Small-angle Neutron Research Articles

The smearing function for a multi-slit very small angle neutron scattering instrument

Besides traditional pinhole geometry, the multi-slit very small angle neutron scattering instrument (MS-VSANS) at the China Spallation Neutron Source also utilizes a multi-slit collimation system to focus neutrons. Using the special focusing structures, the minimum scattering vector magnitude (q) can reach 0.00028 Å−1. The special structures also lead to a significantly different smearing function. By comparing the results of theoretical calculations with experimental data, we have validated the feasibility of a smearing method based on a mature theory for slit smearing. We use the weight-averaged intensity of neutron wavelength as a representative to evaluate the effect from a broad wavelength distribution, concentrating on the effect from the geometry of the multi-slit structures and the detector. The consistency of the theoretical calculation of the smearing function with experimental VSANS scattering profiles for a series of polystyrene standards of different diameters proves the feasibility of the smearing method. This marks the inaugural use of real experimental data from an instrument employing a multi-slit collimation system.

Experimental and simulation study of reverse micelles formed by aerosol-OT and water in non-polar solvents.

The formation of reverse micelles by aerosol-OT [sodium bis(2-ethylhexyl) sulfosuccinate] in hydrocarbon solvents, and in the presence of water, is studied using a combination of atomistic molecular-dynamics simulations and small-angle neutron scattering (SANS). There have been many previous studies of aerosol-OT and its self-assembly in both water and non-aqueous solvents, but this work is focused on a combined experimental and simulation study of reverse-micelle formation. The effects of hydration (with water-to-surfactant molar ratios in the range 0-60) and solvent (cyclohexane and n-dodecane) are investigated. A force field is adapted that results in spontaneous formation of reverse micelles starting from completely randomized configurations. The computed dimensions of the reverse micelles compare very favourably with those determined in SANS experiments, providing validation of the simulation model. The kinetics of reverse-micelle formation are studied with a 50-ns, 1.7-million-atom system which contains, in the steady state, about 50 reverse micelles. The internal structures of reverse micelles are characterized with mass density profiles, and the effects of solvent, and the structural crossover from highly structured water to 'bulk' water in the core, are detailed. The corresponding changes in the molecular reorientation times of sequestered water are also determined. Overall, the combination of experiment and simulation gives a detailed picture of reverse-micelle self-assembly and structure.

The role of annealing and grain boundary controls on the mechanical properties of limestones and marbles

Chemical and mechanical processes are coupled in many geological and geochemical environments. Reactive processes anneal defects and restructure grain boundaries, modifying their elastic properties, levels of internal friction, wave propagation rates and fracture behaviors. The nature of these changes is, however, contingent on the initial state of the rock. In this study, impulse excitation was used to measure changes in mechanical properties as a function of dry and steam heating time at 300 °C for three carbonate rocks: Carrara marble, Carthage marble (Burlington Limestone), and Texas Cream limestone (Edwards limestone), with initial porosities of about 1 %, 3 %, and 27 %, respectively. Frequency-dependent phenomena along with mineral recrystallization were observed. This was coupled with small-angle X-ray and neutron scattering analysis to determine the relationship between changes in bulk mechanical and microstructural properties. An observed decrease in both the Young's and shear moduli in the experimental limestones as a function of heating time reflects and quantifies a reduction in the stiffness of the rock due to annealing. The internal friction of the samples first increases then decreases with reaction time, reflecting defect annealing, but this was balanced against grain boundary dissolution apparently driven by condensation of steam in the confined grain-boundary environment. This suggests an increase in the boiling point under confinement leading to dissolution, increased porosity and widening of the grain boundaries. In addition, comparison of small-angle X-ray and neutron scattering results suggests that it is inappropriate to assume that pores are empty for quantitative analysis of typical small-angle scattering samples.

Probing the Behaviour of Fluids Confined in Porous Materials by Neutron Scattering: Applications to CO2 Sequestration and Enhanced Oil and Gas Recovery.

The current review presents a discussion on the utility of neutron scattering, with emphasis on neutron total scattering and small-angle neutron scattering (SANS), to explore the structural properties and the phase behaviour of fluids confined in nanopores. The effectiveness of contrast matching SANS on the evaluation of accessibility of porous materials to invading fluids is highlighted too. This review provides also an overview regarding the neutron scattering studies on the structure and the accessibility of greenhouse gases in the complex pore network of geomaterials, with applications to CO2 geological sequestration and enhanced oil and gas recovery.

