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101.
Adrien Bessaguet Quentin Blancart-Remaury Pauline Poinot Isabelle Opalinski Sébastien Papot 《Angewandte Chemie (International ed. in English)》2023,62(6):e202216787
Rotaxanes and molecular knots exhibit particular properties resulting from the presence of a mechanical bond within their structure that maintains the molecular components interlocked in a permanent manner. On the other hand, the disassembly of the interlocked architecture through the breakdown of the mechanical bond can activate properties which are masked in the parent compound. Herein, we present the development of stimuli-responsive CuI-complexed [2]catenanes as OFF/ON catalysts for the copper-catalyzed alkyne-azide cycloaddition (CuAAC) reaction. The encapsulation of the CuI ion inside the [2]catenanes inhibits its ability to catalyze the formation of triazoles. In contrast, the controlled opening of the two macrocycles induces the breaking of the mechanical bond, thereby restoring the catalytic activity of the CuI ion for the CuAAC reaction. Such OFF/ON catalysts can be involved in signal amplification processes with various potential applications. 相似文献
102.
Yuxuan Che Muhammad Rizwan Niazi Quentin Chan Pegah Ghamari Ting Yu Cory Ruchlin Han Yu He Yan Dongling Ma Steven S. Xiao Ricardo Izquierdo Dmytro F. Perepichka 《Angewandte Chemie (International ed. in English)》2023,62(40):e202309003
We explore a series of furan-based non-fullerene acceptors and report their optoelectronic properties, solid-state packing, photodegradation mechanism and application in photovoltaic devices. Incorporating furan building blocks leads to the expected enhanced backbone planarity, reduced band gap and red-shifted absorption of these acceptors. Still, their position in the molecule is critical for stability and device performance. We found that the photodegradation of these acceptors originates from two distinct pathways: electrocyclic photoisomerization and Diels–Alder cycloaddition of singlet oxygen. These mechanisms are of general significance to most non-fullerene acceptors, and the photostability depends strongly on the molecular structure. Placement of furans next to the acceptor termini leads to better photostability, well-balanced hole/electron transport, and significantly improved device performance. Methylfuran as the linker offers the best photostability and power conversion efficiency (>14 %), outperforming all furan-based acceptors reported to date and all indacenodithiophene-based acceptors. Our findings show the possibility of photostable furan-based alternatives to the currently omnipresent thiophene-based photovoltaic materials. 相似文献
103.
Dr. Quentin Le Dé Dr. Amal Bouammali Dr. Christian Bijani Dr. Laure Vendier Dr. Iker del Rosal Dr. Dmitry A. Valyaev Dr. Chiara Dinoi Dr. Antoine Simonneau 《Angewandte Chemie (International ed. in English)》2023,62(40):e202305235
We have re-examined the reactivity of the manganese dinitrogen complex [Cp(CO)2Mn(N2)] ( 1 , Cp=η5-cyclopentadienyl, C5H5) with phenylithium (PhLi). By combining experiment and density functional theory (DFT), we have found that, unlike previously reported, the direct nucleophilic attack of the carbanion onto coordinated dinitrogen does not occur. Instead, PhLi reacts with one of the CO ligands to provide an anionic acylcarbonyl dinitrogen metallate [Cp(CO)(N2)MnCOPh]Li ( 3 ) that is stable only below −40 °C. Full characterization of 3 (including single crystal X-ray diffraction) was performed. This complex decomposes quickly above −20 °C with N2 loss to give a phenylate complex [Cp(CO)2MnPh]Li ( 2 ). The latter compound was erroneously formulated as an anionic diazenido compound [Cp(CO)2MnN(Ph)=N]Li in earlier reports, ruling out the claimed and so-far unique behavior of the N2 ligand in 1 . DFT calculations were run to explore both the hypothesized and the experimentally verified reactivity of 1 with PhLi and are fully consistent with our results. Direct attack of a nucleophile on metal-coordinated N2 remains to be demonstrated. 相似文献
104.
Dr. Anis Tlili Sébastien Alazet Quentin Glenadel Dr. Thierry Billard 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10230-10234
Copper‐catalyzed direct perfluoroalkylthiolation of alkynes by using the corresponding perfluoroalkanesulfenamide reagent is reported. The selective mono‐ and bis‐perfluoroalkylthiolation of alkynes can be conducted under very mild conditions (no base, room temperature) in very good to excellent yields. This approach, which uses a low toxicity, inexpensive copper catalyst that incorporates a commercially available ligand, is applied in the absence of any additional base. Preliminary mechanistic investigations shed some light on the nature of the unprecedented reactivity observed. 相似文献
105.
Blandine N. Cretin Quentin Sallembien Lauriane Sindt Nicolas Daugey Thierry Buffeteau Pierre Waffo-Teguo Denis Dubourdieu Axel Marchal 《Analytica chimica acta》2015
Wine expresses its beauty by sending a sensory message to the taster through molecules coming from grapes, yeast metabolism or oak wood. Among the compounds released during barrel aging, lyoniresinol has been recently reported as a relevant contributor to wine bitterness. As this lignan contains three stereogenic carbons, this work aimed at investigating the influence of stereochemistry on wine taste by combining analytical and sensorial techniques. First, an oak wood extract was screened by Liquid Chromatography–High Resolution Mass Spectrometry to target isomers separable in a symmetric environment and a diastereoisomer called epi-lyoniresinol was isolated for the first time. Then, an original racemic resolution based on natural xylose-derivatives was carried out to obtain lyoniresinol enantiomers. Chiroptical spectroscopic measurements associated with theoretical calculations allowed the unambiguous determination of their absolute configuration. The taste properties of all these stereoisomers revealed that only one lyoniresinol enantiomer is strongly bitter whereas the other one is tasteless and the diastereoisomer is slightly sweet. The presence of these three compounds was established in an oaked Bordeaux wine by chiral and non-chiral chromatography, suggesting the significant influence of stereochemistry on wine taste. 相似文献
106.
