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Ionically crosslinked hydrogels containing metal coordination motifs have piqued the interest of researchers in recent decades due to their self-healing and adhesive properties. In particular, catechol-functionalized bulk hydrogels have received a lot of attention because of their bioinspired nature. By contrast, very little is known about thin viscoelastic membranes made using similar chelator–ion pair motifs. This shortcoming is surprising because the unique interfacial properties of these membranes, namely, their self-healing and adhesion, would be ideal for capsule shells, adhesives, or for drug delivery purposes. We recently demonstrated the feasibility to fabricate 10 nm thick viscoelastic membranes from catechol-functionalized surfactants that are ionically crosslinked at the liquid/liquid interface. However, it is unclear if the vast know-how existing on the influence of the chelator–ion pair on the mechanical properties of ionically crosslinked three-dimensional (3D) hydrogels can be translated to two-dimensional (2D) systems. To address this question, we compare the dynamic mechanical properties of ionically crosslinked pyrogallol functionalized hydrogels with those of viscoelastic membranes that are crosslinked using the same chelator–ion pairs. We demonstrate that the storage and loss moduli of viscoelastic membranes follow a trend similar to that of the hydrogels, with the membrane becoming stronger as the ion–chelator affinity increases. Yet, membranes relax significantly faster than bulk equivalents. These insights enable the targeted design of viscoelastic, adhesive, self-healing membranes possessing tunable mechanical properties. Such capsules can potentially be used, for example, in cosmetics, as granular inks, or with additional work that includes replacing the fluorinated block by a hydrocarbon-based one in drug delivery and food applications.

Oil-in-water (O/W) microemulsions typically feature a low viscosity and exhibit the ordinary viscosity reduction as a function of temperature. However, for certain applications avoiding or even reverting the temperature trend might be required. This can be conceived by adding thermoresponsive (TR) block copolymers that induce network formation as temperature rises. Accordingly, various ME–polymer mixtures were studied for which three different block copolymer architectures of BAB*, B2AB*, and B(AB*)2 type were employed. Here, “B” represents a permanently hydrophobic, “A” a permanently hydrophilic, and “B*” a TR block. For the TR-block, three different poly(acrylamide)s, namely poly(N-n-propylacrylamide) (pNPAm), poly(N,N-diethylacrylamide) (pDEAm), and poly(N-isopropylacrylamide) (pNiPAm), were used, which all exhibit a lower critical solution temperature (LCST). For a well selected ME concentration, these block copolymers lead to a viscosity enhancement with rising temperature. At a polymer concentration of about 22 g L-1, the most pronounced enhancement was observed for the pNPAm-based systems with factors up to 3, 5, and 8 for BAB*, B2AB*, and B(AB*)2, respectively. This phenomenon is caused by the formation of a transitory network mediated by TR-blocks, as evidenced by the direct correlation between the attraction strength and the viscosity enhancement. For applications requiring a high hydrophobic payload, which is attained via microemulsion droplets, this kind of tailored temperature-dependent viscosity control of surfactant systems should therefore be advantageous.

In this study, we used small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS) to investigate the formation process of silver (Ag) nanoparticles (NPs) in water-in-oil (w/o) reverse microemulsions comprising sodium bis(2-ethylhexyl) sulfosuccinate (AOT), water, and organic solvents (such as benzene, octane, and decane) by the photoreduction of silver perchlorate (AgClO4). Combining SANS and SAXS, the structural changes in the w/o microemulsions before and after the formation of Ag NPs via photoreduction were quantitatively evaluated. From the SANS experiments performed using the contrast-variation method, the size of water cores containing Ag NPs and the thickness of the AOT shells were calculated using the core-shell hard-sphere model. The size of the Ag NPs and their aggregates was calculated via SAXS analysis based on the polydisperse sphere model with a Schulz-Zimm distribution. We found that aggregates of three or four primary Ag NPs are formed by, first, the aggregation of water droplets through the entanglement of the tails of the AOT shell, followed by the self-assembly of Ag NPs into their aggregates because of particle-particle attractive interactions.

We present a systematic study using real-time small-angle neutron scattering (SANS) and optical microscopy to follow the protein crystallization process in the presence of a metastable intermediate...

