大气压固体分析探头离子源-串联质谱法快速检测蔬菜中多种农药残留

将大气压固体分析探头离子源(ASAP)与多级质谱耦合(ASAP-MS/MS), 在无需净化或浓缩等前处理及无需色谱分离的条件下, 建立了蔬菜中13种农药残留的乙腈提取直接质谱分析方法, 单个样品检测在数分钟内即可完成. 针对常压直接分析质谱易受环境影响和上样精度差的问题, 对ASAP电离源条件如脱溶剂气温度、电晕放电电流、样品溶液组成和进样模式等进行了优化; 采用多反应监测扫描(MRM), 通过产物离子丰度比进行定性, 用内标标准曲线法定量; 对韭菜、油菜和芹菜3种基质进行了考察, 结果表明存在明显的基质效应. 本方法在5.0~500 μg/L浓度范围内的线性相关系数均高于0.995, 检出限为0.04~0.89 μg/kg, 精密度(RSD, n=7)为5.1%~13.0%. 超高效液相色谱-电喷雾串联质谱法对实际样品的检测结果与ASAP-MS/MS的检测结果一致. 该方法分析速度快, 灵敏度高, 无需有机溶剂且结果可靠, 可应用于大批量农药残留的筛查和应急监测任务.     

Polymersome‐forming amphiphilic glycosylated polymers: Synthesis and characterization

Copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) was used to prepare glycosylated polyethylene (PE)–poly(ethylene glycol) (PEG) amphiphilic block copolymers. The synthetic approach involves preparation of alkyne‐terminated PE‐b‐PEG followed by CuAAC reaction with different azide functionalized sugars. The alkyne‐terminated PE‐b‐PEG was prepared by etherification reaction between hydroxyl‐terminated PE‐b‐PEG (M_n ～ 875 g mol^?1) and propargyl bromide and azidoethyl glycosides were prepared by glycosylation of 2‐azidoethanol. Atmospheric pressure solids analysis probe‐mass spectrometry was used as a novel solid state characterization tool to determine the outcome of the CuAAC click reaction and end‐capping of PE‐b‐PEG by the azidoethyl glycoside group. The aqueous solution self‐assembly behavior of these amphiphilic glycosylated polymers was explored by TEM and dye solubilization studies. Carbohydrate‐bearing spherical aggregates with the ability to solubilize a hydrophobic dye were observed. The potential of these amphiphilic glycosylated polymers to self‐assemble via electro‐formation into giant carbohydrate‐bearing polymersomes was also investigated using confocal fluorescence microscopy. An initial bioactivity study of the carbohydrate‐bearing aggregates is furthermore presented. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5184–5193     

A fast and reliable detection of indigo in historic and prehistoric textile samples

We present a method requiring no sample preparation for the direct identification of indigoid colorants in tiny amounts in ancient historic fabrics using ASAP®‐MS. Exact determinations were completed in less than 1 min. Copyright © 2015 John Wiley & Sons, Ltd.     

ASAP模拟变焦系统中鬼像的研究

 非成像光束在光学系统内表面的多次折射反射容易在像面附近形成光晕或鬼像,变焦系统由于镜片多,机构复杂等往往难以进行全面的分析模拟。利用ASAP软件模拟每个透射面作为部分透射、部分反射的表面,对变焦光学系统非轴上光进行分析,模拟出变焦系统的光学元件表面和光机内壁,实行实际光线追迹,然后以像面为研究对象,进一步实施实际光线追迹,模拟出全部散射光在像面上的能量分布,找出鬼像形成的原因,并在此基础上通过改变二次反射所在面的曲率或改变所在面的折射率两种方法对变焦光学系统进行优化,减小鬼点数目,以提高系统的成像质量。     

Rapid analysis of lubricants by atmospheric solid analysis probe–ion mobility mass spectrometry

