文献
80.
Garcia S Chavez L Lowery TJ Han SI Wemmer DE Pines A 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,184(1):72-77
Hyperpolarized xenon associated with ligand derivatized cryptophane-A cages has been developed as a NMR based biosensor. To optimize the detection sensitivity we describe use of xenon exchange between the caged and bulk dissolved xenon as an effective signal amplifier. This approach, somewhat analogous to 'remote detection' described recently, uses the chemical exchange to repeatedly transfer spectroscopic information from caged to bulk xenon, effectively integrating the caged signal. After an optimized integration period, the signal is read out by observation of the bulk magnetization. The spectrum of the caged xenon is reconstructed through use of a variable evolution period before transfer and Fourier analysis of the bulk signal as a function of the evolution time. 相似文献