The aims of this work were to evaluate the effect of freezing and thawing stresses on lactate dehydrogenase (LDH) stability under three conditions. (i) In a solution buffered with sodium phosphate (NaP; 10 and 100 mM). The selective crystallization of disodium hydrogen phosphate during freezing caused a pronounced pH shift. (ii) In a solution buffered with histidine, where there was no pH shift due to buffer salt crystallization. (iii) At different concentrations of LDH so as to determine the self-stabilizing ability of LDH. The change in LDH tetrameric conformation was measured by small-angle neutron scattering (SANS). The pH of the phosphate buffer solutions was monitored as a function of temperature to quantify the pH shift. The conditions of buffer component crystallization from solution were identified using low-temperature X-ray diffractometry. Dynamic light scattering (DLS) enabled us to determine the effect of freeze-thawing on the protein aggregation behavior. LDH, at a high concentration (1000 μg/mL; buffer concentration 10 mM), has a pronounced self-stabilizing effect and did not aggregate after five freeze-thaw cycles. At lower LDH concentrations (10 and 100 μg/mL), only with the selection of an appropriate buffer, irreversible aggregation could be avoided. While SANS provided qualitative information with respect to protein conformation, the insights from DLS were quantitative with respect to the particle size of the aggregates. SANS is the only technique which can characterize the protein both in the frozen and thawed states.

Biopharmaceutical formulations may be compromised by freezing, which has been attributed to protein conformational changes at a low temperature, and adsorption to ice-liquid interfaces. However, direct measurements of unfolding/conformational changes in sub-0 °C environments are limited because at ambient pressure, freezing of water can occur, which limits the applicability of otherwise commonly used analytical techniques without specifically tailored instrumentation. In this report, small-angle neutron scattering (SANS) and intrinsic fluorescence (FL) were used to provide in situ analysis of protein tertiary structure/folding at temperatures as low as -15 °C utilizing a high-pressure (HP) environment (up to 3 kbar) that prevents water from freezing. The results show that the α-chymotrypsinogen A (aCgn) structure is reasonably maintained under acidic pH (and corresponding pD) for all conditions of pressure and temperature tested. On the other hand, reversible structural changes and formation of oligomeric species were detected near -10 °C via HP-SANS for ovalbumin under neutral pD conditions. This was found to be related to the proximity of the temperature of cold denaturation of ovalbumin (TCD ∼ -17 °C; calculated via isothermal chemical denaturation and Gibbs-Helmholtz extrapolation) rather than a pressure effect. Significant structural changes were also observed for a monoclonal antibody, anti-streptavidin IgG1 (AS-IgG1), under acidic conditions near -5 °C and a pressure of ∼2 kbar. The conformational perturbation detected for AS-IgG1 is proposed to be consistent with the formation of unfolding intermediates such as molten globule states. Overall, the in situ approaches described here offer a means to characterize the conformational stability of biopharmaceuticals and proteins more generally under cold-temperature stress by the assessment of structural alteration, self-association, and reversibility of each process. This offers an alternative to current ex situ methods that are based on higher temperatures and subsequent extrapolation of the data and interpretations to the cold-temperature regime.

Perfume solubilization is an important process in the production of commercial products such as beverages, foods, and cosmetics. In the present study, small-angle neutron scattering (SANS) experiments were performed to investigate the solubilization behavior of perfumes in cetyltrimethylammonium bromide (CTAB) micelles. The solubilization of linalool (LL) and l-menthol (MT), which are relatively hydrophilic perfumes, did not change the size of the CTAB micelles although the perfumes were incorporated in the micelles, as indicated by a decrease in scattering length density. On the other hand, the solubilization of d-limonene (LN), a hydrophobic perfume, led to the swelling of CTAB micelles. An internal contrast variation SANS study was performed by the deuteration of CTAB molecules to directly observe the perfumes in the micelles. The radius of d-CTAB micelles solubilizing LL or MT corresponds to that of h-CTAB, which indicates that these perfumes are accommodated in the palisade layers of the micelles and are homogeneously distributed in the micelles. On the other hand, LN formed small droplets, as indicated by the SANS profile, which implies the solubilization of LN molecules in the core of the CTAB micelles. We found that the relatively hydrophilic perfumes (LL and MT) show less impact on the sizes of the cationic micelles in comparison to nonionic micelles. Thus, the internal contrast variation method of SANS allowed the direct observation of the solubilization sites of perfumes with different hydrophilicity-hydrophobicity balances. This method is a powerful tool to determine the solubilization states that affect the solubilization capacity, volatilization, or release speed of perfumes.

