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1.
《Mendeleev Communications》2022,32(6):777-779
The reactions of aryllithium reagents o-LiC6H4CH2NR2 with (MeO)2CO afford two new tris(aryl)carbinols bearing pendant-NR2 donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C6H4CH2NMe2)3CO]Sc(CH2SiMe3)2 featuring rigid binding of the alkoxy anion through a κ1-O, κ2-N chelating coordination mode 相似文献
2.
《Mendeleev Communications》2022,32(4):534-536
Correlation times and diffusion coefficients of water molecules were measured for the first time by 1H spin relaxation and pulsed field gradient NMR in Li+, Na+ and Cs+ ionic forms of Nafion 117 membrane. Hydration numbers of Li+, Na+ and Cs+ cations were calculated. It was shown that at high humidity macroscopic transfer is controlled by the local translational motion of water molecules. 相似文献
3.
Jiraya Kiriratnikom Xun Zhang Xiaohan Cao Bo Chu Chengjian Zhang Xinghong Zhang 《Journal of polymer science. Part A, Polymer chemistry》2022,60(15):2262-2268
Facile construction of sulfur-rich polymers using readily available raw chemicals is an area aggressively pursued but challenging. Herein we use common feedstocks of ethylene oxide (EO), propylene oxide (PO), and carbonyl sulfide (COS) to synthesize copoly(thioether)s which are traditionally produced from unpleasant and difficult to store episulfides. In this protocol, the EO/COS coupling selectively generates a pure poly(ethylene sulfide) (PES) with melting temperature (Tm) values up to 172°C and high yields up to 98%. The EO/PO/COS terpolymerization leads to the incorporation of soft poly(propylene sulfide) (PPS) and hard PES segments together, affording a random PES-co-PPS copoly(thioether) with the complete consumption of EO and PO. Additionally, by simply varying the EO/PO feeding ratio, the obtained copoly(thioether)s possess tunable thermal properties, Tm values in the range of 76–144°C, and excellent solubility. These copolymerizations are conducted in one-pot/one-step at industrially favored reaction temperatures of 100–120°C using catalysts of common organic bases, suggesting a facile and practical manner. Especially, the copoly(thioether) exhibits high refractive indices up to 1.68 owing to its high sulfur content, suggesting a broad application prospect in optical materials. 相似文献
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Chemical bonding in representative astrophysically relevant neutral,cation, and anion HCnH chains 下载免费PDF全文
Ioan Baldea 《中国物理 B》2022,31(12):123101-123101
Most existing studies assign a polyynic and cumulenic character of chemical bonding in carbon-based chains relying on values of the bond lengths. Building on our recent work, in this paper we add further evidence on the limitations of such an analysis and demonstrate the significant insight gained via natural bond analysis. Presently reported results include atomic charges, natural bond order and valence indices obtained from ab initio computations for representative members of the astrophysically relevant neutral and charged HC2k/2k+1H chain family. They unravel a series of counter-intuitive aspects and/or help naive intuition in properly understanding microscopic processes, e.g., electron removal from or electron attachment to a neutral chain. Demonstrating that the Wiberg indices adequately quantify the chemical bonding structure of the HC2k/2k+1H chains—while the often heavily advertised Mayer indices do not—represents an important message conveyed by the present study. 相似文献
6.
Dr. Joaquim Torra Dr. Felipe Viela Dr. Diego Megías Dr. Begoña Sot Prof. Cristina Flors 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(19):e202200026
CRANAD-2 is a fluorogenic curcumin derivative used for near-infrared detection and imaging in vivo of amyloid aggregates, which are involved in neurodegenerative diseases. We explore the performance of CRANAD-2 in two super-resolution imaging techniques, namely stimulated emission depletion (STED) and single-molecule localization microscopy (SMLM), with markedly different fluorophore requirements. By conveniently adapting the concentration of CRANAD-2, which transiently binds to amyloid fibrils, we show that it performs well in both techniques, achieving a resolution in the range of 45–55 nm. Correlation of SMLM with atomic force microscopy (AFM) validates the resolution of fine features in the reconstructed super-resolved image. The good performance and versatility of CRANAD-2 provides a powerful tool for near-infrared nanoscopic imaging of amyloids in vitro and in vivo. 相似文献
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8.
Dr. Chenge Li Dr. Alison G. Tebo Marion Thauvin Marie-Aude Plamont Prof. Dr. Michel Volovitch Dr. Xavier Morin Prof. Dr. Sophie Vriz Prof. Dr. Arnaud Gautier 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18073-18079
Far-red emitting fluorescent labels are highly desirable for spectral multiplexing and deep tissue imaging. Here, we describe the generation of frFAST (far-red Fluorescence Activating and absorption Shifting Tag), a 14-kDa monomeric protein that forms a bright far-red fluorescent assembly with (4-hydroxy-3-methoxy-phenyl)allylidene rhodanine (HPAR-3OM). As HPAR-3OM is essentially non-fluorescent in solution and in cells, frFAST can be imaged with high contrast in presence of free HPAR-3OM, which allowed the rapid and efficient imaging of frFAST fusions in live cells, zebrafish embryo/larvae, and chicken embryos. Beyond enabling the genetic encoding of far-red fluorescence, frFAST allowed the design of a far-red chemogenetic reporter of protein–protein interactions, demonstrating its great potential for the design of innovative far-red emitting biosensors. 相似文献
9.
In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance. 相似文献
10.
研究桉树控制授粉后目标性状的基因作用方式是探索其基因重组规律的重要内容。常规的数量统计分析精度往往不高,而DNA分析的专业要求高,且费时费力。该研究利用近红外光谱(NIRs)研究不同基因型桉树杂交种、亲本及杂交种与亲本间近红外光谱信息的关系,探索NIRs用于桉树杂交种与其亲本判别的可行性和准确性。以控制授粉的桉树亲本及其杂交F1代材料为对象,每种基因型从各自田间试验分别选取10个单株,采集树冠中上部新鲜健康叶片。用手持式近红外仪Phazir Rx(1624)采集桉树杂交种与其亲本叶片的NIRs信息。每单株选10片完全生理成熟的健康叶片,避开叶脉扫描其正面光谱5次,以50条NIRs信息的均值代表单个叶片的NIRs信息,最终每个基因型获得10条NIRs信息。对原始NIRs采用二阶多项式S.G一阶导数预处理。预处理后的NIRs用于多元统计分析,首先对桉树杂交亲本和子代样本进行主成分分析(PCA),直观展示不同基因型的分类情况。然后运用簇类独立软模式(SIMCA)和偏最小二乘判别分析(PLS-DA)两种有监督的判别模式验证NIRs用于桉树杂交种与其亲本树种的分类判别效果。PCA结果显示,不同的亲本间、杂交种间及杂交种与亲本间样本的主因子得分可以清晰地将各基因型分开。SIMCA模式判别分析中,桉树杂交种样本到亲本PCA模型的样本距离显示,待判别样本能够形成单独的聚类,且能直观反映两者的遗传相似。PLS-DA判别结果显示,桉树杂交亲本的PLS模型能通过预测其杂交子代的响应变量将其与亲本准确分开。结果表明,桉树叶片的NIRs信息可以准确地反映桉树杂交子代遗传信息的传递规律,NIRs判别模型可以准确地将各种基因型予以区分。因此,NIRs信息不仅可用于桉树杂交种和纯种的定性判别,还可以分析桉树基因重组过程中加性遗传效应的大小,从而为桉树遗传基础分析及其育种改良研究提供理论支撑。 相似文献