Mechanochemistry and Eco-Bases for Sustainable Michael Addition Reactions

The Michael addition reaction was revisited with a full focus on sustainability combined with efficiency, using mechanochemistry in mild conditions. First, the synthesis of cyclopentenone derivatives was chosen as a model reaction to find optimal conditions in mechanochemistry while using classical but weak bases. The reaction was efficient (84–95% yields), fast (2–6 h), solvent free, and required 0.1 equivalent of base. Aiming to reach greener conditions, classical bases were then replaced using new bio-sourced bases, called Eco-bases, that were easily prepared from plants and led to heterogeneous catalysts. The composition and structure of Eco-bases were characterized by MP-AES, XRPD, EBSD/EDS, HRTEM/EDX and ion chromatography. Interestingly, a high ratio of potassium was observed with the presence of K₂Ca(CO₃)₂ for the most effective Eco-base. The new Eco-bases were used for the mechanical-assisted construction of functionalized alkenone derivatives. The versatility of the method has been successfully applied with good to excellent yields to different Michael donors and acceptors. Eco-bases were recycled and reused four times with the same performances. Combining Eco-bases and mechanochemistry in Michael addition reactions allowed reaching a maximum degree of sustainability (efficient, rapid, low catalyst loading, solvent-free reactions with bio-sourced catalysts) and participating in the development of mechanochemistry in sustainable chemistry.     

模拟污水中氮、磷对水稻幼苗过氧化氢酶和乙醇酸氧化酶的影响

以水稻为材料，研究了不同浓度的模拟污水中Ｎ、Ｐ对幼苗过氧化氢酶（Ｃａｔａｌａｓｅ，ＣＡＴ，ＥＣ１．１１．１．６）、乙醇酸氧化酶（Ｇｌｅｃｏｌａｔｅｏｘｉｄａｓｅ，ＧＯ，ＥＣ１．３．３．１）、过氧化物酶（Ｐｅｒｏｘｉｄａｓｅ，ＰＯＤ，ＥＣ１．１１．１．７）和叶绿素含量的影响．结果表明：低浓度Ｎ、Ｐ（分别；在０～４．２８ｍｍｏｌ·Ｌ－１、０～０．２ｍｍｏｌ·Ｌ－１范围）可诱导ＣＡＴ活性增大，而后下降，Ｎ、Ｐ浓度分别超过８．５６ｍｍｏｌ·Ｌ－１和０．４ｍｍｏｌ·Ｌ－１后，活性又升高；ＰＯＤ的活性变化与ＣＡＴ变化很相似．Ｎ、Ｐ浓度分别在０～６．４２ｍｍｏｌ·Ｌ－１、０～０．３ｍｍｏｌ·Ｌ－１范围，ＧＯ活性随Ｎ、Ｐ浓度增高而活性下降，超过６．４２ｍｍｏｌ·Ｌ－１、０．３ｍｍｏｌ·Ｌ－１后，则随Ｎ、Ｐ浓度增大而增大．这可能是高浓度Ｎ、Ｐ可提高水稻的光呼吸的结果．另外，污水中Ｎ、Ｐ抑制叶绿素的合成，使叶绿素的含量降低；低浓度污水Ｎ、Ｐ促进根生长，高浓度Ｎ、Ｐ抑制根生长     

Influence of pressure on the electrical and electrochemical behaviour of high-temperature steam electrolyser La<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>Co<Subscript>0.2</Subscript>Fe<Subscript>0.8</Subscript>O<Subscript>3</Subscript> anode

This paper is dedicated to the impact of pressure on the electrochemical behaviour of LSCF (La_1-xSr_xCo_yFe_1-yO_3-δ) anode in high-temperature electrolysers. This study was carried out with symmetrical cells associating LSCF electrodes to a 3YSZ (yttrium-stabilised zirconia) electrolyte. Impedance spectroscopy measurements were performed using a three-electrode configuration, at temperature as high as 700 to 800 °C, in a pressure range from 1 to 30 bar. A clear improvement in terms of electrode resistance decrease is highlighted, mainly due to faster oxygen adsorption/desorption kinetics and a better supply of gas to electrochemical reaction sites. Other assumptions were considered and analysed, such as the impact of pressure on LSCF electrical conductivity and on the mechanical contacts. Thus, three contributions were determined as limiting steps at low pressure, up to 5 bar, whilst for higher pressure, the optimised conditions in operation are reached. This study completes a previous one related to a modelling approach.     

