Small-angle X-ray Scattering Curves Research Articles

Small and wide angle X-ray scattering to reveal nanoscale structure evolution of the polyamide RO membranes triggered by ethyl acetate

The intrinsic structure of the polyamide separation layer determines the transport of water and salt through a thin film composite membrane. In this work, we probed nanoscale structure variation of the polyamide layers generated by ethyl acetate through small/wide angle X-ray scattering. The gyration radius and physical radius of the polyamide colloidal particles were calculated from the small angle X-ray scattering (SAXS) curves, and the results are confirmed by AFM and SEM. The form factor derived from SAXS curves and horizontal distance between the centers of adjacent benzene rings calculated from the wide angle X-ray scattering (WAXS) curves showed quantitative relationships with membrane performance including water permeability coefficient and salt permeability coefficient. The results derived from SAXS and WAXS curves provided evidence for the formation mechanism of polyamide layers.

Gold nanoparticles obtained by ns-pulsed laser ablation in liquids (ns-PLAL) are arranged in the form of fractal clusters

Gold nanoparticles (AuNPs), synthesized by ns-pulsed laser ablation in liquid (ns-PLAL) in the absence of any capping agents, are potential model systems to study the interactions with biological structures unencumbered by interference from the presence of stabilizers and capping agents. However, several aspects of the physics behind these AuNPs solutions deserve a detailed investigation. The structure in solution of ns-PLAL-synthesized AuNPs was investigated in solution by means of small-angle X-ray scattering (SAXS) and dynamic light scattering (DLS). Furthermore, the (dried) NPs have been examined using TEM. The analysis of the SAXS curve shows the presence of a large number of small aggregates with a fractal structure stabilized by strong long-range repulsive interactions. Fitting of the SAXS curve to a suitable “fractal model” allows the estimation of the features of the fractal including the fractal dimension d = 1.9. The latter allows to estimate the fraction of light scattered by fractals of different sizes and thus permits a fair comparison between the DLS and TEM data. Here, a stable abundant population of fractal clusters is reported reflecting a mechanism where primary AuNPs (size 7.6 nm) are forced to aggregate forming clusters during the collapse of the cavitation bubble. When these clusters are released in the aqueous phase, their large negative charge builds up repulsive interactions that prevent cluster-cluster aggregation imparting colloidal stability.

A quantitative structural characterisation of active semiconducting materials (mSi; SiO2; Al2O3; TiO2) for use in printed electronics using a combination of Small Angle Light Scattering (SALS) and Ultra Small Angle X-ray Scattering (USAXS)

Four nanostructured active semiconducting materials currently used in electronic inks have been structurally characterised using a combination of small angle scattering techniques and scanning electron microscopy. The percolation theory and scaling laws have been used to obtain quantitative correlations of the network topologies and the local micro-structures with the electronic and electrical properties of the printed, electronic devices.The small angle light scattering has been used to expand the lower q-range of the Ultra Small Angle x-ray Scattering curves of the 2503 metallurgical grade silicon (mSi), silicon dioxide (SiO2), aluminium dioxide (Al2O3) and titanium dioxide (TiO2) materials by close to an order of magnitude, thereby providing valuable clustering properties for each material. Each scattering curve presented a series of multiple structural levels, which are then quantified using the Unified power-law approach to provide valuable clustering characteristics such as the degree of aggregation, polydispersity and geometry standard deviation. Subsequently, a fully screen-printed field effect transistor that uses mSi as the active material is demonstrated. The transistor had an ON/OFF current-ratio of 104; an electron mobility of 0.7 cm2/V s; a leakage current in the order of 5 × 10−9 A, and no current saturation.

