电子显微技术应用于生物纳米材料表征与测试的研究进展

该文简述了电子显微技术的发展历程,并介绍了现代电子显微镜的新功能。针对生物纳米材料理化性能与功能应用的特殊性,结合研究实例,重点阐述运用电子显微结构表征与原位分析测试技术指导构建新颖纳米结构、揭示材料与细胞/组织相互作用并发挥功能的机制。并在此基础上,展望了电子显微技术在生物纳米材料研究领域的发展方向(大尺寸图像拼接、三维重构、动态原位实时成像)。     

ZrO2氧空位显微结构的高分辨电镜研究

基于透射电镜X射线能谱仪得到的微区成分信息及高分辨电子显微结构信息,构建具有氧空位缺陷的ZrO2晶体结构模型,用200 kV透射电子显微镜的参数进行高分辨实验像的多片层法模拟计算,观察分析了ZrO2多晶材料样品的晶格缺陷.沿[001]方向的二维晶格像及相应的傅立叶变换像显示出ZrO2样品的晶格缺陷.将计算机模拟结果与高分辨实验像进行比较,结果表明计算机模拟像的衬度及周期性与实验像之间符合良好.根据晶体结构的缺陷模型和模拟计算,阐明了氧空位缺陷引起的实验像衬度的变化.通过高分辨电子显微观察结果及计算机模拟结果,揭示了陶瓷ZrO2多晶材料样品晶格中氧空位的存在.     

聚酞菁锗氧烷的电子辐照损伤及高分辨电子显微学研究

利用选区电子衍射观察了聚酞菁锗氧烷晶体的电子辐照损伤规律,结果表明,各晶面损伤次序既与所对应衍射班点的衍射级数有关,又与晶面间距有关。同时用选区电子衍射测量该聚合物晶体的耐电子辐照能力,对比不同加速电压对耐电子辐照能力的影响,讨论了获取晶面间距小于1nm的晶面的晶格像的可能性。最后利用高分辨电子显微技术拍摄了该聚合物的间距为0.66nm的晶格像和二维晶格像。     

日本筑波大学小寺泽良—教授应邀来河南省讲学

日本筑波大学教授、日本材料学会电子显微断口专业委员长小寺泽良一先生,应河南省电镜学会等的邀请,于1985年10月7日至20日分别在郑州和洛阳进行了电子显微断口分析应用讲学。其重点内容是交变应力下材料断裂分析及高温蠕变破坏分析等。全国各地的共70多个单位100多名科技工作者听取了这次讲学。     

龙眼花粉形态扫描电子显微摄影测量的研究

本文利用扫描电子显微技术、电子计算机计算技术和摄影测量学原理,对龙眼花粉进行三维定量分析。使孢粉形态学的研究从光学显微镜(OLM)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)进入到扫描电子显微摄影测量(SEMP)立体观察与三维定量分析的高级阶段。为我国龙眼一个野生品种和五个栽培品种进行了形态分类,为改良品种和遗传变异的研究提供了分析数据。     

充分发挥分析电镜的作用

作者积多年电子显微工作之经验，总结出熟悉仪器、不断改进实验方法和能够自行进行常规维修是做好电子显微工作的关键。广泛宣传，和用户深入地讨论并教会更多人操作仪器，使他们的科研与生产少走弯路，分析工作才能取得明显的社会和经济效益。     

一种具有新颖结构和形态的炭须

在高温处理球磨过的石墨材料时,发现了一种结构和形状新颖的炭须.透射电子显微术(TEM)和高分辨透射电子显微术(HREM)证实其石墨片层几乎垂直于炭须的轴向.场发射扫描电子显微镜(FESEM)发现其表面具有螺旋结构.结构分析证明这种螺旋状炭须生成机理同高温处理后的炭材料中含有的微量碳化锆有关.     

MgO掺杂阿利特的结构演变及其调制结构表征

利用X射线衍射(XRD)和透射电子显微镜(TEM)对不同MgO掺量的阿利特结构演变进行了研究。结果表明:当MgO掺量为0.5wt%时,T1和M1型共存;当MgO掺量为1.0wt%时,稳定为M1型;当MgO掺量在1.5wt%以上时,稳定为M3型。基于XRD数据计算得到了不同晶型阿利特的伪六方亚晶胞参数,结果显示各晶型的亚晶胞参数值非常接近。通过选区电子衍射(SAED)和高分辨透射电子显微像(HRTEM)对各晶型中的调制结构进行了观察。结果表明:各晶型阿利特中的超晶胞反射斑点坐标均可用相应的线形表达式描述,调制结构可以在HRTEM像中观察到,并以波状衬度的形式展现,其方向平行于亚晶胞中相应的晶面。     

