Small-angle Neutron Diffraction Research Articles

Nanoscale assembly of enantiomeric supramolecular gels driven by the nature of solvents.

Understanding the key parameters that control the self-assembly process is critical to predict self-assembly modes in multi-component systems, which will lead to the development of nanofibrous materials with tuneable properties. Enantiomeric amino acid-based low-molecular-weight gelators (LMWGs) were mixed in polar (polar protic) and aromatic apolar (aromatic) solvents and compared to their individual counterparts to probe the effect of solvent polarity on the self-assembly process. Scanning electron microscopy (SEM) reveals that xerogels of individual components display hollow needles in polar protic solvents, while chiral coils are observed in aromatic solvents. In contrast, the multi-component gel displays hollow needle morphologies in both solvents, indicating similar morphologies in polar protic solvents but an entirely different nanostructure for the individual gel networks in aromatic solvents. PXRD experiments performed on the dried gels showed that the nature of the solvents plays a vital role in the co-assembly process of multi-component gels. The self-assembly modes and the gel state structure of the gels are analysed by wide-angle X-ray diffraction (WAXS) and small-angle neutron diffraction (SANS), which reveals that the mixed gel undergoes different co-assembly modes depending on the nature of the solvent systems. This study shows that different co-assembly modes can be achieved for structurally similar components by varying the solvent polarity, demonstrating the importance of solvent choice in the self-assembly process of multi-component gels.

Molecular Rearrangements in Protomembrane Models Probed by Laurdan Fluorescence.

Lipid membranes are a key component of living systems and have been essential to the origin of life. One hypothesis for the origin of life assumes the existence of protomembranes with ancient lipids formed by Fischer-Tropsch synthesis. We determined the mesophase structure and fluidity of a prototypical decanoic (capric) acid-based system, a fatty acid with a chain length of 10 carbons, and a lipid system consisting of a 1:1 mixture of capric acid with a fatty alcohol of equal chain length (C10 mix). To shed light on the mesophase behavior and fluidity of these prebiotic model membranes, we employed Laurdan fluorescence spectroscopy, which reports on the lipid packing and fluidity of membranes, supplemented by small-angle neutron diffraction data. The data are compared with data of the corresponding phospholipid bilayer systems of the same chain length, 1,2-didecanoyl-sn-glycero-3-phosphocholine (DLPC). We demonstrate that the prebiotic model membranes capric acid and the C10 mix show formation of stable vesicular structures needed for cellular compartmentalization at low temperatures only, typically below 20 °C. They reveal the fluid-like lipid dynamic properties needed for optimal physiological function. High temperatures lead to the destabilization of the lipid vesicles and the formation of micellar structures.

Singlet-triplet mixing in the order parameter of the noncentrosymmetric superconductor Ru7B3

One of the key effects which is predicted to arise in superconductors without a centre of inversion is the mixing of singlet and triplet order parameters, which are no longer good quantum numbers on their own due to parity. We have probed the gap structure in the noncentrosymmetric superconductor Ru$_7$B$_3$, through small-angle neutron diffraction from the vortex lattice, in order to search for the proposed mixed order parameter. We find that the measured temperature dependence of the vortex-lattice form factor is well characterised by a model constructed to describe the effects of broken inversion symmetry on the superconducting state, indicating the presence of a mixed singlet-triplet gap and confirming the theoretical predictions.

Effects of Silicon, Chromium, and Copper on Kinetic Parameters of Precipitation during Tempering of Medium Carbon Steels.

Understanding the tempering behavior of medium carbon steels is mandatory if their mechanical properties are to be improved. For an optimal technology to be developed for this purpose, a substantial experimental basis is needed to extract quantitative information on the microstructure of the tempered material. This paper reports on the characterization of microstructural changes induced by tempering in medium-carbon steels alloyed with Si, Cr, Cu, and Mn using state-of-the-art experimental techniques. Complementarities among these techniques are highlighted. The evolution of transition carbides, cementite, and copper precipitates is described using data from X-ray diffraction, small and ultra-small angle neutron diffraction, transmission electron microscopy, and dilatometry observation. The effects of silicon, chromium, and copper on the mechanism of carbide and copper precipitation are discussed. The considerable changes found in the size and volume of copper precipitates correlate well with the difference in the yield stress between tempered steels with and without copper.

