透射电镜像转角的测定及应用

论述了完全标定透射电镜像转角所需拍摄的二次曝光电子显微像的数量,推导了由已测的像转角间接计算其它像转角的一般公式,以Philips Cm200电镜为实例,说明了测定像转角的基本步骤,并以实例说明怎样利用像转角,把衍射花样的晶体学信息传递给电子显微像。     

Electrochemical deposition of platinum nanoparticles on carbon: a study by standard and anomalous X-ray diffraction.

This paper is devoted to an alternative method to characterize platinum nanoparticles: X-ray powder diffraction with synchrotron radiation in classical and anomalous dispersion modes. We could straightforwardly determine the mean diameter and the surface concentration of carbon-supported platinum nanoparticles, even down to diameters of 2-3 nm and catalyst amounts of 0.03 mgcm(-2). We could study early stages of the formation of electrochemically prepared platinum nanoparticles from [PtCl4(2-) species preadsorbed on carbon inside a carbon-Nafion layer, to obtain a fuel-cell electrode. Our X-ray diffraction (XRD) results demonstrate that, provided the superficial concentration is not too high, new and smaller particles appear for each current pulse, since there is not any strong nucleation limitation for the high overvoltages obtained. Hydrogen evolution becomes the main electrochemical phenomenon on particles of sufficient size and it explains the noteworthy size limitation. Better yields of Pt metal are obtained for smaller current densities and longer times: the rate-determining step is then not electrochemical, but chemical or related to superficial diffusion.     

模板组装Fe纳米线阵列及其微结构

铝在硫酸溶液中经直流阳极氧化,得到多孔铝阳极氧化膜(AAO). 以AAO膜为模板,通过交流电沉积的方法,在AAO模板孔内成功组装了Fe纳米线.TEM分析表明,Fe纳米线的长度约为2.5 μm,其长度分布十分均匀；粗细均匀,直径约为25 nm. XRD实验分析证实,所制备的Fe纳米线为α-Fe.选区电子衍射（SAED）实验分析表明,α-Fe纳米线具有单晶结构.     

X-ray imaging using the radiation diffracted by polycrystalline materials

Imaging requires not only an area detector but also optics to relate the elements of the object to those of the detector. For X-rays optical elements based on reflection or refraction allowing the imaging of objects of several mm size are not available. Therefore, image formation like in the human eye cannot be achieved, but an approach realized in the eyes of insects where each facet has its own optics, has to be used. In the X-ray regime such a system can be realized by an arrangement of collimating tubes guiding the radiation from a region of the sample to the corresponding area of the detector and suppressing cross-fire from other regions.

Such an imaging system consisting of a microchannel plate in front of a CCD-detector has been installed on the 2Θ-arm of a 4-circle diffractometer at beamline G3 at HASYLAB, DESY. With this instrument, images as a function of one or more parameters can be collected. The structure of the data obtained in this way is distinct from those obtained by conventional diffraction techniques mostly yielding only one intensity value per scanning step and therefore requires different strategies for processing.     

Mapping nanometer and micrometer-scale structures at graphite surface by photoelectron diffraction

A series of C 1s photoelectron intensity angular distribution (PIAD) patterns from a crystalline graphite surface were mapped in two dimensions at intervals of 20 μm. Two kinds of PIAD patterns rotated by 30° from each other, corresponding to the two domains from the twinned crystal, were found. The standard deviation of the diffraction contrast was evaluated for each PIAD pattern from its intensity histogram. Surprisingly, we found that odd-number- (most probably single-) atom-height steps on the flat terrace region and their local atomic arrangement can be identified by two-dimensionally mapping the standard deviation values. Furthermore, we analyzed the photoelectron diffraction patterns and noticed that the normal direction of the sample surface at each point was slightly inclined differently. By connecting all the inclination angle data, the micrometer-scale corrugation of the sample surface was successfully visualized. Scanning photoelectron diffraction microscopy has been shown to be useful for the nanometer- and micrometer-scale structural imaging.     

