Powder diffraction from a continuous microjet of submicrometer protein crystals

Atomic‐resolution structures from small proteins have recently been determined from high‐quality powder diffraction patterns using a combination of stereochemical restraints and Rietveld refinement [Von Dreele (2007), J. Appl. Cryst. 40 , 133–143; Margiolaki et al. (2007), J. Am. Chem. Soc. 129 , 11865–11871]. While powder diffraction data have been obtained from batch samples of small crystal‐suspensions, which are exposed to X‐rays for long periods of time and undergo significant radiation damage, the proof‐of‐concept that protein powder diffraction data from nanocrystals of a membrane protein can be obtained using a continuous microjet is shown. This flow‐focusing aerojet has been developed to deliver a solution of hydrated protein nanocrystals to an X‐ray beam for diffraction analysis. This method requires neither the crushing of larger polycrystalline samples nor any techniques to avoid radiation damage such as cryocooling. Apparatus to record protein powder diffraction in this manner has been commissioned, and in this paper the first powder diffraction patterns from a membrane protein, photosystem I, with crystallite sizes of less than 500 nm are presented. These preliminary patterns show the lowest‐order reflections, which agree quantitatively with theoretical calculations of the powder profile. The results also serve to test our aerojet injector system, with future application to femtosecond diffraction in free‐electron X‐ray laser schemes, and for serial crystallography using a single‐file beam of aligned hydrated molecules.     

Ultrasonic synthesis of hydroxyapatite in non-cavitation and cavitation modes

The size control of materials is of great importance in research and technology because materials of different size and shape have different properties and applications.This paper focuses on the synthesis of hydroxyapatite in ultrasound fields of different frequencies and intensities with the aim to find the conditions which allow control of the particles size. The results are evaluated by X-ray diffraction, Transmission Electron Microscopy, morphological and sedimentation analyses. It is shown that the hydroxyapatite particles synthesized at low intensity non-cavitation regime of ultrasound have smaller size than those prepared at high intensity cavitation regime. The explanation of observed results is based on the idea of formation of vortices at the interface between phosphoric acid and calcium hydroxide solution where the nucleation of hydroxyapatite particles is taken place. Smaller vortices formed at high frequency non-cavitation ultrasound regime provide smaller nucleation sites and smaller resulting particles, compared to vortices and particles obtained without ultrasound. Discovered method has a potential of industrial application of ultrasound for the controlled synthesis of nanoparticles.     

Synchrotron‐based X‐ray diffraction of the lead apatite series Pb10(PO4)6Cl2–Pb10(AsO4)6Cl2

A number of compounds of the pyromorphite–mimetite solid solution series were synthesized at room temperature and analyzed with infrared spectroscopy and powder X‐ray diffraction. High‐resolution high‐quality powder diffraction data were obtained by means of the state‐of‐the‐art instrument at the 11‐BM beamline of the Advanced Photon Source at Argonne National Laboratory, Argonne, IL, USA. The unit‐cell dimensions, atomic position and atomic displacement parameters, as well as site occupancy for analyzed phases, were refined by the Rietveld method and reported herein for the first time. The results of this study indicate that the pyromorphite–mimetite series is continuous in near‐Earth‐surface environments. Detailed structural changes caused by P⁵⁺–As⁵⁺ substitutions in minerals from the pyromorphite–mimetite solid solution series are reported.     