Liquid Structure of Single and Mixed Cation Alkylammonium Bromide Urea Deep Eutectic Solvents.

The liquid structures of three alkyl ammonium bromide and urea DESs, ethylammonium bromide:urea (1:1), butylammonium bromide:urea (1:1), and ethylammonium bromide/butylammonium bromide:urea (0.5:0.5:1), have been studied using small-angle neutron diffraction with H/D substituted sample contrasts. The diffraction data was fit using empirical potential structure refinement (EPSR). An amphiphilic nanostructure was found in all DESs due to cation alkyl chains being solvophobically excluded from charged domains, and due to clustering together. The polar domain was continuous in all three DESs, whereas the apolar domain was continuous for the butylammonium DES and in the mixed DES, but not the ethylammonium DES. This is attributed to solvophobic interactions being weaker for the short ethyl chain. Surprisingly, the urea also forms large clusters in all three DESs. In ethylammonium bromide:urea (1:1), urea-urea orientations are mainly perpendicular, but in butylammonium bromide:urea (1:1) and the mixed system in-plane and perpendicular arrangements are found. The liquid nanostructures found in this work, especially for the ethylammonium DES, are different from those found previously for the corresponding DESs formed using glycerol, revealing that the DES amphiphilic nanostructure is sensitive to the nature of the HBD (hydrogen bond donor).

Arrangement of Ceramides in the Skin: Sphingosine Chains Localize at a Single Position in Stratum Corneum Lipid Matrix Models.

Understanding the structure of the stratum corneum (SC) is essential to understand the skin barrier process. The long periodicity phase (LPP) is a unique trilayer lamellar structure located in the SC. Adjustments in the composition of the lipid matrix, as in many skin abnormalities, can have severe effects on the lipid organization and barrier function. Although the location of individual lipid subclasses has been identified, the lipid conformation at these locations remains uncertain. Contrast variation experiments via small-angle neutron diffraction were used to investigate the conformation of ceramide (CER) N-(tetracosanoyl)-sphingosine (NS) within both simplistic and porcine mimicking LPP models. To identify the lipid conformation of the twin chain CER NS, the chains were individually deuterated, and their scattering length profiles were calculated to identify their locations in the LPP unit cell. In the repeating trilayer unit of the LPP, the acyl chain of CER NS was located in the central and outer layers, while the sphingosine chain was located exclusively in the middle of the outer layers. Thus, for the CER NS with the acyl chain in the central layer, this demonstrates an extended conformation. Electron density distribution profiles identified that the lipid structure remains consistent regardless of the lipid’s lateral packing phase, this may be partially due to the anchoring of the extended CER NS. The presented results provide a more detailed insight on the internal arrangement of the LPP lipids and how they are expected to be arranged in healthy skin.

Application of small-angle neutron diffraction to the localization of general anesthetics in model membranes.

We set out to explore the applicability of small-angle neutron diffraction (SAND) to the localization of biomembrane components by studying the general anesthetic n-decane in a model lipid bilayer system composed of dioleoyl-phosphocholine (DOPC). Samples in the form of planar membrane multilayers were hydrated by varied mixtures of deuterated and protonated water, and examined by the means of SAND. Neutron scattering length density (NSLD) profiles of the system were then reconstructed from the experimental data. We exploited the significantly different neutron scattering properties of hydrogen and deuterium atoms via labeling in addition towater contrast variation. Enhancing the signals from particular components of bilayer system led to a set of characteristic membrane profiles and from their comparison we localized n-decane molecules unequivocally in the bilayer's hydrocarbon chain region.

