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11.
Solvent Influence on Cellulose 1,4‐β‐Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynamics Study 下载免费PDF全文
Claudia Loerbroks Eliot Boulanger Prof. Dr. Walter Thiel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5477-5487
We explore the influence of two solvents, namely water and the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EmimAc), on the conformations of two cellulose models (cellobiose and a chain of 40 glucose units) and the solvent impact on glycosidic bond cleavage by acid hydrolysis by using molecular dynamics and metadynamics simulations. We investigate the rotation around the glycosidic bond and ring puckering, as well as the anomeric effect and hydrogen bonds, in order to gauge the effect on the hydrolysis mechanism. We find that EmimAc eases hydrolysis through stronger solvent–cellulose interactions, which break structural and electronic barriers to hydrolysis. Our results indicate that hydrolysis in cellulose chains should start from the ends and not in the centre of the chain, which is less accessible to solvent. 相似文献
12.
Yi Han Zibo Xue Dr. Guangwu Li Dr. Yanwei Gu Dr. Yong Ni Dr. Shaoqiang Dong Prof. Chunyan Chi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9111-9116
Incorporation of a non-hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene-bridged double [6]helicene and heptagon-containing nanographene by the Scholl reaction, an unexpected azulene-embedded nanographene and its triflyloxylated product were obtained, as confirmed by X-ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring-fused substructure containing two formal azulene units is formed, but only one of them shows an azulene-like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2-phenyl migration and a naphthalene to azulene rearrangement reaction according to an in-silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene-based molecular materials. 相似文献
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Hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) have been deemed as clean and sustainable strategies to solve the energy crisis and environmental problems. Various catalysts have been developed to promote the process of HER and OER. Among them, two-dimensional covalent organic frameworks (2D COFs) have received great attention due to their diverse and designable structure. In this minireview, we mainly summarize the diverse linkages of 2D COFs and strategies for enhancing the catalytic performance of 2D COFs for HER and OER, such as introducing active building blocks, metal ions and tailored linkages. Furthermore, a brief outlook for the development directions of COFs in the field of HER and OER is provided, expecting to stimulate new opportunities in future research. 相似文献
15.
Vyacheslav V. Sentyurin Oleg A. Levitskiy Tatiana V. Magdesieva 《Current Opinion in Electrochemistry》2020
This mini-review highlights key structural features that should be taken into account when creating ambipolar redox-active closed-shell metal-free molecules. This type of compound is strongly required for the fabrication of all-organic ‘poleless’ batteries and semiconductors. The suggested strategies aimed at stabilization of both oxidized (cationic) and reduced (anionic) redox-states are based on the comprehensive analysis of the most successful structures taken from the recent publications. 相似文献
16.
Inside Cover: Ru‐Catalysed CH Arylation of Indoles and Pyrroles with Boronic Acids: Scope and Mechanistic Studies (Chem. Eur. J. 14/2015) 下载免费PDF全文
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miRNA (miR)-155 is a potential biomarker for breast cancers. We aimed at developing a nanosensor for miR-155 detection by integrating hybridization chain reaction (HCR) and silver nanoclusters (AgNCs). HCR serves as an enzyme-free and isothermal amplification method, whereas AgNCs provide a built-in fluorogenic detection probe that could simplify the downstream analysis. The two components were integrated by adding a nucleation sequence of AgNCs to the hairpin of HCR. The working principle was based on the influence of microenvironment towards the hosted AgNCs, whereby unfolding of hairpin upon HCR has manipulated the distance between the hosted AgNCs and cytosine-rich toehold region of hairpin. As such, the dominant emission of AgNCs changed from red to yellow in the absence and presence of miR-155, enabling a ratiometric measurement of miR with high sensitivity. The limit of detection (LOD) of our HCR-AgNCs nanosensor is 1.13 fM in buffered solution. We have also tested the assay in diluted serum samples, with comparable LOD of 1.58 fM obtained. This shows the great promise of our HCR-AgNCs nanosensor for clinical application. 相似文献
19.
A self-propelled object coupled with an enzyme reaction between urease and urea was investigated at the air/aqueous interface. A plastic object that was fixed to a urease-immobilized filter paper was used as a self-propelled object, termed a urease motor, placed on an aqueous urea solution. The driving force of the urease motor is the difference in the surface tension around the object. Oscillatory motion or no motion was triggered depending on the initial pH of the urea solution. Both the frequency and maximum speed of the oscillatory motion varied depending on the initial pH of the water phase. The mechanisms underlying the oscillatory motion and no motion were discussed in relation to the bell-shaped enzyme activity of urease in the enzyme reaction and the surface tension around the urease motor. 相似文献
20.
Marius Lupu Adnana Zaulet Prof. Dr. Francesc Teixidor Prof. Dr. Eliseo Ruiz Prof. Dr. Clara Viñas 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(18):6888-6897
The metallacarborane [3,3′‐Co(1,2‐closo‐C2B9H11)2]? has been synthesized. This species allows the formation of redox couples in which both partners are negatively charged. The E1/2 potential can be tuned by adjusting the nature and number of substituents on B and C. The octaiodinated species [3,3′‐Co(1,2‐closo‐C2B9H7I4)2]? is the most favorable, as it is isolatable and stable in air. A DFT study on stability and redox potentials of complexes has been performed. 相似文献