Kinetics of Chain Exchange in Asymmetric ABA′ Triblock Polymer Micelles by Time-Resolved Small-Angle Neutron Scattering

Kinetics of Chain Exchange in Asymmetric ABA′ Triblock Polymer Micelles by Time-Resolved Small-Angle Neutron Scattering

Shear and cooling effects on lamellar gel network structure: Insights from Rheo-SANS

We investigate the formation of lamellar gel networks (LGNs) composed of long-chain fatty alcohols (C16, C18) and their mixture, combined with the surfactant cetyltrimethylammonium chloride (CTAC). The study aims to understand how fatty alcohol chain length and preparation processes affect the structural and mechanical properties of LGNs. Using small-angle neutron scattering (SANS) and in-situ rheology, we track the effects of mixing and cooling rates on formulations in aqueous solution. Additional insights into the nanostructure are provided by small- and wide-angle X-ray scattering (SAXS/WAXS), while microscopy and rheology shed light on macroscopic behavior. Results show that all formulations form lamellar structures, with C16/C18 mixtures exhibiting properties intermediate to those of pure C16 and C18 systems. While C16 and C16/C18 exhibit hexagonal lateral packing, C18 leads to an orthorhombic structure. Faster cooling rates favor the formation of multilamellar vesicles and promote system homogeneity. A patchy organization of the surfactant within the fatty alcohol bilayers is also observed. These findings enhance our understanding of the role of long-chain fatty alcohols in LGN formation and their behavior during mixing and cooling.

Decomposition of mixed DMPC-aescin vesicles to bicelles is linked to the lipid's main phase transition: A direct evidence by using chain-deuterated lipid

This work investigates the conversion of bicelles into larger sheets or closed vesicles upon dilution and temperature increase for a system composed of the phospholipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and the saponin aescin. Due to its peculiar amphiphilic character, aescin is able to decompose DMPC bilayers into smaller, rim-stabilized bicelles. Aspects of the transition process are analyzed in an aescin content- and temperature-dependent manner by photon correlation spectroscopy (PCS), turbidimetry and small-angle neutron scattering (SANS). Both the conversion of bicelles into vesicles induced by temperature increase and the decomposition process upon cooling are presumably related to the main phase transition temperature Tm of DMPC. Therefore, not only conventional DMPC, but also chain-deuterated d54-DMPC was used due to its significantly lower Tm-value compared to the conventional DMPC. It will be demonstrated that the reconversion of vesicle structures (present at low aescin content) into bicelles shows a strong hysteresis effect whereas this is not observed for the reconversion at high aescin amounts, at which for high temperature still bicelle structures are present. The results indicate formation of a trapped state, correlated with the lipid's Tm and the decomposition of vesicles into bicelles is only possible if the lipid membrane entirely adopts the rigid phase state.

PNIPAM Mesoglobules in Dependence on Pressure.

Poly(N-isopropylacrylamide) (PNIPAM) in aqueous solution forms mesoglobules above its cloud point temperature Tcp. While these are small and compact at atmospheric pressure, they are large and water-rich at high pressure. To identify the transition between these states, we employed optical microscopy and carried out isothermal pressure scans. Using very small angle neutron scattering, we determined the size and water content of the mesoglobules in pressure scans at different temperatures above Tcp. We observe a distinct transition at pressures of 35-55 MPa with the transition pressure depending on temperature. While the transition is smooth at high temperatures, i.e., far away from the coexistence line, it is abrupt at low temperatures, i.e., close to the coexistence line. Hence, at high temperatures, the swelling of the mesoglobules dominates, whereas at low temperatures, the coalescence of mesoglobules prevails. Subsequently decreasing the pressure results in a gradual deswelling of the mesoglobules at high temperature. In contrast, at low temperatures, small and compact mesoglobules form, but the large aggregates persist. We conclude that, on the time scale of the experiment, the disintegration of the large swollen aggregates into small and compact mesoglobules is only partially possible. Erasing the history by cooling the sample at the maximum pressure into the one-phase state does not result in qualitative changes for the behavior with the only difference that Fewer mesoglobules are formed when the pressure is decreased again. The newly identified transition line separates the low-pressure from the high-pressure regime.