This work presents an in situ nanoscale structural characterization of a SrCl2-expanded natural graphite (ENG) composite during ammonia absorption and desorption using small-angle neutron scattering (SANS) together with X-ray powder diffraction and sorption measurements. For the processing of the composite material SANS patterns, we developed and implemented two methods, which showed comparable results. The study allowed following the evolution of the SrCl2 particles and the nanopores inside the particles during five sorption cycles. The structural changes were compared to the absorption and desorption kinetic measurements, allowing us to make qualitative analysis of the impact of the structural changes on the material properties, such as thermal conductivity and permeability. It was shown that the structural evolution of the composite material did not affect the desorption rate but significantly influenced the absorption rate after the first cycle. We also observed a significant improvement of the absorption kinetics due to the formation of nanopores in the fully deammoniated sample. In addition, the ENG matrix was shown to hinder the agglomeration of the SrCl2 particles during sorption processes, which is in contrast to literature findings reported for a nonsupported metal halide. The findings presented in this study can be of great interest in the research areas where SrCl2-ENG composites are widely studied, i.e., heat storage, heat pumps/refrigerators, deNOx removal, and solid-state ammonia storage.

Hydraulic fracturing of low-permeability rocks significantly enhances hydrocarbon production from unconventional reservoirs. However, fluid transport through low-permeability rocks and the influence of geochemical transformations on pore networks are poorly constrained. Mineral reactivity during interactions with injected water may alter the physical nature of the rock, which may affect hydrocarbon mobility. To assess alterations to the rock, we have previously conducted a hydrothermal experiment that reacted cubed rock samples (1 cm

This study demonstrates how the large concentration fluctuations of polymeric liquids under deformation and flow can be quantitatively studied by applying the spherical harmonic expansion technique...

Liquid-like Nanoscale Organic Hybrid Materials or NOHMs consisting of polymer grafted nanoparticles have shown great promise in applications, such as electrochemistry and gas separation, due to the...

Methanol-Water (mw) mixtures, with or without a solute, display a nonideal thermodynamic behavior, typically attributed to the structure of the microphase. However, experimental observation of the microphase structures at the molecular length scale has been a challenge. We report the presence of molecular clusters in mw and formaldehyde-methanol-water (fmw) mixtures using small-angle neutron scattering (SANS) experiments and molecular dynamics (MD) simulations. Hydrophobic clusters of methanol in mw and formaldehyde-methanol in fmw mixtures were observed at low methanol compositions (xm ≤ 0.3). A three-dimensional hydrogen-bonded network of water with the solute is observed at xm = 0.5. Linear chains of methanol surrounding the formaldehyde and water molecules were observed at high methanol compositions (xm ≥ 0.7). The calculated size of the molecular clusters (r ≈ 0.5 nm, spherical) from the SANS data and their volume fraction closely matched the MD simulation results.

Concentrated wormlike micellar fluids form the basis for a vast array of formulated products, from liquid soaps and shampoos to drag reduction and drilling fluids. Typically, these systems are analyzed using bulk rheological measurements to determine their flow properties and cryo-microscopy to detect their nanostructure. Small-angle neutron scattering provides an opportunity to directly and nonperturbatively analyze nanostructure in situ but is complicated for concentrated systems by correlations from interparticle volume exclusion. Here, we use small-angle and ultra-small-angle neutron scattering to probe directly for the first time the nanostructure of concentrated wormlike micellar fluids composed of the widely used surfactant pair sodium laureth sulfate and cocamidopropyl betaine in aqueous electrolytes. Obtained data are analyzed using different approaches to determine scattering contributions from the wormlike particles themselves and interactions between them. It is found that approximating worms as locally rigid cylinders offers some insight into their aggregation dimensions at short length scales, and both volume exclusion and screened Coulombic interaction potentials describe interactions reasonably well. Using the semi-empirical polymer reference interaction site model (PRISM) gives excellent agreement with observed scattering, and physical insight obtained using this approach is discussed in detail. A drawback of this method is the significant complexity in coding the model in order to fit data, so to facilitate this for future researchers, we provide with this paper a fully operational, open-source code to utilize this model.

Determining the structure of nanoconfined compressed fluids is essential for predicting the fate of these fluids in subsurface geologic formations with nanoporous features and to engineer novel nan...

“Real-life” metals inevitably form the oxide layer, thus leading to complex initial hydriding processes, which are still unclear because of the experimental challenges in monitoring elemental steps...

