Crystal Electron Diffraction Research Articles

Large-Angle Rocking Beam Electron Diffraction of Large Unit Cell Crystals Using Direct Electron Detector.

We report a large-angle rocking beam electron diffraction (LARBED) technique for electron diffraction analysis. Diffraction patterns are recorded in a scanning transmission electron microscope (STEM) using a direct electron detector with large dynamical range and fast readout. We use a nanobeam for diffraction and perform the beam double rocking by synchronizing the detector with the STEM scan coils for the recording. Using this approach, large-angle convergent beam electron diffraction (LACBED) patterns of different reflections are obtained simultaneously. By using a nanobeam, instead of a focused beam, the LARBED technique can be applied to beam-sensitive crystals as well as crystals with large unit cells. This paper describes the implementation of LARBED and evaluates the performance using silicon and gadolinium gallium garnet crystals as test samples. We demonstrate that our method provides an effective and robust way for recording LARBED patterns and paves the way for quantitative electron diffraction of large unit cell and beam-sensitive crystals.

Development of sample preparation methods for time-resolved cryogenic electron tomography and micro crystal electron diffraction

Development of sample preparation methods for time-resolved cryogenic electron tomography and micro crystal electron diffraction

Exploring the impact of water on the morphology and crystallinity of xylan hydrate nanotiles

There has been a resurgence of studies on xylan particles describing various properties and exploring new applications. The aim of this study was to analyze xylan hydrate crystals in the wet state and after air-drying using state-of-art imaging techniques in order to assess the impact of water on both crystallinity and particle morphology. Xylan from esparto grass (Stipa tenacissima) was crystallized and formed convex platelets, termed ‘nanotiles’. Fully hydrated xylan crystals were examined in a layer of vitreous ice by cryogenic electron microscopy. Selected area electron diffraction of the xylan hydrate crystals revealed an oriented crystalline core, unlike the dried crystals that showed no orientation. The surface topographies and thickness of wet and air-dried xylan nanotiles were observed using atomic force microscopy imaging in both liquid and in air. X-ray diffraction was used to assess the crystallinity of xylan nanotiles after drying to varying levels. Air-dried crystals gave diffraction maxima corresponding to xylan hydrate, while wet crystals gave diffraction maxima corresponding to xylan dihydrate. This study offers new insight into xylan hydrate particles, focusing on the role of water on their crystallinity, ultrastructure, and orientation of the crystalline layers.

Comonomer Inclusion in Single Crystals of Isodimorphic Random Copolymers of Butylene Succinate and ε-Caprolactone

Random copolymers exhibit diverse crystallization behavior depending on whether comonomers are excluded or included in the crystalline phase. To understand the crystallization behavior of crystallizable isodimorphic random copolymer, in this work, we selected poly[(butylene succinate)-ran-(ε-caprolactone)], BSxCLy, copolyesters and studied their single crystal structure and morphology. The single crystals of PBS homopolymer and BS-rich copolymers were prepared by the self-seeding method in o-dichlorobenzene. The prepared single crystals were characterized by atomic force microscopy (AFM) and transmission electron microscopy. The suitable seeding temperature and the dissolution temperature of the copolymers decreased with the comonomer content. The morphological features, including size, shape, layer number, and thickness, of the single crystals depend on the seeding temperature, crystallization temperature, and, most interestingly, the composition. The size of the single crystals increased with the seeding temperature, while the aspect ratio increased with the crystallization temperature. Higher CL content in the copolymers contributed to multilayered crystals and curved edges. These characteristics were explained by the difference in growth rate and the number of dislocations, both of which are expected to be influenced by the comonomers. As revealed by AFM, the thickness of the single crystals increased with CL contents, which is the opposite of what has been reported for copolymers with high degree of comonomer exclusion. Electron diffraction of the single crystals showed smaller lattice expansion as compared to melt crystallized samples, indicating a lower degree of comonomer inclusion of CL units.

