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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
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In this paper we discuss thermodynamics parameters of black hole horizon and cosmological horizon in general high-dimensional space-time. We obtain that the entropy of a cosmological horizon can be described by the Cardy-Verlinde formula. However, the entropy of black hole horizon will be expressed in a form of the Cardy-Verlinde formula, if one adopts the methods given by Abbott and Deser to compute the mass of a black hole in general high-dimensional space-time. Through discussion, relation among various thermodynamics parameters of the black hole in general high-dimensional space-time is given. That is, differential formula of the first law of thermodynamics is obtained. Because we discuss the general high-dimensional space-time, our result has universality.
PACS: 04.20.Dw, 97.60.Lf 相似文献
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以壳聚糖(CS)对SiO2进行表面修饰, 采用浸渍还原法制备了负载型Ni-B非晶态合金催化剂(Ni-B/CS/SiO2), 并采用XRD、FTIR、电感耦合等离子体发射光谱(ICP)、BET、XPS、TEM、SAED等表征方法研究了催化剂的非晶性质、原子组成、尺寸分布及粒径大小等. 考察了催化剂对糠醇加氢制四氢糠醇反应的催化性能, 并与没有壳聚糖修饰的Ni-B/SiO2催化剂及Raney Ni催化剂进行了对比. 结果表明, 加入壳聚糖制得的Ni-B/CS/SiO2催化剂的活性组分Ni-B团簇粒径更小, 表面活性组分浓度更高, 催化活性更高. 相似文献
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A new highly sensitive and selective chromogenic reagent, 2-(2,5-disulfonic-4-methoxyphenylazo)-7-(2-hydroxyl-5-carboxylphenylazo)-1,8-dihydroxynaphthalene-3,6-disulfonic
acid (1), was synthesized and applied to the spectrophotometric determination of trace thorium. In 5 mL of a 6 M perchloric acid
medium, which greatly increases the selectivity, thorium reacts with 1 to form a 1: 2 green complex, having a sensitive absorption peak at 670 nm. Under optimal conditions, Beer’s law is obeyed
over the range from 0 to 0.8 μg/mL Th(IV) and the apparent molar absorptivity is 2.09 × 105 L/mol cm. It is found that, uranium(VI), Ti(IV), heavy rare earths, and most of other common metal ions do not interfere.
The method has been tested on the determination of thorium in food samples with satisfactory results.
The text was submitted by the authors in English. 相似文献
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A new and very sensitive and selective chromogenic reagent, 2-methylthiophenyldiazoaminoa-zobenzene (MTDAA), was synthesized and studied in detail for the determination of trace mercury(II) in water samples. The method is based on the color reaction between MTDAA and mercury(II). It was found that mercury(II) reacts with MTDAA in Na2B4O7-NaOH buffer solution (pH = 10.0) to form 1 : 2 red complexes; these show maximum absorption at 520 nm. Beer’s law is obeyed in 0–15 µg of mercury(II) in 25 mL of solution. The apparent molar absorptivity of the complex is 1.33 × 105 L/(mol cm); its limit of quantification, limit of detection, and relative standard deviation are 0.75 ng/mL, 0.27 ng/mL, and 1.0%, respectively, giving better sensitivity. The influence of the reaction variables and the effect of interfering ions are reported; most of the metal ions in water samples can be tolerated in considerable amounts. Only a few ions can interfere with the determination of trace mercury(II), but these can be eliminated by prior extraction. The proposed method is sensitive, simple, and rapid. It has been applied to the determination of trace mercury(II) in water samples with satisfactory results.__________From Zhurnal Analiticheskoi Khimii, Vol. 60, No. 7, 2005, pp. 703–706.Original English Text Copyright © 2005 by Guo, Din, Tian, Liu, Chang, Meng.The text was submitted by the authors in English. 相似文献
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为了解大同市居民对室内空气质量的认知情况,并分析认知程度与教育的关系,于2016年3月至5月,在大同市城区的9个社区随机对居民进行问卷调查。问卷内容包括居民对室内空气质量安全知识的了解,检测室内空气质量的意愿和治理意愿3个方面。将居民所处地域、居民的年龄与学历对室内空气质量安全认知程度的影响分别进行统计学分析。结果表明,大同市居民室内空气质量安全认知程度总体得分15.8,得分率为52.7%;新城区的居民对室内空气质量安全认知水平高于老城区居民(p<0.05);学历越高且越年轻的居民对室内空气质量安全的认知水平越高,寻求有关机构进行室内空气检测和治理的意愿更强烈,且对检测和治理的费用承受度较高。大同市居民对室内空气质量安全认知程度总体不高,还应加强对市民的室内空气质量安全方面的教育。 相似文献
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