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951.
Selective Synthesis of 2,5‐Diformylfuran by Sustainable 4‐acetamido‐TEMPO/Halogen‐Mediated Electrooxidation of 5‐Hydroxymethylfurfural 下载免费PDF全文
Dr. Vera P. Kashparova Dr. Victor A. Klushin Dr. Daria V. Leontyeva Prof. Dr. Nina V. Smirnova Prof. Dr. Victor M. Chernyshev Prof. Dr. Valentine P. Ananikov 《化学:亚洲杂志》2016,11(18):2578-2585
A new method was developed for the selective gram‐scale synthesis of 2,5‐diformylfuran (DFF), which is an important chemical with a high application potential, via oxidation of biomass‐derived 5‐hydroxylmethylfurfural (HMF) catalyzed by 4‐acetylamino‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl (4‐AcNH‐TEMPO) in a two‐phase system consisting of a methylene chloride and aqueous solution containing sodium hydrogen carbonate and potassium iodide. The key feature of this method is the generation of the I2 (co‐)oxidant by anodic oxidation of iodide anions during pulse electrolysis. In addition, the electrolyte can be successfully recycled five times while maintaining a 62–65 % yield of DFF. This novel method provides a sustainable pathway for waste‐free production of DFF without the use of metal catalysts and expensive oxidants. An advantage of electrooxidation is utilized in the preparation of demanding chemical. 相似文献
952.
Jianxin Chen Dr. Chunyang Yu Dr. Zengqian Shi Songrui Yu Prof. Zhongyuan Lu Wengfeng Jiang Meng Zhang Prof. Wei He Prof. Yongfeng Zhou Prof. Deyue Yan 《Angewandte Chemie (International ed. in English)》2015,54(12):3621-3625
Well‐defined ultrathin nanotubes (30 nm in diameter and of micrometer‐scale length) were generated through the self‐assembly of a novel alternative copolymer synthesized using an epoxy–thiol click‐chemistry reaction. The self‐assembly mechanism was investigated both by experiments and using dissipative particle dynamics (DPD) simulations. The obtained nanotubes can be readily functionalized with carboxy groups, amino groups, peptides, or other groups by simple modular click copolymerization. 相似文献
953.
954.
Solventless Formation of G‐Quartet Complexes Based on Alkali and Alkaline Earth Salts on Au(111) 下载免费PDF全文
Chi Zhang Likun Wang Lei Xie Huihui Kong Prof. Dr. Qinggang Tan Liangliang Cai Qiang Sun Prof. Dr. Wei Xu 《Chemphyschem》2015,16(10):2099-2105
Template cations have been extensively employed in the formation, stabilization and regulation of structural polymorphism of G‐quadruplex structures in vitro. However, the direct addition of salts onto solid surfaces, especially under ultra‐high‐vacuum (UHV) conditions, to explore the feasibility and universality of the formation of G‐quartet complexes in a solventless environment has not been reported. By combining UHV‐STM imaging and DFT calculations, we have shown that three different G‐quartet‐M (M: Na/K/Ca) complexes can be obtained on Au(111) using alkali and alkaline earth salts as reactants. We have also identified the driving forces (intra‐quartet hydrogen bonding and electrostatic ionic bonding) for the formation of these complexes and quantified the interactions involved. Our results demonstrate a novel route to fabricate G‐quartet‐related complexes on solid surfaces, providing an alternative feasible way to bring metal elements to surfaces for constructing metal–organic systems. 相似文献
955.
In this study, a series of tetrafluoroborates with non-π-conjugated [BF4] tetrahedra are investigated systematically by first-principles calculations. Theoretical studies demonstrate that tetrafluoroborates with alkali and/or alkaline-earth metals are more favorable for deep-ultraviolet transmission and are comparable to the classical deep-ultraviolet (deep-UV) material, MgF2. Furthermore, bandgap decrease with the increasing of ionic radii in alkali and/or alkaline-earth metals. Introducing highly polarizable cations with d10-configuration or cations with lone pair electrons into the structure will decrease the bandgaps. The birefringence and second harmonic generation effects are not large enough in tetrafluoroborates because polarizability anisotropy and hyperpolarizability in non-π-conjugated [BF4] tetrahedra are much smaller than those in π-conjugated groups. However, the second harmonic generation effect for [BF4] tetrahedra has a higher contribution in comparison with that due to birefringence. To effectively synthesize the borate fluorides or fluorooxoborates in the deep-UV region, raw materials with B−F bonds are preferred. 相似文献
956.
We study 2×2 systems of hyperbolic conservation laws near an umbilic point. These systems have Undercompressive shock wave solutions, i.e., solutions whose viscous profiles are represented by saddle connections in an associated family of planar vector fields. Previous studies near umbilic points have assumed that the flux function is a quadratic polynomial, in which case saddle connections lie on invariant lines. We drop this assumption and study saddle connections using Golubitsky-Schaeffer equilibrium bifurcation theory and the Melnikov integral, which detects the breaking of heteroclinic orbits. The resulting information is used to construct solutions of Riemann problems. 相似文献
957.
958.
Michael E. Cates tienne Fodor Tomer Markovich Cesare Nardini Elsen Tjhung 《Entropy (Basel, Switzerland)》2022,24(2)
Many complex fluids can be described by continuum hydrodynamic field equations, to which noise must be added in order to capture thermal fluctuations. In almost all cases, the resulting coarse-grained stochastic partial differential equations carry a short-scale cutoff, which is also reflected in numerical discretisation schemes. We draw together our recent findings concerning the construction of such schemes and the interpretation of their continuum limits, focusing, for simplicity, on models with a purely diffusive scalar field, such as ‘Model B’ which describes phase separation in binary fluid mixtures. We address the requirement that the steady-state entropy production rate (EPR) must vanish for any stochastic hydrodynamic model in a thermal equilibrium. Only if this is achieved can the given discretisation scheme be relied upon to correctly calculate the nonvanishing EPR for ‘active field theories’ in which new terms are deliberately added to the fluctuating hydrodynamic equations that break detailed balance. To compute the correct probabilities of forward and time-reversed paths (whose ratio determines the EPR), we must make a careful treatment of so-called ‘spurious drift’ and other closely related terms that depend on the discretisation scheme. We show that such subtleties can arise not only in the temporal discretisation (as is well documented for stochastic ODEs with multiplicative noise) but also from spatial discretisation, even when noise is additive, as most active field theories assume. We then review how such noise can become multiplicative via off-diagonal couplings to additional fields that thermodynamically encode the underlying chemical processes responsible for activity. In this case, the spurious drift terms need careful accounting, not just to evaluate correctly the EPR but also to numerically implement the Langevin dynamics itself. 相似文献
959.
The scattering of X-rays in quartz monocrystals has been investigated. It has been discovered experimentally, that even for the thick quartz crystals, for which μt = 5, pendular bands can be obtained. The appearance of pendular bands depending on the crystal thickness, the reflecting plane families and the reflection order, was investigated as well. 相似文献
960.