氮气吹扫和费托合成的脉冲过程以提高α-烯烃的选择性

费托合成可以将煤炭或者生物质气化得到的合成气转化为α-烯烃等重要的化工产品。研究将费托合成和氮气吹扫操作组合成一脉冲过程,在稳定的操作状态下保证费托合成和氮气吹扫交替进行。在传统的费托合成条件下(反应气速为2 000 h^-1,温度为497 K, 压力为 2.0 MPa, 氢碳体积比为2.0)考察了Fe-Co催化剂在脉冲过程中费托合成的活性和选择性。结果表明,N₂吹扫温度和压力分别为517 K和0.2 MPa下的费托合成的C₃烯烷比是未脉冲的相同反应条件下的九倍左右。同时,反应过程中CH₄的选择性和CO的转化率有所下降。在此基础上,通过间歇反应在固定床反应器中进行该脉冲过程,实验结果表明,利用脉冲操作在费托反应中可以获得更高的烯烃选择性。     

Determination of three kinds of banned drugs in milk powder by hybrid solid‐phase extraction purification combined with gas chromatography and mass spectrometry

A gradient clean‐up method for the quantification of five kinds of banned drugs (two hormones, two sedatives, and one chloramphenicol) in milk powder was developed. We used the combination of solid‐phase extraction purification with gas chromatography and mass spectrometry. Milk powder was initially hydrolyzed by β‐glucuronidase/arylsulfatase, and then the hydrolyzed solution was concentrated and purified using a C₈ and cation resin solid‐phase extraction column. To isolate hormones and chloramphenicol drugs, products from the previous step were diluted with methanol and further purified using a silica and diatomite solid‐phase extraction column. After derivatization, the drugs were analyzed by gas chromatography with mass spectrometry, and the hydrolyzed solution was diluted with 5% ammoniated methanol to purify sedatives before gas chromatography with mass spectrometry analysis. Results showed that after adding the banned drugs at concentrations of 0.3–10.0 μg/kg, the average recovery range was 78.2–97.3% with relative standard deviations of 5.3–12.5%. The limit of quantification of the banned drugs (S/N ≥ 10) was 0.3–5.0 μg/kg, whereas the limit of detection (S/N ≥ 3) was 0.1–2.0 μg/kg. The solid‐phase extraction gradient purification system was simple, rapid, and accurate, and could satisfy the detection requirements of hormone, sedatives, and chloramphenicol drugs when used together with gas chromatography and mass spectrometry.     

一个高度灵敏和高选择性铝离子比率探针的合成及应用

本文构建了一种基于3-苯丙噻唑基-2-羟基-5-甲基苯甲醛的荧光探针用于检测铝离子。该荧光探针能够灵敏、高选择性地检测铝离子,并显示出颜色和强烈的荧光变化双重响应。研究结果表明,该探针对铝离子表现出非常好的荧光增强效果,检测过程中其它金属离子不会对检测结果产生明显的干扰。其比率荧光强度(I490/I567)与铝离子的浓度(0~20μmol/L)之间具有良好的线性关系,检测限低至0.5μmol/L。由于具有高效的选择性,该探针可以用于检测污染河水中的铝离子含量。     

鸡肉中尼卡巴嗪残留基体标准样品的研制

为填补我国尼卡巴嗪药物残留基体标准样品的空白,建立了鸡肉中尼卡巴嗪残留基体标准样品的研制方法。通过在饲料中添加尼卡巴嗪药粉喂养白羽肉鸡,使药物在鸡体内自然代谢,得到尼卡巴嗪残留阳性动物。取鸡前胸肉制成肉糜,经均质、冷冻干燥、粉碎、筛分、包装、辐照灭菌等处理,制备了355份含有尼卡巴嗪残留的鸡肉冻干粉。按照国家标准样品的规范,进行了均匀性检验、稳定性检验、定值和不确定度分析。采用液相色谱-串联质谱法(LC-MS/MS)测定样品中的尼卡巴嗪含量,以8家具有资质的实验室进行协同定值。结果表明本批标准样品的均匀性和稳定性良好,在-70、4、25、50℃下能稳定保存14天,在-18℃下保存的稳定性可达12个月,符合国家标准样品的相关要求。最终确定标准样品中尼卡巴嗪的标准值为(157.7±11.0)μg·kg^-1(k=2)。该标准样品可用于尼卡巴嗪的检测方法优化、检测实验室的能力评价,对于食品中尼卡巴嗪残留检测具有重要意义。     