Innovation in sustainable composite research: Investigating graphene-reinforced MMCs for liquid hydrogen storage tanks in aerospace and space exploration

The demand for lightweight materials in space exploration applications has seen a significant rise. This study presents a novel approach by integrating graphene with Aluminium alloy (AA) 2900 powder, synthesized through High energy ball milling technique. The resulting powder was used to reinforce Aluminium alloy 2195, creating metal matrix composites (MMCs) via squeeze casting. The findings demonstrate that incorporating 0.5 wt % 2D graphene nanoplatelets (2D-Grnp) in AA 2195 achieved density match, enabling homogeneous dispersion, addressing composite casting challenges. Consequently, the AA 2900 alloy embedded with 2D-Grnp facilitated the homogeneous dispersion of reinforcements during the squeeze casting process, yielding MMCs Ideal for potential use in lightweight liquid hydrogen fuel tank structures for launch vehicles. Following T8 heat treatment, the final casted composite plate exhibited significant enhancements in ultimate tensile strength, with a 4.5% increase over monolithic Al 2195-T8, exhibiting nominal reduction in elongation behavior and higher hardness. Additionally, scanning and transmission electron microscopy (SEM, TEM), Small Angle Neutron Scattering (SANS) and Electron Backscatter Diffraction (EBSD) revealed the squeeze casting technique's effectiveness by exhibiting enhanced bonding among homogeneously reinforced 2D-Grnp, T1/θ’ precipitates, and AA 2195.

Unexpected asymmetric distribution of cholesterol and phospholipids in equilibrium model membranes

Lipid compositional asymmetry across the leaflets of the plasma membrane is a ubiquitous feature in eukaryotic cells. How this asymmetry is maintained is thought to be primarily controlled by active transport of lipids between leaflets. This strategy is facilitated by the fact that long tail phospholipids and sphingolipids diffuse through the lipid bilayer slowly – taking many hours or days. However, a lipid like cholesterol – which is the most abundant lipid in the plasma membrane of animal cells – has been harder to pin-point in terms of its favored side. In the present work we show that when a saturated lipid is added to a mix of the unsaturated lipid palmitoyl-oleoyl-phosphatidylcholine (POPC) and cholesterol, both cholesterol and the long tail phospholipids organize asymmetrically across the membrane’s leaflets naturally. In these extruded unilamellar vesicles, most cholesterol as well as the saturated lipid – dipalmitoylphosphatidylcholine (DPPC) or sphingomyelin (SM) – segregated to the inner leaflet while POPC preferentially localized in the outer leaflet. This asymmetric arrangement generated a slight phospholipid number imbalance favoring the outer leaflet and thus opposite to where cholesterol and the saturated lipids preferentially partitioned. These results were obtained using Magic Angle Spinning (MAS) NMR in combination with Small Angle Neutron Scattering (SANS) using isotope labeling to differentiate lipid species. We suggest that sidedness in membranes can be driven by thermodynamic processes. In addition, our MAS NMR results show that the lower bound for cholesterol’s flip-flop half-time at 45°C is 10ms, which is at least two orders of magnitude slower than current MD simulations predict. This result stands in stark contrast to previous work that suggested that cholesterol’s flip-flop half-time at 37°C has an upper bound of 10ms.

Characterization of Rapeseed Protein Supramolecular Structures Obtained by Aqueous Extractions

Aqueous extraction of rapeseed has the potential to produce mildly refined yet functional protein ingredients. However, the colloidal structures of these mildly refined ingredients are still not fully understood. Therefore, the aim of this work was to examine the structures present in rapeseed extracts by analyzing their scattering characteristics across different length scales. Rapeseed protein concentrates were obtained after aqueous extractions at acidic (pH 5.7) or alkaline (pH 8.5) conditions. The structures were investigated using complementary techniques, cryo-transmission electron microscopy, small angle X-ray scattering and small angle neutron scattering. To understand the scattering contribution of various components at characteristic length scales, D2O contrast variation was performed, and SAXS analysis for extracts at pH 5.7 treated with pectinase were compared to those untreated. All suspensions contained globular proteins within a network of soluble polysaccharides as observed by Cryo-TEM. SANS analysis with different D2O/H2O ratios demonstrated that at low q, both proteins and polysaccharide contributed to scattering, suggesting the presence of large complexes containing both. The signal for pH 8.5 suspensions was mainly attributed to oleosomes. SAXS measurements agreed with the SANS data, and pH 5.7 suspensions measured after pectin hydrolysis revealed that the complexes were formed by rapeseed globulins (∼4 nm) and polysaccharide chains. This research highlights the importance of understanding the protein-polysaccharide interactions occurring in rapeseed aqueous extracts, to fully utilize these less refined fractions as value-added ingredients in future sustainable foods.

Micellar Nanogels from Alginate-Based Diblock Copolysaccharides.