The influence of lithium chloride (LiCl) on the hydration structure of anionic micelles of sodium dodecyl sulfate (SDS) in water was studied using the contrast-variation small-angle neutron scattering (SANS) technique. In the past, extensive computational studies have shown that the distribution of invasive water plays a critical role in the self-organization of SDS molecules and the stability of the assemblies. However, in past scattering studies the degree of the hydration level was not examined explicitly. Here, a series of contrast-variation SANS data was analyzed to extract the intramicellar radial distributions of invasive water and SDS molecules from the evolving spectral lineshapes caused by the varying isotopic ratios of water. By addressing the intramicellar inhomogeneous distributions of water and SDS molecules, a detailed description of how the counterion association influences the micellization behavior of SDS molecules is provided. The extension of our method can be used to provide an in-depth insight into the micellization phenomenon, which is commonly found in many soft matter systems.

A deep eutectic solvent (DES) entrapped in a bacterial cellulose (BC) network gives rise to a gelatin-like, self-supported material termed a bacterial cellulose eutectogel (BCEG). Although this novel material holds potential for numerous industrial, environmental, energy, or medical applications, little is known about the structural features or dynamical behavior within a eutectogel. In this work, we employ X-ray diffraction (XRD), nuclear magnetic resonance (NMR), and small-angle neutron scattering (SANS) to probe the structural and diffusive behavior of the prevailing DES glyceline (1:2 molar ratio of choline chloride:glycerol) confined within bacterial cellulose. XRD investigations demonstrate that the bacterial cellulose maintains its crystallinity even as the glyceline content approaches 95 wt % in the BCEG, an outcome corroborated by molecular dynamics (MD) simulations, which suggest minimal changes in the structural features of the cellulose chains due to the presence of glyceline. SANS measurements reveal a significant reduction in the radius of gyration (Rg) for BC in a BCEG compared to its hydrogel analogue, indicating a collapse in the microfibrillar structure that we attribute to removal of waters from the interfibrillar space due to a higher affinity of DES for water than for cellulose. Furthermore, SANS experiments suggest that the vast majority of DES is hosted within large micropores in the BCEG (i.e., mesoscopic confinement). Interestingly, proton NMR experiments disclose faster diffusional rates for choline and glycerol entrapped in a BCEG compared to neat glyceline. MD simulations offer the possible explanation that this diffusional acceleration results from significant migration of chloride from the bulk to cellulose microfibrillar surfaces, thereby reducing hydrogen bonding with choline and glycerol partners. This study provides the first comprehensive investigation into the structure and diffusional dynamics of glyceline within a eutectogel, offering insights into mass transport that should be useful for tailoring these novel materials to potential applications.

Thanks to the use of small-angle neutron scattering (SANS), a detailed structural description of thermosensitive polymer-grafted cellulose nanocrystals (CNCs) was obtained and the behavior of aqueous suspensions of these derivatized biosourced particles upon temperature increase was revealed. Although literature data show that the surface grafting of thermosensitive polymers drastically enhances the colloidal properties of CNCs, direct space microscopic investigation techniques fail in providing sufficient structural information on these objects. In the case of CNCs decorated with temperature-sensitive polyetheramines following a peptide coupling reaction, a qualitative and quantitative analysis of SANS spectra shows that CNCs are homogeneously covered by a shell comprising polymer chains in a Gaussian conformation with a thickness equal to their radius of gyration in solution, thus revealing a mushroom regime. An increase of the temperature above the lower critical solution temperature (LCST) of the polyetheramine results in the formation of finite size bundles whose aggregation number depends on the particle concentration and suspension temperature deviation from the LCST. SANS analysis further reveals local changes at the CNC surface corresponding to a release of water molecules and a related denser polymer shell conformation. Noticeably, data show a full reversibility at all length scales when a sample was cooled down to below the LCST after being heated above it. Overall, the results obtained by SANS allow an in-depth structural investigation of derivatized CNCs, which is of high interest for the design of functional materials comprising these biosourced colloids.

Unconventional oil and gas from shale formations have emerged as some of the fastest growing energy resources in the United States, providing both cleaner energy to consumers and reducing the natio...

While metal-organic nanotubes (MONTs) are the one-dimensional analogue of metal-organic frameworks (MOFs), in their crystalline form they exist almost exclusively as aggregates, where their assembl...

