Neutron Scattering Research Articles

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

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.

Data Analysis of Dynamics in Protein Solutions Using Quasi-Elastic Neutron Scattering─Important Insights from Polarized Neutrons.

Protein dynamics play a vital role in biology. Quasi elastic neutron scattering (QENS) is an ideal method to access these dynamics. To isolate protein dynamics, it is important to separate the signal of the buffer and the protein. Normally data analysis is performed based on the assumption that the scattering spectrum is incoherent. To observe the full range of protein dynamics, it is necessary to perform the experiments in solution. This solution is usually a fully deuterated buffer, while the protein remains protonated. It is generally assumed that subtracting the buffer contribution removes all coherent signal from the measured spectrum, and the rest can be considered as purely incoherent. Up until recently, there was no way to experimentally verify this assumption. Polarized QENS experiments allow for the coherent and incoherent contributions to be separated. By comparing the results from the polarized QENS experiment and the standard analysis method from unpolarized QENS, we are thus able to check this assumption experimentally. We show that the pure incoherent spectrum obtained from polarization analysis does not match the results for unpolarized QENS. We discuss the implications of this for data analysis and possible solutions to the problem, as well as mitigation techniques for standard QENS.

Revealing the Structural Intricacies of Biomembrane-Interfaced Emulsions with Small- and Ultra-Small-Angle Neutron Scattering.

Utilizing cell membranes from diverse cell types for biointerfacing has demonstrated significant advantages in enhancing colloidal stability and incorporating biological properties, tailored specifically for various biomedical applications. However, the structures of these materials, particularly emulsions interfaced with red blood cell (RBC) or platelet (PLT) membranes, remain an underexplored area. This study systematically employs small- and ultra-small-angle neutron scattering (SANS and USANS) with contrast variation to investigate the structure of emulsions containing perfluorohexane within RBC (RBC/PFH) and PLT membranes (PLT/PFH). The findings reveal that the scattering length density of RBC and PLT membranes is 1.5 × 10-6Å-2, similar to 30% (w/w) deuterium oxide. Using this solvent as a cell membrane-matching medium, estimated droplet diameters are 770nm (RBC/PFH) and 1.5µm (PLT/PFH), based on polydispersed sphere model fitting. Intriguingly, calculated patterns and invariant analysis reveal native droplet architectures featuring entirely liquid PFH cores, differing significantly from the observed bubble-droplet core system in electron microscopy. This highlights the advantage of SANS and USANS in differentiating genuine colloidal structures in complex dispersions. In summary, this work underscores the pivotal role of SANS and USANS in characterizing biointerfaced colloids and in uncovering novel colloidal structures with significant potential for biomedical applications and clinical translation.

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.

Polarized and Unpolarized Neutron Scattering for Magnetic Materials at the Triple-axis Spectrometer PONTA in JRR-3

Polarized and Unpolarized Neutron Scattering for Magnetic Materials at the Triple-axis Spectrometer PONTA in JRR-3

Electron Dynamics in Neutron Scattering with Hydrogen Atoms

Abstract Gas targets have been used to measure scattering length in neutron-proton (n-p) scattering experiments. Changes in electron dynamics within the gas target have a negligible effect on dynamics of nucleons. However, electron dynamics are sensitively related to the specific form of the n-p interaction during the scattering process. We propose a theoretical approach to explore electron dynamics and determine parameters of the n-p interaction. This approach is based on a three-body scattering process involving a neutron, a proton and an electron. Numerical results indicate significant differences in electron dynamics with varying values of n-p interaction parameters, providing additional information beyond scattering cross-sections to accurately determine these parameters.

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.

4-Methoxypicolinic Acid N-Oxide: One of the Shortest Hydrogen Bonds Known Characterized by Neutron Diffraction, Inelastic Neutron Scattering, Infrared Spectroscopy, and Periodic DFT Calculations.

