透射电镜三维重构技术在螺旋纳米材料手性判断中的应用

螺旋材料在手性催化、手性拆分以及手性光学材料等领域的潜在应用价值引起了研究者的广泛兴趣,手性的判断在研究应用中也显得尤为重要。单一的透射电镜和扫描电镜的二维图像不能作为准确判定螺旋材料手性的唯一依据。透射电镜三维重构技术可作为一种直观有效的方法确定螺旋材料的手性。本文通过透射电镜的三维重构技术对两种单手螺旋的3-氨基苯酚-甲醛树脂及单手螺旋碳质纳米管样品的手性做出了判断。     

透射电镜三维重构确定金纳米粒子的立体结构

贵金属纳米颗粒具有局域表面等离激元这一特性使其具有丰富的光学性质,而这一特性受制于纳米颗粒所形成的立体几何形状,而透射电镜和扫描电镜的二维图像不能真切地观测和确定纳米颗粒所形成的立体几何结构。透射电镜三维重构技术可作为一种确定纳米颗粒立体结构的直观有效的方法。本文利用透射电镜的三维重构技术,选择合适的参数进行二维图像的采集、图像匹配对中及重构、立体模型的构建,从而通过构建的模型对两种金纳米颗粒样品的不同几何形状所产生的边界形态进行了确认和分析。     

透射电镜三维重构确定杂化嵌段共聚物两相空间分布

多金属氧酸盐(POM)簇-聚合物杂化物是一类兼有无机材料催化性能和聚合物可加工性的,具有优异应用前景的杂化材料。POM簇-聚合物杂化物中两相的空间分布对材料的性能有至关重要的影响。但该材料纳米尺度的3D两相空间形貌和结构无法用常规的透射电镜观察和表征。本文利用透射电镜的三维重构技术,选择合适的参数和方法进行二维图像的采集、图像匹配对中及重构,并完成立体模型的构建,从而通过构建的模型对三种杂化共聚物的两相空间分布进行了确认和分析。     

原位冷冻电子断层扫描的发展及在生物研究方面的应用

对生物大分子复合物的研究和结构分析对于全面了解其功能和生物学意义至关重要. 冷冻电子显微镜在提供生物大分子结构及大分子分布等方面起到重要的作用. 近年来, 冷冻电子显微镜的硬件和软件的发展进一步提高了冷冻电子显微镜的有效性, 使其对各种生物结构、 蛋白质结构的解析更加准确快捷. 但是, 对于生物系统来说, 蛋白质和大分子复合物等均处于复杂的生理环境中, 因此原位检测生物分子的三维结构对于生物体系和结构生物学具有重要意义. 冷冻电子断层扫描作为一种功能强大的技术, 可以无需标记直接通过冷冻样品的固有衬度识别生物大分子的结构, 并且可在原位生理环境中对生物分子进行纳米级分辨率的三维成像. 本文综述了与冷冻电子断层扫描相关的样品制备和数据处理技术, 并总结了冷冻电子断层扫描技术在分离的大分子复合物和整个细胞或组织中的生物学应用.     

基于固体核磁共振方法的蛋白质组装体三维结构解析

蛋白质组装体广泛存在于生物体内,具有相关生物学功能或与人类的重要疾病密切相关。蛋白质组装体分子量大,通常难以溶解和结晶,限制了常用的结构研究手段如X射线晶体学和液体NMR等在其高分辨三维结构解析中的应用。固体核磁共振技术(ssNMR)在难溶、非结晶样品的三维结构解析中具有独特的优势,尤其随着固体NMR硬件包括高场磁体和高性能的探头、固体NMR多维脉冲实验技术和样品制备技术特别是同位素标记技术的快速发展,固体NMR已经成为了蛋白组装体三维结构解析的重要手段。在样品制备方法方面,强调了样品制备条件的优化对得到构象均一样品的重要性,以及丰富的同位素标记方法的使用对固体NMR谱图分辨率提高的重要作用。同时多种脉冲序列如质子驱动自旋扩散技术(PDSD),偶极辅助旋转共振技术(DARR),质子辅助重偶技术(PAR)或转移回波双共振技术(TEDOR)等的建立和发展为结构约束条件收集提供了基本的技术方法。此外,固体NMR与其它实验技术如扫描透射电镜(STEM),冷冻电镜(Cryo-EM)等和理论模拟方法的联用能显著地提高固体NMR的能力,从而能解析分子量更大、结构更复杂的蛋白质组装体的三维结构。本文以Aβ纤维和T3SS针状体的三维结构解析为例介绍固体NMR在蛋白质组装体结构研究的最新实验方法,重点介绍最新的距离约束条件获取的实验方法进展,以及固体NMR与其它实验和理论模拟研究手段的联用在蛋白质组装体结构解析上的最新进展,期望有助于读者对固体NMR技术在蛋白质组装体的三维结构解析方面的研究进展有所了解。     