Structural characterization of Rh/pumice SMAD catalysts

The structure of Rh/pumice catalysts prepared by the SMAD (Solvated Metal Atoms Dispersion) technique at different metal loadings has been investigated by EXAFS (Extended X-ray Absorption Fine Structure Spectroscopy), XPS (X-ray Photoelectron Spectroscopy), SAXS (Small-Angle X-ray Scattering), WAXS (Wide-Angle X-ray Scattering) and TEM (Transmission Electron Microscopy). According to EXAFS and XPS, a fraction of the Rh atoms is oxidised, but a noticeable part is also present as Rh ⁰. The Rh oxidation is attributed to the interaction of the Rh atoms with the hydroxyls of the support; after the formation of the oxide, the nucleation of metallic rhodium becomes possible. The WAXS data do not show evidence of rhodium fcc crystallites; the metal-bearing particles are probably amorphous and/or very small, as results from the SAXS and TEM data analysis. The disagreement between the latter two techniques, resulting in a small-angle determination of the average size of the particles that is about half that of TEM in the catalyst with the higher Rh loading, is acknowledged and discussed. Preliminary catalytic tests are described, demonstrating the suitability of using a low surface area support for the preparation of SMAD catalysts. Received 2 February 1999     

In situ X‐ray diffraction study on the growth kinetics of NiO nanoparticles

The growth kinetics of NiO nanoparticles have been studied by in situ X‐ray diffraction using two detection systems (conventional and imaging plate). NiO nanoparticles were formed by thermal decomposition after heating of an amorphous compound formed by the coprecipitation method. It was found that the detection method using an imaging plate is more efficient than the conventional detection mode for observing changes in the crystallite growth of nanocrystalline materials. Studies have been carried out to investigate the effects of the heating rates on the particles growth. The results suggest that the growth process of the particles is accelerated when the samples are treated at low heating rates. The evolution of particles size and the diffusion coefficient obtained from X‐ray powder diffraction patterns are discussed in terms of the thermal conditions for the two types of detection.     

Synthesis of Cu–Ni Alloy Powder Directly from Metal Salts Solution

Cu–Ni alloy powders were synthesized directly from metal nitrate solution. Combustion, ultrasonic mist combustion and ultrasonic pyrolysis processes were applied and Cu–Ni alloy powder was successfully synthesized by mist combustion and ultrasonic pyrolysis of nitrate salts in a reducing atmosphere. X-ray diffraction data showed that the copper and the nickel atoms were completely mixed. For Cu–Ni alloy powder prepared by ultrasonic mist combustion, powder was a hollow sphere and consisted of nano-sized particles. For Cu–Ni alloy powder prepared by ultrasonic pyrolysis, particles consisted of nano-scale particles loosely coagulated. The synthesis temperature was 800°C, which is much lower than the liquidus of a Cu–Ni binary system. Metal alloying by mist pyrolysis, named chemical alloying, has many advantages: (1) no crucible, ball or jar is needed, (2) low synthesis temperature below the liquidus of the alloy system, (3) no extraction step is needed, (4) no cation contamination, (5) direct synthesis of fine powder from metal salts and (6) a simple and inexpensive process. The disadvantage is the contamination of organic elements from the solvent and the salt.     

Biomimetic synthesis of HgS nanoparticles in the bovine serum albumin solution

HgS nanocrystals conjugated with protein were synthesized in aqueous solution of Bovine Serum Albumin (BSA) at room temperature. The obtained HgS nanoparticles with average diameter about 20–40 nm were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), selected-area electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM). The quantum-confined effect of the HgS nanoparticles is confirmed by the ultraviolet-visible (UV-vis) and photoluminescence (PL) spectrum. The rescults indicate that the BSA not only induce the nucleation, but inhibit the further growth of HgS nanoparticles. The effect of Hg²⁺ on BSA and the change of BSA conformation were studied through Fourier transform infrared (FTIR) spectroscopy and Circular dichroism (CD) spectroscopy. The possible mechanism of HgS nanoparticles growth in the BSA solution was also discussed.     

