Experimental and theoretical studies of (CsI)n Cs+ cluster ions produced by 355 nm laser desorption ionization

Collision cross-sections of gas-phase (CsI)n = (1-7)Cs(+) cluster ions formed by pulsed-UV laser (355 nm) desorption ionization are measured by ion mobility-mass spectrometry. Experimental collision cross-sections are compared with calculated cross sections of candidate structures generated from a search for the lowest energy structures at the DFT/B3LYP/LACV3P** and MP2/LACVP3P** levels. The relative stabilities of these candidate structures are examined by IM-CID-MS, and the experimental results are compared to theoretical predictions. Analysis of (CsI)n = (1-7)Cs(+) cluster ion dissociation energies shows that the lower fragmentation thresholds are observed for cluster ions with the lower predicted stability.     

基于液体阵列味觉仿生传感器鉴别白酒香型的新方法

通过模拟哺乳动物的味觉系统, 建立了交叉响应的液体阵列传感器, 为鉴别白酒香型提供了新方法. 选用7种染料和1种卟啉化合物作为传感单元, 构建液体阵列传感器, 集合8个传感单元的光谱响应信号构成分析物的指纹图谱, 达到识别的目的. 使用96孔板酶标仪采集响应数据, 结合主成分分析(PCA)、分层聚类分析(HCA)和判别分析(LDA)等模式识别方法进行数据处理, 对9种具有代表性的不同香型白酒样品进行了鉴别分析. PCA结果表明, 该方法对于白酒的检测主要基于酒体微量成分, 其中酸类物质对识别的贡献最大(贡献率达54.3%), 芳香类物质贡献率为18.6%; 同时, 仅用63.4%的数据信息量即可对白酒香型进行区分. HCA结果表明, 平行样均正确归类, 各白酒之间的相似程度在聚类图上得到体现. LDA结果表明, 该阵列对于9种白酒样品香型识别的准确率达到100%.     

A Dual Read-out Molecularly Imprinted Composite Membrane Sensor Based on Zinc Porphyrin for the Detection of Dimethyl Methylphosphonate

Molecularly imprinted membrane-zinc porphyrin-mathacrylate(MIM-Zn-MAA), a dual read-out sensor based on a molecularly imprinted membrane, was developed to recognize and detect dimethyl methylphosphonate (DMMP) as an intermediate molecule of organophosphorus pesticides. The membranes were prepared via thermal polymerization of two functional monomers(zinc porphyrin and mathacrylate) on the surface of a glass slide functionalized with ethylene glycol dimethacrylate and azobisisobutyronitrile. The morphology of the as-synthesized MIM-Zn-MAA was determined with scanning electronic microscopy. The composite membranes exhibited macrovoid morphologies, which were affected by the functional monomers. These membranes were selectively adsorbed onto the template molecule and displayed higher adsorbing capacity toward DMMP compared with their structural analogs. Changes in the fluorescent spectra were qualitatively and quantitatively monitored via fluorescence photometry. Difference maps were also obtained using colorimetry before and after the reaction between MIM-Zn-MAA and DMMP at various concentrations. The maps showed a wide linear range varying from 0.1 μmol/L to 10 mmol/L with a low detection limit of 0.1 μmol/L. These preliminary results demonstrate that the as-fabricated dual read-out sensor displays good sensitivity and selectivity toward DMMP, indicating its considerable potential in DMMP detection in practical applications.     

羟基卟啉化合物的电化学、顺磁共振及时间分辨光电压性质

通过循环伏安法、电子顺磁共振谱和时间分辨电压光谱研究了羟基取代基数目和位置的不同对羟基苯基卟啉化合物的电化学、电子顺磁共振和时间分辨光电压性质的影响. 研究结果表明, 所有氧化还原反应都是在卟啉环上进行的. 卟啉周边取代基数目的增加使得卟啉共轭体系平均电子云密度增大, 导致体系易氧化而难以还原. 对称性增强可能使卟啉化合物的半波电位值向正方向移动, 羟基取代基的给电子效应对于卟啉化合物电化学性质的影响起主导作用. 常态下卟啉分子没有EPR信号, 在光的激发下, 卟啉分子由原来的逆磁性分子变成顺磁性的激发三重态分子, 这种激发三重态分子在分子轨道上具有两个未成对电子, 这两个电子相距很近, 彼此之间发生很强的相互作用而产生电子, 它的g值随卟啉共轭体系平均电子云密度增大而变大. 时间分辨光电压是由分子中的自由光声载流子的存在而产生的, 光电压的衰减与分子结构密切相关, 它们的电荷分离速度基本上随卟啉周边羟基取代基数目的增加而减慢.     