Synthesis and Structure of COE-11, a New Borosilicate Zeolite with a Two-Dimensional Pore System of 12-Ring Channels

The new zeolite, COE-11, was synthesized at 155 °C to 168 °C by hydrothermal synthesis from a reaction mixture of SiO2/tetraethylammonium hydroxide/H3BO3/NaOH/H2O. Because tetraethylammonium is an unspecific structure directing agent, COE-11 crystallizes in all cases together with at least one impurity phase from a selection of phases: zeolite types *BEA, CHA, FER, MFI, MOR, MTW; the layered silicates magadiite and kenyaite; and searlsite and silica polymorph quartz. The crystal structure was solved from 3D electron diffraction (3D ED) data. Subsequent structure refinements of X-ray powder diffraction (PXRD) data and single crystal electron diffraction data converged to residual values of RF = 0.039, chi2 = 3.6 (PXRD) and RF = 21.81% (3D ED) confirming the structure model. COE-11 crystallizes in space group C2 with unit cell dimensions of a0 = 17.3494(11) Å, b0 = 17.3409(11) Å, c0 = 14.2789(4) Å and β = 113.762(2) °. The structure of COE-11 is characterized by a microporous borosilicate framework with intersecting, highly elliptical 12-ring channels running parallel (110) and (1–10) and forming a two-dimensional pore system. The Rietveld refinement provided a hint that boron partly substitutes silicon on three specific T sites of the framework. The idealized chemical composition of as-made COE-11 is [(CH3CH2)4N]4[B4Si62O132] per unit cell. Physico-chemical characterization using solid-state NMR spectroscopy, SEM, TG-DTA, and ATR-FTIR spectroscopy confirmed that COE-11 is a microporous borosilicate zeolite. COE-11 is structurally closely related to zeolite beta polymorph B but differs concerning the dimensionality of the pore system, which is 2D instead of 3D.

National Electron Diffraction Facility

World-class centre for single crystal electron diffraction will be UK first

Photochemical reactions of a diamidocarbene: cyclopropanation of bromonaphthalene, addition to pyridine, and activation of sp3 C-H bonds.

We report unprecedented photochemistry for the diamidocarbene 1. Described within are the double cyclopropanation of 1-bromonaphthalene, the double addition to pyridine, and remarkably, the insertion into the unactivated sp3 C-H bonds of cyclohexane, tetramethylsilane, and n-pentane to give compounds 2-6, respectively. All compounds have been fully characterized, and the solid state structure of 4 was obtained using single crystal electron diffraction.

High-Resolution Electron Diffraction of Protein Crystals in Their Liquid Environment at Room Temperature Using a Direct Electron Detection Camera

High-Resolution Electron Diffraction of Protein Crystals in Their Liquid Environment at Room Temperature Using a Direct Electron Detection Camera

Electron Diffraction of Graphene-covered Protein Crystals at Room Temperature

Electron Diffraction of Graphene-covered Protein Crystals at Room Temperature

Molecular beam epitaxy of polar III-nitride resonant tunneling diodes

Advances in molecular beam epitaxy (MBE) have been crucial for the engineering of heterostructures in which the wave nature of electrons dictates carrier transport dynamics. These advances led to the first demonstration of negative differential conductance (NDC) in arsenide-based resonant tunneling diodes (RTDs) in 1974. In contrast to the 17 years elapsed between the initial MBE growth of arsenide semiconductors and the first demonstration of room-temperature GaAs/AlAs RTDs, the development of polar III-nitride RTDs has been remarkably different. After pioneering growths of nitride materials by MBE in 1973, it would take 43 years—until 2016—to demonstrate the first GaN/AlN RTD that exhibits repeatable NDC at room temperature. Here, we discuss, from the crystal growth point of view, the key developments in the epitaxy of III-nitride heterostructures that have led us to the demonstration of robust resonant tunneling transport and reliable NDC in III-nitride semiconductors. We show that in situ tracking of the crystal electron diffraction allows us to deterministically control the number of monolayers incorporated into the tunneling barriers of the active region. Employing this technique, we fabricate various GaN/AlN RTD designs showing the exponential enhancement of the resonant tunneling current as a function of barrier thickness. In addition, we experimentally demonstrate that tunneling transport in nitride RTDs is sensitive to epitaxial parameters such as the substrate growth temperature and threading dislocation density. This new insight into the MBE growth of nitride resonant tunneling devices represents a significant step forward in the engineering of new functionalities within the family of III-nitride semiconductors, allowing to harness quantum interference effects for the new generation of electronic and photonic devices.

London dispersion-driven hetero-aryl-aryl interactions in 1,2-diaryldisilanes.

Non-covalent aryl-aryl interactions for the molecular structures of three 1,2-diaryltetramethyldisilanes X5C6-(SiMe2)2-C6Y5 (X ≠ Y; X, Y = H, F, Cl) were studied by single crystal X-ray and gas electron diffraction as well as by SAPT calculations. Aryl-aryl interactions cause all to adopt exclusively rather untypical eclipsed syn-conformers in the gas phase, and C6F5-(SiMe2)2-C6Cl5 also in the solid state.