Characterization of colorants and opacifiers in roman glass mosaic tesserae through spectroscopic and spectrometric techniques

Several glass mosaic tesserae were recovered during the archeological excavation of the thermal baths at the ‘Villa dei Quintili’ in Rome and dated to the second century ad . This work reports the results of an archeometrical investigation performed, through a multi‐technique approach, on 19 colored opaque tesserae. The aims of the study were (1) the characterization of coloring and opacifying agents used for the production of the glass tesserae and (2) the definition of the technological processes involved. Colorimetric measurements allowed us to classify the tesserae in color groups, while the glassy matrix and the dispersed crystallites were characterized in detail through micro‐Raman spectroscopy, field emission scanning electron microscopy with energy dispersive X‐ray spectroscopy, laser ablation‐inductively coupled plasma‐mass spectrometry, and X‐ray powder diffraction analyses. Most of the glass shows the typical soda‐lime‐silicate composition (except for the orange and red tesserae). Raman results and elemental analysis prove the use of Sn–Pb antimonates to create yellow glass and of Ca‐antimonates for the white tesserae. A mixture of Sn–Pb antimonates and copper ions was used to obtain the emerald green color, while Ca‐antimonates were employed in both copper‐colored and cobalt‐colored blue glass to obtain different shades (blue‐green, dark, and light blue). X‐ray powder diffraction analyses reveal the presence of metallic copper (Cu⁰) and Cu₂O particles (cuprite) in red and orange tesserae, respectively. These results confirm the high technological level reached by the glassmakers of the Imperial Age. Copyright © 2014 John Wiley & Sons, Ltd.     

Understanding the instrumental profile of synchrotron radiation X‐ray powder diffraction beamlines

A Monte Carlo algorithm has been developed to calculate the instrumental profile function of a powder diffraction synchrotron beamline. Realistic models of all optical elements are implemented in a ray‐tracing software. The proposed approach and the emerging paradigm have been investigated and verified for several existing X‐ray powder diffraction beamlines. The results, which can be extended to further facilities, show a new and general way of assessing the contribution of instrumental broadening to synchrotron radiation data, based on ab initio simulations.     

A high‐pressure single‐crystal‐diffraction experimental system at 4W2 beamline of BSRF

Information on the structural evolution of materials under high pressure is of great importance for understanding the properties of materials exhibited under high pressure. High‐pressure powder diffraction is widely used to investigate the structure evolution of materials at such pressure. Unfortunately, powder diffraction data are usually insufficient for retrieving the atomic structures, with high‐pressure single‐crystal diffraction being more desirable for such a purpose. Here, a high‐pressure single‐crystal diffraction experimental system developed recently at beamline 4W2 of Beijing Synchrotron Radiation Facility (BSRF) is reported. The design and operation of this system are described with emphasis on special measures taken to allow for the special circumstance of high‐pressure single‐crystal diffraction. As an illustration, a series of diffraction datasets were collected on a single crystal of LaB₆ using this system under various pressures (from ambient pressure to 39.1 GPa). The quality of the datasets was found to be sufficient for structure solution and subsequent refinement.     

Evidences of the evolution from solid solution to surface segregation in Ni‐doped SnO2 nanoparticles using Raman spectroscopy

Ni‐doped SnO₂ nanoparticles, promising for gas‐sensing applications, have been synthesized by a polymer precursor method. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) data analyses indicate the exclusive formation of nanosized particles with rutile‐type phase (tetragonal SnO₂) for Ni contents below 10 mol%. The mean crystallite size shows a progressive reduction with the Ni content. Room‐temperature Raman spectra of Ni‐doped SnO₂ nanoparticles show the presence of Raman active modes and modes activated by size effects. From the evolution of the A_1g mode with the Ni content, a solubility limit at ∼2 mol% was estimated. Below that content, Raman results are consistent with the occurrence of solid solution (ss) and surface segregation (seg.) of Ni ions. Above ∼2 mol% Ni, the redshift of A_1g mode suggests that the surface segregation of Ni ions takes place. Disorder‐activated bands were determined and their integrated intensity evolution with the Ni content suggest that the solid‐solution regime favors the increase of disorder; meanwhile, that disorder becomes weaker as the Ni content is increased. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of LiFePO4 prepared by sol–gel technique

LiFePO₄ powder was synthesized by means of a new route, using a two step process. In the first step, an intermediate compound was synthesized by the sol–gel method. This precursor compound to LiFePO₄ was characterized by thermal analysis (TG/DTG and DSC), Mössbauer spectroscopy, Transmission Electronic Microscopy (TEM) and Small Angle Scattering (SAXS). In the second step, the precursor was sintered and analyzed by X-ray diffraction (XRD), showing the formation of the proposed single phase material.     