IPET:测定独个生物大分子三维空间结构的实验方法

蛋白质的动态特性和结构活性对于蛋白质功能的调控具有根本意义。传统的结构确定方法(包括X射线和电子显微镜单颗粒分析技术等)往往需要成千上万不同蛋白质分子的平均信号,因此难以确定蛋白质分子的动态结构。而电子显微断层成像技术是一种对独个生物个体结构从不同的观测角度照相、并计算来恢复该个体的三维结构密度图的方法。传统的冷冻电子断层成像重构方法采用整个大尺寸电镜图像进行重构计算,通常用来研究细菌、细胞切片等大尺寸生物个体在较低分辨率下的结构;由于分辨率的限制,不足以获得小尺寸的蛋白质分子的结构细节。最近,任罡研究小组提出一种独个生物颗粒的电子显微断层成像方法(individual-particle electron tomography,IPET)。该方法通过减小图像尺寸(直至所选区域只包含单个蛋白质分子)的策略,运用提出的FETR(focused electron tomography reconstruction)算法来提高独个大分子重构的分辨率。此方法不需要初始模型和大量分子的平均信号,同时能够容忍一定的测角误差。本文综述了IPET/FETR方法在确定独个分子结构过程中的具体步骤以及如何应用该方法来研究蛋白动态特性和结构变化特征。期望通过该综述和国内同行交流,分享最新的前沿研究,为赶超世界科技前沿的建设添砖加瓦。     

光学相干层析技术在法庭科学中的新应用

光学影像技术是法庭科学物证检验分析的重要技术手段，具有无损、原位、快速等优势。近年来，随着光学影像技术的不断发展，一些新技术、新方法不断被引入法庭科学领域并付诸应用。光学相干层析技术（简称OCT技术）是一种光学断层成像技术，具有无损、高分辨、快速、断层成像的特点，特别是其可以无损地得到材料或生物组织内部的结构信息，突破了传统二维成像只能进行物质表面分析的局限，因此可成为一种很有前景的新型法庭科学光学影像技术。本文首先介绍了自主搭建的一套三维OCT成像系统，并着重介绍了基于该系统应用于法庭科学油漆物证检验、胶带指纹显现和毛囊特征分析等方面的研究。结果表明，OCT技术非常适合用于法庭科学物证检验分析，作为其他检验的先导技术手段，获取样品内部信息，提取新型光学特征参数。由于其采用光纤化技术，还有望实现便携化、小型化，在现场勘查中开展相关应用。     

石墨烯量子点荧光开关综合实验的设计

以柠檬酸为原料通过脱水缩合的方法合成荧光石墨烯量子点,结合透射电镜、红外及荧光光谱仪对其结构、组成及性能进行表征,并利用过渡金属离子与石墨烯量子点之间的电子转移作用、乙二胺四乙酸与金属离子之间的络合作用使其发生荧光淬灭与恢复,实现石墨烯量子点荧光“关”与“开”的设计,并总结出过渡金属离子电子结构与荧光开关之间的作用规律。将实验教学与前沿研究紧密结合,涵盖了材料合成、表征和性能研究等3方面的内容,内容丰富、综合性强,有利于培养学生的科研素养与实验技能,并提高其分析问题、解决问题的能力。     

