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排序方式: 共有1502条查询结果,搜索用时 15 毫秒
1.
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
2.
Lubomír Havlk Jan Fbry Margarida Henriques Michal Duek 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(7):623-630
The title structures of KScS2 (potassium scandium sulfide), RbScS2 (rubidium scandium sulfide) and KLnS2 [Ln = Nd (potassium neodymium sufide), Sm (potassium samarium sulfide), Tb (potassium terbium sulfide), Dy (potassium dysprosium sulfide), Ho (potassium holmium sulfide), Er (potassium erbium sulfide), Tm (potassium thulium sulfide) and Yb (potassium ytterbium sulfide)] are either newly determined (KScS2, RbScS2 and KTbS2) or redetermined. All of them belong to the α‐NaFeO2 structure type in agreement with the ratio of the ionic radii r3+/r+. KScS2, the member of this structural family with the smallest trivalent cation, is an extreme representative of these structures with rare earth trivalent cations. The title structures are compared with isostructural alkali rare earth sulfides in plots showing the dependence of several relevant parameters on the trivalent cation crystal radius; the parameters thus compared are c, a and c/a, the thicknesses of the S—S layers which contain the respective constituent cations, the sulfur fractional coordinates z(S2−) and the bond‐valence sums. 相似文献
3.
This study compares the physicochemical properties of six electrolytes comprising of three salts: LiFTFSI, NaFTFSI and KFTFSI in two solvent mixtures, the binary (3EC/7EMC) and the ternary (EC/PC/3DMC). The transport properties (conductivity, viscosity) as a function of temperature and concentration were modeled using the extended Jones-Dole-Kaminsky equation, the Arrhenius model, and the Eyring theory of transition state for activated complexes. Results are discussed in terms of ionicity, solvation shell, and cross-interactions between electrolyte components. The application of the six formulated electrolytes in symmetrical activated carbon (AC)//AC supercapacitors (SCs) was characterized by cyclic voltammetry (CV), galvanostatic cycling with potential limitation (GCPL), electrochemical impedance spectroscopy (EIS) and accelerated aging. Results revealed that the geometrical flexibility of the FTFSI anion allows it to access and diffuse easily in AC whereas its counter ions (Li+, Na+ or K+) can remain trapped in porosity. However, this drawback was partially resolved by mixing LiFTFSI and KFTFSI salts in the electrolyte. 相似文献
4.
XU Jun YAN Ai-Zhen XU Qin-Hua Department of Chemistry Nanjing University Nanjing Jiangsu China 《中国化学》1995,(2)
The strength of basic sites has been measured by pyrrole-IR on alkali metal cation exchanged β and X zeolites, as well as NaOH loaded Naβ. The influence of cation type and the structure of zeolites on their basicity has been studied. The acidic and basic properties of the samples were investigated by NH3-TPD and isopropanol reaction. It was shown that the strength of basic sites on samples could be characterized by the shift of vNH band in the pyrrole-IR spectra. The framework oxygen charges were calculated from the Sanderson electronegativity. The changes in basic properties with various alkali metal cation are consistent with the changes of local oxygen charges of the zeolite framework. 相似文献
5.
Danny E. Akin W. Herbert Morrison III Luanne L. Rigsby Franklin E. Barton II David S. Himmelsbach Kevin B. Hicks 《Applied biochemistry and biotechnology》2006,129(1-3):104-116
Information is presented on structure, composition, and response to enzymes of corn stover related to barriers for bioconversion
to ethanol. Aromatic compounds occurred in most tissue cell walls. Ferulic acid esterase treatment before cellulase treatment
significantly improved dry weight loss and release of phenolic acids and sugars in most fractions over cellulase alone. Leaf
fractions were considerably higher in dry weight loss and released sugars with esterase treatment, but stem pith cells gave
up the most phenolic acids. Results help identify plant fractions more appropriate for coproducts and bioconversion and those
more suitable as residues for soil erosion control. 相似文献
6.
The present paper reports the dislocation unpinning model of acoustic emission (AE) from alkali halide crystals. Equations
are derived for the strain dependence of the transient AE pulse rate, peak value of the AE pulse rate and the total number
of AE pulse emitted. It is found that the AE pulse rate should be maximum for a particular strain of the crystals. The peak
value of the AE pulse rate should depend on the volume and strain rate of the crystals, and also on the pinning time of dislocations.
Since the pinning time of dislocations decreases with increasing strain rate, the AE pulse rate should be weakly dependent
on the strain rate of the crystals. The total number of AE should increase linearly with deformation and then it should attain
a saturation value for the large deformation. By measuring the strain dependence of the AE pulse rate at a fixed strain rate,
the time constantτ
s for surface annihilation of dislocations and the pinning timeτ
p of the dislocations can be determined. A good agreement is found between the theoretical and experimental results related
to the AE from alkali halide crystals. 相似文献
7.
Leda M. F. Gottschalk Ronaldo Nobrega Elba P. S. Bon 《Applied biochemistry and biotechnology》2003,108(1-3):799-807
The effect of aeration on lignin peroxidase production by Streptomyces viridosporus T7A was studied in a bench-scale bioreactor using a previously optimized growth medium (0.65% yeast extract and 0.1% corn
oil, pH7.0) at 37°C and natural pH. Airflow rates of 0.3, 1.0, and 1.5 vvm and a fixed agitation of 200 rpm were initially
studied followed by 1.0 vvm and 200, 300, 400, and 500 rpm. The use of 1.0 vvm and 400 rpm increased enzyme concentration
1.8-fold (100–180 U/L) and process productivity 4.8-fold (1.4–6.7 U/[L·h]) in comparison with the use of 200 rpm and 0.3 vvm.
The inexpensive corn oil, used as carbon source, besides its antifoam properties, proved to be nonrepressive for enzyme production. 相似文献
8.
Catalytic nitrobenzene oxidation of lignins 总被引:1,自引:0,他引:1
A. F. Gogotov N. A. Rybal'chenko T. I. Makovskaya V. A. Babkin 《Russian Chemical Bulletin》1996,45(12):2854-2857
Alkaline nitrobenzene oxidation of hardwood and softwood lignins in the presence of redox and phase-transfer catalysts was studied. The selectivity of oxidation of lignins increased by 1.7 to 1.9 times. A possible mechanism of catalysis is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 3004–3007, December, 1996. 相似文献
9.
Chiral α,ω-diesters react under high-pressure conditions (10 kbar) with α,ω-diamines to give chiral cyclic tetraamides of C2-symmetry. The complexation properties of tetraamides towards alkali metal cations (Li+, Na+, K+, Rb+ and Cs+) were estimated on the basis of ESI-MS spectra. 相似文献
10.
Alessandro D' Aprano Dorina Ines Donato Antonio Carrubba Doctor in Chemistry thesis of A. Carrubba 《Journal of solution chemistry》1983,12(3):209-220
Conductance measurements are reported for LiPi, NaPi, KPi, RbPi, CsPi, Bu4NPi, Bu4NBr, Bu4NClO4, Bu4NNO3, and Bu4NBBu4 at 25°C in -butyrolactone-sulfolane mixtures. In these mixtures of solvents that are practically homomorphous, isodielectic and with comparable dipole moments, the ion pair association and ionic mobilities of large ions conform to the expectations of the primitive model. Electrolytes containing lithium or sodium ions show anomalies indicating that other factors besides shape, dipole moment, and polarizability of the solvent molecules are involved in the association and transport processes of these ions. 相似文献