Efficient Intersystem Crossing and Long-lived Charge-Separated State Induced by Through-Space Intramolecular Charge Transfer in a Parallel Geometry Carbazole-Bodipy Dyad

The design of efficient heavy atom-free triplet photosensitizers (PSs) based on through bond charge transfer (TBCT) features is a formidable challenge due to the criteria of orthogonal donor-acceptor geometry. Herein, we propose using parallel (face-to-face) conformation carbazole-bodipy donor-acceptor dyads (BCZ-1 and BCZ-2) featuring through space intramolecular charge transfer (TSCT) process as efficient triplet PS. Efficient intersystem crossing (Φ_Δ=61 %) and long-lived triplet excited state (τ_T=186 μs) were observed in the TSCT dyad BCZ-1 compared to BCZ-3 (Φ_Δ=0.4 %), the dyad involving TBCT, demonstrating the superiority of the TSCT approach over conventional donor-acceptor system. Moreover, the transient absorption study revealed that TSCT dyads have a faster charge separation and slower intersystem crossing process induced by charge recombination compared to TBCT dyad. A long-lived charge-separated state (CSS) was observed in the BCZ-1 (τ_CSS=24 ns). For the first time, the TSCT dyad was explored for the triplet-triplet annihilation upconversion, and a high upconversion quantum yield of 11 % was observed. Our results demonstrate a new avenue for designing efficient PSs and open up exciting opportunities for future research in this field.     

偏硼酸锂-四硼酸锂熔融-电感耦合等离子体原子发射光谱(ICP-AES)法测定石膏中多组分含量

石膏在我国储量丰富,应用广泛,快速准确分析其成分含量对石膏资源的综合利用具有重要意义。针对酸溶法无法测定SiO2,碱熔法无法测定K2O、Na2O的问题,本文建立一种偏硼酸锂-四硼酸锂熔融-电感耦合等离子体发射光谱法同时测定石膏中CaO、SO3、Al2O3、Fe2O3、MgO、TiO2、K2O、Na2O、SiO2含量。实验优化了熔剂用量、熔融温度,结果表明采用试样与偏硼酸锂-四硼酸锂混合熔剂质量比例1：5,在铂金坩埚中1000 ℃熔融10 min,在超声条件下,于50 mL 10 %盐酸中浸取熔融物,能够有效分解试样而浸取待测组分。向标准溶液系列中加入偏硼酸锂-四硼酸锂-盐酸基体溶液以消除基体对测试结果的影响。各待测组分的校准曲线的相关性系数均大于0.9990,方法检出限在3~292 μg/g范围内;采用实验方法分别对国家一级标准物质GBW03109a、GBW03110和实际样品进行测定,标准物质的5次平行测试的相对标准偏差在0.14 %~8.86 %之间,测定结果的相对误差在0.03~8.75 %之间,测试结果与标准值无显著性差异;实际样品中各成分测定值的RSD（n=5）为0.24~8.80 %。该方法操作简单、准确度高、精密度好、检出限低,可以同时测定石膏中的多组分含量,能够为石膏资源综合利用调查评价提供一定的技术支撑 。     

One-pot synthesis of CuO/TiO2 nanocomposites for improved photocatalytic hydrogenation of 4-nitrophenol to 4-aminophenol under direct sunlight

