X-ray diffraction study of human serum

Blood serum from people suffering from cancer and healthy subjects was subjected to a comparative study by X-ray diffraction. The diffraction patterns were referred to that of pure water. The patterns obtained for blood serum of healthy subjects were similar to that of pure water, while those of cancer patients (two kinds of cancer changes) were different. The former similarity is accounted for by the dominant interaction of water molecules in healthy blood serum with non-polar side chains of amino acids, stabilising the serum structure. In samples from cancer patients the structure of water in blood serum is destroyed because of enhanced interactions of water with polar molecules of conformationally changed proteins. This observation suggests X-ray examination of blood serum from cancer patients and healthy subjects, indicating X-ray diffraction as a diagnostic tool for the occurrence of cancer. The results of this work have shown that the presence of protein affected by cancer has a destructive effect on the structure of water in human serum. The results reported confirm the earlier finding relating cancer changes to optical circular birefringence effects.     

Image processing and lattice determination for three-dimensional nanocrystals

Three-dimensional nanocrystals can be studied by electron diffraction using transmission cryo-electron microscopy. For molecular structure determination of proteins, such nanosized crystalline samples are out of reach for traditional single-crystal X-ray crystallography. For the study of materials that are not sensitive to the electron beam, software has been developed for determining the crystal lattice and orientation parameters. These methods require radiation-hard materials that survive careful orienting of the crystals and measuring diffraction of one and the same crystal from different, but known directions. However, as such methods can only deal with well-oriented crystalline samples, a problem exists for three-dimensional (3D) crystals of proteins and other radiation sensitive materials that do not survive careful rotational alignment in the electron microscope. Here, we discuss our newly released software AMP that can deal with nonoriented diffraction patterns, and we discuss the progress of our new preprocessing program that uses autocorrelation patterns of diffraction images for lattice determination and indexing of 3D nanocrystals.     

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometric detection of bacterial biomarker proteins isolated from contaminated water, lettuce and cotton cloth

Matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectra of bacterial proteins were obtained from water, lettuce and cloth samples contaminated with Shigella flexneri, Escherichia coli, and Aeromonas hydrophila. Spectra were obtained using proteins directly isolated from water (or water used for rinsing samples) without culturing the bacteria. For S. flexneri and E. coli, two marker ions for specific proteins associated with a virulence-related property (acid resistance) were easily detected. For A. hydrophila, ions from two specifically selected marker proteins, as well as ions from the larger group of proteins isolated from pure cultures, all matched spectra from a contaminated water sample, providing strong evidence that A. hydrophila was the bacterial contaminant. Rinse water from contaminated lettuce and cloth samples showed the same marker ions as the contaminated water samples.     

Features of the real structure of pseudoboehmites: Violations of the structure and layer packing caused by crystallization water

Rietveld structure refinement and simulation of the diffraction patterns of partially disordered materials are used to study the real structure of nanoscale pseudoboehmite samples obtained by different technologies. The effect of various violations in the structure of these nanomaterials on diffraction patterns is analyzed. The introduction of corrections for the Lorentz and polarization factors in the determination of the cell parameter b by the position of the 020 diffraction peak in the pattern is shown to be important. A model for the atomic structure of pseudoboehmite is proposed. The model involves additional water molecules as compared to the structure of boehmite. The water molecules in the interlayer space of the layered boehmite structure are found to violate its regularity, which results in a decrease in the size of crystallites.     

Mesophases in monolayers of fatty acids and phospholipids

Langmuir monolayers at the air/water interface are distinguished by their richness of phases. These can be assigned to smectic categories, although the dominant competing interactions are not yet well elaborated. For single chain compounds, there are van der Waals attractions of the chains and repulsive forces of the head groups competing in determining the local structure. For larger molecules like phospholipids there appear also to be important dipolar interactions of the head groups. In order to study these interactions, we report surface X-ray diffraction studies of films of fatty acids and phospholipids at the air/water interface, with varying environmental parameters, as well as head group size and shape. We observe a wealth of mesophases and also the influence of molecular chirality on the structure. The defined control of the monolayer structure can be made use of to control crystal formation by diffusion from the subphase and nucleation at the interface. This is studied spectroscopically, microscopically and via electron diffraction of transferred films of cyanine dyes. In that case one observes epitaxy between the dye crystal and surfactant layer, and the relative lattices can be varied via suitable dye mixtures. A very peculiar interfacial influence results from the orientation of molecular dipoles at the interface. This causes long-range repulsive interactions leading to periodic superlattices in two phase coexistence regions. These forces are observed and quantified via fluorescence microscopy.     