The present work focuses on the case of an extremely short intramolecular O-H···O hydrogen bond (H-bond) found in 4-methoxypicolinic acid N-oxide (MPANO). The donor···acceptor separation of 2.403 Å makes the H-bond in MPANO one of the shortest H-bonds known. We elucidated the structure and dynamics of the H-bond by two neutron-based techniques, namely, single-crystal diffraction and inelastic scattering (INS) vibrational spectroscopy. We also utilized conventional infrared (IR) spectroscopy as well as quantum chemical computations on isolated and periodic models. Both the protiated and deuterated variants of MPANO were investigated by INS and IR. All the methods used unequivocally confirm the existence of an extremely short, asymmetric H-bond, with the proton located near yet off the midpoint. The main relevant feature of the IR spectrum is an extremely broad, complex, and red-shifted OH (OD) stretching band spanning between 1800 and 500 cm-1 and centered at about 1360 cm-1, which indicates the presence of extensive anharmonicity and coupling with other H-bond modes. Of the modes characteristic of H-bond dynamics, only the out-of-plane OH (OD) bending can clearly be detected in the INS spectra; it has a relatively high frequency indicative of the strength of the H-bond. The computed structure is in excellent agreement with the diffraction measurement when periodicity is taken into account. The calculated harmonic frequencies show a reasonable match with the observed spectral features, whereby the assignment of the IR and INS spectra is facilitated. The hydrogen stretching frequency, however, appears to be significantly overestimated, on account of the limitations of the harmonic approximation and the complex nature of the short H-bond.

Confined Segmental Diffusion in Nanophase Separated Janus Polynorbornenes as Investigated by Quasielastic Neutron Scattering

Confined Segmental Diffusion in Nanophase Separated Janus Polynorbornenes as Investigated by Quasielastic Neutron Scattering

The Unusual Functional Role of Protein Flexibility in Photosynthetic Light Harvesting: Protein Dynamics Studied Using Neutron Scattering

In addition to investigations of the three-dimensional protein structure, information on the dynamical properties of proteins is indispensable for an understanding of protein function in general. Correlations between protein dynamics and function are typically anticipated when both molecular mobility and function are concurrently affected under specific temperatures or hydration conditions. In contrast, excitation energy transfer within the major photosynthetic light-harvesting complex II (LHC II) presents an atypical case, as it remains fully operational even at cryogenic temperatures, primarily depending on the interactions between electronic states and involving harmonic protein vibrations only. This review summarizes recent work on vibrational and conformational protein dynamics of LHC II and directly relates these findings to its light-harvesting function. In addition, we give a comprehensive introduction into the use of neutron spectroscopy and molecular dynamics simulations to investigate the protein dynamics of photosynthetic protein complexes in solution, which is information complementary to that obtained by protein crystallography.

Neutron and X-ray Scattering Characterization of Silica Nanoparticle-Stabilized Polymer Hybrid Latex Particles.

A robust route to produce poly(methyl methacrylate) (pMMA) hybrid latex particles (radius ∼250 nm) that are selectively "armored" with silica nanoparticles (radius 12.5 nm) through addition of vinyltriethoxysilane was previously shown ( J. Colloid Interface Sci. 2018, 528, 289-300).Depending on synthesis conditions, the extent of nanoparticle attachment could be varied; however, the mechanism behind this attachment during latex growth remained unclear. The dual population of particles present (silica + polymer) means that particle sizing by dynamic light scattering is ambiguous. Furthermore, the low glass transition temperature (Tg) of polymers such as poly(butyl acrylate) (pBA) typically used in film-forming applications for decorative coatings (i.e., paints) means that the hybrid latex particles are too "soft" for robust analysis through atomic force microscopy (AFM) and scanning electron microscopy (SEM). Here, we show that small- and ultrasmall-angle neutron scattering (SANS and USANS), along with complementary data from small-angle X-ray scattering (SAXS), reveals that these armored hybrid latex particles adopt a raspberry-type configuration, supporting their core-shell structure. The number of nanoparticles present on the surface of the hybrid latex can be adjusted by addition of one of a diverse range of alkyl- or perfluoroalkyl-silanes to alter silica nanoparticle hydrophobicity, and quantified through analysis of scattering data. The approach therefore provides a novel, nonperturbative, and in situ method of quantifying nanoparticle attachment to polymer latex particles.

Probing the Distribution and Mobility of Aminopolymers after Multiple Sorption-Regeneration Cycles: Neutron Scattering Studies.