Efficient computation of the exchange-correlation contribution in the density functional theory through multiresolution

A new algorithm is presented to improve the efficiency of the computation of exchange-correlation contributions, a major time-consuming step in a density functional theory (DFT) calculation. The new method, called multiresolution exchange correlation (mrXC), takes advantage of the variation in resolution among the Gaussian basis functions and shifts the calculation associated with low-resolution (smooth) basis function pairs to an even-spaced cubic grid. The cubic grid is much less dense in the vicinity of the nuclei than the atom-centered grid and the computation on the former is shown to be much more efficient than on the latter. MrXC does not alter the formalism of the current standard algorithm based on the atom-centered grid (ACG), but instead employs two fast and accurate transformations between the ACG and the cubic grid. Preliminary results with local density approximation have shown that mrXC yields three to five times improvement in efficiency with negligible error. The extension to DFT functionals with generalized gradient approximation is also briefly discussed.     

Some aspects of doping mechanism in Polyschwefelnitrid (SN)x

(SN)x crystals doped with iodine atoms showed ten or more additional diffuse streaks perpendicular to the b^*-axis, appearing between the layer lines of the electron diffraction pattern of pristine (SN)x. However, only four of these were observed in the X ray diffraction pattern. These four diffuse streaks suggest that the iodine atoms are structured with a one-dimensional order. The extra diffuse streaks can be explained by the double diffraction between the four streaks and the spotty diffractions of (SN)x. The double diffraction results from the microfibrillar nature of the (SN)x. From X-ray microanalysis of doped (SN)x, the iodine content in the specimen was found to change mainly in the direction along the chain axis and almost constant in the direction perpendicular to it. The distribution of iodine atoms indicates that the dopants diffuse preferentially along the molecular axis through disordered domains between fine fibrils comprised in (SN)x crystals. Then the dopants are settled in the narrow disordered domains and give the extra streaked diffraction.     

Modeling of scattering on the residual gas in an electron diffraction experiment

The scattering on the residual gas in an electron diffraction chamber is modeled. A comparison with experimental data reveals that is this scattering that may make a major contribution to the extraneous signal inevitably present in the recorded diffraction pattern. Practical recommendations on the development of the electron diffraction apparatus design are given.     

PA6／PET共混体系的X射线衍射分析

用宽角Ｘ射线衍射分析,考察尼龙６／ＰＥＴ共混体系的结晶态,表明在共混物中尼龙６和ＰＥＴ是各自结晶的,即晶相分离的。研究了结晶条件,组份比等对晶态结构的影响,发现共混体系相对结晶度低于纯组份的算术加和,说明共混体系的结晶相分离过程中,由于存在相互作用导致的干扰,使结晶度下降。     

A Rapid and Efficient Way to Dynamic Creation of Cross‐Reactive Sensor Arrays Based on Ionic Liquids

Based on the simple counterion exchange of ionic liquids, a rapid, facile, and efficient strategy to create a cross‐reactive sensor array with a dynamic tunable feature was developed, and exemplified by the construction of a sensor array for the identification and classification of nitroaromatics and explosives mimics. To achieve a good sensing system with fast response, good sensitivity, and low detection limit, the synthesized ionic liquid receptors were tethered onto a silica matrix with a macro‐mesoporous hierarchical structure. Through the facile anion exchange approach, abundant ionic‐liquid‐based individual receptors with diversiform properties, such as different micro‐environments, diverse molecular interactions, and distinctive physico‐chemical properties, were easily and quickly synthesized to generate a distinct fingerprint of explosives for pattern recognition. The reversible anion exchange ability further endowed the sensor array with a dynamic tunable feature as well as good controllability and practicality for real‐world application. With the assistance of statistical analysis, such as principal component analysis (PCA) and linear discrimination analysis (LDA), an optimized‐size array with a good resolution was rationally established from a large number of IL‐based receptors. The performed experiments suggested that the ionic‐liquid‐based sensing protocol is a general and powerful strategy for creating a cross‐reactive sensor array that could find a wide range of applications for sensing various analytes or complex mixtures.     

A fast pairlist-construction algorithm for molecular simulations under periodic boundary conditions

A new grid-cell algorithm is presented that permits the fast construction of cutoff-based nonbonded pairlists in molecular simulations under periodic boundary conditions based on an arbitrary box shape. The key features of the method are (1) the use of a one-dimensional mask array (to determine which grid cells contain interacting atoms) that incorporates the effect of periodicity, and (2) the grouping of adjacent interacting cells of the mask array into stripes, which permits the handling of empty cells with a very low computational overhead. Testing of the algorithm on water systems of different sizes (containing about 2000 to 11,000 molecules) shows that the method (1) is about an order of magnitude more efficient compared to a standard (double-loop) algorithm, (2) achieves quasi-linear scaling in the number of atoms, (3) is weakly sensitive in terms of efficiency to the chosen number of grid cells, and (4) can be easily parallelized.     

