古代陶衣的微区拉曼光谱与电子探针线扫描分析

利用微区拉曼光谱与扫描电镜配置的电子探针等技术,分析了两块陶器样品的陶衣.拉曼光谱的分析结果表明,黑色陶衣的主要显色物质为炭黑,红色陶衣的显色物质为赤铁矿.电子探针线扫描分析的结果表明,红色陶衣中铁的含量明显高于内部坯体.陶器样品剖面的微区拉曼光谱分析可有效地避免样品表面其他掺杂原子的影响.     

3种基源莪术的显微及理化鉴定

对莪术的3种基源生药进行显微及理化鉴定,建立1种简单易行的方法作为不同基源莪术的鉴定依据。通过显微成像系统观察莪术切片和粉末的显微特征,绘制墨线图;采用水蒸气蒸馏法提取莪术的挥发油,进行薄层色谱分离。3种基源莪术在显微鉴定及理化鉴定方面均存在较大差异可作为药材的鉴定依据。     

通用型激光诱导荧光微流控芯片分析仪的研制与性能考察

设计和研制了一种通用型激光诱导荧光微流控芯片分析仪.检测部分按共聚焦检测原理设计,采用CCD(电荷耦合器件)监测通道,三维自动调节聚焦,发射波长滤光片可方便地更换以适应多种染料选择,能分别显示进样和分离通道2条电流-时间曲线.考察了该分析仪的检测灵敏度、检测极限和线性范围,显示了分析灵敏度高,检测限低和线性范围宽等特点,在自制注塑型PMMA塑料芯片上实现了φX174Haedi-gesT_dNA片段的分离测定和烟叶act基因PCR产物的分析     

~(12)CO_2/~(13)CO_2体系中碳同位素的显微激光拉曼光谱研究

采用自行设计的装置制备了一系列不同比例的12CO2/13 CO2混合物,对混合物样品进行显微激光拉曼测试,获得CO2气体碳同位素分子的拉曼特征峰。对实验数据分析发现,12CO2的摩尔分数[x(12CO2)]与12CO2/13 CO2混合物中拉曼特征峰峰面积比之间存在数学关系式。根据拟合的关系式,利用显微激光拉曼光谱可以预测CO2气体碳同位素的组成,并为以后预测单个流体包裹体中12CO2的摩尔分数奠定了理论基础。     

基于极少量采样的彩绘文物颜料成分分析

随着文物保护理念的提升,越来越提倡文物样品的无损或微损分析;同时由于文物样品的复杂性,对分析技术提出了更加严苛的要求.彩绘类文物的颜料分析研究,对其文物信息的提取,以及古代人类历史、社会、文化的研究和阐述具有重要作用.结合本研究组前期的研究成果,本研究提出了一种在极少量采样的情况下,分析研究文物颜料的方法,并用于榆林卧...     

基于拉曼光谱技术的联苯苄唑药物有效成分的快速鉴定和生产溯源研究

有效成分的定性和定量分析是药物分析的核心。实际样品测定中,通常需要进行样品前处理,以消除复杂辅料成分的干扰,此过程耗时长,且难度较大。因此,发展快速定性筛查技术,提高药物分析的工作效率非常必要。本研究以联苯苄唑药品作为模型药物,将拉曼光谱技术和主成分分析(Principal components analysis, PCA)和支持向量机(Support vector machine, SVM)等机器学习算法联用,探讨了其用于药物有效成分快速定性分析的可行性。针对不同药品中辅料成分复杂、组成不一,并且其拉曼光谱谱图与低含量(1%)的联苯苄唑分子的谱图存在明显交叠的问题,以原料药的拉曼光谱为基准,利用PCA方法精准定位和提取成品药拉曼谱图中联苯苄唑分子的特征拉曼光谱信息,实现了准确定性分析。本研究无需获得每一种辅料的特征拉曼光谱谱图,根据拉曼谱图中1600和1650 cm^-1等处谱峰的细微差异,采用PCA方法结合SVM分类器策略,实现了药物生产溯源的准确区分和鉴定。本研究为药物分析研究提供了一种无损快速溯源的分析方法。     