Further insights into the evolution of starch assembly during retrogradation using SAXS

A new and effective method for evaluating the reassembly of starch molecules at large scale (>2 nm) during retrogradation has been developed based on the small angle X-ray scattering (SAXS) technique. The SAXS curves fitted by the Cauchy plus Power-law functions are decomposed into peak- and non-peak-derived sub-patterns. The peak-derived patterns are used for calculating (i) the size of ordered aggregate structures (d) using Lorentz correction and (ii) the proportion of ordered structures within starch samples (Rpeak) by estimating the ratio of the area under the peak-derived sub-pattern (Speak) to the total area under SAXS curve. The Imax and fractal-like dimension (α) of the scattering aggregates (the fitted parameters of SAXS curve), d, Speak, Snon-peak (the area under the non-peak-derived sub-pattern) and Rpeak change as a function of retrogradation time. Importantly, the Snon-peak interrogates the continuous reduction of amorphous starch molecules during the aging, SAXS parameters including α and d describe starch ordered aggregate structures with larger scale than 2 nm are fitted well with pseudo Avrami equation. The SAXS in this study can be used to unravel the evolution of both amorphous starch structures and ordered aggregates with larger scale during retrogradation.

Inhibitory Effect of a KSL-W Peptide-Loaded Poloxamer 407-Based Microemulsions for Buccal Delivery on Fusobacterium nucleatum Biofilm.

KSL-W peptide has demonstrated antibacterial and antifungal activity and inhibitory effects against oral biofilm. This study aimed to check out the effect of chlorhexidine (CLX) or KSL-W peptide-loaded poloxamer 407-based microemulsions for buccal delivery on Fusobacterium nucleatum (F. nucleatum) biofilm. The formulation (F) containing 10% copolymer poloxamer 407 dispersion (1%), 40% oleic acid and 50% PPG-5-CETETH-20 was characterized by polarized light microscopy (PLM), small-angle X-ray scattering (SAXS), rheology, bioadhesive and syringeability; and in the treatment of a biofilm produced by F. nucleatum. The darkfield images obtained by PLM and the SAXS curves with an extended peak indicated that the system was characteristic of microemulsions. In a continuous analysis, microemulsions exhibited Newtonian behavior. In frequency, the oscillatory analysis profile presented predominantly viscous behavior. Bioadhesive force detected in the analysis of F (7.4 ± 1.81 mN˙ s) and syringeability (17.83± 5.97 N · mm) being adequate values for buccal administration. After 4 h, KSL-W-loaded F shown over 20% higher effectiveness than chlorhexidine-loaded microemulsions. In conclusion, the KSL-W-loaded microemulsions showed a considerable reduction in F. nucleatum biofilm formation and presented promising structural properties for buccal drug delivery.

Effect of silica coating on the catalytic activity of maghemite nanoparticles impregnated into mesoporous silica matrix

Abstract The search for more efficient catalysts and less polluting and less costly reagents has made heterogeneous catalysis one of the most advantageous processes in this scenario. In this work, recoverable heterogeneous catalysts were prepared by incorporating maghemite nanoparticles (M-NP) into mesoporous silica matrix and further coated with dense or mesoporous layers by the sol-gel process. The catalytic activity of the nanocomposites was evaluated in hydrocarbon oxidation accomplished by the epoxidation of Z-cyclooctene. The materials were characterized by small-angle-x-ray scattering (SAXS), transmission electron microscopy (TEM), nitrogen adsorption-desorption analysis that confirms the coating over the nanocomposites and also the dependence of the reagent amount on the thickness of coating. SAXS curves and nitrogen adsorption-desorption analysis are in agreement with typical profiles of well-ordered hexagonal lattice with the surface area obtained from BET analysis of 454 m2/g and the pore volume of 0.917 cm3/g for the non-coated mesoporous silica. TEM and XRD results show the formation of maghemite phase with nanoparticle diameters between 3.5 and 20 nm. In addition, the catalytic results show that the nanocomposites coated with a mesoporous silica coating displayed higher substrate conversion than those coated with dense silica coating.

Validation of electron microscopy initial models via small angle X-ray scattering curves.

