Determination of Polybrominated Diphenyl Ethers in Coastal and River Sediments by Pressurized Liquid Extraction Coupled with Gas Chromatography‐Mass Spectrometry

This study presents a time‐ and solvent‐saving method, pressurized liquid extraction (PLE), to extract polybrominated diphenyl ethers (PBDEs) in sediment samples. The effects of various operating parameters (i.e., extraction solution, temperature, pressure, static/dynamic extraction times) for the quantitative extraction of PBDEs by home‐made PLE were systematically investigated and optimized. The analytes were then identified and quantitated by gas chromatography‐mass spectrometry (GC‐MS) in selected ion monitoring (SIM) mode. The 16 PBDE congeners (from tri‐ to deca‐BDE) can be completely extracted by dichloromethane: n‐hexane (3/2, v/v) at 100 °C and 100 atm combined with 15 min static and then 15 min dynamic extraction steps. Recovery of PBDEs in spiked sediment samples ranged from 52 to 104% with 2‐16% RSD, except for BDE‐206. Limits of quantitation (LOQ) were established between 4 and 400 pg/g (dry weight) in 10 g of sediment sample. The extraction efficiency of the PLE was also compared with the traditional Soxhlet extraction method. The total contents of PBDEs ranged from 8.0 to 37.9 ng/g (dry weight) in various river and coastal sediment samples in Taiwan. Deca‐BDE (BDE‐209) was the major PBDE detected in these sediment samples.     

High-performance Flexible Symmetric Supercapacitor Based on Heterostructured PANI@MoS2 Nanocomposite Electrode

Three-dimensional (3D) heterostructured molybdenum disulfide (MoS₂) is used as base materials for aniline monomer in situ polymerization on its surface. It is found that the aniline addition has a remarkable effect on the energy storage of the final compounds due to the improvement of the conductivity and structure stability combined with the synergistic effect between the two types of species. The optimal compound of PANI@MoS₂-150 not only shows a high capacitance value of 801.4 F ⋅ g⁻¹ at a current density of 0.5 A ⋅ g⁻¹ but also provides a high retention rate of 77.4 % after 10,000 cycles. The capacitance fading may be due to the increase of the internal resistance analyzed by EIS. Furthermore, a flexible symmetric supercapacitor based on PANI@MoS₂-150 has also been fabricated and the specific capacitance reaches 105 F ⋅ g⁻¹ at a current density of 1 A ⋅ g⁻¹. Impressively, the capacitance retention is larger than 100 % undergoing 10,000 cycles. Besides, the highest energy density of 21 Wh ⋅ kg⁻¹ was obtained. Additionally, the fabricated symmetric supercapacitor demonstrates excellent flexibility.     

Different experimental results for the influence of immersion angle on the resonant frequency of a quartz crystal microbalance in a liquid phase: with a comment

This paper presents different experimental results of the influence of an immersion angle (θ, the angle between the surface of a quartz crystal resonator and the horizon) on the resonant frequency of a quartz crystal microbalance (QCM) sensor exposed one side of its sensing surfaces to liquid. The experimental results show that the immersion angle is an added factor that may influence the frequency of the QCM sensor. This type of influence is caused by variation of the reflection conditions of the longitudinal wave between the QCM sensor and the walls of the detection cell. The frequency shifts, measured by varying θ, are related to the QCM sensor used. When a QCM sensor with a weak longitudinal wave is used, its resonant frequency is nearly independent of θ. But, if a QCM sensor with a strong longitudinal wave is employed, the immersion angle is a potential error source for the measurements performed on the QCM sensor. When the reflection conditions of the longitudinal wave are reduced, the influence of θ on the resonant frequency of the QCM sensor is negligible. The slope of the plot of frequency shifts (ΔF) versus (ρη)^1/2, the square root of the product of solution density (ρ) and viscosity (η), may be influenced by θ in a single experiment for the QCM sensor with a strong longitudinal wave in low viscous liquids, which can however, be effectively weakened by using the averaged values of reduplicated experiments. In solutions with a large (ρη)^1/2 region (0-55 wt% sucrose solution as an example, with ρ value from 1.00 to 1.26 g cm⁻³ and η value from 0.01 to 0.22 g cm⁻¹ s⁻¹, respectively), the slope of the plot of ΔF versus (ρη)^1/2 is independent of θ even for the QCM sensor with a strong longitudinal wave in a single experiment. The influence of θ on the resonant frequency of the QCM sensor should be taken into consideration in its applications in liquid phase.     

运用分子模拟计算和NMR研究确定化合物3-(3,5-二甲基-2-吡咯亚甲基)-5-溴-吲哚酮的绝对构型

用MM2和半经验AM1方法对化合物进行计算,获得化合物两种构型的原子间距离参数,依据¹H NMR产生NOE效应所需条件预报分子中可能存在的NOE.通过与实验测得的核磁共振NOE效应结果对比,确定化合物构型.     