钙稀土氟碳酸盐矿物中三种B8S6型新规则混层结构伯高分辨电镜研究

用选区电子衍射和高分辨电子显微术研究钙稀土氟碳酸盐矿物及其衍生物多晶体结构，发现三种不同的氟碳铈矿与直氟碳钙铈矿具８：６新规则混层结构，确定了各自的晶体结构类型，晶胞参数，堆垛模式及晶体化学式等。高分辨像的观察分析，揭示出了三种Ｂ８Ｓ６规则混层结构中的Ｃｅ－Ｆ离子层以及两个Ｃｅ－Ｆ离子层之间的ＣＯ３离子组具有不同的排列方式，观察和讨论了上述规则支结构中的无序夹层及堆垛层错等非均匀结构现象。     

低电压扫描电子显微术

低电压扫描电子显微术是研究半导体、绝缘体和生物材料的有效方法。本文综述了这种方法的优点、限制和关于扫描电镜的改进,并且提供了实际操作的某些要领。     

Spin labeling methods in molecular biology : G.I. Likhtenshtein,John Wiley & Sons,New York,London, Sydney and Toronto, 1976, pp. xiii + 258, price £26.00

As a consequence of intramolecular vibrations distorted apparent structures may result from an electron diffraction analysis of molecules possessing symmetrical equilibrium configuration. The amount of torsional distortion gives information concerning the barrier height to internal rotation. An approach is suggested to estimate barrier heights on the basis of average torsional angles as determined from electron diffraction, and expressions of the rotation-dependent distances as obtained from a Taylor expansion by neglecting higher order terms.     

Molecular structure of acetyldeyiethylphosphine,MeC(O)PMe2: II. CNDO/2 calculations

The sp, spd and spd' approximations of the CNDO/2 method have been applied to energy calculations for some models of the acetyldimethylphosphine molecule generated during treatment of the electron diffraction data. The results obtained for trial configurations with different angles of rotation of the acetyl group about the PC _ac bond predict two symmetric energy minima separated by a rather low barrier. This is in agreement with the electron diffraction data which are compatible with the suggestion of large amplitude torsional vibrations of the acetyl group. Energy calculations have also been performed for the final electron diffraction models. The calculations, however, fail to remove ambiguity from the question of a preferred model of the acetyldimethylphosphine molecule.     

Internal rotation and equilibrium structure of the 2-methyl-2-nitropropane molecule from joint processing of gas phase electron diffraction data,vibrational and microwave spectroscopy data,and quantum chemical calculation results

The structure and internal rotation of the 2-methyl-2-nitropropane molecule is studied by electron diffraction and quantum chemical calculations with the use of microwave and vibrational spectroscopy data. The electron diffraction data are analyzed within the general intramolecular anharmonic force field model and the quantum chemical pseudoconformer model, considering the adiabatic separation of the degree of freedom of large amplitude motion, i.e., the internal rotation of the NO₂ group. The equilibrium eclipsed configuration of the C _s symmetry molecule has the following experimental bond lengths and valence angles: r _e(N=O) = 1.226//1.226(8) Å, r _e(C–N)//r _e(C–C) = 1.520//1.515/1,521(4) Å, ∠_еC–C–N = = 109.1/106,1(8)°, ∠_еO=N=O = 124.2(6)°, ∠_eC–C–H_avg = 110(3)°. The equilibrium geometry parameters are well consistent with MP2/cc-pVTZ quantum chemical calculations and microwave spectroscopy data. The thermally average parameters previously obtained within the small vibration model show a satisfactory agreement with the new results. The electron diffraction data used in this work do not allow a reliable determination of the barrier to internal rotation. However, at a barrier of 203(2) cal/mol, which is derived from the microwave study, it follows from the electron diffraction data that the equilibrium configuration must correspond to an eclipsed arrangement of C–C and N=O bonds, which is also consistent with the results of quantum chemical calculations of various levels.     

An electron diffraction study of the molecular structure of BIS(trifluoromethyl) monoselenide

The molecular structure of (F₃C)₂Se has been determined in the vapour phase by the sector microphotometer method of electron diffraction. Two structures, differing essentially in the angles of rotation of the CF₃- groups about the C-Se bonds, are in good agreement with the data. The mean C-Se and C-F bond lengths are 1.978 and 1.333 Å, respectively.     

Electron‐Beam Irradiation in TEM of Hard‐Segment Homopolymers and Polyurethanes with Different Hard‐Segment Content

Summary: A hard‐segment homopolymer (HSH) and segmented poly(ester urethanes) (PESU) were studied by TEM to estimate their stability against electron‐beam irradiation. The bright‐field image and electron‐diffraction modes in TEM and optical polarised microscopy were used. It is shown that both soft and hard segments are sensitive to the electron beam. None of the films was stable enough to register an electron‐diffraction pattern without damage.

Electron‐diffraction pattern taken from the film of hard‐segment homopolymer crystallised at 100 °C from DMF: (a) the pattern registered immediately; (b) the pattern registered after 5 s of exposure in the TEM at the same place.     