Cryo electron microscopy (EM) is currently one of the main tools to reveal the structural information of biological macromolecules. The re-construction of three-dimensional (3D) maps is typically carried out following an iterative process that requires an initial estimation of the 3D map to be refined in subsequent steps. Therefore, its determination is key in the quality of the final results, and there are cases in which it is still an open issue in single particle analysis (SPA). Small angle X-ray scattering (SAXS) is a well-known technique applied to structural biology. It is useful from small nanostructures up to macromolecular ensembles for its ability to obtain low resolution information of the biological sample measuring its X-ray scattering curve. These curves, together with further analysis, are able to yield information on the sizes, shapes and structures of the analyzed particles. In this paper, we show how the low resolution structural information revealed by SAXS is very useful for the validation of EM initial 3D models in SPA, helping the following refinement process to obtain more accurate 3D structures. For this purpose, we approximate the initial map by pseudo-atoms and predict the SAXS curve expected for this pseudo-atomic structure. The match between the predicted and experimental SAXS curves is considered as a good sign of the correctness of the EM initial map. The algorithm is freely available as part of the Scipion 1.2 software at http://scipion.i2pc.es/.

X-Ray Study of the Superstructure in Heavily Doped Porous Indium Phosphide

An indium-phosphide InP sample subjected to the pore-generation procedure and then doped with S atoms is studied by the methods of X-ray diffraction analysis (XRD) and small-angle X-ray scattering (SAXS) (with CuKα1-radiation). The XRD data demonstrate that the sample consists of (coherent) aligned homogeneous components. A point detector is used to obtain, in the anomalous transmission mode by Borrmann, a set of SAXS curves at sample positions varied by azimuthal rotations. The SAXS data are used to simulate a 2D SAXS pattern for the sample under study, which makes it possible to determine the long-distance translation symmetry and, consequently, the presence of a superstructure. The interplanar distances in the superstructure in the directions (110) and (1 0) of the InP lattice are found to be ~260 and 450 nm, respectively. The symmetry group of the superstructure is determined as C2v in the (001) plane of the sample lattice.

Amphiphilic single and double networks: a small-angle X-ray scattering investigation

We investigated the microphase-separated morphologies of water-swollen amphiphilic single and double polymer networks using small-angle X-ray scattering (SAXS). The networks consist of (i) a first conetwork containing hydrophobic blocks from either 2-ethylhexyl methacrylate (EHMA) or lauryl methacylate (LauMA) and hydrophilic blocks from 2-(dimethylamino)ethyl methacrylate (DMAEMA) and (ii) a second polyacrylamide (PAAm) network. The SAXS curves are modeled by spherical core-shell micelles, where densely packed hydrophobic cores are surrounded by swollen hydrophilic chains. The correlation between these hydrophobic cores is described using a hard-sphere structure factor. A Porod law and an Ornstein-Zernike structure factor are adopted to capture the strong forward scattering due to large-scale inhomogeneities and the correlation between polymer strands, respectively. The size of the hydrophobic cores depends on the degree of polymerization of the hydrophobic block: for medium and long hydrophobic blocks, several hydrophobic cores merge together to form a larger core. When the second PAAm network is present, the nanostructures of the first amphiphilic network are less well-defined.

Interactions among spherical poly(acrylic acid) brushes: Observation by rheology and small angle X-ray scattering

Interactions among annealed spherical polyelectrolyte brushes (SPB) in concentrated aqueous dispersion under the effect of concentration, pH, and salt concentration are investigated by means of rheology, and small angle X-ray scattering (SAXS). SPB consist of a solid polystyrene (PS) core and linear poly(acrylic acid) (PAA) chains densely grafted onto the core by one end. Rheological investigation demonstrates that the viscosity, the storage modulus G′ and the loss modulus G″ of SPB dispersion increase significantly upon increasing the SPB concentration and pH value which reflects the enhanced interactions among SPB. At high pH, a further increase in pH from 8 to 13 has almost no impact on the rheological properties and SAXS curves, while a “Uniform Shell Model” can fit the SAXS data very well probably due to the uniform filling of polyelectrolyte chains among SPB. When increasing the salt concentration from 10−5 to 10−3 M, the so-called “polyelectrolyte peak” appears at middle to high q range in SAXS curves which means the overlapped polyelectrolyte chains are associated under the bridging effect of counterions, which disappears at higher salt concentration due to the screening effect of further added salts. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015