Alginates are marine polysaccharides known for their ability to selectively bind calcium ions and form hydrogels. They are widely used in biomedical applications but are challenging to produce as nanogels. Here we introduce a self-assembly route to create stable alginate-based nanogels under near-equilibrium conditions. Guluronate (G) blocks, which interact with divalent cations such as Ca2+, Ba2+, and Sr2+, were extracted from alginates and covalently linked through their reducing end to the reducing end of dextran (Dex) chains, forming linear block copolymers that self-assemble into micellar nanogels with a core-corona structure in the presence of these ions. Real-time dynamic light scattering (DLS) and small-angle neutron scattering (SANS) were used to study the self-assembly mechanism of the copolymer during dialysis against divalent ions. For the G12-b-Dex51 copolymer, we achieved spherical micelles with an 8 nm radius and an aggregation number of around 20. Although the type of divalent cation affected micelle stability, it did not influence their size. Micellar nanogels are dynamic structures, capable of ion exchange, and can disassemble with chelating agents like ethylenediamine tetraacetic acid (EDTA).

Supramolecular Architectures of Dendritic Polymers Provide Irreversible Inhibitor to Block Viral Infection.

In Nature, most known objects can perform their functions only when in supramolecular self-assembled from, e.g. protein complexes and cell membranes. Here, a dendritic polymer is presented that inhibits severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) with an irreversible (virucidal) mechanism only when self-assembled into a Two-dimmensional supramolecular polymer (2D-SupraPol). Monomeric analogs of the dendritic polymer can only inhibit SARS-CoV-2 reversibly, thus allowing for the virus to regain infectivity after dilution. Upon assembly, 2D-SupraPol shows a remarkable half-inhibitory concentration (IC50 30nM) in vitro and in vivo in a Syrian Hamster model has a good efficacy. Using cryo-TEM, it is shown that the 2D-SupraPol has a controllable lateral size that can be tuned by adjusting the pH and use small angle X-ray and neutron scattering to unveil the architecture of the supramolecular assembly. This functional 2D-SupraPol, and its supramolecular architecture are proposed, as a prophylaxis nasal spray to inhibit the virus interaction with the respiratory tract.

Pinhole small-angle neutron scattering based approach for desmearing slit ultra-small-angle neutron scattering data.

Presented here is an effective approach to desmearing slit ultra-small-angle neutron scattering (USANS) data, based on complementary small-angle neutron scattering (SANS) measurements, leading to a seamless merging of these data sets. The study focuses on the methodological aspects of desmearing USANS data, which can then be presented in the conventional manner of SANS, enabling a broader pool of data analysis methods. The key innovation lies in the use of smeared SANS data for extrapolating slit USANS, offering a self-consistent integrand function for desmearing with Lake's iterative method. The proposed approach is validated through experimental data on porous anodized aluminium oxide membranes, showcasing its applicability and benefits. The findings emphasize the importance of accurate desmearing for merging USANS and SANS data in the crossover q region, which is particularly crucial for complex scattering patterns.

Probing structural modification of milk proteins in the presence of pepsin and/or acid using small- and ultra-small-angle neutron scattering

Acid- and pepsin-induced milk protein coagulation plays a crucial role in the gastric digestion of milk. Real-time structural evolution at a nano- (e.g. colloidal calcium phosphate (CCP) and micelle) and micro- (gel network) level of unheated and heated (85 °C for 30 min) bovine milk was examined under acidic conditions and at low and high concentrations of pepsin using ultra-small- and small-angle neutron scattering (USANS and SANS), small-amplitude oscillatory rheometry and confocal scanning laser microscopy. Milk was treated with glucono-δ-lactone (GDL), pepsin or a combination of GDL and pepsin to induce coagulation. Heat-treated milk showed a faster increase in elastic storage modulus (G′) and scattering intensity (USANS and SANS) compared with unheated milk when coagulated with GDL or the combination of GDL and pepsin. At pH 6.3, heat treatment retarded pepsin (1.10 U/mL)-induced milk coagulation, with slower increases in G′ and scattering intensity. At a high concentration of pepsin (2000 U/mL) that mimics the concentration found in the stomach, general proteolysis followed coagulation. Heat treatment retarded coagulation but accelerated curd proteolysis. This study demonstrates how time-resolved USANS and SANS can be used to investigate the structural evolution of protein coagulation and degradation under gastric environment conditions at nano- and micro-metre length scales.