Magnetic structure of the inverse opal-like structures: Small angle neutron diffraction and micromagnetic simulations

Geometrical frustration arised in spin ices leads to fascinating emergent physical properties. Nowadays there is a wide diversity of the artificial structures, mimicking spin ice at the nanoscale and demonstrating some new effects. Most of the nanoscaled spin ices are two dimensional. Ferromagnetic inverse opal-like structures (IOLS) are among inspiring examples of the three-dimensional system exhibiting spin ice behaviour. However detailed examination of its properties is not straightforward. Experimental technique which is able to unambiguously recover magnetization distribution in 3D mesoscaled structures is lacking. In this work we used an approach based on complementary exploiting of small-angle neutron diffraction technique and micromagnetic simulations. External magnetic field was applied along three main directions of the IOLS mesostructure. Comparison of the calculated and measured data allowed us to determine IOLS magnetic state. The results are in good agreement with the spin ice model. Moreover influence of the demagnetizing field and vortex states on the magnetizing process were revealed. Additionally, we speculate that this approach can be also applied to other 3D magnetic mesostructures.

Location of the general anesthetic n-decane in model membranes

The location of n-decane molecules within the model biological membrane consisting of dioleoyl-phosphocholine (DOPC) bilayers has been investigated via small angle neutron diffraction (SAND) method and molecular dynamics (MD) simulations. Diffraction patterns of the samples containing varied amounts of labeled and unlabeled n-decane have been obtained at various H2O:D2O scattering contrasts and utilized in the reconstruction of their neutron scattering length density (NSLD) profiles. The experimental data analysis based on mutual comparison of contrast varied NSLD profiles revealed unambiguously the location of n-decane molecules within our complex liquid system. They are distributed mostly in the lipid bilayer center while oriented both perpendicular to the bilayer normal, as well as in orientation parallel to the bilayer normal. In this, the mode of n-decane incorporation differs very little for the different concentrations examined (1:1 and 2:1 n-decane:DOPC molar ratios). The results of MD simulations corroborate experimental observations qualitatively and offer an explanation for the persistence of n-decane incorporation mode.

Alcohol Interactions with Lipid Bilayers.

We investigate the structural changes to lipid membrane that ensue from the addition of aliphatic alcohols with various alkyl tail lengths. Small angle neutron diffraction from flat lipid bilayers that are hydrated through water vapor has been employed to eliminate possible artefacts of the membrane curvature and the alcohol’s membrane-water partitioning. We have observed clear changes to membrane structure in both transversal and lateral directions. Most importantly, our results suggest the alteration of the membrane-water interface. The water encroachment has shifted in the way that alcohol loaded bilayers absorbed more water molecules when compared to the neat lipid bilayers. The experimental results have been corroborated by molecular dynamics simulations to reveal further details. Namely, the order parameter profiles have been fruitful in correlating the mechanical model of structural changes to the effect of anesthesia.

Effect of alkan-1-ols on the structure of dopc model membrane

Abstract The effect of general anaesthetics alkan-1-ols (CnOH, where n = 10, 12, 14, 16 and 18 is the number of carbon atoms in the molecule) on the structure of dioleoylphosphatidylcholine (DOPC) model membrane was studied by small-angle neutron scattering (SANS) and small-angle neutron diffraction (SAND). Fluid bilayers were prepared at CnOH:DOPC = 0.3 molar ratio. The results of both the experiments show that bilayer thickness - a thickness parameter dg in the case of SANS and lamellar repeat distance D in the case of SAND - increases with increasing n. A coexistence of two lamellar phases with different D was detected by measuring the C18OH+DOPC oriented sample.

Cation-containing lipid membranes – experiment and md simulations

Abstract Using small angle neutron diffraction and molecular dynamics simulations we studied the interactions between calcium (Ca2+) or zinc (Zn2+) cations, and oriented gel phase dipalmitoyl-phosphatidylcholine (DPPC) bilayers. For both cations studied at ~1:7 divalent metal ion to lipid molar ratio (Me2+:DPPC), bilayer thickness increased. Simulation results helped reveal subtle differences in the effects of the two cations on gel phase membranes.