电子束敏感材料的原子尺度结构研究

分子筛和金属有机骨架(MOF)材料以其独特的孔道和骨架结构在催化、 储能、 干燥及净化和吸附分离等领域有着广泛应用, 对其结构的原子尺度表征对于深入理解其构效关系具有重要意义. 但其大孔道结构和有机骨架使得它们对电子束辐照极为敏感, 在常规透射电镜成像模式下结构会很快被破坏变为非晶, 从而无法获得孔道和骨架的原子排列信息. 最近发展起来的基于积分差分相位衬度扫描透射电子显微(iDPC-STEM)技术在电子敏感材料和轻元素组分成像方面展现出明显优势, 使得对多孔骨架材料及烃池物种的表征成为了可能. 本文综述了本课题组近期利用该技术对分子筛和MOF材料原子尺度结构方面的研究. 将iDPC-STEM技术应用到ZSM-5分子筛催化剂中, 实现了对该分子筛的原子级骨架结构的成像分析. 在MOF体系中, 利用该技术观察到MIL-101骨架内部有机连接体与金属节点的配位方式, 在此基础上解析了MIL-101结构中有机配体的连接和金属节点的苯环结构, 并观察了MOF的原子级表面、 界面和缺陷等局域结构特征. 最后对iDPC-STEM技术在原子尺度成像方面的应用潜力进行了总结与展望.     

基于共价有机框架的电化学生物传感器在生物样品检测中的应用

共价有机框架材料(Covalent Organic Frameworks, COFs)是一种具有纳米级结构有序性的二维或三维有机结晶材料, 具有高度周期性和可修饰性等结构优点. 基于COFs制备的电化学生物传感器具有灵敏度高、特异性强、重复性好等特点, 在检测生物样品方面具有广阔前景. 本综述简要概述了COFs的合成方法与策略、电化学生物传感器的介绍与分类以及COFs在电化学生物传感检测生物样品领域的应用. 最后本综述对COFs材料在生物传感领域的技术瓶颈与未来的发展方向进行了总结与讨论.     

Creation of magnetic cerasomes through electroless plating and their manipulation using external magnetic fields

Magnetic cerasome, an artificial cell membrane having ultrathin magnetic metal layers on the surface, was prepared through electroless plating of magnetic metal alloy onto an organic–inorganic vesicular nanohybrid “cerasome.” Morphological and functional characteristics of the magnetic cerasome were evaluated using various physical measurements: scanning and transmission electron microscopies, energy-dispersive X-ray spectroscopy, electron tomography, and vibrating sample magnetometry. The results proved that high morphological stability of the cerasome was important for constructing the magnetic lipid vesicle and that insertion of an alkylated metal ligand into the cerasome was essential to the magnetic metal alloy deposition on the cerasome surface. Fluorescence microscopic observations revealed that the magnetic cerasomes were collected reversibly on the slide glass surface and manipulated depending on external motion of a magnet. The potential use of the magnetic cerasomes as a novel vesicular nanohybrid is also described in this report.     

Minerals and aligned collagen fibrils in tilapia fish scales: structural analysis using dark-field and energy-filtered transmission electron microscopy and electron tomography

The mineralized structure of aligned collagen fibrils in a tilapia fish scale was investigated using transmission electron microscopy (TEM) techniques after a thin sample was prepared using aqueous techniques. Electron diffraction and electron energy loss spectroscopy data indicated that a mineralized internal layer consisting of aligned collagen fibrils contains hydroxyapatite crystals. Bright-field imaging, dark-field imaging, and energy-filtered TEM showed that the hydroxyapatite was mainly distributed in the hole zones of the aligned collagen fibrils structure, while needle-like materials composed of calcium compounds including hydroxyapatite existed in the mineralized internal layer. Dark-field imaging and three-dimensional observation using electron tomography revealed that hydroxyapatite and needle-like materials were mainly found in the matrix between the collagen fibrils. It was observed that hydroxyapatite and needle-like materials were preferentially distributed on the surface of the hole zones in the aligned collagen fibrils structure and in the matrix between the collagen fibrils in the mineralized internal layer of the scale.     