Using the extended-SARA method to fractionate asphaltenes based on their interfacial activity, the current study reports the first results on the estimated size and shape of interfacially active asphaltene (IAA) and remaining asphaltene (RA) nanoaggregates. These fractions have been reported to exhibit distinctly different chemical architectures that influence the size of asphaltene clusters in good and poor solvents. However, little is known about the building blocks, commonly referred to as nanoaggregates, which form these clusters and how those subtle differences in chemical architecture impact aggregation of asphaltenes. The nanoaggregate size and shape of IAA and RA was measured using small-angle neutron scattering (SANS). The characteristic length and asymptotic power-law exponent of whole asphaltenes (WAs) extracted from heavy crude oil and dispersed in deuterated toluene were 28.0 ± 0.2 A and 2.86 ± 0.01, respectively, showing negligible variations with changing asphaltene concentration, source of asphaltenes (bitumen and heavy crude oil), and solvent aromaticity. For RA fractions, which account for 98.5 wt % of WA, the characteristic length and power-law exponent of 28.8 A and 2.86 were comparable to that of WA but in contrast to 59.7 A and 2.20 for IAA. A ∼100% increase in the characteristic length and reduced power-law exponent of the IAA fraction confirms that these two asphaltene subfractions form dissimilar nanoaggregate structures.

Partially deuterated poly(ethylene glycol) (PEG) networks were fabricated by cross-linking a protonated four-arm PEG prepolymer (4hPEG) with a deuterated linear PEG (2dPEG) via a cross-end-coupling...

We report on small-angle neutron scattering (SANS) investigations of separate phase domains in high fat (70%) oil-in-water emulsions emulsified with the combination of sodium caseinate (CAS) and phosphatidylcholine (PC). The emulsion as a whole was studied by contrast variation to identify scattering components dominated by individual emulsifiers. The emulsion was subsequently separated into the aqueous phase and the oil-rich droplet phase, which were characterized separately. Emulsions produced with 1.05% (w/w) CAS and PC fraction which varies between 1.75% (w/w) and 0.35% (w/w) provided droplets between 10 and 19 μm in surface weighted mean in 70% fish oil-in-water emulsions. At least two-third of the overall CAS is associated with the interface, while the rest remains with the aqueous phase. Six percent of PC formed a monolayer in the interface, while the rest of the PC remains in the droplet phase in the form of multilayers. When the separated components were resuspended, the resuspended emulsion showed similar characteristics compared to the original emulsion in terms of droplet size distribution and neutron scattering. Instead, CAS in the aqueous phase separated from the emulsion shows aggregation not present in the corresponding CAS-in-D2O system.

We have measured the effect of added salt on the chain dimensions of mixtures of poly(ethylene oxide) (PEO) and lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI) in the melt state through small-angle neutron scattering (SANS) experiments. Scattering profiles from blends of hydrogenated and deuterated PEO mixed with LiTFSI were measured as a function of salt concentration. Scattering profiles from pure deuterated PEO/LiTFSI mixtures were used for background-subtraction purposes. The densities of PEO/LiTFSI mixtures of varying salt concentrations were measured to calculate partial molar monomer volumes of PEO and LiTFSI to account for nonideal mixing. Kratky plots of the scattering profiles were used to calculate the salt concentration dependence of statistical segment length. At low salt concentrations, segment length decreases with increasing salt concentration, before increasing with increasing salt concentration in the high salt concentration regime. The random phase approximation was used to predict theoretical scattering profiles from the calculated segment lengths and partial molar volumes; there is excellent agreement between the theoretical and measured scattering profiles at all salt concentrations. There appears to be a correlation between chain dimensions and coordination between lithium ions and EO monomers. The scattering profiles of the pure deuterated PEO/LiTFSI mixtures suggested the presence of ion clusters of characteristic size of 0.6 nm at high salt concentrations.

This study reports the use of operando small-angle neutron scattering to investigate processes in an operating Li/S battery. The combination with impedance spectroscopy yields valuable insights int...