A flow‐through reaction cell for in situ X‐ray diffraction and absorption studies of heterogeneous powder–liquid reactions and phase transformations

A portable powder–liquid high‐corrosion‐resistant reaction cell has been designed to follow in situ reactions by X‐ray powder diffraction (XRD) and X‐ray absorption spectroscopy (XAS) techniques. The cell has been conceived to be mounted on the experimental stations for diffraction and absorption of the Spanish CRG SpLine‐BM25 beamline at the European Synchrotron Radiation Facility. Powder reactants and/or products are kept at a fixed position in a vertical geometry in the X‐ray pathway by a porous membrane, under forced liquid reflux circulation. Owing to the short pathway of the X‐ray beam through the cell, XRD and XAS measurements can be carried out in transmission configuration/mode. In the case of the diffraction technique, data can be collected with either a point detector or a two‐dimensional CCD detector, depending on specific experimental requirements in terms of space or time resolution. Crystallization processes, heterogeneous catalytic processes and several varieties of experiments can be followed by these techniques with this cell. Two experiments were carried out to demonstrate the cell feasibility: the phase transformations of layered titanium phosphates in boiling aqueous solutions of phosphoric acid, and the reaction of copper carbonate and l ‐isoleucine amino acid powders in boiling aqueous solution. In this last case the shrinking of the solid reactants and the formation of Cu(isoleucine)₂ is observed. The crystallization processes and several phase transitions have been observed during the experiments, as well as an unexpected reaction pathway.     

Continuous‐scan capability at SSRL and applications to X‐ray diffraction

Typical X‐ray diffraction measurements are made by moving a detector to discrete positions in space and then measuring the signal at each stationary position. This step‐scanning method can be time‐consuming, and may induce vibrations in the measurement system when the motors are accelerated and decelerated at each position. Furthermore, diffraction information between the data points may be missed unless a fine step‐scanning is used, which further increases the total measurement time. To utilize beam time efficiently, the motor acceleration and deceleration time should be minimized, and the signal‐to‐noise ratio should be maximized. To accomplish this, an integrated continuous‐scan system was developed at the Stanford Synchrotron Radiation Lightsource (SSRL). The continuous‐scan system uses an in‐house integrated motor controller system and counter/timer electronics. SPEC software is used to control both the hardware and data acquisition systems. The time efficiency and repeatability of the continuous‐scan system were tested using X‐ray diffraction from a ZnO powder and compared with the step‐scan technique. Advantages and limitations of the continuous‐scan system and a demonstration of variable‐velocity continuous scan are discussed.     

A reaction cell for time‐resolved in situ XAS studies during wet chemical synthesis: the Cu2(OH)3Cl case

The use of in situ time‐resolved dispersive X‐ray absorption spectroscopy (DXAS) to monitor the formation of Cu₂(OH)₃Cl particles in an aqueous solution is reported. The measurements were performed using a dedicated reaction cell, which enabled the evolution of the Cu K‐edge X‐ray absorption near‐edge spectroscopy to be followed during mild chemical synthesis. The formed Cu₂(OH)₃Cl particles were also characterized by synchrotron‐radiation‐excited X‐ray photoelectron spectroscopy, X‐ray diffraction and scanning electron microscopy. The influence of polyvinylpyrrolidone (PVP) on the electronic and structural properties of the formed particles was investigated. The results indicate clearly the formation of Cu₂(OH)₃Cl, with or without the use of PVP, which presents very similar crystalline structures in the long‐range order. However, depending on the reaction, dramatic differences were observed by in situ DXAS in the vicinities of the Cu atoms.     