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.     

Prediction of glycoprotein secondary structure using ATR-FTIR

Glycoproteins are important biomolecules with a diverse array of structural and signaling functions in biology. Determination of glycoprotein secondary structure is becoming increasingly important in aiding the understanding of how these molecules function in biological environments and disease. Furthermore, glycoproteins such as mucins are being evaluated in various nano-engineering processes that require knowledge of how the underlying secondary structure might alter in different target environments. We have developed an analytical procedure for predicting the secondary structures of glycoprotein using ATR-FTIR on dry film. Using Bovine submaxillary mucin (BSM) as a glycoprotein model, we determined the additive infrared spectral pattern of acetyl amino sugars and amino acids that could contribute to the absorbance in the Amide I band of BSM through empirical data. We show through subtraction of these spectra how the absorbance pattern of the protein backbone can be determined in order to predict glycoprotein secondary structure. The analysis predicted a predominant pattern of random coil, beta sheet and beta turn secondary structure for BSM after carbohydrate and amino acid spectral subtraction in agreement with other methods. Our relatively simple approach can be applied to predict secondary structure in other glycoproteins.     

NMR crystallography of zeolites: How far can we go without diffraction data?

Nuclear magnetic resonance (NMR) crystallography—an approach to structure determination that seeks to integrate solid-state NMR spectroscopy, diffraction, and computation methods—has emerged as an effective strategy to determine structures of difficult-to-characterize materials, including zeolites and related network materials. This paper explores how far it is possible to go in determining the structure of a zeolite framework from a minimal amount of input information derived only from solid-state NMR spectroscopy. It is shown that the framework structure of the fluoride-containing and tetramethylammonium-templated octadecasil clathrasil material can be solved from the 1D ²⁹Si NMR spectrum and a single 2D ²⁹Si NMR correlation spectrum alone, without the space group and unit cell parameters normally obtained from diffraction data. The resulting NMR-solved structure is in excellent agreement with the structures determined previously by diffraction methods. It is anticipated that NMR crystallography strategies like this will be useful for structure determination of other materials, which cannot be solved from diffraction methods alone.     

Spontaneous pattern formation due to modulation instability of incoherent white light in a photopolymerizable medium

Spontaneous pattern formation due to modulation instability was observed in a broad uniform beam of incoherent white light propagating in an optically isotropic, photopolymerizable organosiloxane. Pattern formation originates from intensity-dependent refractive index changes due to polymerization, which cause competition between the natural diffraction (broadening) and self-induced refraction of the beam. Under these nonlinear conditions, weak intensity modulations in the beam, noise, that would be negligible under linear conditions are amplified. The amplified patterns become unstable over time and spontaneously divide into individual self-trapped filaments of white light of essentially identical diameter (76 +/- 3 microm), which propagate through the medium without diffracting. In the case of noise with a weak 1-D periodic modulation, for example, the uniform beam transformed into a 1-D periodic array of self-trapped lamellae, which in turn formed a 2-D array of self-trapped cylindrical filaments. Although the rate of pattern formation varied inversely with optical power (measured from 8.4 to 59.8 mW), the uniform beam always split into discrete filaments, demonstrating that they are the most stable form of light propagation under the nonlinear conditions created by polymerization. Each filament of light retained the spectral composition and incoherence of white light, which showed that the entire polychromatic, incoherent and unpolarized wavepacket collectively participated in pattern formation. These findings are consistent with recent theoretical models of nonlinear white light propagation and with experimental observations of pattern formation in coherent and partially coherent light. Because refractive index changes due to polymerization are permanent, pattern formation imparts microstructure to the organosiloxane. Optical micrographs revealed that, after pattern formation, the initially homogeneous medium consisted entirely of a closely packed array of narrow channel waveguides induced by self-trapped filaments.     