Recently developed chain walking (CW) catalysis is an elegant approach to produce materials with controllable structure and properties. However, there is still a lack in understanding of how the reaction mechanism influences the macromolecular structures. In this study, a series of dendritic polyethylenes (PE) synthesized by Pd-α-diimine-complex through CW catalysis (CWPE) is investigated by means of theory and experiment. Thereby, the exceptional ability of in situ tailoring polymer structure by varying synthesis parameters was exploited to tune the branching architecture, which allowed us to establish a precise relationship between synthesis, structure, and solution properties. The systematically produced polymers were characterized by state-of-the-art multidetector separation and neutron scattering experiments as well as atomic force microscopy to access molecular properties of CWPE. On a global scale, the CWPE appear in a worm-like conformation independently on the synthesis conditions. However, severe differences in their contraction factors suggested that CWPE differ substantially in topology. These observations were verified by NMR studies that showed that CWPE possess a constant total number of branches but varying branching distribution. Small angle neutron scattering experiments gave access to structural characteristics from global to segmental scale and revealed the unique heterogeneity of CWPE, which is predominantly based on differences in their dendritic side chains. The experimental data were compared to theoretical CW structures modeled with different reaction-to-walking probabilities. Simple theoretical arguments predict a crossover from dendritic to linear topologies yielding a structural range from purely linear to dendritic chain growth. Yet, comparison of theoretical and empirical scattering curves gave the first evidence that a transition state to worm-like topologies is actually experimentally accessible. This crossover regime is characterized by linear global features and dendritic local substructures contrary to randomly hyperbranched systems. Instead, the obtained CWPE systems have characteristics of disordered dendritic bottle brushes and can be adjusted by the walking rate/reaction probability of the catalyst.

Droplet-stabilized emulsions (DSEs) were made from oil droplets coated with whey protein microgel (WPM) particles. The WPM particles with z-average hydrodynamic diameters of 270.9 ± 4.7 and 293.8 ± 6.7 nm were obtained by heating whey proteins with 10 mM phosphate buffer, pH 5.9 (-PB) and no buffer (-NPB), respectively. The primary emulsions coated by WPM-NPB and WPM-PB particles had mass fractal dimensions of ∼2.75, as determined by small- and ultra-small-angle neutron scattering (SANS and USANS). The size of the subsequently formed DSEs (D32 ≈ 7-23 μm), which were stabilized by the primary emulsion droplets, made with either WPM-NPB (termed DSE-NPB) or WPM-PB (termed DSE-PB) was dependent on the concentration of the primary emulsion (10-60 wt %) in the aqueous phase. At the DSE-NPB interface, the adsorbed primary emulsion droplets formed a fractal network with a surface fractal dimension of about 3, indicating a rough interfacial layer. Combined SANS and USANS allowed a comprehensive understanding of the multilength scale structures from WPM particles to DSEs.

Fluid–mineral interactions can alter the pore structure and mineral composition of earth materials, sometimes leading to complete replacement of one mineral phase by another. A quantitative underst...

The properties of ligand protected gold nanoparticles are determined by the synergistic interplay of their structural components, including the metal core, the ligand shell, and the solvation layer. However, the simultaneous characterization of all these components remains a major challenge given their disparate chemical nature. In the case of mixed ligand nanoparticles, this task becomes daunting due to the presence of intercorrelated additional parameters such as the ligand ratio, ligand spatial distribution, and solvation of the heterogeneous ligand shell. Here we show that small angle neutron scattering (SANS) is a tool capable of simultaneously characterizing the core and the ligand shell of monodisperse mixed ligand gold nanoparticles. We systematically examine how each parameter (e.g., the core size, the thickness, composition and the spatial heterogeneity of the ligand shell) affects nanoparticles' scattering profile. Quantitative information on these parameters is retrieved using analytical fitting as well as 3D modeling. Importantly, we show that SANS can evaluate the solvation degree of mixed ligand protected gold nanoparticles, a challenging task for any other characterization methods.

Permian shales of Barakar formation in India were investigated to study their pore structure to understand their potential for natural gas production and possible CO2 sequestration. The studied sha...

Silicon in the form of nanoparticles has attracted significant interest in the field of lithium-ion batteries due to the enormous capability of lithium intake. In the present work we demonstrate the characterization of silicon nanoparticles using small-angle neutron scattering and complementary microscopy to elucidate the structure changes through the ball milling process with respect to the particle’s functionality in lithium-ion batteries. Small-angle neutron scattering is a unique method for analysis of the nanoparticles as an ensemble, providing information which is often not accessible by the conventional methods for characterization of silicon nanoparticles such as microscopy. Herein we demonstrate that the analysis of neutron scattering allows to extract the specific surface area for silicon nanoparticles which was found to correlate with the first cycle Coulombic efficiency of the corresponding lithium-ion battery. In addition, using neutron scattering and electrochemical evaluation, we demonstrate that ball milling of silicon nanoparticles has different effects depending on the amorphous or crystalline nature of the material. This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