X-ray resonant powder diffraction

X-ray resonant diffraction can be applied in structural chemistry studies on powder samples. It enables an important limitation of powder diffraction to be overcome. This limitation is related to the low ability of powder diffraction to differentiate elements with close atomic numbers when they occupy the same or close crystallographic sites (mixed occupancy case) and also to discriminate cations with different valence states in different sites. However the resonant effect usually has a second order influence on the measured intensity. As a consequence, the efficiency of this method directly implies the need for excellent quality data collection and has generally been better assessed on elements present in single phase powder samples. In recent years, instrumental developments have been made in synchrotron radiation facilities which allow easier use of resonant powder diffraction for site-specific contrast and valence i.e. oxidation state analyses. Moreover, resonant contrast diffraction tools also have been proposed for better visualization of the anomalous effect both in direct and reciprocal space by using differences between electron density maps or diffraction patterns. Finally the potentialities of this technique for de novo structure solution on macromolecular systems are mentioned.     

Synthesis of wide band gap nanocrystalline NiO powder via a sonochemical method

A sonochemistry-based synthesis method was used to produce nanocrystalline nickel oxide powder with ∼20 nm average crystallite diameter from Ni(OH)₂ precursor. Ultrasound waves were applied to the primary solution to intensify the Ni(OH)₂ precipitation. Dried precipitates were calcined at 320 °C to form nanocrystalline NiO particles. The morphology of the produced powder was characterized by transmission electron microscopy. Using sonochemical waves resulted in lowering of the size of the nickel oxide crystallites. FT-IR spectroscopy and X-ray diffraction revealed high purity well-crystallized structure of the synthesized powder. Photoluminescence spectroscopy confirmed production of a wide band-gap structure.     

Nanosized titania encapsulated silica particles using an aqueous TiCl4 solution

In this study, sub-micron sized silica particles were encapsulated with nanosized titania particles using an aqueous TiCl₄ solution. The particle size distribution of the synthesized titania particles in the coating layer was estimated to be 10 nm from X-ray powder diffraction and transmission electron microscopy. The thickness of the coating layer ranged from a few nm to about 30 nm from transmission electron microscopy analysis. Zeta potential analysis demonstrated the presence of a titania particle coating layer and the extent of its coverage on the surface of silica particles. X-ray photoelectron spectroscopy analysis also demonstrated that titania particles were successfully deposited on the surface of core silica particles from the chemical shift of binding energies of O 1s, Ti 2p and Si 2p.     

水热合成ZnTe纳米粉的发光性能

利用Zn粉和Te粉为原材料,通过水热法在160℃下合成了ZnTe纳米粉,并用X射线衍射仪、x射线能谱仪、透射电子显微镜和显微Raman光谱对其进行了表征.X射线衍射谱表明合成的ZnTe具有闪锌矿结构.X射线能谱给出的结果表明合成的ZnTe中主要元素是Zn和Te,并含有杂质O.透射电子显微镜照片显示出合成的ZnTe纳米粉...     

Magnetic behavior and physicochemical properties of Ni and NiO nano-particles

A series of nano-crystalline Ni/NiO particles was synthesized by a combustion route depending upon the glycine-nitrate process. The as prepared samples were characterized by X-ray diffraction (XRD), scanning electron micrograph (SEM), transmission electron micrograph (TEM), nitrogen adsorption isothems at 77 K and vibrating sample magnetometer (VSM) techniques.The XRD results revealed that the Ni powder crystallizes was formed with the cubic phase when the molar ratio of glycine to nitrate is 1.5. Above or below that molar ratio, NiO phase coexists as an impurity along with the Ni phase. The SEM and TEM measurements of the as synthesized powders showed that the particles are irregular in shapes and have porous morphology. Increasing the ratio between glycine and Ni-nitrate resulted in slightly agglomeration and grain growth of nano-particles with subsequent decrease in the value of surface area depending upon high combustion heat. The magnetization value of Ni measured at room temperature is very close to the value observed for commercial Ni powder.