The excellent photocatalytic hydrogenation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with NaBH₄ in the aqueous medium is still a big challenge. Herein, we report a facile one-pot evaporation-induced self-assembly (EISA) method to synthesize a series of CuO/TiO₂ nanocomposites. The as-synthesized CuO/TiO₂ photocatalysts exhibit remarkable catalytic activity under direct sunlight in selective hydrogenation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) due to the synergistic interaction of guest copper nanoparticles with host titanium dioxide (TiO₂) species. Especially, 5 wt% CuO/TiO₂ nanocomposite revealed superior reaction rate constant (k) value (0.306 min⁻¹) when compared to 3 wt% CuO/TiO₂ (0.192 min⁻¹) and 7 wt% CuO/TiO₂ (0.240 min⁻¹). Moreover, several characterization techniques (XRD, TEM, N₂ adsorption–desorption isotherm, DRS, and XPS) were executed to deeply investigate the effect of copper content on the bulk and interfacial properties of the catalysts. The characterization results proved that the superior photocatalytic hydrogenation over 5 wt% CuO/TiO₂ catalyst can be ascribed to moderate CuO loading as well as even dispersion of CuO species on the surface of active TiO₂ host, which can largely improve the light absorption ability within visible light region. Besides, the 5 wt% CuO/TiO₂ catalyst exhibits remarkable recyclability and durability, retaining its superior activity (above 95%) up to several repeating cycles, proving its practical applicability for hydrogenation reactions at domestic and industrial levels.     

雨课堂与腾讯课堂联用的“有机化学”线上教学设计与实践*

基于智慧教学工具“雨课堂”为主和“腾讯课堂”为辅的双平台联用组合,将“雨课堂”优秀的教学互动和全周期记录学习活动表现的功能与“腾讯课堂”网络直播高峰期画面卡顿少、师生可以语音互动的优点结合起来,充分发挥“以学生为中心”的教学理念,探讨了有机化学课程的线上教学设计,并在教学班级中进行了广泛实践。实践证明,“雨课堂”直播为主和“腾讯课堂”为辅的双平台联用教学模式能保证教学质量、激发学生的学习兴趣和提高学生的学习效果。     

医学留学生化学实验全英文教学资源建设与实践*

针对目前化学实验全英文在线教学资源匹配度较低、相对匮乏等问题,以医学留学生为中心,建设了有声课件、模块化实景实验操作视频以及测试题库3种不同类型的化学实验全英文教学资源,通过资源的线下使用和基于雨课堂的在线预习,实现从“集中、定时、定点”的传统教学模式向“模块化、碎片化、信息化”的混合教学模式转变,可以丰富教学资源和教学手段,改进教学秩序,提高医学留学生化学知识和技能学习的积极性和主动性,使“教”“学”良性循环,可切实提高化学实验国际化教学质量。     

丹荷颗粒治疗高脂血症质量标志物发现研究

为寻找丹荷颗粒治疗高脂血症的质量标志物,该研究基于丹荷颗粒体内成分分析结果,采用Cytoscape软件构建高脂血症-共有靶点-丹荷颗粒体内成分作用网络,利用DAVID及String数据库分别对共有靶点进行生物过程、通路富集及网络拓扑分析,明确丹荷颗粒降脂作用关键靶点及成分,再建立油酸诱导的HepG2细胞脂质堆积模型验证关键成分的降脂药效,最后结合相关成分在制剂中的含量、稳定性、特征性综合确定质量标志物。结果发现,丹荷颗粒体内成分作用于CES1、ADORA2A、ADORA1、APOB、LDLR、PPARA、PPARG、INSR、ESR2、ESR1共10个高脂血症疾病靶点,主要参与脂质代谢过程以及PPAR、cAMP信号通路,其中LDLR、PPARA、PPARG可能是关键靶点,而网络中与关键靶点直接作用的成分为白藜芦醇、柚皮素。白藜芦醇和柚皮素均可降低油酸诱导的HepG2细胞内脂滴数量,改善细胞脂质堆积严重程度,并显著降低细胞内甘油三酯含量,可能为关键成分;鉴于入体成分白藜芦醇和柚皮素来源于制剂中虎杖苷及柚皮苷,且制剂中虎杖苷及柚皮苷特征明显、含量丰富、稳定,故虎杖苷及柚皮苷可作为丹荷颗粒治疗高脂血症的质量标志物。该研究为丹荷颗粒质量标准的建立提供了合理的候选质控指标。