Morphological investigations of block sulfonated poly(arylene ether ketone) copolymers as potential proton exchange membranes

AbstractA series of block sulfonated poly(arylene ether ketone) (SPAEK) copolymers with different block lengths and ionic contents were synthesized by a two‐stage process. The morphology of these block SPAEK copolymers was investigated by various methods, such as differential scanning calorimetry (DSC), transmission electron microscope (TEM), and small angle X‐ray scattering (SAXS). Dark colored ionic domains of hundreds of nanometers spreading as a cloud‐like belt were observed in TEM images. The sizes of the ionic domains as a function of block copolymer composition were determined from SAXS curves. The results for the evolution of ionic domains revealed that the block copolymers exhibited more clearly phase‐separated microstructure with increasing ionic contents and hydrophobic sequence lengths. Proton conductivity is closely related to the microstructure, especially the presence of large interconnected ionic domains or ionic channels. Block SPAEK membranes have interconnected ionic clusters to provide continuous hydrophilic channels, resulting in higher proton conductivity. Copyright © 2010 John Wiley & Sons, Ltd.

Human LDL core cholesterol ester packing: three-dimensional image reconstruction and SAXS simulation studies

Human LDL undergoes a reversible thermal order-disorder phase transition associated with the cholesterol ester packing in the lipid core. Structural changes associated with this phase transition have been shown to affect the resistance of LDL to oxidation in vitro studies. Previous electron cryo-microscopy studies have provided image evidence that the cholesterol ester is packed in three flat layers in the core at temperatures below the phase transition. To study changes in lipid packing, overall structure and particle morphology in three dimensions (3D) subsequent to the phase transition, we cryo-preserved human LDL at a temperature above phase transition (53°C) and examined the sample by electron microscopy and image reconstruction. The LDL frozen from 53°C adopted a different morphology. The central density layer was disrupted and the outer two layers formed a "disrupted shell"-shaped density, located concentrically underneath the surface density of the LDL particle. Simulation of the small angle X-ray scattering curves and comparison with published data suggested that this disrupted shell organization represents an intermediate state in the transition from isotropic to layered packing of the lipid. Thus, the results revealed, with 3D images, the lipid packing in the dynamic process of the LDL lipid-core phase transition.

Conformational stability of peanut agglutinin using small angle X-ray scattering

In this work, quaternary conformational studies of peanut agglutinin (PNA) have been carried out using small-angle X-ray scattering (SAXS). PNA was submitted to three different conditions: pH variation (2.5, 4.0, 7.4 and 9.0), guanidine hydrochloride presence (0.5–2M) at each pH value, and temperature ranging from 25 to 60°C. All experiments were performed in the absence and presence of T-antigen to evaluate its influence on the lectin stability. At room temperature and pH 4.0, 7.4 and 9.0, the SAXS curves are consistent with the PNA scattering in its crystallographic native homotetrameric structure, with monomers in a jelly roll fold, associated by non-covalent bonds resulting in an open structure. At pH 2.5, the results indicate that PNA tends to dissociate into smaller sub-units, as dimers and monomers, followed by a self-assembling into larger aggregates. Furthermore, the conformational stability under thermal denaturation follows the pH sequence 7.4>9.0>4.0>2.5. Such results are consistent with the conformational behavior found upon GndHCl influence. The presence of T-antigen does not affect the protein quaternary structure in all studied systems within the SAXS resolution.

