A DFT study on mechanisms of CO2 coupling with propargylic alcohols using alkali carbonates

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.     

Direct visualization of the nanoscopic three‐phase structure and stiffness of NBR/PVC blends by AFM nanomechanical mapping

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     

Determination of sulfa antibiotic residues in river and particulate matter by field-amplified sample injection-capillary zone electrophoresis

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.     

基于声源定位的高校在线巡课系统设计与研究

随着网络建设以及信息化教学方法在高校教学过程中的应用普及,越来越多的高校使用在线巡课系统对教师的教学过程进行跟踪和管理,以便发现课堂教学中的亮点、问题和不足。文章提出的在线巡课系统,基于声源定位的技术,对传统的在线巡课系统做出了改进,解决了已有巡课系统中“只闻其声,不见其人”的问题,能够更直观地跟踪到教师的教学过程,包括教学行为以及师生互动过程,有效提升教务人员巡课效果和体验感受。     

Improved error performance for generalised spatial modulation with enhanced spectral efficiency

The existing analytical average bit error rate (ABER) expression of conventional generalised spatial modulation (CGSM) does not agree well with the Monte Carlo simulation results in the low signal‐to‐noise ratio (SNR) region. Hence, the first contribution of this paper is to derive a new and easy way to evaluate analytical ABER expression that improves the validation of the simulation results at low SNRs. Secondly, a novel system termed CGSM with enhanced spectral efficiency (CGSM‐ESE) is presented. This system is realised by applying a rotation angle to one of the two active transmit antennas. As a result, the overall spectral efficiency is increased by 1 bit/s/Hz when compared with the equivalent CGSM system. In order to validate the simulation results of CGSM‐ESE, the third contribution is to derive an analytical ABER expression. Finally, to improve the ABER performance of CGSM‐ESE, three link adaptation algorithms are developed. By assuming full knowledge of the channel at the receiver, the proposed algorithms select a subset of channel gain vector (CGV) pairs based on the Euclidean distance between all CGV pairs, CGV splitting, CGV amplitudes, or a combination of these.     

基于物联网的智慧林业可持续发展策略研究

随着我国科技的不断进步,在“互联网+”大数据的背景下,林业的智慧化发展是必经之路。虽然我国智慧林业的发展已经取得了一定的突破,但是仍然存在着许多问题。基于此,文章在物联网技术的基础上,对智慧林业的可持续发展策略进行探讨。     

无人机在输电线路巡检中的多种应用

无人机技术目前的快速发展使得我们国家输电线路自身的巡检能力得到了持续的提升,基于此本文在对无人机技术给予认识的情况下,在了解了输电线路巡检过程中的使用优势之后,还总结了无人机技术在当前我国线路巡检过程中的应用路径以及应用方法;之后使用案例分析的方式分析了无人机技术在当前输电线路巡检过程中的应用方法。     

Nanocomposite hydrogel consisting of Na‐montmorillonite with enhanced mechanical properties

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