一种可视化液体传感阵列农药检测新方法

以筛选出的7种染料与合成的纳米金共同构建了液体传感器阵列,每个敏感点对不同农药样品产生不同的响应光谱,通过酶标仪采集光谱数据,结合主成分分析(PCA)、分层聚类分析(HCA)、判别分析(LDA)等模式识别方法建立了一种快速检测有机磷、氨基甲酸酯、有机氯、拟除虫菊酯类农药残留的新方法。PCA结果表明,前三个主成分反映了总信息量的92.69%,且能够对5种农药进行区分;HCA结果表明,对25个样品能够正确的归类;LDA结果表明,对5种农药识别的准确率达100%。表明这种可视化的液体阵列可为农药残留检测提供一个可靠平台,在农药残留检测中具有潜在的应用价值。     

基于新型可视化学传感阵列的氨基酸快速识别

以卟啉和其衍生物及指示剂为传感元件,构建了一种对氨基酸敏感的可视传感阵列.可视化学传感阵列以交互响应的敏感元件组成阵列,对不同物质产生特异的响应,并通过信号识别处理系统,将检测结果以图谱的方式显示,实现检测的可视化.研究中筛选了对氨基酸敏感的36种化学物质,构建了6×6的传感阵列,使用自主研发的阵列数据采集与处理系统,对10种具有代表性的常见氨基酸进行了检测,氨基酸溶液与阵列的反应时间为5 min.对实验检测结果数据采用主成分分析和判别分析进行了计算和分析.实验结果显示,通过阵列响应的可视差图可以将浓度为375 μmol/L的10种氨基酸明显区分.判别分析结果显示,本可视阵列对氨基酸识别的准确率达到97%.二维主成分散点图和判别分析散点图对10种氨基酸都有显著分辨效果.本可视传感阵列可用于氨基酸的快速识别.     

羟基系列卟啉对三聚氰胺的检测研究

研究了四苯基卟啉(TPP)及5种羟基系列卟啉对三聚氰胺的检测,结果表明,TPP及羟基系列卟啉可以用来检测三聚氰胺,三聚氰胺与卟啉发生作用,导致其soret带特征峰强度的变化,其中邻二羟基卟啉对三聚氰胺的检测效果最好,检测限为0.2μg/L,摩尔吸光系数ε为0.6×106L·mol-1.cm-1。并对其作用机理进行了简要分析。     

Fluorescence and Thermostability of Nanometer Porphyrin Trimer

IntroductionPorphyrin possesses some unique properties.Incomparison with the porphyrin monomer,porphyrin oli-gomers are much attracting owing to their much betterproperties in some aspects,such as light harvest,ener-gy transformation and electron transiti…     

Analysis of Fluorescent Proteins with a Nanoparticle Probe

This letter presents the first application of high energy, single nanoparticle probes (e.g., 520 keV Au(400) 2nm NP) in the characterization of surfaces containing fluorescent proteins (e.g., GFP variants) by their co-emitted photon, electron and secondary ion signals. NP induced protein luminescence increases with the NP incident energy, is originated by the NP impact and is transferred to the protein fluorophor via electronic energy transfer. Multi-electron emission is observed per single NP impacts and their distributions are specific to the target morphology and composition. Fragment ions of protein sub-units consisting of 2-7 amino acid peptides are observed under individual NP impacts that can be correlated to the random protein orientation relative to the impact site (e.g., outer layer or "skin" of the protein).     

用纵横波声时比法测螺栓轴力精度研究

用纵横波测量螺栓轴力的技术已取得较大发展,本文介绍了纵横波比值法原理,通过理论推导,获得比值法计算的简易公式。建立试验平台,用现场用螺栓进行标定和测量,得出比值法在工程实践状态下的测量误差为10%以内,基本能满足工程应用的要求。此外,针对试验结果,本文还初步探讨了误差出现的原因以及提高精度的方法。本文介绍的比值法,无需精确测量标定螺栓长度和纵横波声速,现场应用更加简洁,具有较大的工程应用价值。