Formulated lubricants are complex mixtures composed of base oil(s) and additives with various functions (detergents, corrosion inhibiter, antioxidant, viscosity modifiers, etc.). Because of the aliphatic nature of base oil and the chemical diversity of additives, the characterization of lubricant is currently a long and complex process. The comprehensive analysis of lubricant samples involves several techniques such as nuclear magnetic resonance, mass spectrometry, chromatography and infrared spectroscopy. The coupling of atmospheric solid analysis probe (ASAP) with ion mobility‐mass spectrometry (IM‐MS) has been shown to be an efficient tool for the characterization of complex mixture containing vaporizable polar to non‐polar compounds. This approach affords the coupling of a direct ionization technique that does not require sample preparation, with a bi‐dimensional separation method with high peak capacity. In this work, we show that ASAP‐IM‐MS is a suitable method for rapid and direct characterization of lubricant samples. Indeed, base oil and additives yielded, by ASAP, ions series which could be separated by IM‐MS. Molecular additives such as Zn‐dithiocarbamate, phosphite, thiophosphate and Alkyl diphenylamine were ionized as molecular ions [M]^+? or protonated molecules [M + H]⁺, depending of their polarity. In some cases, fragment ions were observed, confirming the additive identification. In addition, high molecular weight polymeric additives such as poly(alkyl methacrylate) (PAM) were pyrolized in the ASAP source leading to characteristic fragment ions. ASAP‐IM‐MS is shown to be a powerful tool for studying complex mixtures, allowing the first comprehensive analysis of lubricants in just a few minutes. Copyright © 2014 John Wiley & Sons, Ltd.     

胜利褐煤和小龙潭褐煤在甲醇中的热溶及热溶物分析

研究了胜利褐煤(SL)和小龙潭褐煤(XLT)在甲醇中的热溶行为,并利用傅里叶变换红外光谱、气相色谱/质谱(GC/M S)和大气压固体分析探针/飞行时间质谱(ASAP/TOF-M S)对320℃热溶物的组成和结构特征进行了分析。两种褐煤热溶物产率均随温度升高而增加,但240℃后XLT热溶物(SPXLT)产率明显高于SL热溶物(SPSL)。GC/MS分析表明,两种褐煤热溶物以含氧化合物为主,尤其酚类的相对含量超过49%;与SPXLT相比,SPSL中烯烃、芳烃、醚类、羧酸、酯类和有机硫化合物(OSCs)含量较高,而烷烃、酚类、酮类和有机氮化合物含量较低;SPSL中的OSCs以噻吩为主,而SPXLT中的OSCs以硫醇为主。ASAP/TOF-M S可检测出热溶物中大量GC/M S无法检测出的较强极性和难挥发化合物;与SPXLT相比,SPSL中CHO和CHS族分含量较低,而CHN、CHNO、CHOS、CHNS和CHNOS族分含量较高;两种褐煤热溶物中化合物的碳数和双键数(double bond equivalent,DBE)主要分布在3-15和0-10,SPXLT中化合物的碳数和DBE分布相对集中。     

多椭球投射式LED前照灯光学设计

LED光源具有寿命长、点亮速度快、节能等优点,非常适合作为新一代的汽车前照灯的主要光源。研究了使用LED光源和多椭球反射镜的投射式前照灯的设计方法,建立了光学系统模型。阐述了反射镜、挡板、透镜的设计思想。采用Cree xre-7090 LED作为光源,并在此基础上采用ASAP进行了计算机模拟。结果表明,可产生宽广但不高的光型,明暗截止线清晰。     

平面光栅杂散光测试仪模型设计及消杂光技术研究

杂散光是平面光栅的重要性能指标,光栅杂散光的测量一直是光栅研制领域的难题。为实现仪器自身杂光低于10-8量级,以满足对平面光栅杂散光10-7量级的精确测量要求,基于标量衍射理论和经典Fresnel-Kirchhoff衍射理论,对光谱仪器中的光栅杂散光进行了理论分析,设计了平行光照射条件下光栅杂散光测试仪的光机模型。利用杂散光分析软件ASAP建立紫外单色光入射下光栅杂散光测试仪的散射模型并对其进行仿真计算,分析仪器杂光的主要来源及散射路径,据此提出了用于降低仪器散射光和光栅多次衍射光的挡光环、叶片、光阑、光学陷阱等四种杂光抑制结构。最后,采用ASAP软件对增加抑制结构前后的仪器杂光相对强度进行了对照分析。仿真及分析结果表明,仪器杂光在测试波长±100 nm范围内的最大值由采用杂光抑制结构前的10-6量级以上降低至10-8量级以下,已满足光栅杂散光测试仪的设计需求,即可实现刻线密度为300～3 600 gr·mm-1的光栅杂散光10-7量级精确测量。该研究方法及结果将为平面光栅杂散光测试仪研制提供理论依据。     

高折射玻璃微珠粒径与折射率关系的研究

利用激光照射高折射率玻璃微珠下形成的二次彩虹现象,以艾里的虹理论为基础对玻璃微珠折射率进行了测量。推导了玻璃微珠尺寸对折射率影响的计算公式,表明半径差异在10μm时,折射率的测量误差为10^-3数量级。此外,通过软件模拟计算玻璃微珠的二次彩虹现象,并对微珠的折射率进行了测量,验证了二次彩虹方法的正确性,同时也表明玻璃微...