模板法制备高度有序的聚苯胺纳米纤维阵列

近年来,利用化学或物理方法制备多种材料的纳米有序阵列复合结构已成为学术界的研究热点．用具有纳米孔洞的模板(多孔阳极氧化铝、多孔硅以及聚碳酸脂膜)制备的金属、半导体、碳纳米管等材料的纳米有序阵列复合结构已在润滑、微电极、单电子器件、传感器、垂直磁记录、场致电     

A splicing model‐based DNA‐computing approach on microfluidic chip

DNA computing is a new computation form based on DNA biochemical reactions, which is mainly composed of sticker and splicing computation models. In this work, a microfluidic chip‐based approach was established for splicing model‐based DNA computing. A finite automaton with two input symbols (a, b) and three states (S0, S1, and S2) was applied in the pattern recognition for isosceles triangles. The DNA computation processes of automaton were realized through DNA digestion, ligation, DNA separation, and detection on the microfluidic chip. The established approach is efficient, controllable, and easy to integrate, which paves the way for the building of complete biomolecular computers in the future.     

Position determination of scatter signatures--a novel sensor geometry

A novel diffraction sensor geometry able to provide the diffraction pattern of a suspect material without prior knowledge of the samples location is introduced. The sensor geometry can also resolve diffraction patterns originating from multiple unknown materials overlapped along the primary X-ray beam path. This is achieved through tracking Bragg peak maxima that linearly propagate from the inspection volume at a series of X-ray detector positions. A series of simulations and experiments have been performed to verify this technique and provide an insight into its characteristics. Such a technique could have widespread appeal in the security industry. Areas of most relevance include the materials characterisation of volumes such as those prevalent in an airport screening environment or equally the rapid screening for illicit drugs trafficked through the postal system.     

Accurate and efficient algorithm for Bader charge integration

We propose an efficient, accurate method to integrate the basins of attraction of a smooth function defined on a general discrete grid and apply it to the Bader charge partitioning for the electron charge density. Starting with the evolution of trajectories in space following the gradient of charge density, we derive an expression for the fraction of space neighboring each grid point that flows to its neighbors. This serves as the basis to compute the fraction of each grid volume that belongs to a basin (Bader volume) and as a weight for the discrete integration of functions over the Bader volume. Compared with other grid-based algorithms, our approach is robust, more computationally efficient with linear computational effort, accurate, and has quadratic convergence. Moreover, it is straightforward to extend to nonuniform grids, such as from a mesh-refinement approach, and can be used to both identify basins of attraction of fixed points and integrate functions over the basins.     

One-step preparation,structural assignment,and X-ray study of 2,2-di-n-butyl- and 2,2-diphenyl-6-aza-1,3-dioxa-2-stannabenzocyclononen-4-ones derived from amino acids

Twenty-four 2,2-di-n-butyl- and 2,2-diphenyl-6-aza-1,3-dioxa-2-stannabenzocyclononen-4-ones, each having a transannular N-->Sn bond, have been prepared by one-step reactions of alpha-amino acids (1 a-l), salicylaldehyde (2), and either di-n-butyltin(IV) oxide (3) or diphenyltin(IV) oxide (4). The new methodology constitutes an easy, highly efficient one-step synthesis of diorganotin(IV) derivatives, such as 5 a-l and 6 a-l, from iminic tridentate ligands without isolation of the Schiff bases. The structures of all the compounds have been established by a combination of (1)H, (13)C, (15)N, and (119)Sn NMR spectroscopy, IR spectroscopy, mass spectrometry, and elemental analysis. In all cases, the (119)Sn chemical shifts, as well as the (1)J((119)Sn,(13)C) coupling constants, are indicative of pentacoordinated tin atoms in solution. The structures of compounds 5 a, d, f, 6 a, b, b-racemic, c, d, f, g, and l have been established by single-crystal X-ray diffraction analyses. The tin atoms in 5 d, f, 6 a, b, b-racemic, c, d, g, and l each have a distorted trigonal-bipyramidal (TBP) geometry, with the oxygen atoms from the phenol and carboxylate moieties occupying the axial positions, and the imine nitrogen and phenyl or n-butyl substituents occupying the equatorial positions. Compounds 5 a and 6 f show distorted octahedral (DOC) geometries due to intermolecular coordination of the carbonyl oxygen to the tin atom, in a trans disposition to the N-->Sn bond, leading to trimeric 5 a and a polymeric structure for compound 6 f. Additionally, measurement of the one-bond coupling constants (1)J((119)Sn,(13)C) in diphenyltin(IV) complexes (6 a-l) and their correlation with the CSn-C bond angles has allowed the derivation of an equation that can be applied to assess the geometry around the tin atom for other diphenyltin(IV) compounds in solution.