Solid-supported amines are effective CO2 adsorbents capable of capturing CO2 from flue gas streams (10-15 vol % CO2) and from ultradilute streams, such as ambient air (∼400 ppm CO2). Amine sorbents have demonstrated promising performance (e.g., high CO2 uptake and uptake rates) with stable characteristics under repeated, idealized thermal swing conditions, enabling multicycle application. Literature studies suggest that solid-supported amines such as PEI/SBA-15 generally exhibit slowly reducing CO2 uptake rates or capacities over repeated thermal swing capture-regeneration cycles under simulated DAC conditions. While there are experimental reports describing changes in supported amine mass, degradation of amine sites, and changes in support structures over cycling, there is limited knowledge about the structure and mobility of the amine domains in the support pores over extended use. Furthermore, little is known about the effects of H2O on cyclic applications of PEI/SBA-15 despite the inevitable presence of H2O in ambient air. Here, we present a series of neutron scattering studies exploring the distribution and mobility of PEI in mesoporous silica SBA-15 as a function of thermal cycling and cyclic conditions. Small-angle neutron scattering (SANS) and quasielastic neutron scattering (QENS) are used to study the amine and H2O distributions and amine mobility, respectively. Applying repeated thermal swings under dry conditions leads to the thorough removal of water from the sorbent, causing thinner and more rigid wall-coating PEI layers that eventually lead to slower CO2 uptake rates. On the other hand, wet cyclic conditions led to the sorption of atmospheric water at the wall-PEI interfaces. When PEI remains hydrated, the amine distribution (i.e., wall-coating PEI layer thickness) is retained over cycling, while lubrication effects of water yield improved PEI mobility, in turn leading to faster CO2 uptake rates.

Insight into the Competitive Adsorption Behavior of Polymer Chains in Silica Nanopores by Small-Angle Neutron Scattering

Insight into the Competitive Adsorption Behavior of Polymer Chains in Silica Nanopores by Small-Angle Neutron Scattering

Pegylated surfactants based on fatty acids: 12-hydroxystearic acid versus stearic acid

We describe the aqueous behavior of short Polyethylene glycol (PEG) chains of Mw 4 kDa that are either mono-functionalized or di-functionalized by 12-hydroxy stearic acid (HSA), and stearic acid (SA), respectively. The end capping of the chains by the fatty acids is achieved by Steglich esterification, after a step of protection of the 12-OH functional group in the case of HSA. Small Angle Neutron Scattering (SANS) shows that mono-functionalized chains with both SA or HSA sticky ends self-assemble in star micelles in aqueous solution, and interact through repulsive steric interactions. The di-functionalized telechelic chains self-assemble in flower micelles that interact through interactions that are attractive on average due to the formation of bridges by chains that share their both ends in two different micelles. Solutions of telechelic chains undergo a phase separation between a dilute solution of micelles and a dense hexagonal crystalline network of flower micelles above a given polymer concentration threshold. This threshold is lower for SA-PEG-SA than for HSA-PEG-HSA. We postulate that this difference of behavior arises from the formation of hydrogen bonds between the OH groups at the C12 of the alkyl chain in case of HSA that increase the stability of the hydrophobic core of the micelles.

Structure, Microheterogeneity, and Transport Properties of Ethaline Decoded by X-ray/Neutron Scattering and MD Simulation.

Ethaline, a deep eutectic solvent (DES) composed of choline chloride (ChCl)-ethylene glycol (EG) in a 1:2 molar ratio, is garnering significant interest for its wide potential applications. The nature of liquid formation and the structure of H-bonds within ethaline were investigated by X-ray scattering (XRS), neutron scattering (NS), and MD simulations. The sum of the dissociation energy barriers of Ch-EG (3.31 kJ·mol-1) and EG-Cl (4.28 kJ·mol-1) exceeds that of Ch-Cl (5.97 kJ·mol-1). This results in a more pronounced solvation of ChCl by EG compared to ChCl association, facilitating the solubilization of ChCl crystals by EG to form a DES. A partial radial distribution function (PDF) reveals that Cl- solvation is dominated by the hydroxyl group of EG, while the methylene group dominates Ch+ solvation. The spatial distribution function (SDF) shows that the distribution of EG and Cl- around Ch+ partially overlaps with that of the quaternary ammonium group. However, the center of mass distance of Ch-Cl (4.95 Å) is significantly lower than that of Ch-EG (5.65 Å), suggesting a favorable advantage for Cl- in this competition. Chain and ring structure distributions provide direct evidence of the microheterogeneity of ethaline. Hydroxyl groups on the EG promote the formation of a chain structure in ethaline, while methylene groups favor a ring structure. H-bond, carbon H-bond, and Cl- bridge bond restrict Cl- diffusion. This new understanding is crucial for a deeper comprehension of the microstructure of ethaline and for elucidating its mechanisms in applications.