Role of critical fluctuations in the formation of a skyrmion lattice in MnSi

The region in the H–T phase diagram near the critical temperature (T c ) of the cubic helicoidal MnSi magnet is comprehensively studied by small-angle neutron diffraction. Magnetic field H is applied along the [111] axis. The experimental geometry is chosen to simultaneously observe the following three different magnetic states of the system: (a) critical fluctuations of a spin spiral with randomly orientated wavevector k f , (b) conical structure with k c ǁ H, and (c) hexagonal skyrmion lattice with ksk ⊥ H. Both states (conical structure, and skyrmion lattice) are shown to exist above critical temperature T c = 29 K against the background of the critical fluctuations of a spin spiral. The conical lattice is present up to the temperatures where fluctuation correlation length ξ becomes comparable with pitch of spiral d s . The skyrmion lattice is localized near T c and is related to the fluctuations of a spiral with correlation length ξ ≈ 2d s , and the propagation vector is normal to the field (ksk ⊥ H). These spiral fluctuations are assumed to be the defects that stabilize the skyrmion lattice and promote its formation.

Calcium and Zinc Differentially Affect the Structure of Lipid Membranes.

Interactions of calcium (Ca2+) and zinc (Zn2+) cations with biomimetic membranes made of dipalmitoylphosphatidylcholine (DPPC) were studied by small angle neutron diffraction (SAND). Experiments show that the structure of these lipid bilayers is differentially affected by the two divalent cations. Initially, both Ca2+ and Zn2+ cause DPPC bilayers to thicken, while further increases in Ca2+ concentration result in the bilayer thinning, eventually reverting to having the same thickness as pure DPPC. The binding of Zn2+, on the other hand, causes the bilayers to swell to a maximum thickness, and the addition of more Zn2+ does not result in a further thickening of the membrane. Agreement between our results obtained using oriented planar membranes and those from vesicular samples implies that the effect of cations on bilayer thickness is the result of electrostatic interactions, rather than geometrical constraints due to bilayer curvature. This notion is further reinforced by MD simulations. Finally, the radial distribution functions reveal a strong interaction between Ca2+ and the phosphate oxygens, while Zn2+ shows a much weaker binding specificity.

X-ray studies of dynamic aging in an aluminum alloy subjected to severe plastic deformation

In this work, X-ray scattering methods were applied for a quantitative characterization of the microstructure of an aluminum alloy of the Al–Mg–Si system during dynamic aging realized through the high pressure torsion technique. A qualitative and quantitative phase analysis of the alloy was performed, together with Al alloy lattice parameter determination. From the reflections broadening the effective size of the coherent scattering domains and the lattice microstrain were determined in the framework of the Halder–Wagner approach. Using the method of small-angle X-ray scattering, the quantitative characteristics of the size, shape and spatial distribution of the secondary phase particles formed in the Al alloy during dynamic aging were established. In order to validate the obtained results, the method of small-angle X-ray scattering was preliminarily tested on similar samples after artificial aging and compared with the results from small-angle neutron diffraction widely known in literature.

Ice rule for a ferromagnetic nanosite network on the face-centered cubic lattice

The magnetic properties of an inverse opal-like cobalt-based structure having the symmetry of the face-centered cubic lattice are studied. The magnetization reversal of the structure in a magnetic field applied along the [\(1\overline 1 0\)] axis is described using a phenomenological model, which uses the ice rule for the local magnetization of nanostructure elements. This description predicts the absence of a long-range magnetic order in two directions that are normal to the magnetic field. The magnetic structure is analyzed by smallangle neutron diffraction. Neutron diffraction patterns are measured in an external magnetic field varying from −1.2 to 1.2 T and applied along the crystallographic [\(1\overline 1 0\)] direction. A magnetic contribution to the neutron scattering intensity is extracted. It is shown that this contribution is close to zero over the entire applied magnetic field range for all scattering planes that are normal to the field, which agrees well with the proposed model.