Identification and Capture of Phenolic Compounds from a Rapeseed Meal Protein Isolate Production Process By-Product by Macroporous Resin and Valorization Their Antioxidant Properties

In this study, phenolic compounds from an aqueous protein by-product from rapeseed meal (RSM) were identified by HPLC-DAD and HPLC-ESI-MS, including sinapine, sinapic acid, sinapoyl glucose, and 1,2-di-sinapoyl gentibiose. The main phenolic compound in this by-product was sinapine. We also performed acid hydrolysis to convert sinapine, and sinapic acid derivatives present in the permeate, to sinapic acid. The adsorption of phenolic compounds was investigated using five macroporous resins, including XAD4, XAD7, XAD16, XAD1180, and HP20. Among them, XAD16 showed the highest total phenolic contents adsorption capacities. The adsorption behavior of phenolic compounds was described by pseudo-second-order and Langmuir models. Moreover, thermodynamics tests demonstrated that the adsorption process of phenolic compounds was exothermic and spontaneous. The highest desorption ratio was obtained with 30% (v/v) and 70% (v/v) ethanol for sinapine and sinapic acid, respectively, with a desorption ratio of 63.19 ± 0.03% and 94.68 ± 0.013%. DPPH and ABTS tests revealed that the antioxidant activity of the hydrolyzed fraction was higher than the non-hydrolyzed fraction and higher than the one of vitamin C. Antioxidant tests demonstrated that these phenolic compounds could be used as natural antioxidants, which can be applied in the food industry.     

Modification of Cary 14H Spectrophotometer into a Fiberoptic Absorption Spectrophotometer

An efficient fiberoptic interface system was developed to convert a Gary 14 H spectrophotometer into a fiberoptic instrument. This new spectrophotometer can be used to study the UV-visible and near-IR absorption spectroscopy of radioactive samples and wastes in a confined environment.     

Double perturbation calculations of spin-spin coupling constants using localized orbitals

The Fermi contact contribution to N.M.R. spin-spin coupling constants has been calculated to the fourth order by a double perturbation development starting from a fully localized determinant, according to the assumptions of the PCILO-CNDO method. The use of diagrammatic techniques greatly simplifies the evaluation. There is a cancellation of certain types of diagram. The coupling constant between bonded atoms appears in the second order through a contribution which only depends on the appropriate bond orbital. The next orders involve the other bonds and correlation effects. For nonbonded atoms, the first contribution appears in the fourth order and results from direct delocalization through space, involving only the bonds on the two atoms.

An analytical and numerical comparison with previous calculations is performed for H-H and C-H coupling constants on small organic molecules. The relative importance of the various processes is discussed for the J _HH vicinal coupling constants of ethylene.     

Absorption Spectrum from Europium Ions in Europium Oxychloride,EuOCl

We have recorded part of the UV-visible region of the electronic spectrum of EuOCl at both 292 and 77 K by diffuse reflectance spectroscopy. Illumination of the sample and collection of the reflected light was accomplished through the use of an all-quartz fiberoptic probe. Several absorption maxima were observed which result from transitions from the ⁷F₀ ground state and ⁷F₁ excited state to the ⁵D₄ ⁵G_2,4,6 ⁵L₆, and ⁵D₃ excited states of the Eu³⁺ ion.     

Texture analysis of magnetic resonance images of rat muscles during atrophy and regeneration

OBJECTIVES: The goals of the current study were (i) to introduce texture analysis on magnetic resonance imaging (MRI-TA) as a noninvasive method of muscle investigation that can discriminate three muscle conditions in rats; these are normal, atrophy and regeneration; and (ii) to show consistency between MRI-TA results and histological results of muscle type 2 fibers' cross-sectional area. METHOD: Twenty-three adult female Wistar rats were randomized into (i) control (C), (ii) immobilized (I) and (iii) recovering (R) groups. For the last two groups, the right hind limb calf muscles were immobilized against the abdomen for 14 days; then, the hind limb was remobilized only for the R group for 40 days. At the end of each experimental period, MRI was performed using 7-T magnet Bruker Avance DRX 300 (Bruker, Wissembourg); T1-weighted MRI acquisition parameters were applied to show predominantly muscle fibers. Rats were sacrificed, and the gastrocnemius muscle (GM) was excised immediately after imaging. (A) Histology: GM type 2 fibers (fast twitch) were selectively stained using the adenosine triphosphatase (ATPase) technique. The mean cross-sectional areas were compared between the three groups. (B) Image analysis: regions of interest (ROIs) were selected on GM MR images where statistical methods of texture analysis were applied followed by linear discriminant analysis (LDA) and classification. RESULTS: Histological analysis showed that the fibers' mean cross-sectional areas on GM transversal sections represented a significant statistical difference between I and C rats (ANOVA, P<.001) as well as between R and I rats (ANOVA, P<.01), but not between C and R rats. Similarly, MRI-TA on GM transversal images detected different texture for each group with the highest discrimination values (Fisher F coefficient) between the C and I groups, as well as between I and R groups. The lowest discrimination values were found between C and R groups. LDA showed three texture classes schematically separated. CONCLUSION: Quantitative results of MRI-TA were statistically consistent with histology. MRI-TA can be considered as a potentially interesting, reproducible and nondestructive method for muscle examination during atrophy and regeneration.