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11.
12.
Zaira Domínguez Javier Hernández Lorena Silva-Gutiérrez Magali Salas-Reyes Mario Sánchez Gabriel Merino 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4):772-784
The effect of electron-withdrawing (EW) and electron-releasing (ER) substituents on the 31P NMR chemical shifts and the structural parameters of a series of tris-(p-X-aryl)selenophosphates is reported in this article. Similarly to O-aryl phosphates and O-aryl thiophosphates, EW groups attached to aromatic rings induce a shielding effect on the 31P NMR signal. After a detailed experimental and theoretical analysis, we confirmed that the selenium atom is the main part responsible for the charge density transfer toward phosphorus through a back-bonding effect. The obtained 1JP-Se values for the complete series agree with this observation. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. 相似文献
13.
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
14.
Dr. Antoine Leliège M. Sc. Jérémie Grolleau M. Sc. Magali Allain Dr. Philippe Blanchard Dr. Dora Demeter Dr. Théodulf Rousseau Dr. Jean Roncali 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(30):9948-9960
Donor–acceptor (D–π–A) systems that combine triarylamine donor blocks and dicyanovinyl (DCV) acceptor groups have been synthesized. Starting from the triphenylamine (TPA)? thiophene? DCV compound ( 1 ) as a reference system, various synthetic approaches have been developed for controlling the light‐harvesting properties and energy levels of the frontier orbitals in this molecule. Thus, the introduction of methoxy groups onto TPA, the replacement of one phenyl ring of TPA by a thiophene ring, or the extension of the π‐conjugating spacer group lead to the modulation of the HOMO level. On the other hand, the fusion of the DCV group onto the vicinal thiophene ring by an ortho‐phenylene bridge allows for a specific fine‐tuning of the LUMO level. The electronic properties of the molecules were analyzed by using UV/Vis spectroscopy and cyclic voltammetry and the compounds were evaluated as donor materials in basic bilayer planar heterojunction solar cells by using C60 as acceptor material. The relationships between the electronic properties of the donors and the performance of the corresponding photovoltaic devices are discussed. Bilayer planar heterojunction solar cells that used reference compound 1 and C70 afforded power‐conversion efficiencies of up to 3.7 %. 相似文献
15.
Dr. Luka Ðorđević Cataldo Valentini Dr. Nicola Demitri Cécile Mézière Magali Allain Prof. Dr. Marc Sallé Dr. Andrea Folli Prof. Dr. Damien Murphy Samuel Mañas-Valero Prof. Dr. Eugenio Coronado Prof. Dr. Davide Bonifazi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(10):4135-4143
Herein we report an efficient synthesis to prepare O-doped nanographenes derived from the π-extension of pyrene. The derivatives are highly fluorescent and feature low oxidation potentials. Using electrooxidation, crystals of cationic mixed-valence (MV) complexes were grown in which the organic salts organize into face-to-face π-stacks, a favorable solid-state arrangement for organic electronics. Variable-temperature electron paramagnetic resonance (EPR) measurements and relaxation studies suggest a strong electron delocalization along the longitudinal axis of the columnar π-stacking architectures. Electric measurements of single crystals of the MV salts show a semiconducting behavior with a remarkably high conductivity at room temperature. These findings support the notion that π-extension of heteroatom-doped polycyclic aromatic hydrocarbons is an attractive approach to fabricate nanographenes with a broad spectrum of semiconducting properties and high charge mobilities. 相似文献
16.
Serhii Krykun Maksym Dekhtiarenko David Canevet Vincent Carr Frdric Aubriet Eric Levillain Magali Allain Zoia Voitenko Marc Sall Sbastien Goeb 《Angewandte Chemie (International ed. in English)》2020,59(2):716-720
Developing methodologies for on‐demand control of the release of a molecular guest requires the rational design of stimuli‐responsive hosts with functional cavities. While a substantial number of responsive metallacages have already been described, the case of coordination‐tweezers has been less explored. Herein, we report the first example of a redox‐triggered guest release from a metalla‐assembled tweezer. This tweezer incorporates two redox‐active panels constructed from the electron‐rich 9‐(1,3‐dithiol‐2‐ylidene)fluorene unit that are facing each other. It dimerizes spontaneously in solution and the resulting interpenetrated supramolecular structure can dissociate in the presence of an electron‐poor planar unit, forming a 1:1 host–guest complex. This complex dissociates upon tweezer oxidation/dimerization, offering an original redox‐triggered molecular delivery pathway. 相似文献
17.
Margarita Sanchez-Dominguez Magali Boutonnet Conxita Solans 《Journal of nanoparticle research》2009,11(7):1823-1829
A novel and straightforward approach, based on oil-in-water (o/w) microemulsions, was developed for the synthesis of inorganic nanoparticles at ambient conditions. It implies the use of organometallic precursors dissolved in nanometre-scale oil droplets of o/w microemulsions. Addition of reducing or oxidizing/precipitating agents results in the formation of metallic or metal oxide nanoparticles, respectively. Nonionic o/w microemulsion systems were chosen, and several key compositions were selected for nanoparticle synthesis at 25 °C. High Resolution Electron Microscopy revealed that small nanoparticles of metals (Pt, Pd and Rh) and nanocrystalline metal oxide (cerium (IV) oxide with cubic type crystalline structure confirmed by XRD), of less than 7 nm can be obtained in mild conditions. 相似文献
18.
[structure: see text] Planarized star-shaped oligothiophenes 1 have been synthesized by connecting short-chain oligothiophenes on a benzo[1,2-b:3,4-b':5,6-b' ']trithiophene central core. Their electrochemical and optical properties have been characterized by cyclic voltammetry and UV-visible spectroscopy, respectively. These results associated with theoretical calculations show the advantage of benzotrithiophene as a central core in terms of pi-electron delocalization. 相似文献
19.
Let R(t)=P(t)/Q(t) be a quotient of real polynomials. We show that ∫exp(iR(t)) dt/t has a uniform bound with a bound depending only on the degrees of P and Q and not on their coefficients. Also
LP estimates are obtained for certain associated singular integral operators. 相似文献
20.
This paper develops the basic analytical theory related to some recently introduced crowd dynamics models.Where well posedness was known only locally in time,it is here extended to all of R+.The result... 相似文献