南海神狐海域及祁连山冻土区天然气水合物的拉曼光谱特征

采用显微激光拉曼光谱对我国在南海神狐海域及祁连山冻土区首次钻获的天然气水合物实物样品进行了详细的研究, 探讨了其笼型结构特征及其气体组成. 结果表明, 南海神狐海域天然气水合物样品是典型的I型结构(sI)水合物, 气体组分主要是甲烷, 占99%以上; 水合物大笼的甲烷占有率大于99%, 小笼为86%, 水合指数为5.99. 祁连山冻土区天然气水合物气体组分相对复杂, 主要成分除甲烷外(70%左右), 还有相当数量的乙烷、丙烷及丁烷等烃类气体, 从拉曼谱图上可初步判断其为II型结构(sII)水合物; 水合物的小、大笼的甲烷占有率的比值(θ_S/θ_L)为26.38, 远远大于南海神弧海域水合物的0.87, 这主要是由于祁连山水合物气体组分中的大分子(乙烷、丙烷及丁烷等)优先占据水合物的大笼, 大大减少了大笼中甲烷分子的数量.     

拉曼光镊流式细胞仪的构建及其在地中海贫血分析中的应用

为自动检测和分析地中海贫血(地贫)红细胞内部的物质变化情况,建立拉曼光镊-微流控芯片自动化系统平台。应用此装置收集β地贫红细胞和正常红细胞的拉曼光谱,并对其进行多元统计分析,从拉曼特征峰(1004,1130,1450,1545,1604和1618cm-1)的数据统计分析可见,β地贫红细胞的血红蛋白分布比正常红细胞广,平均强度差在6%以内。采用主成分分析法,可较好地将正常红细胞和β地贫的红细胞区分开,从载荷图可以更明显的看到它们的变化情况。此装置实现了快速、准确、非损伤的全自动化检测,为生物学的研究和医学诊断提供新的研究手段。     

串联飞行时间质谱中亚胺离子的断裂特征及其在肽段鉴定中的作用

基质辅助激光解吸电离-串联飞行时间质谱(MALDI-TOF/TOF)产生的亚胺离子可以提供丰富的肽段组成信息,该方法通常用于基于数据库搜索的蛋白质鉴定,或者结合化学衍生法用于从头测序,因而在一定程度上限制了对亚胺离子的认识及应用。本研究利用239个串联质谱探索MALDI-TOF/TOF中亚胺离子的断裂特征以及它们在肽段鉴定中的应用,发现在高能碰撞诱导解离条件下组氨酸等14种氨基酸可产生较强的亚胺离子信号(>50%阳性率),氨基酸的化学结构、位置效应和氨基酸残基个数是影响碎片离子强度的主要因素。此外,探讨了亚胺离子应用过程中的假阳性问题,提出亚胺离子相对强度的比较可以降低假阳性和提高肽段鉴定确定度,有助于完善目前的数据库搜索算法和辅助从头测序分析。     

乙酰胺基阿维菌素的成分分析与鉴定

用元素分析,13CNMR,IR,以及正负离子质谱对乙酰胺基阿维菌素（EPR）工业品的主要成分进行了确证.用HPLC-ESI MS对EPR工业品的组成成分进行了分离,并根据其准分子离子和特征紫外光谱鉴定了它的5个组分,其主要成分是EPR-B1a.     

Spatial Resolution of a Wavelength-Dispersive Electron Probe Microanalyzer Equipped with a Thermal Field Emission Gun

In this study, a prototype WDS-EPMA equipped with a thermal field emitter (TFE) was used. By using X-ray mapping technique with this instrument, we analyzed sub-micron inclusions in highly pure copper compounds used for manufacturing electronic devices. The analytical conditions of the accelerating voltages were 10 keV and 15 keV; the measured elements were Ni and Si. We measured 160000 points (400 × 400 points) within a couple of hours (1.5 hours at 10 keV, 0.5 hour at 15 keV). The analysis of the X-ray mapping data revealed very small inclusions with diameters estimated to be less than 100 nm. The new EPMA could be used for the elemental analysis of various materials including very light elements in a wide area with a spatial resolution of 100 nm.     