Diamond-type lipid cubic phase with large water channels

This paper describes a diamond cubic phase with large water channels and determines the temperature dependence of the bilayer thickness in the cubic monoolein/octylglucoside/water system based on time-resolved synchrotron X-ray diffraction data. The X-ray diffraction study established a diamond-type lipid cubic phase with large water channels (Dlarge), which has not been previously reported. It is a distinct phase, different from the diamond cubic phase with normal water channels (Dnormal). The larger channels might allow an enhanced entrapment efficiency of biomolecules in lipid cubic phases. The X-ray diffraction patterns recorded during a thermal scan showed a cubic-cubic structural transition from Dlarge to Dnormal. The obtained cubic phases displayed much larger lattice spacings as compared to those of pure monoolein at full hydration.     

Water dynamics at protein interfaces: ultrafast optical Kerr effect study

The behavior of water molecules surrounding a protein can have an important bearing on its structure and function. Consequently, a great deal of attention has been focused on changes in the relaxation dynamics of water when it is located at the protein surface. Here we use the ultrafast optical Kerr effect to study the H-bond structure and dynamics of aqueous solutions of proteins. Measurements are made for three proteins as a function of concentration. We find that the water dynamics in the first solvation layer of the proteins are slowed by up to a factor of 8 in comparison to those in bulk water. The most marked slowdown was observed for the most hydrophilic protein studied, bovine serum albumin, whereas the most hydrophobic protein, trypsin, had a slightly smaller effect. The terahertz Raman spectra of these protein solutions resemble those of pure water up to 5 wt % of protein, above which a new feature appears at ~80 cm(-1), which is assigned to a bending of the protein amide chain.     

水热合成一锅法制备FePO4-SBA-15及其水热稳定性能

通过两种水热处理方式，即800 oC水汽条件和100 oC沸水处理，考察了一锅法制备的FePO4–SBA-15(OP)的水热稳定性.水热处理前后样品的结构变化通过小角X射线衍射和N2物理吸附表征.研究发现，经水热条件下原位生成FePO4修饰后的OP样品具有良好的水热稳定性，并且FePO4的担载量(5%和40%)对OP样品的水热稳定性几乎没有影响.这与文献报道的金属担载量会影响介孔材料水热稳定性的结果不同.此外，还对比研究了浸渍法制备的FePO4/SBA-15(IMP)和商品SBA-15的水热稳定性.结果表明，各样品水热稳定性由强到弱的顺序是OP>IMP>>SBA-15. OP和IMP样品水热稳定性优于纯硅分子筛SBA-15的原因可能是FePO4保护层能抑制介孔材料在水热环境下的结构塌陷. OP样品水热稳定性较IMP样品好的原因可能主要是由于OP样品中存在稳定的Si–O–Fe键和较多的微孔.     

Investigation of structure of liquid 2,2,2 trifluoroethanol: neutron diffraction, molecular dynamics, and ab initio quantum chemical study

The molecular conformation and intermolecular H bonding in liquid 2,2,2 trifluoroethanol (TFE) have been studied by neutron diffraction with hydrogen/deuterium isotopic substitution at room temperature. For comparison, conformations of molecules and their dimers in the gas phase have also been calculated, based on the density functional theory. Energies, geometry, and vibrational frequencies of dimers were analyzed. Diffraction data analyzed by the "Monte Carlo determination of g(r)" (MCGR) method resulted in a molecular structure in agreement with the findings from gas phase electron diffraction experiments and density functional calculations. The intermolecular structure functions were compared to the same functions obtained from a molecular dynamics simulation. All of the composite radial distribution functions are in good agreement with the simulation results. According to our calculation the hydrogen-bonded aggregation size is smaller in pure liquid TFE than in pure liquid ethanol.     

