基于室温溶液悬浮法共价有机骨架的制备及其对茶叶中拟除虫菊酯固相微萃取的应用

拟除虫菊酯(PYs)类农药被广泛用于茶园病虫害的防治。随着国内外对进出口茶叶中农药残留限量的要求日益严格,我国迫切地需要开发能应用于检测茶叶中痕量PYs的方法。研究通过简单、温和的溶液悬浮法(SSA),在室温下制备了共价有机骨架(COF)材料TpBD,该材料具有优异的热/化学稳定性、较高的孔隙度和比表面积。通过简单物理黏附的方法,将TpBD制备成固相微萃取(SPME)纤维。将准备好的纤维应用于固相微萃取技术并与气相色谱-串联质谱(GC-MS/MS)联用,建立用于检测PYs的高灵敏分析方法。该方法对氟氯氰菊酯、氯氰菊酯、氟氰菊酯、氰戊菊酯和溴氰菊酯的富集倍数为702~2687,并表现出低的检出限(0.1~0.5 ng/L)、宽的线性范围(0.2~800 ng/L)、良好的线性关系(相关系数≥0.9991)、可接受的重复性(RSD≤11.0%, n=3)。将所建立的方法用于实际绿茶和乌龙茶样品中PYs残留量的检测,并成功地从实际茶样中检测出5种痕量PYs,并且具有满意的回收率(80.2%~109.5%)。实验结果表明,所建立的分析方法适用于茶叶中PYs农药残留量的分析和检测。此外,通过SSA成功地制备了TpBD材料,证实了该方法具有较好的普适性,具有简便合成其他COFs材料的潜力。     

金属有机骨架衍生材料在样品前处理中的应用研究进展

样品前处理技术在复杂样品的整个分析过程中起着至关重要的作用,其不仅可以提高痕量目标物在样品中的浓度,而且能有效消除样品基质对分析的干扰。对于样品前处理技术而言,吸附剂是其最为核心部分。因此开发高效、稳定的新型吸附剂已成为前处理技术领域的研究热点。近年来,由金属有机骨架(metal-organic frameworks, MOFs)衍生的多孔材料因其形貌结构多样、孔径可调、比表面积高、热稳定性良好、耐化学腐蚀等优异性能,使其在样品前处理领域拥有广阔的应用前景,基于MOFs衍生材料的样品前处理新方法也层出不穷。然而,MOFs衍生材料仍存在MOFs前驱体合成工艺复杂、生产成本高、量产困难等问题。该文总结了近几年来MOFs衍生材料在分散固相萃取(dSPE)、磁固相萃取(MSPE)、固相微萃取(SPME)、搅拌棒固相萃取(SBSE)和分散微固相萃取(DMSPE)等样品前处理技术中的研究进展,并对多种MOFs衍生材料的制备方法、功能化调控、富集效率等方面进行了评述。最后,展望了MOFs衍生材料在该领域中的应用前景,为进一步研究MOFs衍生材料的应用提供了参考。     

Tunable dual-band infrared polarization filter based on a metal-dielectric-metal compound rectangular strip array

A tunable dual-band infrared polarization filter is proposed and investigated. Based on the perfect absorption characteristic of the metal-dielectric-metal sandwich structure, the reflection spectrum performs as a filter. The filter consists of three layers. The top layer is a compound metal nano-structure array comprised of rectangular strips. The middle and bottom layers are a dielectric spacer and metal film, respectively. The calculated results show that the filter properties are closely related to the polarization of the incident light. Different dual-band wavelengths are filtered while the incident light has different polarizations, which are parallel or vertical to the x axis. Moreover, it is found that the resonant wavelength strongly depends on the length of the rectangular strip(which causes the resonant effect) and is independent of other strips. Therefore, the filter wavelengths can be tuned freely by adjusting the length of the corresponding rectangular strip. In addition, the calculated results show that all of the intensities at the filter wavelengths are closed to zero, which implies that the filter exhibits good filtering performance.     

柚皮素三乙胺盐一水合物的制备、晶体结构及溶解度

柚皮素是一种天然黄酮类化合物,几乎不溶于水。利用晶体工程学原理可以有效改善天然产物的溶解性。本文合成了柚皮素和三乙胺的有机盐一水合物[C_(15)H_(11)O_5]-·[C_6H_(16)N]+·H_2O,测定了其晶体结构。解析结果表明,有机盐水合物属于单斜晶系,P2_1/n空间群。柚皮素7取代位的羟基上的质子转移到了三乙胺的N原子上,并形成了N~+—H....O~-氢键。羟基阴离子与4'取代位上的羟基形成了O—H....O~-氢键,产生了一维的氢键链状结构。水分子通过两种氢键作用将一维的氢键链连接成二维的氢键网络。形成三乙胺盐一水合物后,柚皮素在水中的溶解度增加了20倍。     