Recent advances in electron tomography: TEM and HAADF-STEM tomography for materials science and semiconductor applications.

Electron tomography is a well-established technique for three-dimensional structure determination of (almost) amorphous specimens in life sciences applications. With the recent advances in nanotechnology and the semiconductor industry, there is also an increasing need for high-resolution three-dimensional (3D) structural information in physical sciences. In this article, we evaluate the capabilities and limitations of transmission electron microscopy (TEM) and high-angle-annular-dark-field scanning transmission electron microscopy (HAADF-STEM) tomography for the 3D structural characterization of partially crystalline to highly crystalline materials. Our analysis of catalysts, a hydrogen storage material, and different semiconductor devices shows that features with a diameter as small as 1-2 nm can be resolved in three dimensions by electron tomography. For partially crystalline materials with small single crystalline domains, bright-field TEM tomography provides reliable 3D structural information. HAADF-STEM tomography is more versatile and can also be used for high-resolution 3D imaging of highly crystalline materials such as semiconductor devices.     

Focused ion beam sectioning and lift-out method for copper and resist vias in organic low-k dielectrics.

The focused ion beam lift-out technique for scanning electron microscope (SEM) and transmission electron microscope (TEM) sample preparation was shown to be applicable to copper/low-k dielectric semiconductor technology. High resolution SEM, TEM, and scanning transmission electron microscope analyses were performed on metal contacts and resist vias with no evidence of the interface damage or metal smearing commonly observed with mechanical polishing. Ion milling of the sample ex situ to the substrate provided decoration and adjustment of the exposed plane of the section when necessary for SEM analysis.     

浸渍-煅烧法合成纳米氧化铜的研究

纳米氧化铜是一种重要的功能材料,在高温超导、有机催化、传感器、锂离子电极材料等方面均具有广泛的应用前景.由于CuO在应用效果上与其形貌、粒径大小以及粒径分布有密切关系,因此,纳米CuO的可控研究仍具有重要意义.     

Off-axis electron holography of unbiased and reverse-biased focused ion beam milled Si p-n junctions.

Off-axis electron holography is used to measure electrostatic potential profiles across a silicon p-n junction, which has been prepared for examination in the transmission electron microscope (TEM) in two different specimen geometries using focused ion beam (FIB) milling. Results are obtained both from a conventional unbiased FIB-milled sample and using a novel sample geometry that allows a reverse bias to be applied to an FIB-milled sample in situ in the TEM. Computer simulations are fitted to the results to assess the effect of TEM specimen preparation on the charge density and the electrostatic potential in the thin sample.     

Solvothermal Synthesis and Characterization of HgTe Nanoplatelets Using Mercury(Ⅰ) Source

Mercury telluride (HgTe) nanoplatelets were obtained via a facile solvothermal reaction of mercury(Ⅰ) chloride and tellurium powder in ethylenediamine (en). Mercury(Ⅰ) was first applied as the mercury sources to prepare nanocrystal HgTe; moreover, the proposed mechanism for the fabrication of the sample was discussed in detail. The HgTe nanoplatelets were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM),transmission electron microscopy (TEM), high-resolution transmission electron microscopy(HRTEM) and Fourier transform infrared spectroscopy (FT-IR). The absence of IR absorption may render the title nanocrystal useful as an IR transparent material in the region.     

Solvothermal Synthesis and Characterization of HgTe Nanoplatelets Using Mercury（I） Source

Mercury telluride （HgTe） nanoplatelets were obtained via a facile solvothermal reaction of mercury（I） chloride and tellurium powder in ethylenediamine （en）. Mercury（I） was first applied as the mercury sources to prepare nanocrystal HgTe; moreover, the proposed mechanism for the fabrication of the sample was discussed in detail. The HgTe nanoplatelets were characterized by powder X-ray diffraction （PXRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, high-resolution transmission electron microscopy （HRTEM） and Fourier transform infrared spectroscopy （FT-IR）. The absence of IR absorption may render the title nanocrystal useful as an IR transparent material in the region.