Preparation and photocatalytic activity of B,Ce Co-doped TiO2 hollow fibers photocatalyst

A series of B, Ce co-doped TiO₂ (B, Ce-TiO₂) photocatalytic materials with a hollow fiber structure were successfully prepared by template method using boric acid, ammonium ceric nitrate and tetrabutyltitanate as precursors and cotton fibers as template, followed by calcination at 500°C in an N₂ atmosphere for 2 h. Scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen adsorption-desorption measurements, and UV-visible spectroscopy (UV-Vis) were employed to characterize the morphology, crystal structure, surface structure, and optical absorption properties of the samples. The photocatalytic performance of the samples was studied by photodegradation phenol in water under UV light irradiation. The results showed that the TiO₂ fiber materials have hollow structures, and the fiber structure materials showed better photocatalytic properties for the degradation of phenol than pure TiO₂ under UV light. In the experiment condition, the photocatalytic activity of B, Ce co-doped TiO₂ fibers was optimal of all the prepared samples. In addition, the possibility of cyclic usage of B, Ce co-doped TiO₂ fiber photocatalyst was also confirmed, the photocatalytic activity of TiO₂ fibers remained above 90% of that of the fresh sample after being used four times. The material was easily removed by centrifugal separation from the medium. It can therefore be potentially applied for the treatment of water contaminated by organic pollutants.     

失活加氢精制催化剂中硫铁相的高分辨透射电镜研究

利用高分辨透射电镜(HRTEM)结合X射线能谱仪(EDS)和选区电子衍射(SAED)分析,对运转后的加氢精制催化剂中含有的微量未知相的化学组成、晶体结构进行了研究.通过X射线能谱仪确定该未知相主要成分为硫和铁.根据选区电子衍射结果,该硫铁相为单晶结构.采用样品倾转的方法,获得3幅不同取向的选区电子衍射图,根据衍射谱中衍射斑点对应的晶体学信息及3幅电子衍射图取向间的夹角关系,确定该硫铁化合物属于正交晶系的硫化亚铁,分子式为Fe0.91S.该催化剂应用于高温高压下的加氢环境中,其中原料油中的酸性物质,尤其是环烷酸对加氢设备材质的腐蚀是导致硫铁化合物相形成的主要原因,并由此探讨了硫铁化合物相的形成机制.     

Iron Oxide Nanocrystals Synthesis by Laser Ablation in Water: Effect of Laser Wavelength

In this research the synthesis of nanocrystalline iron oxides by laser ablation in pure water has been performed by two different wavelengths (first and second harmonics) of high frequency Nd:YAG laser. The obtained results from the X-ray diffraction and transmission electron microscopy analysis of the synthesized samples show the formation of spherical nanocrystalline magnetite with narrow particle size distribution and average diameters of 7 and 17 nm for the samples obtained by first and second harmonics of laser, respectively. According to the hysteresis loops measured by vibrating sample magnetometer, formation of the superparamagnetic nanoparticles (NPs) is confirmed. Investigating the magnetic properties of the two samples indicates a rise in the amount of magnetization of the sample produced by first harmonic of the laser compared to the one produced by the second harmonic wavelength. So it is obtained that the main wavelength of Nd:YAG laser (1,064 nm) results to finer iron oxide NPs with better magnetic properties.     

Effect of the Al/Si atomic ratio on surface and structural properties of sol-gel prepared aluminosilicates

A series of aluminosilicates with an Al/Si ratio ranging from 0 to ∞ (0 for pure silica and ∞ for pure alumina) was prepared by sol-gel process and characterized by surface and structure techniques. Aluminum trisecbutoxide and tetramethylorthosilicate were used as precursors for the sol-gel synthesis. The acidic properties of the oxides were studied by determination of the zero point charges, through mass titration method, and, for selected samples, by FT-IR spectroscopy of adsorbed pyridine used as a probe for both Brønsted and Lewis acidity. A dependence of the acidity on the Al/Si atomic ratio was found. According to the X-ray diffraction patterns, all the oxides have an amorphous structure except pure alumina exhibiting a γ-alumina pattern. The surface areas of the mixed oxides increase with increasing amount of alumina and are higher as compared to the individual oxides. The surface elemental distribution and electronic properties were investigated by X-ray photoelectron spectroscopy. According to the results, good agreement between the surface Al/Si atomic ratio and the analytical ratio is obtained.     

Alternative mobile phases for the reversed-phase high-performance liquid chromatography of peptides and proteins

