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41.
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
42.
Pengjin Qin Li-An Wang Prof. Joseph M. O'Connor Prof. Kim K. Baldridge Yifan Li Burak Tufekci Jiyue Chen Prof. Arnold L. Rheingold 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18114-18121
Triene 6π electrocyclization, wherein a conjugated triene undergoes a concerted stereospecific cycloisomerization to a cyclohexadiene, is a reaction of great historical and practical significance. In order to circumvent limitations imposed by the normally harsh reaction conditions, chemists have long sought to develop catalytic variants based upon the activating power of metal–alkene coordination. Herein, we demonstrate the first successful implementation of such a strategy by utilizing [(C5H5)Ru(NCMe)3]PF6 as a precatalyst for the disrotatory 6π electrocyclization of highly substituted trienes that are resistant to thermal cyclization. Mechanistic and computational studies implicate hexahapto transition-metal coordination as responsible for lowering the energetic barrier to ring closure. This work establishes a foundation for the development of new catalysts for stereoselective electrocyclizations. 相似文献
43.
Dr. Yong-Sheng Wei Dr. Liming Sun Miao Wang Dr. Jinhua Hong Dr. Lianli Zou Hongwen Liu Dr. Yu Wang Dr. Mei Zhang Dr. Zheng Liu Prof. Yinwei Li Prof. Satoshi Horike Prof. Kazu Suenaga Prof. Qiang Xu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16147-16156
Understanding the thermal aggregation behavior of metal atoms is important for the synthesis of supported metal clusters. Here, derived from a metal–organic framework encapsulating a trinuclear FeIII2FeII complex (denoted as Fe3) within the channels, a well-defined nitrogen-doped carbon layer is fabricated as an ideal support for stabilizing the generated iron nanoclusters. Atomic replacement of FeII by other metal(II) ions (e.g., ZnII/CoII) via synthesizing isostructural trinuclear-complex precursors (Fe2Zn/Fe2Co), namely the “heteroatom modulator approach”, is inhibiting the aggregation of Fe atoms toward nanoclusters with formation of a stable iron dimer in an optimal metal–nitrogen moiety, clearly identified by direct transmission electron microscopy and X-ray absorption fine structure analysis. The supported iron dimer, serving as cooperative metal–metal site, acts as efficient oxygen evolution catalyst. Our findings offer an atomic insight to guide the future design of ultrasmall metal clusters bearing outstanding catalytic capabilities. 相似文献
44.
Weiyi Li Geng Leng Caiqin Li Yajing Lyu 《International journal of quantum chemistry》2020,120(8):e26150
The mechanisms of CO2 coupling with the propargylic alcohol using alkali carbonates M2CO3 (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs2CO3-mediated carboxylative cyclization of the propargylic alcohol with CO2, and (b) the conversion of the αACC intermediate with Cs2CO3 to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO3 together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO2 with the propargylic alcohol. Compared to other alkali carbonates M2CO3 (M = Li, Na, K), the stronger basicity of Cs2CO3 and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield. 相似文献
45.
Wenpin Wang Qing Yao Jianhui Song Binbin Yao Hui Wang Zhibo Li 《Journal of Polymer Science.Polymer Physics》2019,57(11):662-669
The PeakForce Quantitative Nanomechanical Mapping based on atomic force microscope (AFM) is employed to first visualize and then quantify the elastic properties of a model nitrile rubber/poly(vinyl chloride) (NBR/PVC) blend at the nanoscale. This method allows us to consistently observe the changes in mechanical properties of each phase in polymer blends. Beyond measuring and discriminating elastic modulus and adhesion forces of each phase, we tune the AFM tips and the peak force parameters in order to reliably image samples. In view of viscoelastic difference in each phase, a three‐phase coexistence of an unmixed NBR phase, the mixed phase, and PVC microcrystallites is directly visualized in NBR/PVC blends. The nanomechanical investigation is also capable of recognizing the crosslinked rubber phase in cured rubber. The contribution of the mixed phase was quantified and it was found that the mechanical properties of blends are mainly determined by the homogeneity and stiffness of the mixed phase. This study furthers our understanding the structure–mechanical property relationship of thermoplastic elastomers, which is important for their potential design and applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 662–669 相似文献
46.
使用实验轧机旁冷却装置配合轧机进行轧制实验,研究轧制道次间不同冷却工艺对特厚钢板组织和性能的影响规律.研究结果表明:采用道次间冷却工艺可以在全厚度方向获得组织细化及强韧性提高效果,采用强冷道次间冷却实验钢1/4处晶粒尺寸可细化至10μm,强度为376MPa,-40℃冲击功为169J;心部晶粒尺寸可细化至15μm,强度为360MPa,-40℃冲击功为123J.本工艺可形成470μm厚表层细晶层,晶粒尺寸可细化至5μm;粗轧道次间插入冷却工艺轧制钢板强度和冲击韧性优于中间坯冷却工艺;随冷却强度增加,钢板内部组织明显细化且强度大幅提高. 相似文献
47.
