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The short and efficient asymmetric synthesis of (-)-1-hydroxyquinolizidinone was achieved in seven steps and 25.2% overall yield from readily available 5-chloropentanal. It is a key intermediate in the formal syntheses of (-)-homopumilotoxin 223G and (-)-epiquinamide. 相似文献
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N Arnaud J Georges 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2001,57(6):1295-1301
The thermal lens effect produced in binary mixtures of water and ethanol has been investigated. It is shown that the sensitivity of the thermal lens method upon the addition of ethanol in water varies as the temperature-dependent refractive index gradient to thermal conductivity ratio of the mixture. The dependence of k and dn/dT upon the ethanol volume fraction follows a second-order and fourth-order polynomial, respectively, and cannot be precisely predicted using the additive rule. Moreover, depending on the experimental conditions and the mixture composition, the temperature gradient produced subsequently to relaxation of the excited species induces mutual migration of the solvent molecules and the formation of a concentration gradient in the irradiated area. This effect, known as the Soret effect, can locally change the thermo-optical properties of the solution and produce an additional signal, especially when steady-state experiments are done. This may result in errors as large as 20% when quantitative informations have to be derived from experimental data. 相似文献
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Joy Ann Panis Prof. Marine Louis Arnaud Brosseau Shouhei Katao Florencio de los Reyes Prof. Takuya Nakashima Dr. Rémi Métivier Dr. Clémence Allain Prof. Tsuyoshi Kawai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(44):e202201012
We synthesized two bichromophoric difluoroboron-β-diketonates (DFB) connected in para and meta positions by using cyclohexane diamine as a chiral bridge ( para and meta (R/S)-CyDFB ). TD-DFT calculations revealed that the variation in connectivity of the DFB units leads to different spatial arrangements and a chirality inversion of the bichromophoric DFB. Higher gabs values were obtained in (R/S)-CyDFB connected in para as compared to meta position. Aggregation of para (R/S)-CyDFB in mixture of solvents increase the glum values as compared to its monomeric form. Ultrasonication and heating induced the formation of highly ordered nano-helical wires of para (R/S)-CyDFB that increased the glum values to 0.015. On the other hand, meta (R/S)-CyDFB failed to form highly ordered self-assembled wires due to hindered H-binding sites. These observations indicate that the chiroptical properties of DFB bi-chromophore system can be modulated with self-assembly and spatial arrangement of the chromophores. 相似文献
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Florian Venel Dr. Hiroki Nagashima Dr. Andrew G. M. Rankin Christelle Anquetil Dr. Vytautas Klimavicius Dr. Torsten Gutmann Prof. Gerd Buntkowsky Dr. Sylvie Derenne Prof. Olivier Lafon Dr. Arnaud Huguet Dr. Frédérique Pourpoint 《Chemphyschem》2021,22(18):1907-1913
Estuaries are key ecosystems with unique biodiversity and are of high economic importance. Along the estuaries, variations in environmental parameters, such as salinity and light penetration, can modify the characteristics of dissolved organic matter (DOM). Nevertheless, there is still limited information about the atomic-level transformations of DOM in this ecosystem. Solid-state NMR spectroscopy provides unique insights into the nature of functional groups in DOM. A major limitation of this technique is its lack of sensivity, which results in experimental time of tens of hours for the acquisition of 13C NMR spectra and generally precludes the observation of 15N nuclei for DOM. We show here how the sensitivity of solid-state NMR experiments on DOM of Seine estuary can be enhanced using dynamic nuclear polarization (DNP) under magic-angle spinning. This technique allows the acquisition of 13C NMR spectra of these samples in few minutes, instead of hours for conventional solid-state NMR. Both conventional and DNP-enhanced 13C NMR spectra indicate that the 13C local environments in DOM are not strongly modified along the Seine estuary. Furthermore, the sensitivity gain provided by the DNP allows the detection of 15N NMR signal of DOM, in spite of the low nitrogen content. These spectra reveal that the majority of nitrogen is in the amide form in these DOM samples and show an increased disorder around these amide groups near the mouth of the Seine. 相似文献