The use of a high content of acetic acid as mobile phase additive for the reversed-phase high-performance liquid chromatography (RP-HPLC) of several proteins and extracts of biological tissues was evaluated for a divinylbenzene (DVB)-based stationary phase, and the separations obtained with acetic acid gradients in acetonitrile, isopropanol or water were compared with classical polypeptide RP-HPLC on silica C4 with trifluoroacetic acid (TFA)-acetonitrile. The separation patterns for recombinant derived interleukin-1 beta (IL-1 beta) on the C4 column eluted with TFA-acetonitrile and the DVB column eluted with acetic acid-acetonitrile were similar, but only the polymeric column was able to separate the components present in an iodinated IL-1 beta preparation. Neither eluent had any harmful effect on the biological activity of IL-1 beta isolated after RP-HPLC. Several standard proteins could be separated when the polymeric column was eluted with acetic acid gradients in acetonitrile, isopropanol or water and, although the separation efficiency with acetic acid in water was lower than that in combination with classical organic modifiers, insulin, glucagon and human growth hormone (hGH) were eluted as sharp, symmetrical peaks. The recoveries of insulin and hGH were comparable for all three mobile phases (80-90%). The separation patterns obtained from a crude acetic acid extract of a normal and a diabetic, human pancreas analysed using acetic acid gradients with or without organic modifiers were found to be similar and comparable to those obtained on a silica C4 column eluted with an acetonitrile gradient in TFA. The principal differences resulted from the use of different UV wavelengths (215 nm for TFA-acetonitrile, 280 nm for acetic acid). Acetic acid extracts of recombinant derived hGH-producing Escherichia coli were separated on the DVB column eluted with an acetic acid gradient in water. Although the starting material was a highly complex mixture, the hGH isolated after this single-step purification was surprisingly pure (as judged by sodium dodecyl sulphate-polyacrylamide gel electrophoresis). Consequently several (pure) polypeptides and complex biological samples were separated on a polymeric stationary phase eluted with acetic acid gradients in water without the use of organic modifiers.     

热处理对尼龙6及其与聚酰胺嵌段共聚物共混体系晶体熔融行为和结晶结构的影响

采用溶液共混-共沉淀的办法获得尼龙6及聚酰胺嵌段共聚物/尼龙6共混体系粉末,样品在260℃下熔融之后经程序降温的方法得到非淬火样品,然后分别在190℃下高温退火不同时间(0~48 h),采用示差扫描量热仪(DSC)、广角X射线衍射仪(WAXD)、偏光显微镜(POM)等表征手段研究热处理对体系晶体熔融行为和结晶结构的影响.结果表明,(1)在相同的热历史条件下,嵌段共聚物的存在影响了尼龙6的结晶行为及结晶结构;(2)退火处理对两种样品有着不同的影响,对于尼龙6体系,退火处理促进了非晶相向晶相的转变,大大提高样品的结晶完善程度和结晶度;对于共混体系,退火处理同样促进了非晶相向晶相的转变,同时形成新的α型和γ型结晶,体系的结晶完善程度明显提高,退火48 h后,结晶度比原始样品提高约84%.     

X-ray and Thermal Analysis of Selected Drugs Containing Acetaminophen

Studies carried out by X-ray and thermal analysis confirmed that acetaminophen (paracetamol), declared by the manufacturers as an Active Pharmaceutical Ingredient (API), was present in all studied medicinal drugs. Positions of diffraction lines (2θ angles) of the studied drugs were consistent with standards for acetaminophen, available in the ICDD PDF database Release 2008. |Δ2θ| values were lower than 0.2°, confirming the authenticity of the studied drugs. Also, the values of interplanar distances d_hkl for the examined samples were consistent with those present in the ICDD. Presence of acetaminophen crystalising in the monoclinic system (form I) was confirmed. Various line intensities for API were observed in the obtained diffraction patterns, indicating presence of the preferred orientation of the crystallites in the examined samples. Thermal analysis of the studied substances confirmed the results obtained by X-ray analysis. Drugs containing only acetaminophen as an API have melting point close to that of pure acetaminophen. It was found that presence of other active and auxiliary substances affected the shapes and positions of endothermal peaks significantly. A broadening of endothermal peaks and their shift towards lower temperatures were observed accompanying an increase in the contents of additional substances being “impurities” in relation to the API. The results obtained by a combination of the two methods, X-ray powder diffraction (XRPD) and differential scanning calorimetry/thermogravimetry (DSC/TGA), may be useful in determination of abnormalities which can occur in pharmaceutical preparations, e.g., for distinguishing original drugs and forged products, detection of the presence of a proper polymorphic form or too low content of the active substance in the investigated drug.     