快速测定植物油胆固醇含量在地沟油筛查中的应用

采用皂化气相色谱氢火焰离子检测器法测试了多个植物油样品,发现胆固醇峰被干扰比较严重,很难得出植物油与地沟油胆固醇含量的界定值。采用SPE进行样品前处理,对SPE处理条件进行优化,得出优化条件为称样量0.25 g ,20 mL 0.6%乙醚-正己烷(V/V)作为淋洗液,20 mL 15%乙醚-正己烷(V/V)作为洗脱液。用SPE气相色谱氢火焰离子检测器法分析了84个植物油样品和13个地沟油样品中胆固醇含量,测定结果表明,植物油胆固醇含量与地沟油胆固醇含量有明显区别,所有植物油胆固醇含量都小于50μg/g,13个地沟油样中11个样胆固醇含量大于50μg/g。因此,采用上述植物油胆固醇测定方法,胆固醇含量超过50μg/g可判定为疑似地沟油,反之不成立。本方法在0~760 mg/L浓度范围内相关系数R2=0.9999,方法检出限为6. 0μg/g,两个浓度水平(17.7和695 mg/L)的相对标准偏差分别为1.6%和1.5%,回收率为103%。     

翻转课堂在仪器分析实验教学中的应用

将翻转课堂这一新型教学模式应用于仪器分析实验的教学过程中,从材料获取、课前引导、课堂授课和实施结果等方面提出一些认识,以期为仪器分析实验教学改革提供借鉴.     

Photonic drop splitters based on self-collimation ring resonators in a silicon photonic crystal

We report here 1 × 3 and 1 × 2 photonic drop splitters (PDSs) with different splitting ratios based on self-collimation ring resonators (SCRRs) in an air-hole silicon photonic crystal. An 1 × 3 PDS consists of four beam splitters and an 1 × 2 PDS consists of three beam splitters and one mirror. Light propagates in the PDSs employing self-collimation effect. The theoretical transmission spectra at different drop ports in PDSs were analyzed with the multiple-beam interference theory. Then they were investigated with the finite-difference time-domain (FDTD) simulation technique. The simulation results agree well with the theoretical prediction. For the drop wavelength 1550 nm, the free spectral range of the PDSs is about 29 nm, which almost covers the whole optical communication C-band window. Because of small dimensions, air-hole structure and whole-silicon material, the proposed PDSs hold great potentials for applications in photonic integrated circuits.     

Lateral shifts of an optical beam in an anisotropic metamaterial slab

The lateral shift of a light beam at the surface of an anisotropic metamaterial slab is investigated. Analytical expressions of the lateral shifts are derived using the stationary-phase method, in the case that total reflection does and does not occur at the first interface. The sign of the lateral shift in two situations is discussed, and the necessary conditions for the lateral shift to be positive or negative are given. It is shown that the thickness and physical parameters of the anisotropic metamaterial slab, as well as the incident angle of the light beam, strongly affect the properties of the lateral shift, and numerical results validate these conclusions. The effect of a lossy metamaterial on the lateral shift is also investigated. A restriction on the thickness of the slab is obtained, which is necessary for the stationary-phase method to remain valid.     

Special control of the cutoff frequencies in a 2D photonic crystal coupled-cavity waveguide

We show theoretically that the upper and lower cutoff frequencies of the guided band in a 2D photonic crystal coupled-cavity waveguide can be controlled independently or synchronously by changing two configuration parameters of the waveguide simultaneously. The independent control range for the lower and upper cutoff frequencies can be as large as 68.6% and 67.9% of photonic band gap, respectively. The two cutoff frequencies can also be tuned in the same direction over equal distances up to 25.7% of photonic band gap. These results offer an efficient way for designing the various dispersion relations for photonic crystal waveguides.     

负载离子液体纳米钯催化芳卤羰化反应

研究了高分散性的负载离子液体纳米钯催化剂的制备及其催化芳卤羰化反应的性能. 用XRD、HRTEM和XPS等方法对催化剂进行了表征, 结果表明, 钯组分处于高分散零价态, 其平均粒径小于5 nm, 且催化剂表面存在一厚度适中的离子液体液膜, 有利于提高催化剂的稳定性; 该催化剂对PhI、PhBr、PhCl的羰化反应的催化活性优于离子液体两相催化体系, 在优化的反应条件下, 碘苯的转化率可达99.3％, 生成苯甲酸乙酯的转化频率(TOF)可高达4926 h−1, 反应产物中苯甲酸乙酯的选择性大于99％.