Fabien J. T. Talbot Dr. Quentin Dherbassy Dr. Srimanta Manna Dr. Chunling Shi Shibo Zhang Dr. Gareth P. Howell Dr. Gregory J. P. Perry Prof. Dr. David J. Procter 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(46):20454-20465
Copper-catalyzed borylative multicomponent reactions (MCRs) involving olefins and C−N electrophiles are a powerful tool to rapidly build up molecular complexity. The products from these reactions contain multiple functionalities, such as amino, cyano and boronate groups, that are ubiquitous in medicinal and process chemistry programs. Copper-catalyzed MCRs are particularly attractive because they use a relatively abundant and non-toxic catalyst to selectively deliver high-value products from simple feedstocks such as olefins. In this Minireview, we explore this rapidly emerging field and survey the borylative union of allenes, dienes, styrenes and other olefins, with imines, nitriles and related C−N electrophiles. 相似文献
107.
Nauleau P Cochard E Minonzio JG Grimal Q Laugier P Prada C 《The Journal of the Acoustical Society of America》2012,131(4):EL289-EL294
The femoral neck cortical shell was recently demonstrated to act like a waveguide for circumferential waves. Femoral neck assessment with ultrasound could be enhanced by guided waves measurement. In this study, the decomposition of the time reversal operator (DORT) method is used to measure the phase velocities of circumferential guided modes in a circular tube with dimensions characteristic of femoral neck. The tube is made of a bone-mimicking material. Five guided modes are obtained and compared to theoretical predictions. The work substantiates the feasibility of measuring guided waves in a relatively thick tube of attenuating material with the DORT method. 相似文献
108.
Michael Quentin Dirk Blondin Janina Klasen Rotem Shlomo Lanzman Falk-Roland Miese Christian Arsov Peter Albers Gerald Antoch Hans-Jörg Wittsack 《Magnetic resonance imaging》2012
Purpose
To evaluate which mathematical model (monoexponential, biexponential, statistical, kurtosis) fits best to the diffusion-weighted signal in prostate magnetic resonance imaging (MRI).Materials and Methods
24 prostate 3-T MRI examinations of young volunteers (YV, n= 8), patients with biopsy proven prostate cancer (PC, n= 8) and an aged matched control group (AC, n= 8) were included. Diffusion-weighted imaging was performed using 11 b-values ranging from 0 to 800 s/mm2.Results
Monoexponential apparent diffusion coefficient (ADC) values were significantly (P<.001) lower in the peripheral (PZ) zone (1.18±0.16 mm2/s) and the central (CZ) zone (0.73±0.13 mm2/s) of YV compared to AC (PZ 1.92±0.17 mm2/s; CZ 1.35±0.21 mm2/s). In PC ADCmono values (0.61±0.06 mm2/s) were significantly (P<.001) lower than in the peripheral of central zone of AC. Using the statistical analysis (Akaike information criteria) in YV most pixels were best described by the biexponential model (82%), the statistical model, respectively kurtosis (93%) each compared to the monoexponential model. In PC the majority of pixels was best described by the monoexponential model (57%) compared to the biexponential model.Conclusion
Although a more complex model might provide a better fitting when multiple b-values are used, the monoexponential analyses for ADC calculation in prostate MRI is sufficient to discriminate prostate cancer from normal tissue using b-values ranging from 0 to 800 s/mm2. 相似文献109.
Heuskin S Godin B Leroy P Capella Q Wathelet JP Verheggen F Haubruge E Lognay G 《Journal of chromatography. A》2009,1216(14):2768-2775
The chemical composition of Matricaria chamomilla L. and Nepeta cataria L. essential oils was determined by GC-MS on an apolar stationary phase by comparison of the characteristic fragmentation patterns with those of the Wiley 275L database. The GC-MS chromatograms were compared with those obtained by fast GC equipped with a direct resistively heated column (Ultra Fast Module 5% phenyl, 5 mx 0.1 mm, 0.1 microm film thickness). Analytical conditions were optimised to reach a good peak resolution (split ratio=1:100), with analysis time lower than 5 min versus 35-45 min required by conventional GC-MS. The fast chromatographic method was completely validated for the analysis of mono- and sesquiterpene compounds. Essential oils were then fractionated by column chromatography packed with silica gel. Three main fractions with high degree of purity in E-beta-farnesene were isolated from the oil of M. chamomilla. One fraction enriched in (Z,E)-nepetalactone and one enriched in beta-caryophyllene were obtained from the oil of N. cataria. These semiochemical compounds could act as attractants of aphid's predators and parasitoids. 相似文献
110.
Morant PE Thommen Q Pfeuty B Vandermoere C Corellou F Bouget FY Lefranc M 《Chaos (Woodbury, N.Y.)》2010,20(4):045108
The microscopic green alga Ostreococcus tauri is rapidly emerging as a promising model organism in the green lineage. In particular, recent results by Corellou et al. [Plant Cell 21, 3436 (2009)] and Thommen et al. [PLOS Comput. Biol. 6, e1000990 (2010)] strongly suggest that its circadian clock is a simplified version of Arabidopsis thaliana clock, and that it is architectured so as to be robust to natural daylight fluctuations. In this work, we analyze the time series data from luminescent reporters for the two central clock genes TOC1 and CCA1 and correlate them with microarray data previously analyzed. Our mathematical analysis strongly supports both the existence of a simple two-gene oscillator at the core of Ostreococcus tauri clock and the fact that its dynamics is not affected by light in normal entrainment conditions, a signature of its robustness. 相似文献