The electron microanalyzer (EPMA): a powerful device for the microanalysis of filled polymeric materials

The electron probe microanalyzer is a device often used in the field of geology or in the glass and steel industries. However, it is barely known or used in the polymer field. Thus, in this paper, we investigate the use of electron probe microanalyzer for polymer microanalyses and compared it with a scanning electron microscope equipped with an energy dispersive spectrometer. To show the unique potential of this technique only develop in our lab for polymer application, three different samples were studied: (i) a fire protective epoxy‐based coating submitted to aging in salt water, (ii) the distribution of organometallic catalysts into a thermal isolative silicone polymer, and (iii) the fouling growth of milk protein (biopolymer) on a stainless steel surface. Compared to an energy dispersive spectrometer, with an electron probe microanalyzer it is possible to quickly create X‐ray mappings of low concentration elements at a good resolution, as well as allowing the interpretation of the mechanism of action for the three samples which was impossible using only an energy dispersive spectrometer because of its too low detection resolution. Copyright © 2015 John Wiley & Sons, Ltd.     

Characterization of a laser‐nitrided titanium alloy by electron backscattered diffraction and electron probe microanalysis

After a laser gas nitriding treatment of the Ti‐7.5Al (atom %) titanium‐based alloy, we used a combination of electron backscattered diffraction (EBSD) in scanning electron microscope and electron probe microanalysis (EPMA) techniques in order to efficiently characterize the different phases in the resolidified layer. Representative measurements of chemical composition and reliable determination of crystal structure were possible for each phase of the complex microstructure. The reaction zone is formed by a mixture of isostructural TiN phases with dendritic and/or ‘coarse’ needles morphology, fixed into a α′‐Ti matrix (martensite) with a thin needle aspect. The nitrogen solubility was found to remain very low in the α′‐Ti matrix (up to 2–3 atom %), while in the TiN phase, an aluminum solubility as high as 4 atom % was measured, reducing drastically the nitrogen content into a Ti₇₉N₁₇Al₄ chemical composition. Copyright © 2005 John Wiley & Sons, Ltd.     

Identification by Electron Probe Microbeam Analysis of Submicron Borides in Joints of Nickel Base Superalloys

The phases formed at the interface between an intermetallic (NiAl) and a nickel base superalloy joined by combustion synthesis were investigated, particularly the eutectic phases. Owing to their small size, the characterisation of these phases using a Castaings electron microprobe encounters difficulties. The analysis volume size is generally too large to differentiate the phases from their surrounding matrix, even by using low accelerating voltage. Moreover, the eutectic phases contain boron, which is difficult to characterise by EPMA. Independently of the phases shape, the characterisation can be solved by viewing this complex system as a surrounding matrix and a multi layer system. The results of these simulations revealed the presence of two categories of borides: the eutectic boride MM₂B₂ (M=Mo and M=Co, Cr) and the solid solution boride [Cr_1–x (Mo, W)_x]B.     

眼动仪视角下的化学实验基本操作中师生关注点初探

针对化学实验课堂中学生事故频出、教学效果低下的问题,以无机与分析化学实验(I)中部分基础操作为例,借助眼动热点图研究对比了师生在实验操作中的关注点,分析了造成学生注意力发散的原因,并尝试从新的视角阐述存在已久的教育问题。在此基础上提出了一些相应建议,明确实验操作的规范化需遵循循序渐进、反复训练并逐步强化的原则,为进一步优化实验课程设计、发展化学实验教学活动实践提供科学的理论基础与支持。     

Laser microprobe mass analysis for the identification of asbestos fibers in lung tissue and broncho-alveolar washing fluid

Laser microprobe mass analysis (LAMMA) provides qualitative information on mineral fibers in human lung tissue, ashed lung samples and bronchoalveolar lavage fluid (BAL). Chemical surface alternations caused by fluids in the human lung can be characterized. In laser desorption conditions the negative spectra indicate the presence of ferritin. The measurements support and complement data obtained by electron microscopy.     