A metal\u2013organic framework for efficient water-based ultra-low-temperature-driven cooling

Efficient use of energy for cooling applications is a very important and challenging field in science. Ultra-low temperature actuated (Tdriving < 80 °C) adsorption-driven chillers (ADCs) with water as the cooling agent are one environmentally benign option. The nanoscale metal-organic framework [Al(OH)(C6H2O4S)] denoted CAU-23 was discovered that possess favorable properties, including water adsorption capacity of 0.37 gH2O/gsorbent around p/p0 = 0.3 and cycling stability of at least 5000 cycles. Most importantly the material has a driving temperature down to 60 °C, which allows for the exploitation of yet mostly unused temperature sources and a more efficient use of energy. These exceptional properties are due to its unique crystal structure, which was unequivocally elucidated by single crystal electron diffraction. Monte Carlo simulations were performed to reveal the water adsorption mechanism at the atomic level. With its green synthesis, CAU-23 is an ideal material to realize ultra-low temperature driven ADC devices.

Tetravalent lead in nature – plattnerite crystals from Mine du Pradet (France) and Mount Trevasco (Italy)

Abstract Natural lead dioxide samples (β modification) from Cap Garonne, Mine du Pradet, France and Mount Trevasco, Italy were studied by single crystal X-ray and electron diffraction, clearly manifesting the rutile-type structure. A needle from the Mount Trevasco sample was investigated on a single crystal diffractometer: P42/mnm, a = 495.81(10), c = 338.66(7) pm, wR = 0.0513, 117 F 2 values (all data) and nine variables (293 K data). An additional data set at T = 90 K gave no hint for structural distortions.

Nanoscale mosaicity revealed in peptide microcrystals by scanning electron nanodiffraction

Changes in lattice structure across sub-regions of protein crystals are challenging to assess when relying on whole crystal measurements. Because of this difficulty, macromolecular structure determination from protein micro and nanocrystals requires assumptions of bulk crystallinity and domain block substructure. Here we map lattice structure across micron size areas of cryogenically preserved three−dimensional peptide crystals using a nano-focused electron beam. This approach produces diffraction from as few as 1500 molecules in a crystal, is sensitive to crystal thickness and three−dimensional lattice orientation. Real-space maps reconstructed from unsupervised classification of diffraction patterns across a crystal reveal regions of crystal order/disorder and three−dimensional lattice tilts on the sub-100nm scale. The nanoscale lattice reorientation observed in the micron-sized peptide crystal lattices studied here provides a direct view of their plasticity. Knowledge of these features facilitates an improved understanding of peptide assemblies that could aid in the determination of structures from nano- and microcrystals by single or serial crystal electron diffraction.

Crystal structure analysis of a star-shaped triazine compound: a combination of single-crystal three-dimensional electron diffraction and powder X-ray diffraction

The solid-state structure of star-shaped 2,4,6-tris{(E)-2-[4-(dimethylamino)-phenyl]ethenyl}-1,3,5-triazine is determined from a powder sample by exploiting the respective strengths of single-crystal three-dimensional electron diffraction and powder X-ray diffraction data. The unit-cell parameters were determined from single crystal electron diffraction data. Using this information, the powder X-ray diffraction data were indexed, and the crystal structure was determined from the powder diffraction profile. The compound crystallizes in a noncentrosymmetric space group, P212121. The molecular conformation in the crystal structure was used to calculate the molecular dipole moment of 3.22 Debye, which enables the material to show nonlinear optical effects.

Ab initio structure determination and quantitative disorder analysis on nanoparticles by electron diffraction tomography.

Nanoscaled porous materials such as zeolites have attracted substantial attention in industry due to their catalytic activity, and their performance in sorption and separation processes. In order to understand the properties of such materials, current research focuses increasingly on the determination of structural features beyond the averaged crystal structure. Small particle sizes, various types of disorder and intergrown structures render the description of structures at atomic level by standard crystallographic methods difficult. This paper reports the characterization of a strongly disordered zeolite structure, using a combination of electron exit-wave reconstruction, automated diffraction tomography (ADT), crystal disorder modelling and electron diffraction simulations. Zeolite beta was chosen for a proof-of-principle study of the techniques, because it consists of two different intergrown polymorphs that are built from identical layer types but with different stacking sequences. Imaging of the projected inner Coulomb potential of zeolite beta crystals shows the intergrowth of the polymorphs BEA and BEB. The structures of BEA as well as BEB could be extracted from one single ADT data set using direct methods. A ratio for BEA/BEB = 48:52 was determined by comparison of the reconstructed reciprocal space based on ADT data with simulated electron diffraction data for virtual nanocrystals, built with different ratios of BEA/BEB. In this way, it is demonstrated that this smart interplay of the above-mentioned techniques allows the elaboration of the real structures of functional materials in detail - even if they possess a severely disordered structure.