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Bushra Asad Taimoor Khan Faiza Zareen Gul Muhammad Asad Ullah Samantha Drouet Sara Mikac Laurine Garros Manon Ferrier Shankhamala Bose Thibaut Munsch Duangjai Tungmunnithum Arnaud Lanoue Nathalie Giglioli-Guivarch Christophe Hano Bilal Haider Abbasi 《Molecules (Basel, Switzerland)》2021,26(15)
In vitro cultures of scarlet flax (Linum grandiflorum L.), an important ornamental flax, have been established as a new possible valuable resource of lignans and neolignans for antioxidant and anti-inflammatory applications. The callogenic potential at different concentrations of α-naphthalene acetic acid (NAA) and thidiazuron (TDZ), alone or in combinations, was evaluated using both L. grandiflorum hypocotyl and cotyledon explants. A higher callus induction frequency was observed on NAA than TDZ, especially for hypocotyl explants, with a maximum frequency (i.e., 95.2%) on 1.0 mg/L of NAA. The presence of NAA (1.0 mg/L) in conjunction with TDZ tended to increase the frequency of callogenesis relative to TDZ alone, but never reached the values observed with NAA alone, thereby indicating the lack of synergy between these two plant growth regulators (PGRs). Similarly, in terms of biomass, NAA was more effective than TDZ, with a maximum accumulation of biomass registered for medium supplemented with 1.0 mg/L of NAA using hypocotyls as initial explants (DW: 13.1 g). However, for biomass, a synergy between the two PGRs was observed, particularly for cotyledon-derived explants and for the lowest concentrations of TDZ. The influence of these two PGRs on callogenesis and biomass is discussed. The HPLC analysis confirmed the presence of lignans (secoisolariciresinol (SECO) and lariciresinol (LARI) and neolignan (dehydrodiconiferyl alcohol [DCA]) naturally accumulated in their glycoside forms. Furthermore, the antioxidant activities performed for both hypocotyl- and cotyledon-derived cultures were also found maximal (DPPH: 89.5%, FRAP 866: µM TEAC, ABTS: 456 µM TEAC) in hypocotyl-derived callus cultures as compared with callus obtained from cotyledon explants. Moreover, the anti-inflammatory activities revealed high inhibition (COX-1: 47.4% and COX-2: 51.1%) for extract of hypocotyl-derived callus cultures at 2.5 mg/L TDZ. The anti-inflammatory action against COX-1 and COX-2 was supported by the IC50 values. This report provides a viable approach for enhanced biomass accumulation and efficient production of (neo)lignans in L. grandiflorum callus cultures. 相似文献
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Eva Pospisilova Alexis Renaud Marc Poorteman Marjorie Olivier Ludovic Dumas Philippe Dubois Leila Bonnaud Konstantin Moshkunov Bernard Nysten Arnaud Delcorte 《Surface and interface analysis : SIA》2019,51(6):674-680
Phenol-paraphenylenediamine (P-pPDA) benzoxazines exhibit excellent barrier properties, adequate to protect aluminum alloys from corrosion, and constitute interesting candidates to replace chromate-containing coatings in the aeronautical industry. For the successful application of P-pPDA coatings, it is necessary to decrease the curing temperature to avoid the delamination of the coating while preserving the mechanical properties of the alloy, as well as the barrier properties of the coating. However, decreasing the curing temperature leads to less polymerized films, the extent of which requires a quantitative assessment. While the conversion rate of the polymerization reaction is commonly evaluated for bulk samples using differential scanning calorimetry (DSC), a tool for its evaluation in thin films is missing. Therefore, a new approach was developed for that matter using time-of-flight secondary ion mass spectrometry (ToF-SIMS). The relation between the SIMS data integrated from inside thin films and the DSC results obtained on bulk samples with the same curing cycle allowed to calibrate the SIMS data. With this preliminary calibration of the technique, the polymerization of P-pPDA coatings can be locally determined, at the surface and along the depth of the coating, using dual-beam depth profiling with large argon cluster beam sputtering. 相似文献