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91.
Cover Picture: Theoretical and Experimental Study on Boron β‐Diketonate Complexes with Intense Two‐Photon‐Induced Fluorescence in Solution and in the Solid State (ChemPhysChem 14/2016) 下载免费PDF全文
92.
Dr. Jean Rouillon Dr. Cyrille Monnereau Dr. Chantal Andraud 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(30):8003-8007
Although tetraphenylethylene (TPE) and its derivatives have been the most commonly used building blocks in the construction of molecules with aggregation-induced emission (AIE) properties, no absolute consensus exists regarding the mechanisms at the origin of the phenomenon. Restriction of intramolecular rotations (RIR) of peripheral phenyls has historically been a dominant paradigm, which has served as a valuable guideline in the molecular engineering of AIEgens. Yet, an increasing number of recent works have established that photoisomerization or photocyclization may actively participate in the nonradiative dissipation of the excitation energy. In this paper, the first experimental evaluation of the quantum efficiencies of these different processes is reported, and photoisomerization is shown to be by far the dominant photophysical pathway in solution, accounting for virtually all nonradiative decay of the molecule‘s excited state in degassed solution. 相似文献
93.
Chantal Staquet 《Meccanica》1994,29(4):489-505
A numerical study is conducted to find out the conditions of occurrence of a secondary Kelvin-Helmholtz instability in the thin layers (referred to as baroclinic layers) that form in a stably-stratified shear layer. For this purpose, three high resolution calculations of a moderately stratified shear layer have been carried out, at a fixed Reynolds number. The wavelength of the initial perturbation is progressively increased, starting from the fundamental wavelength predicted by linear stability theory up to twice this fundamental wavelength. The baroclinic layer of the flow is shown to lengthen and destabilize progressively from one calculation to the other, eventually bearing a secondary Kelvin-Helmholtz instability. The structure and dynamics of the baroclinic layers of the three calculations are examined in the frame of a theoretical model proposed by Corcos and Sherman ([1]). An excellent agreement with the predictions of this model have been found. We next show that the stability of the layer is controlled by the large-scale Kelvin-Helmholtz vortex, via the strain field that it induces in the stagnation point region of the layer. A consequence of this study is that secondary Kelvin-Helmholtz instabilities are fostered by the pairing of primary Kelvin-Helmholtz vortices in a strongly-stratified shear layer.
Sommario E stato condotto uno studio numerico per trovare le condizioni in cui insorge una instabilità secondaria di Kelvin-Helmholtz negli strati sottili che si formano in uno strato di scorrimento stabilmente stratificato. A questo scopo sono state effettuate tre simulazioni ad alta risoluzione a fissato numero di Reynolds e stratificazione bassa. La lunghezza d'onda della perturbazione iniziale è stata progressivamente aumentata dalla lunghezza fondamentale predetta dalla teoria lineare della stabilità fino a due volte questa stessa lunghezza. È stato osservato che da una simulazione all'altra lo strato baroclino del flusso si allunga e si destabilizza progressivamente, generando eventualmente un'instabilità di Kelvin-Helmholtz secondaria. Utilizzando il modello teorico proposto da Corcos e Sherman (1976), per le tre simulazioni sono state analizzate la struttura e la dinamica dello strato baroclino. È stato trovato un accordo eccellente con le predizioni di questo modello. È stato in seguito mostrato che la stabilità dello strato è controllato dai vortici di Kelvin-Helmholtz di larga scala attraverso il campo di deformazione che inducono nella regione del punto di ristagno dello strato. Una conseguenza di questo studio è che le instabilità secondarie di Kelvin-Helmholtz sono forzate dall'accoppiamento dei vortici primari in uno strato di scorrimento fortemente stratificato.相似文献
94.
Touahir L Galopin E Boukherroub R Gouget-Laemmel AC Chazalviel JN Ozanam F Saison O Akjouj A Pennec Y Djafari-Rouhani B Szunerits S 《The Analyst》2011,136(9):1859-1866
The use of an amorphous silicon-carbon alloy overcoating on silver nanostructures in a localized surface plasmon resonance (LSPR) sensing platform allows for decreasing the detection limit by an order of magnitude as compared to sensors based on gold nanostructures deposited on glass. In addition, silver based multilayer structures show a distinct plasmonic behaviour as compared to gold based nanostructures, which provides the sensor with an increased short-range sensitivity and a decreased long-range sensitivity. 相似文献
95.
Sanz E Valeriani C Zaccarelli E Poon WC Pusey PN Cates ME 《Physical review letters》2011,106(21):215701
In supercooled liquids, vitrification generally suppresses crystallization. Yet some glasses can still crystallize despite the arrest of diffusive motion. This ill-understood process may limit the stability of glasses, but its microscopic mechanism is not yet known. Here we present extensive computer simulations addressing the crystallization of monodisperse hard-sphere glasses at constant volume (as in a colloid experiment). Multiple crystalline patches appear without particles having to diffuse more than one diameter. As these patches grow, the mobility in neighboring areas is enhanced, creating dynamic heterogeneity with positive feedback. The future crystallization pattern cannot be predicted from the coordinates alone: Crystallization proceeds by a sequence of stochastic micronucleation events, correlated in space by emergent dynamic heterogeneity. 相似文献
96.