Study of readout system for 3He linear position sensitive detectors

This study introduces a readout system for 3He linear position-sensitive detectors (LPSDs), tailored for the Small Angle Neutron Scattering (SANS) spectrometer of the Compact Pulsed Hadron Source (CPHS) at Tsinghua University. Central to this system is the employment of a trapezoidal filter as the primary signal shaper, selected for its enhanced noise filtering capabilities and efficacy in mitigating ballistic deficit. Additionally, the integration of a digital CR filter aims to counteract baseline drift within trigger signals. This innovative architecture underwent validation via computer programs using experimental data, demonstrating superior performance in spatial resolution compared to conventional Gaussian filter-based approaches. Meanwhile, the improvement in spatial resolution comes with a narrower pulse width, promising a higher throughput at high count rates. When applied to a 16-tube detector module, the system achieved an average position resolution of 3.63 mm (FWHM) at the central region and 4.03 mm at the end regions. Furthermore, with a pusle width of 0.6 μs, the 96-tube detector array is promised to sustain a count rate over 1 Mcps.

Morphology evolution of lipid nanoparticle discovered by small angle neutron scattering

The structure of mRNA lipid nanoparticles (LNPs) is still under debate, with different studies presenting varying morphological characteristics, significantly hindering their biomedical potential. A typical formulation process of mRNA LNPs involves three steps: initial rapid mixing of lipids in an ethanol phase and mRNA in an acidic aqueous phase, followed by the swift removal of ethanol, and finally adjusting the solution to a neutral environment. In this study, we utilize Small Angle Neutron Scattering (SANS) with contrast matching to reveal the kinetic pathway-dependent of mRNA LNPs morphology. We find that the formulation process of the Moderna COVID-19 vaccine is controlled by a competition between aggregation and microphase separation, dictating the diverse morphologies observed in mRNA LNPs. The first step leads to the formation of polydisperse spherical droplets with an average diameter of 42±6.0 nm in an acidic ethanol aqueous solution. Ethanol removal initiates both aggregation and internal microphase separation, resulting in a polydisperse core-shell structure with an average diameter of 48±3.7 nm. Heptadecan-9-yl 8-((2-hydroxyethyl) (6-oxo-6-(undecyloxy) hexyl) amino) octanoate (SM-102) binds to mRNA via electrostatic interaction to form a reverse-wormlike micelle structure inside. The 1,2-Distearoyl-sn‑glycero-3-phosphocholine (DSPC) and PEG-lipid are just in the shell and cholesterol acting as a filler throughout the core-shell structure. Upon transitioning to a neutral environment, SM-102 loses its charge and neither the periphery nor the reverse-wormlike micelle can maintain their stabilities, leading to further aggregation and microphase separation. The average diameter of core-shell structure turns to be 66±5.2 nm. In the actual formulation process of the Moderna COVID-19 vaccine, steps 2 and 3 occur simultaneously, and the competition between aggregation and microphase separation determines the final morphology. These findings offer crucial insights into optimizing the morphology of mRNA LNPs, thereby facilitating advancements in vaccine development and mRNA vaccine delivery technologies.

The Influence of SC-CO2 on the Nanopore Structures of Different Types of Shales Based on Small-Angle Neutron Scattering and Multifractal Methods

The Influence of SC-CO₂ on the Nanopore Structures of Different Types of Shales Based on Small-Angle Neutron Scattering and Multifractal Methods