黄花菜中黄酮的超声波提取、纯化及鉴定

用正交实验法对黄花菜中黄酮的超声波提取工艺中的超声功率、样品细度、固液比例、提取时间4个因素进行了研究,优选出简便可靠的黄酮提取工艺。其最佳提取工艺条件是:黄花菜过60目筛后,超声波功率为高档,固液比为1:10,提取为20 min。通过红外光谱、紫外光谱、色谱分析可以确定黄花菜中的黄酮是黄酮醇类黄酮。     

Chemical Modification of Biomarkers through Accelerated Degradation: Implications for Ancient Plant Identification in Archaeo-Organic Residues

Biochemical and biomolecular archaeology is increasingly used to elucidate the consumption, use, origin, and trade of plants in the past. However, it can be challenging to use biomarkers to identify the taxonomic origin of archaeological plants due to limited knowledge of molecular survival and degradation for many key plant compounds in archaeological contexts. To gain a fundamental understanding of the chemical alterations associated with chemical degradation processes in ancient samples, we conducted accelerated degradation experiments with essential oil derived from cedar (Cedrus atlantica) exposed to materials commonly found in the archaeological record. Using GC-MS and multivariate analysis, we detected a total of 102 compounds across 19 treatments that were classified into three groups. The first group comprised compounds that were abundant in fresh cedar oil but would be unlikely to remain in ancient residues due to rapid degradation. The second group consisted of compounds that remained relatively stable or increased over time, which could be potential biomarkers for identifying cedar in archaeological residues. Compounds in the third group were absent in fresh cedar oil but were formed during specific experiments that could be indicative for certain storage conditions. These results show that caution is warranted for applying biomolecular profiles of fresh plants to ancient samples and that carefully designed accelerated degradation experiments can, at least in part, overcome this limitation.     

黑紫橐吾化学成分的分离与鉴定

利用各种色谱技术对黑紫橐吾的乙酸乙酯萃取部位进行分离纯化, 并且根据一维和二维波谱数据进行结构鉴定. 共分离得到4个呋喃雅槛蓝型倍半萜: 1α-氯-6β-异丁酰基-9-酮-10β-羟基-呋喃雅槛蓝烷(1), 1α-羟基-6β-异丁酰基-9-酮-10β-氢-呋喃雅槛蓝烷(2), 1α-羟基-6β-异丁酰基-9-酮-10α-氢-呋喃雅槛蓝烷(3)和1α,10β-二羟基-6β-当归酰基-9-酮-呋喃雅槛蓝烷(4). 其中化合物1为新化合物, 并且通过X射线单晶衍射确定了绝对构型; 化合物2~4为首次从该植物中分离得到.     

基于锂离子电池老化行为的析锂检测

析锂会极大地影响锂离子电池的寿命和安全性,锂离子电池的析锂检测十分必要. 本文根据锂离子电池的两种主要老化机理-SEI(Solid Electrolyte Interface)膜生长和析锂对老化行为上的不同影响,基于多应力作用下的锂离子电池循环老化实验结果,提出了两种检测析锂的方法,分别为内阻-容量轨迹法和阿伦尼乌斯准则法. 两种方法的判定结果具有良好的一致性. 之后,利用微分电压法区分了电池容量损失的不同来源,并进行了电池负极片EDS（Energy Dispersive Spectrometer）能谱分析,对析锂检测方法进行了验证. 本文方法只需利用电池老化过程中可测的容量和内阻等电学量,判断方法简便,可实现非解体检测;同时,利用了单次循环的微量析锂在时间尺度上的累积,对析锂工况的辨识具有较高的敏感性. 本文方法对锂离子电池的寿命加速测试、延寿使用、安全管理等具有重要意义.