Physical properties of nano-titania hollow fibers and their photocatalytic activity in the decomposition of phenol

A series of nano-titania (TiO₂) photocatalytic materials with a hollow fiber structure were successfully prepared using tetra-n-butyl titanate (Ti(OC₄H₉)₄) as precursor and cotton fiber as the template. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and N₂ adsorption-desorption measurements were employed to characterize the morphology, crystal structure, and surface structure of the samples. The photocatalytic activities of the samples were studied by phenol photodegradation in water under UV irradiation. The effect of calcination temperature, photocatalyst dosage, initial concentration of phenol and irradiation time on the photodegradation of phenol was studied. Results showed that the TiO₂ fiber materials have hollow structures, indicating that these materials had a large specific surface area. The fiber structure material showed better photocatalytic properties for the degradation of phenol than pure TiO₂ under UV light, and the sample calcined at 500°C exhibited the highest phenol photodegradation efficiency. In addition, the possibility of cyclic usage of the photocatalyst was also confirmed, the photocatalytic activity of TiO₂ fiber remained ca. 90% of photocatalytic activity of the fresh sample after being used four times. Moreover, TiO₂ fiber was easily recovered by centrifugal separation from water.     

Small angle x-ray scattering of a supercritical electrolyte solution: the effect of density fluctuations on the hydration of ions

Synchrotron small angle x-ray scattering measurements on water and zinc bromide ZnBr2 aqueous solutions were carried out from ambient to supercritical conditions. For both systems several isobars (between 285 and 600 bars) were followed beyond the critical isochore. The data were analyzed through an Ornstein-Zernike formalism in terms of correlation length and null angle structure factor. The results for pure water are in agreement with previously published values. Solutions of different electrolyte concentrations were studied. In each case, the values of the correlation length and null angle structure factor are larger than those of pure water. This effect is more pronounced for higher concentrations and/or for pressure closer to the critical point of pure water. This is in agreement with the shift of the critical point determined in the literature for NaCl solutions. Comparing these results to previous x-ray absorption measurements carried out on identical samples we propose the following two step sequence for ionic hydration up to supercritical conditions: (1) from ambient to about 300 degrees C, an increase of ion pairing and formation of multi-ionic complexes which can be correlated to the decrease of the dielectric constant; (2) an enhancement of the local solvation shell of ions due to the onset of the thermal density fluctuations at high temperature, leading to a screening effect between ions and inhibiting the ion pairing processes.     

Protein films adsorbed on experimental dental materials: ToF-SIMS with multivariate data analysis

The proteins lysozyme, amylase, and bovine serum albumin (BSA) were adsorbed on two experimental dental materials, made of fluoroapatite particles embedded in polymer matrices, and on silicon wafers. The protein films were prepared as single-component layers, as binary mixtures, and as double layers. These systems were investigated by time-of-flight secondary ion mass spectrometry (ToF-SIMS) and the multivariate data analysis technique of discriminant principal-component analysis (DPCA). During adsorption of a single protein film on to the solid surfaces, the three proteins could be clearly distinguished by the scores of their mass spectra after selection of amino acid-related peaks and DPCA. Furthermore, very similar results were obtained on the two different fluoroapatite substrates. For samples coated with binary layers of two proteins adsorbed simultaneously, it was found for both substrate types that BSA shows the strongest ability to adsorb followed by lysozyme, while amylase has the smallest ability. By contrast, the consecutive adsorption of two protein layers showed a strong influence of substrate type on the adsorption ability of the proteins.     

In‐Plane Structures of Synthetic Oligolactose Lipid Monolayers—Impact of Saccharide Chain Length

Grazing incidence X‐ray diffraction (GIXD) was used to investigate the in‐plane structure of monolayers of synthetic glycolipids with oligolactose head groups (Lac N, with N=number of lactose units) at the air/water interface. The Lac 1 monolayer exhibits three sharp diffraction peaks. One peak can be deconvoluted into two diffraction peaks, which suggests that alkyl chains in the monolayer form an orthorhombic lattice. On the other hand, the other two peaks are related to bulk crystalline materials residing at the interface. Another weak peak from the head group correlation, either in a monolayer or in bulk crystals, can also be observed in some experiments. The scattering patterns of the Lac 2 monolayer indicate that the alkyl chains order in an orthorhombic lattice, where a shift in the hydrophilic/hydrophobic balance seems to fluidize the film. Alkyl chains in the Lac 3 monolayer also seem to assume an orthorhombic lattice; however, a weak diffraction peak from the correlation between trilactose head groups can also be observed. The estimated lattice dimensions are compared systematically to those of bulk dispersions, as well as to the viscoelastic properties of the monolayer. The obtained results strongly suggest that the in‐plane structure of synthetic glycolipid monolayers can provide a well‐defined basis to understand the impact of the chemical structure on the cooperativity and function of the glycocalix of cellular surfaces.