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1.
Dr. Jordan Donat Mr. Patrick Dubourdeaux Dr. Martin Clémancey Dr. Julia Rendon Clara Gervasoni Mr. Morgan Barbier Jessica Barilone Dr. Jacques Pécaut Prof. Dr. Serge Gambarelli Prof. Dr. Pascale Maldivi Prof. Dr. Jean-Marc Latour 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(70):e202201875
Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from FeII and FeIII precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an FeIV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the FeII precursor was expected by a two-electron oxidative addition, its formation from an FeIII precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the FeIII precursor, an FeIII tosyliodinane adduct was formed and decomposed into an FeV tosylimido species which generated the catalytically active FeIV tosylimide through a comproportionation process with the FeIII precursor. 相似文献
2.
Peralta Cecilia Mariana Acosta Gimena Henestrosa Cecilia Gil Raúl Andrés Fernández Liliana Patricia 《Journal of Analytical Chemistry》2022,77(3):308-317
Journal of Analytical Chemistry - The present development involved a flow injection strategy using a mini-column of multiwalled carbon nanotubes and fluorescent detection (λex of 283 nm,... 相似文献
3.
Verdecho María-José Alarcón-Valero Faustino Pérez-Perales David Alfaro-Saiz Juan-José Rodríguez-Rodríguez Raúl 《Central European Journal of Operations Research》2021,29(4):1231-1251
Central European Journal of Operations Research - Sustainability practice within supply chains remains in an early development phase. Enterprises still need tools that support the integration of... 相似文献
4.
In this paper, we design a Branch and Bound algorithm based on interval arithmetic to address nonconvex robust optimization problems. This algorithm provides the exact global solution of such difficult problems arising in many real life applications. A code was developed in MatLab and was used to solve some robust nonconvex problems with few variables. This first numerical study shows the interest of this approach providing the global solution of such difficult robust nonconvex optimization problems.
相似文献5.
Laguel Yassine Pillutla Krishna Malick Jérôme Harchaoui Zaid 《Set-Valued and Variational Analysis》2021,29(4):967-996
Set-Valued and Variational Analysis - R. Tyrell Rockafellar and his collaborators introduced, in a series of works, new regression modeling methods based on the notion of superquantile (or... 相似文献
6.
硒是动植物及人体生长必需的十五种微量元素之一,具有清除体内自由基、抗氧化、增强免疫力等功能,但其安全剂量的范围却很窄。利用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对湿法球磨制备的硫铁矿形貌进行了表征。SEM观测发现加乙醇助磨后的硫铁矿为粒径大小较均匀的球形颗粒团聚体,粒径范围在17~200 nm之间,平均粒径138 nm。XRD衍射图谱中的特征峰与FeS2衍射图谱中各峰位置基本一致,因此判定硫铁矿中主要化学组分为FeS2,且图谱中基本没有杂峰,表明制备过程中并未混入杂质,样品纯度较高。实验结果表明,该法制备的硫铁矿具有颗粒粒径小、比表面积大、反应活性高等优点。研究中利用X射线光电子能谱仪(XPS)对硫铁矿去除水体中SeO2-3的机理进行了研究。研究结果表明, (1)在较为广泛的实验pH范围(pH 2.2~11.5),硫铁矿均能有效去除水体中SeO2-3,去除效率(除pH值7.8以外)均达到90%以上;(2)硫铁矿与SeO2-3发生反应后,其主要组成元素的XPS特征峰结合能有所减小,表明硫铁矿表面发生了一定化学变化;(3)酸碱环境下硫铁矿去除SeO2-3的机理不完全相同,酸性环境下,硫铁矿对SeO2-3的去除是单纯的氧化还原过程,即硫铁矿中被酸活化的S2-2将SeO2-3还原为单质Se(0),并且酸性越强,SeO2-3去除效果越好;碱性环境下,SeO2-3的去除过程中氧化还原与络合反应并存,硫铁矿表面有络合态Fe(OH)SeO3和单质Se(0)两种存在形态,且碱性越强,络合态Fe(OH)SeO3含量越高。以上研究结果为硫铁矿去除固定水体和土壤中以SeO2-3为代表的可变价金属阴离子提供重要理论依据和应用基础。 相似文献
7.
8.
Corinne Rondeau-Mouro Mireille Cambert Laurent Blondel Yves Diascorn Léo Mbaya Nor Nadiah Binti Ahmad Nazari Sarah Helary Tiphaine Lucas 《Magnetic resonance in chemistry : MRC》2022,60(7):678-691
A temperature control unit was implemented to vary the temperature of samples studied on a commercial Mobile Universal Surface Explorer nuclear magnetic resonance (MOUSE-NMR) apparatus. The device was miniaturized to fit the maximum MOUSE sampling depth (25 mm). It was constituted by a sample holder sandwiched between two heat exchangers placed below and above the sample. Air was chosen as the fluid to control the temperature at the bottom of the sample, at the interface between the NMR probe and the sample holder, in order to gain space. The upper surface of the sample was regulated by the circulation of water inside a second heat exchanger placed above the sample holder. The feasibility of using such a device was demonstrated first on pure water and then on several samples of bread dough with different water contents. For this, T1 relaxation times were measured at various temperatures and depths and were then compared with those acquired with a conventional compact closed-magnet spectrometer. Discussion of results was based on biochemical transformations in bread dough (starch gelatinization and gluten heat denaturation). It was demonstrated that, within a certain water level range, and because of the low magnetic field strength of the MOUSE, a linear relationship could be established between T1 relaxation times and the local temperature in the dough sample. 相似文献
9.
The European Physical Journal Special Topics - The removal of suspended particles from the interior of a thermocapillary liquid bridge via a finite-particle-size effect restricting the particle... 相似文献
10.