电泳法制备的致密氧化锡薄膜及其在高稳定性钙钛矿太阳能电池中的应用

在平面型钙钛矿太阳能电池中常采用SnO₂作为电子传输层材料,相应的SnO₂薄膜常采用溶液旋涂法制备。但是由于前驱液中的纳米颗粒可能会发生部分团聚、基底和溶液难以完全避免灰尘等杂质颗粒混入,且最佳的SnO₂电子传输层的厚度通常仅有约20 nm,所以这种方法制备的电子传输层难以保证严格致密和无纳米针孔。在本工作中,我们报道了一种电泳沉积制备致密SnO₂薄膜的方法,并用其有效地提高了钙钛矿太阳能电池的光电转换效率和工况稳定性。通过电泳法,表面带负电荷的SnO₂纳米颗粒在电场的作用下沉积到氧化铟锡(ITO)阳极表面,这种方法得到的薄膜比旋涂法制备的更为致密。将其应用于n-i-p结构的钙钛矿太阳能电池中,能够使得暗电流降低并抑制载流子的非辐射复合,从而提高电池的短路电流和开路电压,进而实现更高的光电转换效率(从18.17%提高到19.52%),且能消除迟滞效应。更重要的是,长期工况稳定性测试表明基于电泳-旋涂法制备的器件在1个太阳的光照下、最大功率点处连续工作960 h后,仍然能够保持71%的初始效率;然而基于旋涂法制备的器件在工作100 h后即降低到初始效率的70%。本工作提供了一种全新的SnO₂电子传输层的制备方法,显著地提高了器件性能和工况稳定性,后续有望应用于制备大面积器件和电池模组。     

数理统计在地球化学样品分析质量控制中的应用

使用Excel2013和Minitab两种常用软件对地球化学样品中CaO含量分布情况进行了研究,运用描述性统计、正态分布、背景值与异常方法对实验室分析的广西某地地球化学样品的分析数据进行了质量评价,结果表明:综合运用计算机软件和数理统计方法,能快速找到分析数据的详细信息和数据特征,判别地球化学样品实验室分析数据的准确性,找出元素的背景值和异常值并剔除异常值,比较发现,样品中CaO含量分析数据对数转换后比原始数据的分布更趋于正态分布,相比于X射线荧光光谱方法,用电感耦合等离子体发射光谱法测定的结果更符合正态分布。方法对地球化学调查样品的分析数据质量评价作了有益的尝试,揭示了数理统计方法是地球化学样品分析质量控制的有效手段。     

A Conjugated Copolymer Bearing Imidazolium-based Ionic Liquid:Electrochemical Synthesis and Electrochromic Properties

An imidazolium-based ionic liquid(IL) modified triphenylamine derivative,namely 1-(4-((4-(diphenylamino)benzoyl) oxy)butyl)-3-methyl imidazole tetrafluoroborate(TPAC_6 IL-BF_4),was designed and synthesized,and further applied with 3,4-ethylene dioxythiophene(EDOT)to prepare conjugated copolymer P(EDOT:TPAC_6 IL-BF_4) via electrochemical polymerization.The cyclic voltammetry curves show that the copolymer P(EDOT:TPAC_6 IL-BF_4) possesses two pairs of redox peaks,which should be ascribed to the redox behaviors of EDOT and triphenylamine.The ultraviolet-visible(UV-Vis) absorption spectrum of P(EDOT:TPAC_6 IL-BF_4) exhibits one maximum absorption peak at 580 nm and a small shoulder characteristic peak at 385 nm under neutral state which are assigned to π-π~* conjugated structure of EDOT and triphenylamine.After being applied at the positive voltage,the copolymer color changes from dark blue to light blue,which is close to the color of poly(3,4-ethylenedioxythiophene)(PEDOT).Surprisingly,the copolymer P(EDOT:TPAC_6 IL-BF_4) shows shorter switching time of 0.37 s,0.30 s at 580 nm and 0.38 s,0.45 s at 1100 nm compared with PEDOT.It is more intriguing that the copolymer P(EDOT:TPAC_6 IL-BF_4) exhibits electrochromism even in free supporting electrolyte.The results confirm that the existence of imidazolium-based ionic liquid has an improvement on the ion diffusion properties and the switching time of conjugated polymer,which may provide a potential direction for the preparation of high-performance electrochromic materials.     