SAXS Ensemble Refinement of ESCRT-III CHMP3 Conformational Transitions

We developed and implemented an ensemble-refinement method to study dynamic biomolecular assemblies with intrinsically disordered segments. Data from small angle X-ray scattering (SAXS) experiments and from coarse-grained molecular simulations were combined by using a maximum-entropy approach. The method was applied to CHMP3 of ESCRT-III, a protein with multiple helical domains separated by flexible linkers. Based on recent SAXS data by Lata etal. (J. Mol. Biol. 378, 818, 2008), we constructed ensembles of CHMP3 at low-and high-salt concentration to characterize its closed autoinhibited state and open active state. At low salt, helix α(5) is bound to the tip of helices α(1) and α(2), in excellent agreement with a recent crystal structure. Helix α(6) remains free in solution and does not appear to be part of the autoinhibitory complex. The simulation-based ensemble refinement is general and effectively increases the resolution of SAXS beyond shape information to atomically detailed structures.

Calculation of accurate small angle X-ray scattering curves from coarse-grained protein models

BackgroundGenome sequencing projects have expanded the gap between the amount of known protein sequences and structures. The limitations of current high resolution structure determination methods make it unlikely that this gap will disappear in the near future. Small angle X-ray scattering (SAXS) is an established low resolution method for routinely determining the structure of proteins in solution. The purpose of this study is to develop a method for the efficient calculation of accurate SAXS curves from coarse-grained protein models. Such a method can for example be used to construct a likelihood function, which is paramount for structure determination based on statistical inference.ResultsWe present a method for the efficient calculation of accurate SAXS curves based on the Debye formula and a set of scattering form factors for dummy atom representations of amino acids. Such a method avoids the computationally costly iteration over all atoms. We estimated the form factors using generated data from a set of high quality protein structures. No ad hoc scaling or correction factors are applied in the calculation of the curves. Two coarse-grained representations of protein structure were investigated; two scattering bodies per amino acid led to significantly better results than a single scattering body.ConclusionWe show that the obtained point estimates allow the calculation of accurate SAXS curves from coarse-grained protein models. The resulting curves are on par with the current state-of-the-art program CRYSOL, which requires full atomic detail. Our method was also comparable to CRYSOL in recognizing native structures among native-like decoys. As a proof-of-concept, we combined the coarse-grained Debye calculation with a previously described probabilistic model of protein structure, TorusDBN. This resulted in a significant improvement in the decoy recognition performance. In conclusion, the presented method shows great promise for use in statistical inference of protein structures from SAXS data.

SAXS study of monodispersed silica nanospheres obtained by an amino acid route

Spherical silica nanoparticles were prepared using a basic amino acid catalysis route and the kinetics of the particles growth was investigated by small angle X-ray scattering (SAXS). l-arginine was used in the polar aqueous phase as the basic catalyst whereas the tetraethylorthosilicate (TEOS) was dissolved in the cyclohexane oil phase as the silicate monomer source. The SAXS measurements were taken in the aqueous phase at different reaction times. A high degree of monodispersity was clearly evidenced for the spherical nanoparticles as a result of the pronounced high-order oscillations observed in the SAXS curves. The SAXS data show that the particles number density remains unchanged since both the particle size as well as the volume fraction gradually increase. This process was discussed based on a reaction-controlled addition of monomer species at the surface of the growing particles. Consequently, the monodispersed spherical nanoparticles radius can as such be finely tuned from 7 to 12 nm by varying the reaction time.

Nanoparticles/Ionic Linkers of Different Lengths: Short-Range Order Evidenced by Small-Angle X-ray Scattering

Small-angle X-ray scattering (SAXS) experiments were carried out to investigate systems consisting of silica nanoparticles bridged by imidazolium-based linkers. This characterization method delivers a quantitative description of the efficiency to order nanoparticles obtained from different chemical approaches. Two packing factors were extracted from the SAXS curves, where one characterizes the stacking of the ligands and the other the order of the nanoparticles. The amount of order can be controlled by using different ligands such as mono- and diimidazolium-based ones with different flexibilities or by varying the ligand length.