Internal Rotation and Equilibrium Structure of the Bromonitromethane Molecule According to Gas Electron Diffraction Data and Quantum Chemical Calculations

The structure and internal rotation of the bromonitromethane molecule are studied using electron diffraction analysis and quantum chemical calculations. The electron diffraction data are analyzed within the models of a general intramolecular anharmonic force field and quantum chemical pseudoconformers to account for the adiabatic separation of a large amplitude motion associated with the internal rotation of the NO₂ group. The following experimental bond lengths and valence angles are obtained for the equilibrium orthogonal configuration of the molecule with C_s symmetry: r_e(N=O) = 1.217(5) Å, r_e(C–N) = 1.48(2) Å, r_e(C–Br) = 1.919(5) Å, ∠_еBr–C–N = 109.6(9)°, ∠_еO=N=O = 125.9(9)°. The equilibrium geometry parameters are in good agreement with CCSD(T)/cc-pVTZ calculations. Thermally averaged parameters are calculated using the equilibrium geometry and quadratic and cubic quantum chemical force constants. The barrier to internal rotation cannot be determined reliably based on the electron diffraction data used in this work. There is a 82% probability that the equilibrium configuration with orthogonal C–Br and N=O bonds is most preferable, and internal rotation barrier does not exceed 280 cm^-1, which agrees with CCSD(T)/cc-pVTZ calculations.     

Molecular conformation of bilirubin from semiempirical molecular orbital calculations

Semiempirical methods were utilized in the computation of a fully optimized structure of bilirubin. Bond lengths and bond angles obtained using either AM1 or PM3 calculations showed excellent agreement with those obtained by X-ray diffraction. This indicated that molecular orbital methods satisfactory reproduced the complex conjugation found in bilirubin. Dihedral angles of the crucial “hinge” and the dihedral angles of the propionic acid side chains agreed well with those found by X-ray diffraction. Calculated hydrogen- bond parameters (distance and angles) showed substantial differences from experimental values, probably due to inherent weakness in the parameterization of the molecular orbital techniques. Conformational studies were carried out using AM1 by rotating the C9? C10 bond in 5° increments showed that the most stable structure exhibited a minimum at about 125° and exhibited a structure similar to those postulated from X-ray and NMR experiments. The hydrogen bonds showed remarkable tenacity during rotation of the C9? C10 bond and resisted breaking until the molecule was under extreme strain. © 1992 John Wiley & Sons, Inc.     

Determining molecular structures and conformations directly from electron diffraction using a genetic algorithm.

A global optimization strategy, based upon application of a genetic algorithm (GA), is demonstrated as an approach for determining the structures of molecules possessing significant conformational flexibility directly from gas-phase electron diffraction data. In contrast to the common approach to molecular structure determination, based on trial-and-error assessment of structures available from quantum chemical calculations, the GA approach described here does not require expensive quantum mechanical calculations or manual searching of the potential energy surface of the sample molecule, relying instead upon simple comparison between the experimental and calculated diffraction pattern derived from a proposed trial molecular structure. Structures as complex as all-trans retinal and p-coumaric acid, both important chromophores in photosensing processes, may be determined by this approach. In the examples presented here, we find that the GA approach can determine the correct conformation of a flexible molecule described by 11 independent torsion angles. We also demonstrate applications to samples comprising a mixture of two distinct molecular conformations. With these results we conclude that applications of this approach are very promising in elucidating the structures of large molecules directly from electron diffraction data.     

A re-investigation of the molecular structure of trifluoroacetic acid by means of gas phase electron diffraction

Analysis of the electron diffraction patterns of trifluoroacetic acid at 140°C indicates the existence of one conformation with the CF₃-group rotated 17.3± 0.9° from a position with a fluorine atom eclipsed with respect to the CO bond. The data does not exclude the possibility of free internal rotation but it seems improbable.The important bond lengths, r_g(1), and bond angles with their standard deviations in parentheses, are: C-F: 1.325 (0.003), C-C: 1.546 (0.005), CO: 1.192 (0.003), C-O: 1.353 (0.014) Å, C-C-F: 109.5 (0.3), C-CO: 126.8 (0.8), C-C-O: 111.1 (0.9)°.     

Ultrafast electron diffraction: oriented molecular structures in space and time.

The technique of ultrafast electron diffraction allows direct measurement of changes which occur in the molecular structures of isolated molecules upon excitation by femtosecond laser pulses. The vectorial nature of the molecule-radiation interaction also ensures that the orientation of the transient populations created by the laser excitation is not isotropic. Here, we examine the influence on electron diffraction measurements--on the femtosecond and picosecond timescales--of this induced initial anisotropy and subsequent inertial (collision-free) molecular reorientation, accounting for the geometry and dynamics of a laser-induced reaction (dissociation). The orientations of both the residual ground-state population and the excited- or product-state populations evolve in time, with different characteristic rotational dephasing and recurrence times due to differing moments of inertia. This purely orientational evolution imposes a corresponding evolution on the electron scattering pattern, which we show may be similar to evolution due to intrinsic structural changes in the molecule, and thus potentially subject to misinterpretation. The contribution of each internuclear separation is shown to depend on its orientation in the molecular frame relative to the transition dipole for the photoexcitation; thus not only bond lengths, but also bond angles leave a characteristic imprint on the diffraction. Of particular note is the fact that the influence of anisotropy persists at all times, producing distinct differences between the asymptotic "static" diffraction image and the predictions of isotropic diffraction theory.