衰减全反射傅里叶变换红外光谱法同时测定叔丁醇和二叔丁基过氧化物

分别应用914 cm-1和875 cm-1处的甲基特征峰作为叔丁醇和二叔丁基过氧化物的定量分析峰,使用峰面积作为吸光度的评估方法,得到的标准曲线的相关系数(R2)分别是0.9987和0.9952,叔丁醇的加标回收率在95％～110％之间,应用衰减全反射傅里叶变换红外光谱法测定3个样品,计算结果的F值、t值和p值,数据表明衰减全反射傅里叶变换红外光谱法与气相色谱法的测定结果一致.     

Determination of Phosphatidylcholine in Shrimp by High-Resolution Mass Spectrometry

The molecular species of phosphatidylcholine from freshwater sources (Macrobranchium nipponense and Macrobranchium rosenbergii) and marine sources (Euphausia superba and Penaeus chinesis) were characterized by high-resolution mass spectrometry. The tandem secondary mass spectrometry (MS/MS) fragmentation allowed for the identification of fatty acyl residues of phosphatidylcholine molecular species. (16:0–18:1)Phosphatidylcholine was the main phosphatidylcholine molecular species determined in all shrimp samples, especially in E. superba. Macrobranchium rosenbergii phosphatidylcholine was particularly rich in (16:0–20:5)phosphatidylcholine and (16:0–22:6)phosphatidylcholine. The proportion of the two molecular species was next to the phosphatidylcholine of E. superba. Therefore, M. rosenbergii appears to be a potential freshwater source for the supplementation of polyunsaturated fatty acids, particularly eicosapentaenoic acid (20:5) and docosahexaenoic acid (22:6). This approach may be used as an efficient method for the identification of natural phosphatidylcholine sources from the broad range of plant, animal, and marine origins.     

Surface properties and doxorubicin delivery in mixed systems comprising a natural rosin-based ester tertiary amine and an anionic surfactant

A rosin-based ester tertiary amine salt (RETAS) cationic surfactant was obtained using natural rosin as raw material. GC-MS of RETAS was detailed analyzed. The pH-responsive mechanism of rosin-based ester tertiary amine (RETA) and RETAS was confirmed by applying theoretical calculations about electrostatic potential maps of RETA and RETAS cation using Gaussian software. Mixed system surfactants were obtained by blending RETAS cationic surfactant with sodium dodecyl benzene sulfonate (SDBS) anionic surfactant. The binary mixed surfactant systems of RETAS and SDBS had obvious synergistic effect. The γ_cmc and CMC were 39.40?mN/m and 0.56?mmol/L at the optimum molar fraction of RETAS (α)?=?0.6, respectively. The stability time of emulsion with the optimum mixed system as emulsifier increased to 309?s at α?=?0.6. The emulsifying capacity of RETAS was much better than that of RETA. RETAS had pH-responsive targeted release and the optimum mixed system showed a relatively sustained drug release by using doxorubicin (DOX) as a model drug. These results indicate that RETAS surfactant and mixed system surfactant are both promising for applications in drug delivery and emulsification.     

Preparation and application of molecularly imprinted polymer solid‐phase microextraction fiber for the selective analysis of auxins in tobacco

As signal molecules, auxins play an important role in mediating plant growth. Due to serious interfering substances in plants, it is difficult to accurately detect auxins with traditional solid‐phase extraction methods. To improve the selectivity of sample pretreatment, a novel molecularly imprinted polymer ‐coated solid‐phase microextraction fiber, which could be coupled directly to high‐performance liquid chromatography, was prepared with indole acetic acid as template molecule for the selective extraction of auxins. The factors influencing the polymer formation, such as polymerization solvent, cross‐linker, and polymerization time, were investigated in detail to enhance the performance of indole acetic acid‐molecularly imprinted polymer coating. The morphological and chemical stability of this molecularly imprinted polymer‐coated fiber was characterized by scanning electron microscopy, infrared spectrometry, and thermal analysis. The extraction capacity of the molecularly imprinted polymer‐coated solid‐phase microextraction fiber was evaluated for the selective extraction of indole acetic acid and indole‐3‐pyruvic acid followed by high‐performance liquid chromatography analysis. The linear range for indole acetic acid and indole‐3‐pyruvic acid was 1–100 µg/L and their detection limit was 0.5 µg/L. The method was applied to the simultaneous determination of two auxins in two kinds of tobacco (Nicotiana tabacum L and Nicotiana rustica L) samples, with recoveries range from 82.1 to 120.6%.     