Association and liquid structure of pyridine-acetic acid mixtures determined from neutron scattering using a 'free proton' EPSR simulation model.

The liquid structure of pyridine-acetic acid mixtures have been investigated using neutron scattering at various mole fractions of acetic acid, χHOAc = 0.33, 0.50, and 0.67 and compared to the structures of neat pyridine and acetic acid. Data has been modelled using empirical potential structure refinement (EPSR) with a 'free proton' reference model, which has no prejudicial weighting towards either the existence of molecular or ionised species. Analysis of the neutron scattering results shows the existence of hydrogen-bonded acetic acid chains with pyridine inclusions, rather than the formation of an ionic liquid by proton transfer.

Pore ordering in mesoporous matrices induced by different directing agents

Mesoporous silica particles of MCM-41 type were synthesized by sol-gel method from tetraethyl orthosilicate (TEOS) in 2-methoxyethanol and deionized water mixture in base conditions at room temperature. Ammonia or sodium hydroxides were used as catalysts and cetyl-trimethylammonium bromide (CTAB) and n-dodecyl-trimethylammonium bromide (DTAB) as structure directing agents. The porosities and the ordered structure have been analyzed using transmission and scanning electron microscopy, small angle neutron and X-ray diffraction, nitrogen adsorption, thermal analysis and FTIR spectroscopy. The samples consist of spherical particles of sub-micrometer size, with radially arranged pores. The comparison of the effect of the different surfactants and catalysts shows that by varying the surfactant type and their proportion, the pore sizes can be controlled. As compared to the commonly used ammonia catalyst, the use of NaOH as catalyst results in a much smaller porosity of the as-prepared materials. These materials are not resisting to the heat treatment at 700 C used for the template removal, and the ordered porous structure is completely lost.

α-Tocopherol's Location in Membranes Is Not Affected by Their Composition.

To this day, α-tocopherol's (aToc) role in humans is not well known. In previous studies, we have tried to connect aToc's biological function with its location in a lipid bilayer. In the present study, we have determined, by means of small-angle neutron diffraction, that not only is aToc's hydroxyl group located high in the membrane but its tail also resides far from the center of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) bilayers. In addition, we located aToc's hydroxyl group above the lipid backbone in 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (POPE), 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-L-serine (POPS), and sphingomyelin bilayers, suggesting that aToc's location near the lipid-water interface may be a universal property of vitamin E. In light of these data, how aToc efficiently terminates lipid hydroperoxy radicals at the membrane center remains an open question.

Hexagonal spin structure of A-phase in MnSi: Densely packed skyrmion quasiparticles or two-dimensionally modulated spin superlattice?

We have studied in detail the A-phase region in the field-temperature (H-T) phase diagram of the cubic heli-magnet MnSi using small angle neutron diffraction. The A-phase revealed itself as a two-dimensional hexagonal pattern of Bragg spots with k h(1, 2, 3) ⊥ H. The directions and magnitudes of the wave vectors k h(1, 2, 3) are well preserved over the whole crystal of the size of 100 mm3, but in the small room of the (H-T) phase diagram just below T c = 29 K. The droplets of the orientationally disordered, presumably hexagonal, spin structure with k h ⊥ H are observed in the wide range beyond the A-phase boundaries in the field range from B T1 ≈ 0.1 T to B T2 ≈ 0.25 T at temperatures down to 15 K. No melting of these droplets into individual randomly located skyrmions is observed for all temperatures and magnetic fields. The wave vector of two-dimensional modulations k h is equal to the wave vector of the cone phase k c . We conclude that observable is a two dimensionally modulated hexagonal spin superlattice built on the same competition of interactions (ferromagnetic exchange and Dzyaloshinskii-Moriya interactions) similar to a case of one-dimensionally modulated simple spin spiral.