Sm(CobalFexCu0.049Zr0.024)7.5(x=0.102～0.282)的结构和磁性能

采用XRD,AFM等检测方法研究了Fe含量对Sm（CobalFexCu0.049Zr0.024）7.5（x=0.102-0.282）的磁性能和显微结构的影响。结果表明,磁体的Br先随Fe含量的增加而增加,在x=0.239时达最大值1.099 T,进一步增加Fe含量由于FeCo软磁性相的形成而导致Br下降。当Fe含量由x=0.239增加至0.282时,Hci由最大值1660.3 kA·m^-1迅速降低至979.1kA·m^-1。Fe含量对磁体的相结构没有显著的影响,主要由2∶17R相、1∶5相和2∶17H相构成。但当Fe含量x〈0.197时,Sm（CobalFexCu0.049Zr0.024）7.5的胞状组织未发生显著变化,平均尺寸约为80nm;当Fe含量x〉0.197时,胞状结构发生长大,均匀性变差,胞状结构的变化导致矫顽力的温度稳定性随Fe含量的增高而大幅降低;当x=0.282时,磁体在500℃下的Hci只有114 kA·m^-1,磁通不可逆损失达-36.7%。     

Rb2BaNb2Se11: A new quaternary niobium polyselenide with infinite anionic chains composed of Nb2Se11 building block

The quaternary compound Rb₂BaNb₂Se₁₁ has been synthesized by reacting Nb metal with an in situ formed flux of Rb₂Se₃, BaSe and Se at 773 K. Rb₂BaNb₂Se₁₁ crystallizes in the monoclinic space group P2₁/c with four formula units and lattice parameters a=7.8438(5) Å, b=13.6959(6) Å, c=17.0677(13) Å, β=97.917(9)°. The structure consists of one-dimensional anionic chains formed by interconnection of dimeric [Nb₂Se₁₁] units. The chains are directed along the crystallographic c-axis with Rb⁺ and Ba²⁺ ions being located between the chains. The [Nb₂Se₁₁] units are formed by face sharing of two NbSe₇ bipyramids and are joined by Se₂²⁻ dianions to form infinite ¹_∞[Nb₂Se₁₁⁴⁻] chains. The compound was characterized with infrared spectroscopy in the FIR region, Raman and UV/Vis diffuse reflectance spectroscopy.     

Simulation of pulse responses of lithium salt‐doped poly ethyleneoxide

Ionic migration in organic electrolytes resembles that in neural system involving signal transportation. Here, ionic dynamic simulations are applied to explore pulse responses of lithium‐doped polyethyleneoxide complexes. Two main interactions were considered: diffusion of ions and directional movement guided by an applied electric field. Frequency responses are simulated using arbitrary wave shape. It is found that redistribution of ions results in accumulation of charge and establishes a reverse inbuilt electric field controlling the discharging process and the frequency response. The charging current's wave shape is controlled mainly by contribution from the diffusion process, which strengthens the charging current in the first millisecond before weakening it. For stimulation with higher energy density (higher frequency), activation of ion channels should be considered and an active ion number is introduced to describe the process. The weights of calculated discharging current agree well with the experimental results. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 831–837     

Evaluating redox reactivity of CuO-based oxygen carriers synthesized with organometallic precursors

The highly efficient CuO-based oxygen carrier is prospectively applied in chemical-looping combustion process. The metal precursors and synthetic methods greatly affect the performance of the synthetic CuO-based oxygen carriers. The inorganic precursors are commonly used to synthesize CuO-based oxygen carriers, while the organometallic precursors are scarcely adopted. In this work, the organometallic copper precursor [copper (II) acetate] and three other different organometallic support precursors (magnesium l-lactate hydrate, silicon tetraacetate and magnesium acetate) were adopted to produce CuO-based oxygen carriers via the methods of wet-mixing and spray-drying, respectively. It is found that the synthetic oxygen carriers incorporated with inert supports (MgO and SiO₂) exhibit remarkably stable redox reactivity, compared to the pure CuO. Moreover, the redox reactivity of the MgO-incorporated CuO-based oxygen carriers is superior to that of the SiO₂-incorporated CuO-based oxygen carriers. It is mainly attributed to the higher Tammann temperature of MgO (1549 K) compared to that of SiO₂ (937 K), which more effectively contribute CuO to inhibit particle growth and agglomeration due to sintering. Additionally, the MgO-incorporated CuO-based oxygen carriers prepared via scalable spray-drying method also exhibit the relatively high redox reactivity. It indicates that the spray-dried, synthetic CuO-based oxygen carriers from organometallic precursors possess the potential to be industrialized amplification.

     

四配位硫属中红外非线性光学材料结构-性能分析

中红外非线性光学晶体通过典型的变频技术可高效输出中红外激光,是中红外激光器的重要部件,在军事和民用领域有着广泛的应用.目前有实际应用前景的中红外非线性光学材料大多是由四面体基元构成结构框架的四配位硫属化合物.本文回顾了21种代表性四配位硫属化合物的晶体结构、光学性能,以及理论计算结果,分析总结了四配位硫属中红外非线性光学晶体的晶体结构与光学性能之间的关系,这对探索性能优异的新型中红外非线性光学晶体具有重要指导意义.