Hierarchical Structure of Soft Materials Studied at Small-Angle Neutron Scattering Instrument, SANS-U

Hierarchical Structure of Soft Materials Studied at Small-Angle Neutron Scattering Instrument, SANS-U

Legume protein gelation: The mechanism behind the formation of homogeneous and fractal gels

Protein gelation can provide texture in plant-based foods and can be influenced by many factors, including protein extraction method and salt addition. However, the protein gelation mechanism is still not well understood for plant proteins, especially for isolates obtained using commercial protein extraction processes. Therefore, the structural changes that legume sources such as yellow pea, faba bean, and soybeans undergo during the gelation process to understand the differences in their gelation mechanisms was investigated herein by using small-angle neutron scattering. Among these protein sources, the commercial extraction method was found to play a major part in the gelation pathway. Intensive protein extraction methods involving isoelectric precipitation led to lower protein solubility (∼1–38% w/w), larger insoluble protein particle sizes (60–100 μm), and a gelation pathway that is dependent on the changes of the insoluble protein particles. In contrast, extraction using ultrafiltration instead of precipitation resulted in higher protein solubility (∼18–88% w/w) and smaller insoluble protein particle sizes (40–70 μm), and the structural changes observed during gelation involved the structural changes of both soluble proteins and insoluble proteins. SEM imaging also showed different gel networks, with fractal networks formed by insoluble proteins (for sources with low solubility) or more homogenous networks formed by the interactions between the soluble proteins (for sources with high solubility). Despite the differences observed in the gelation network and the protein solubility, the gelation strength exhibited by protein sources at low protein solubility were similar to the ones by protein sources at high protein solubility, demonstrating the potential of fractal gel networks in providing texture.

A time-resolved investigation at multiple-length scales of the structure of liquid foam stabilized by albumins from pea

HypothesisThe structural details of foams made with pea albumins are affected by the pH of the initial solution and followed heat treatment. ExperimentsAn in situ, time-resolved investigation of foams prepared with pea albumins was conducted using small-angle neutron scattering (SANS) in combination with imaging and conductance measurements. Solutions were tested at pH three pH values (3, 4.5, and 8) before and after heating (90 °C for 1 and 5 min). FindingsThe characteristic structures present in the foam from the nano to the meso-scale differed during drainage depending on solution pH. Foams obtained at pH 3, had the largest bubble radius and thinnest plateau border, as well as the highest extent of liquid drainage. At pH 4.5, close to the isoelectric point of the proteins, foams displayed similar bubbles’ behavior to those at pH 8, but with the largest film thickness. In this case, the proteins were extensively aggregated. Heating of the solutions prior to foaming did not significantly affect the foam aging regardless of pH. The quantification of specific surface areas and film thickness over time without sample disruption shows to be a powerful approach to designing foam structures.

Selective deuteration of an RNA:RNA complex for structural analysis using small-angle scattering.

The structures of RNA:RNA complexes regulate many biological processes. Despite their importance, protein-free RNA:RNA complexes represent a tiny fraction of experimentally-determined structures. Here, we describe a joint small-angle X-ray and neutron scattering (SAXS/SANS) approach to structurally interrogate conformational changes in a model RNA:RNA complex. Using SAXS, we measured the solution structures of the individual RNAs in their free state and of the overall RNA:RNA complex. With SANS, we demonstrate, as a proof-of-principle, that isotope labeling and contrast matching (CM) can be combined to probe the bound state structure of an RNA within a selectively deuterated RNA:RNA complex. Furthermore, we show that experimental scattering data can validate and improve predicted AlphaFold 3 RNA:RNA complex structures to reflect its solution structure. Our work demonstrates that in silico modeling, SAXS, and CM-SANS can be used in concert to directly analyze conformational changes within RNAs when in complex, enhancing our understanding of RNA structure in functional assemblies.

Wetting mechanism and alteration of nano-sized shale pores: Insights from contrast variation small angle neutron scattering

Wettability of tight shale is crucial for fluid flow and mass transport process in energy geosciences. However, understanding the interfacial chemistry and wetting mechanisms at sub-nano-pore scales remains a formidable challenge. In this study, the Contrast Variation technique of Small Angle Neutron Scattering (CV-SANS) is employed to investigate shale’s interfacial chemistry using reagents that possess a range of different polarities, including water, n-decane, toluene, and dimethyl methanamide. Through five different experimental strategies, we have demonstrated a successful modification of shale wettability, ranging from enhancement, weakening, to reversal. Delving into the mechanisms, we illustrated the crucial role of pre-existing liquid films in these changes, where the uniquely co-existing polar and non-polar functional groups in dimethyl methanamide acted as a conduit for interfacial chemistry adjustments. Furthermore, a solvent immersion led to matrix dilation as well as liberation of residual oil-occupied pores, resulting in altered pore size distributions, with hydrogen bonding playing a significant role in the polar groups. Interestingly, despite shale exhibiting a stronger affinity for oil over water, hydrophilic solvents induced more substantial dilation than lipophilic ones. Collectively, this work elucidates the dynamic change of interfacial chemistry via the configuration of polarity using chemical reagents, and the CV-SANS technique underscores its invaluable utilities in decoding the interfacial wettability traits in nanopore space of shale.