Xinghua Li Yuqin Yang Junjie Miao Zhendong Yin Yijing Zhai Hongmei Shi Zengning Li 《Electrophoresis》2020,41(18-19):1584-1591
In the present research, field-amplified sample injection–CZE (FASI–CZE) coupled with a diode array detector was established to determine trace level sulfa antibiotic. Sulfathiazole, sulfadiazine, sulfamethazine, sulfadimethoxine, sulfamethoxazole, and sulfisoxazole were selected as analytes for the experiments. The background electrolyte solution consisted of 70.0 mmol/L borax and 60.0 mmol/L boric acid (including 10% methanol, pH 9.1). The plug was 2.5 mmol/L borax, which was injected into the capillary at a pressure of 0.5 psi for 5 s. Then the sample was injected into the capillary at an injection voltage of –10 kV for 20 s. The electrophoretic separation was carried out under a voltage of +19 kV. The capillary temperature was maintained at 20˚C throughout the analysis, and six sulfonamides were completely separated within 35 min. Compared with pressure injection-CZE, the sensitivity of FASI-CZE was increased by 6.25–10.0 times, and the LODs were reduced from 0.2–0.5 to 0.02–0.05 μg/mL. The method was applied to the determination of sulfonamides in river water and particulate matter samples. The recoveries were 78.59–106.59%. The intraday and interday precisions were 2.89–7.35% and 2.77–7.09%, respectively. This provides a simpler and faster method for the analysis of sulfa antibiotic residues in environmental samples. 相似文献
48.
49.
微生物共生普遍存在于自然界中,真菌-细菌联合体能以多种方式相互作用,共同发挥各种生态功能。有些细菌驻留在真菌菌丝内部,借以调控真菌的生长、发育、分布和次级代谢过程,这些细菌被称为菌丝内生细菌(endohyphal bacteria, EHB)。EHB的研究揭开了微生物生态学的一个新篇章,是真菌与细菌共生关系中最紧密的代表。在逆境条件下,EHB可以调节寄主生殖机制相关的关键成分或步骤,诱导植物激素类物质的产生,对寄主真菌具有辅助性保护作用。研究最深入的真菌-EHB共生体系是植物致病性根霉菌Rhizopus sp.与伯克霍尔德氏菌Burkholderia sp.,引起水稻幼苗枯萎病所必需的植物毒素——根霉素是由伯克霍尔德氏菌所产生的,而非寄主根霉菌本身产生的。EHB也会影响定殖于高等植物的内生真菌的生态和多样性。在某些情况下,EHB还有助于激活参与识别、转录调节和初级代谢蛋白合成过程的相关基因。目前已开发出了无菌培养分离EHB的方法,然而对真菌-EHB共生体系的研究尚不够深入。综述了菌丝内生细菌EHB及其与宿主真菌的共生体系,阐述这些伴侣之间复杂微妙的相互关系,以及EHB对宿主真菌和宿主植物生长和发育的影响,并对该领域的研究方向提出了建议。 相似文献
50.
Nanocomposite hydrogel consisting of Na‐montmorillonite with enhanced mechanical properties 下载免费PDF全文
Ting Li Shuangfei Xiang Piming Ma Huiyu Bai Weifu Dong Mingqing Chen 《Journal of Polymer Science.Polymer Physics》2015,53(14):1020-1026
A new kind of nanocomposite (NC) hydrogel with Na‐montmorillonite (MMT) is presented in this article. The NC hydrogels were synthesized by free radical copolymerization of acrylamide and (3‐acrylamidopropyl) trimethylammonium chloride (ATC) in the presence of MMT and N,N′‐methylene‐bis‐acrylamide used as chemical cross‐linker. Due to the cation‐exchange reaction between MMT and ATC (cationic monomer) during the synthesis of NC hydrogels, MMT platelets were considered chemical “plane” cross‐linkers, different from “point” cross‐linkers. With increasing amount of MMT, the crosslinking degree enhanced, causing a decrease of the swelling degree at equilibrium. Investigations of mechanical properties indicated that NC hydrogels exhibited enhanced strength and toughness, which resulted from chemical interaction between exfoliated MMT platelets and polymer chains in hydrogels. Dynamic shear measurements showed that both storage modulus and loss modulus increased with increasing MMT content. The idea described here provided a new route to prepare hydrogels with high mechanical properties by using alternative natural Na‐MMT. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1020–1026 相似文献