Structure and flexibility within proteins as identified through small angle X-ray scattering

Flexibility between domains of proteins is often critical for function. These motions and proteins with large scale flexibility in general are often not readily amenable to conventional structural analysis such as X-ray crystallography, nuclear magnetic resonance spectroscopy (NMR) or electron microscopy. A common evolution of a crystallography project, once a high resolution structure has been determined, is to postulate possible sights of flexibility. Here we describe an analysis tool using relatively inexpensive small angle X-ray scattering (SAXS) measurements to identify flexibility and validate a constructed minimal ensemble of models, which represent highly populated conformations in solution. The resolution of these results is sufficient to address the questions being asked: what kinds of conformations do the domains sample in solution? In our rigid body modeling strategy BILBOMD, molecular dynamics (MD) simulations are used to explore conformational space. A common strategy is to perform the MD simulation on the domains connections at very high temperature, where the additional kinetic energy prevents the molecule from becoming trapped in a local minimum. The MD simulations provide an ensemble of molecular models from which a SAXS curve is calculated and compared to the experimental curve. A genetic algorithm is used to identify the minimal ensemble (minimal ensemble search, MES) required to best fit the experimental data. We demonstrate the use of MES in several model and in four experimental examples.

Superparamagnetic Maghemite Nanorods: Analysis by Coupling Field-Flow Fractionation and Small-Angle X-ray Scattering

We report on the online coupling of asymmetrical flow field-flow fractionation (A4F) with small-angle X-ray scattering (SAXS) for the detection of nanoparticles. The A4F was used to fractionate superparamagnetic maghemite nanoparticles, which were prepared continuously with a micromixer. The outlet of the A4F was directly coupled to a flow capillary of a SAXSess instrument (Kratky type of camera). SAXS curves were recorded in a 1 s time interval. This was possible by using intense synchrotron radiation. The radii of gyration of the nanoparticles, as determined from Guinier plots, increased from 2 to 6 nm with increasing fractionation time of the A4F. A more detailed analysis of the scattering curves revealed that the particles were cylindrical in shape (nanorods), which we attributed to the micromixing preparation technique. The radii of the nanorods increased only slightly from 1.2 to 1.7 nm with increasing fractionation time, while the lengths increased strongly from 7.0 to 30.0 nm. The volume distribution of the nanorods was determined and described by Schultz-Zimm and log-normal distributions. Nanorod volumes increased from 45 to 263 nm(3), corresponding to molar masses of 140 x 10(3) to 820 x 10(3) g mol(-1). We propose A4F-SAXS coupling as a new method for analysis of nanoparticles of complex composition in solution. It allows precise online determination of the particle's shape and size distributions. This method can be applied to mixtures of nanoparticles of arbitrary shapes and sizes (1-100 nm). Moreover, the total time needed for fractionation and online SAXS data recording is usually only 20 min.

Multiple-length-scale small-angle X-ray scattering analysis on maghemite nanocomposites

Small-angle X-ray scattering (SAXS) analysis has been performed on maghemite–poly(4-vinylpyridine) nanocomposites prepared by in situ precipitation from iron–polymer coordination compounds. According to electron microscopy observations, the nanocomposites contain isolated spherical particles with a narrow size distribution, uniformly distributed throughout the polymer matrix. The scattering intensity of nanocomposites has relevant contributions from both the polymer and the nanocomposites, showing features characteristic of multiscale structured systems, namely two power laws and a Guinier regime. The data have been analysed in terms of Beaucage's unified approach and it is found that the maghemite particle size increases with the iron/polymer weight ratio used in the preparation of the nanocomposites. SAXS curves also feature a bump that was analysed as arising from a second particle population or from interactions. Magnetization and transmission electron microscopy results give arguments favouring the latter interpretation. It is found that the maghemite particle sizes vary linearly with the iron weight ratio used in the preparation of the nanocomposites.