大学生学习成绩分析及相应的差异教学策略

以SPSS、Origin为主要数据分析工具,对某大学化工学院本科生期末考试成绩进行分析。对降序排列的平均学分绩点一元拟合曲线的残差进行了拟合,对其拟合函数进行求导,发现可以将样本按照20%、50%、30%的比例分为3个集团。通过层次聚类也得到类似的结果。不同集团的学生的学分获得率的组成、标准偏差分布明显不同。重要的专业基础课程在学生学习集团的形成中起到了重要的作用,基于统计结果,建议针对不同集团学生的学习特点应采取相应的差异化教学策略。     

Energy‐resolved technique for discovery and identification of malonyl‐triterpene saponins in Caulophyllum robustum by UHPLC‐electrospray Fourier transform mass spectrometry

Malonyl‐triterpene saponins (MTSs) attract scientific attentions because of their structural diversities and valuable bioactivities. However, its thermal instability brings a huge amount of challenges for isolation and purification of this class of compounds. To our best knowledge, there has been no report on isolation and analysis of MTSs from genus Caulophyllum. In this study, a strategy combining data acquisition using an energy‐resolved technique and the narrow widow extracted ion chromatograms as data mining method was developed for discovery and identification of MTSs in Caulophyllum robustum hair roots by ultra high liquid chromatography coupled to electrospray ionization Fourier transform mass spectrometry. The method was performed at an independent MS full scan using our bottom‐up energies by in‐source collision induced dissociations with 0, 25, 50 and 100 eV in both positive and negative modes. Precursor ion as well as fragment ion information was simultaneously collected from four energy‐resolved MS spectra in a single run of 18 min. The fragmentation pathways of intact deprotonated, protonated and sodium ions of MTSs were proposed for the structural elucidation of Caulophyllum MTSs. A flowchart involving a stepwise procedure based on key fragments from ESI^?/ESI⁺‐FT‐MS^{(1, 1)} to MS^{(1, 4)} spectra was constructed for the identification of structural elements in the MTSs. As a result, a total of 23 MTSs were discovered and tentatively identified, which had not been reported from Caulophyllum species before. All of these were potentially new compounds. This study provides an excellent example for discovery and identification of MTSs in herb medicines. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis,Structures, and Fluorescent Properties of Three Cobalt‐Based Coordination Polymers with a Rigid Tripodal Carboxylate Ligand

Three cobalt(II) coordination polymers, [Co₂(tatb)₂(2,2′‐bipy)₂ (H₂O)₂ · DMA · 2H₂O] ( 1 ), [Co₂(tatb)₂(1,10‐phen)₂(H₂O)₂ · 2H₂O] ( 2 ) and [Co(tatb)(1,3‐dpp) · H₂O] ( 3 ) (H₃tatb = 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)tribenzoic acid; 2,2′‐bipy = 2,2′‐bipyridyl; 1,10‐phen = 1,10‐phenanthroline; 1,3‐dpp = 1,3‐bis(pyridin‐4‐yl)propane), were synthesized solvothermally and characterized by single‐crystal and powder X‐ray diffraction (PXRD), as well as IR spectroscopy. Complexes 1 and 2 exhibit 1D double‐chain structures, which further connect into interesting 3D networks by hydrogen bond and strong π–π interactions. Complex 3 possesses 2D 4⁴‐sql topology, which is packed parallel in an AA fashion. Moreover, thermal stability properties and photoluminescence properties of 1 , 2 and 3 were also investigated.