Jonathan Mendy Dr. Anh Thy Bui Dr. Amandine Roux Jean-Christophe Mulatier Damien Curton Dr. Alain Duperray Dr. Alexei Grichine Dr. Yannick Guyot Dr. Sophie Brasselet Dr. François Riobé Dr. Chantal Andraud Dr. Boris Le Guennic Dr. Véronique Patinec Pr. Raphael Tripier Dr. Maryline Beyler Dr. Olivier Maury 《Chemphyschem》2020,21(10):1036-1043
Cationic lanthanide complexes are generally able to spontaneously internalize into living cells. Following our previous works based on a diMe-cyclen framework, a second generation of cationic water-soluble lanthanide complexes based on a constrained cross-bridged cyclam macrocycle functionalized with donor-π-conjugated picolinate antennas was prepared with europium(III) and ytterbium(III). Their spectroscopic properties were thoroughly investigated in various solvents and rationalized with the help of DFT calculations. A significant improvement was observed in the case of the Eu3+ complex, while the Yb3+ analogue conserved photophysical properties in aqueous solvent. Two-photon (2P) microscopy imaging experiments on living T24 human cancer cells confirmed the spontaneous internalization of the probes and images with good signal-to-noise ratio were obtained in the classic NIR-to-visible configuration with the Eu3+ luminescent bioprobe and in the NIR-to-NIR with the Yb3+ one. 相似文献
97.
Comparative Analysis of Conjugated Alkynyl Chromophore–Triazacyclononane Ligands for Sensitized Emission of Europium and Terbium 下载免费PDF全文
Marine Soulié Frédéric Latzko Emmanuel Bourrier Dr. Virginie Placide Dr. Stephen J. Butler Dr. Robert Pal Dr. James W. Walton Dr. Patrice L. Baldeck Dr. Boris Le Guennic Dr. Chantal Andraud Dr. Jurriaan M. Zwier Dr. Laurent Lamarque Prof. David Parker Dr. Olivier Maury 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(28):8636-8646
A series of europium and terbium complexes based on a functionalized triazacyclononane carboxylate or phosphinate macrocyclic ligand is described. The influence of the anionic group, that is, carboxylate, methylphosphinate, or phenylphosphinate, on the photophysical properties was studied and rationalized on the basis of DFT calculated structures. The nature, number, and position of electron‐donating or electron‐withdrawing aryl substituents were varied systematically within the same phenylethynyl scaffold in order to optimize the brightness of the corresponding europium complexes and investigate their two‐photon absorption properties. Finally, the europium complexes were examined in cell‐imaging applications, and selected terbium complexes were studied as potential oxygen sensors. 相似文献
98.
Emmanuel Allard Chantal Larpent 《Journal of polymer science. Part A, Polymer chemistry》2008,46(18):6206-6213
The synthesis and pH‐sensing properties of fluorescent polymer nanoparticles (NPs) in the 20 nm diameter range with a sensitive dye covalently attached to the particle surface and a reference dye entrapped within the particle core are presented. Fluorescein‐functionalized NPs were readily obtained by conjugation of fluorescein isothiocyanate (FITC) to amine‐coated crosslinked polystyrene‐based nanoparticles prepared by microemulsion polymerization followed by postfunctionalization. This all water‐based method gave access to stable aqueous suspensions of pH‐sensing fluorescent NPs. The encapsulation of the insensitive reference fluorescent dye (1,9‐diphenylanthracene, DPA) was then conveniently achieved by soaking leading to dual fluorescent NPs containing about 20 DPA and 55 fluorescein, as deduced from spectroscopic analyses. This core‐shell type architecture maximizes the interactions of the sensing dye with the medium while protecting the reference dye. The variations of the ratio of the fluorescence emission intensities of the sensitive dye (fluorescein) to the reference dye (DPA) with pH show that the dual fluorescent NPs act as a ratiometric pH sensor with a measuring range between pH 4 and pH 8. This pH nanosensor was found to be fast, fully reversible, and robust without any leaching of dye over a long period of time. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6206–6213, 2008 相似文献
99.
The effect of molecular chirality in thermotropic mesomorphic H-bonded polymeric systems has not really been investigated so far. Therefore, five new chiral mesogenic diamides have been prepared and described. Besides more ordered mesophases, the enantiomers exhibit a chiral nematic polymorphism detected by microcalorimetry and probably corresponding to different modes of chiral coiling to give these singular twisted nematic phases. 相似文献
100.
Comparing the 2,2′‐Biphenylenedithiophosphinate Binding of Americium with Neodymium and Europium 下载免费PDF全文
Dr. Justin N. Cross Dr. Joseph A. Macor Dr. Jeffery A. Bertke Dr. Maryline G. Ferrier Dr. Gregory S. Girolami Dr. Stosh A. Kozimor Joel R. Maassen Dr. Brian L. Scott Dr. David K. Shuh Dr. Benjamin W. Stein Prof. Dr. S. Chantal E. Stieber 《Angewandte Chemie (International ed. in English)》2016,55(41):12755-12759
Advancing our understanding of the minor actinides (Am, Cm) versus lanthanides is key for developing advanced nuclear‐fuel cycles. Herein, we describe the preparation of (NBu4)Am[S2P(tBu2C12H6)]4 and two isomorphous lanthanide complexes, namely one with a similar ionic radius (i.e., NdIII) and an isoelectronic one (EuIII). The results include the first measurement of an Am?S bond length, with a mean value of 2.921(9) Å, by single‐crystal X‐ray diffraction. Comparison with the EuIII and NdIII complexes revealed subtle electronic differences between the complexes of AmIII and the lanthanides. 相似文献