Morphology and stability of orthorhombic and hexagonal phases in a lamellar γ-Ti-42Al-8.5Nb alloy-A transmission electron microscopy study

Intermetallic titanium aluminides are often alloyed with niobium to improve oxidation resistance and mechanical properties. Depending on the overall alloy composition and on the solubility of the present phases for niobium, new phases may be introduced in the alloys' microstructure upon niobium addition. Here we describe the microstructure of the alloy Ti-42Al-8.5Nb produced by powder metallurgy after annealing at 550 °C and 650 °C. We identify the orthorhombic O-phase within α2 laths of lamellar (α2 + γ) colonies by single crystal electron diffraction and high-resolution imaging. Domains of O-phase variants and α2 phase form columnar crystallites in α2 (0001) planes having low indexed α2 {11-20} and {1-100} interface planes. The nm-sized domains are rotated with respect to each other resulting in elastic strains across the domain boundaries. No elemental segregation of Nb was detected in α2/O-phase lamellae.

MicroED: three-dimensional electron diffraction of microscopic crystals

My laboratory studies the structures of membrane proteins that are important in maintaining homeostasis in the brain. Understanding structure (and hence function) requires scientists to build an atomic resolution map of every atom in the protein of interest, that is, an atomic structural model of the protein of interest captured in various functional states. In 2013 we unveiled the method MicroED, electron diffraction of microscopic crystals, and demonstrated that it is feasible to determine high-resolution protein structures by electron crystallography of three-dimensional crystals in an electron cryo-microscope (CryoEM). The CryoEM is used in diffraction mode for structural analysis of proteins of interest using vanishingly small crystals. The crystals are often a billion times smaller in volume than what is normally used for other structural biology methods like x-ray crystallography. In this seminar I will describe the basics of this method, from concept to data collection, analysis and structure determination, and illustrate how samples that were previously unattainable can now be studied by MicroED. I will conclude by highlighting how this new method is helping us understand major brain diseases like Parkinson's disease.

Microed: Three Dimensional Electron Diffraction of Microscopic Crystals

My laboratory studies the structures of membrane proteins that are important in maintaining homeostasis in the brain. Understanding structure (and hence function) requires scientists to build an atomic resolution map of every atom in the protein of interest, that is, an atomic structural model of the protein of interest captured in various functional states. In 2013 we unveiled the method MicroED, electron diffraction of microscopic crystals, and demonstrated that it is feasible to determine high-resolution protein structures by electron crystallography of three-dimensional crystals in an electron cryo-microscope (CryoEM). The CryoEM is used in diffraction mode for structural analysis of proteins of interest using vanishingly small crystals. The crystals are often a billion times smaller in volume than what is normally used for other structural biology methods like x-ray crystallography. In this seminar I will describe the basics of this method, from concept to data collection, analysis and structure determination, and illustrate how samples that were previously unattainable can now be studied by MicroED. I will conclude by highlighting how this new method is helping us understand major brain diseases like Parkinson's disease.

Series of Highly Stable Isoreticular Lanthanide Metal–Organic Frameworks with Expanding Pore Size and Tunable Luminescent Properties

A series of highly porous isoreticular lanthanide-based metal–organic frameworks (LnMOFs) denoted as SUMOF-7I to SUMOF-7IV (SU = Stockholm University; Ln = La, Ce, Pr, Nd, Sm, Eu, and Gd) have been synthesized using tritopic carboxylates as the organic linkers. The SUMOF-7 materials display one-dimensional pseudohexagonal channels with the pore diameter gradually enlarged from 8.4 to 23.9 Å, as a result of increasing sizes of the organic linkers. The structures have been solved by single crystal X-ray diffraction or rotation electron diffraction (RED) combined with powder X-ray diffraction (PXRD). The SUMOF-7 materials exhibit robust architectures with permanent porosity. More importantly, they exhibit exceptionally high thermal and chemical stability. We show that, by inclusion of organic dye molecules, the luminescence properties of the MOFs can be elaborated and modulated, leading to promising applications in sensing and optics.