Poly(methyl methacrylate) (PMMA) and poly(α-methyl styrene-co-acrylonitrile) (PαMSAN) form partially miscible blends with lower critical solution temperature (LCST) behaviour. We revisit this system using small angle neutron scattering (SANS), examining the effect of molecular weight (Mw) of deuterated PMMA (dPMMA), blend composition (φ) and temperature (T) in the homogeneous region. All data are well described by the Random Phase Approximation (RPA) theory, enabling us to determine thermodynamic and structural parameters, including the correlation length ξ, G00 (the second derivative of the free energy of mixing with respect to composition), and the statistical segment length a of each component. Phase boundaries are computed by extrapolation of G00 with temperature, to yield the spinodal, and inspection of Kratky plots to yield the binodal. For PαMSAN, a is determined to be 10.1±0.4 ˚A. Unsurprisingly, this system deviates strongly from Flory-Huggins expectations, exhibiting a minimal Mw dependence of the phase boundaries and φ-dependence of effective interaction parameter (˜χ). Comparison of G00 with values for other blend systems places PαMSAN/dPMMA in a class of highly interacting blends, expected from Cahn-Hilliard theory to yield small initial phase sizes upon spinodal demixing. This is confirmed experimentally, with an illustrative temperature jump resulting in an initial phase size of ' 30 nm.

Pore structure is an important parameter to quantify the reservoir rock adsorption capability and diffusivity, both of which are fundamental reservoir properties to evaluate the gas production and carbon sequestration potential for coalbed methane (CBM) and shale gas reservoirs. In this study, we applied small-angle neutron scattering (SANS) to characterize the total and accessible pore structures for two coal and two shale samples. We carried out in situ SANS measurements to probe the accessible pore structure differences under argon, deuterated methane (CD4), and CO2 penetrations. The results show that the total porosity ranges between 0.25 and 5.8% for the four samples. Less than 50% of the total pores are accessible to CD4 for the two coals, while more than 75% of the pores were found to be accessible for the two shales. This result suggests that organic matter pores tend to be disconnected compared to mineral matter pores. Argon pressurization can induce pore contraction because of the mechanical com...

Aqueous dispersions of poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PCBM) nanoparticles (NPs) have been fabricated using a thiophene-based surfactant 2-(3-thienyl)ethyloxybutylsulfonate sodium salt (TEBS) for the first time via the mini-emulsion process. The use of TEBS resulted in a stable colloidal dispersion of P3HT:PCBM NPs, of which the effect of various fabrication parameters is investigated. The fabricated NPs were characterized by dynamic light scattering, scanning electron microscopy, UV-visible spectroscopy, contrast-variation small and ultra-small angle neutron scattering, and cyclic voltammetry. The internal structure and electrochemical performance of TEBS-stabilized P3HT:PCBM NPs were compared to those of sodium dodecyl sulfate-stabilized core-shell (PCBM-P3HT) NPs at the same surfactant concentration. Neutron scattering and cyclic voltammetry results reveal a homogeneous distribution of small de-mixed P3HT and PCBM domains in the internal structure of TEBS-stabilized P3HT:PCBM NPs, reminiscent of cast film. Moreover, electron microscopy images show evidence of diffused NP surface/interface upon drying (without annealing), which indicates that the thiophene-containing TEBS may improve compatibility and film-forming properties of fabricated P3HT:PCBM NPs, and consequently be more suited for conventional film-processing methods for organic solar cell applications.

Limoncello, the Italian liquor based on lemon essential oils, is becoming increasingly popular around the world. This digestive is not only an iconic representative of Italian food culture, but it is also a complex colloidal system, made of essential oils, ethanol, sucrose, and water. Smell, aroma, taste, and appearance of Limoncello do, of course, depend on the components, in particular on the peculiar essential oil mixture. Accordingly, several studies are available in the literature investigating the composition of various Limoncellos. However, the microscopic structure plays an equally important role when it comes to the sensory properties of food and beverages. In this work, small-angle neutron scattering was used to probe the microscopic structure of Limoncello, revealing the presence of spontaneously formed 100 nm-sized droplets over a large range of composition and temperature. The results are not limited to this famous drink but can be extended to the rapidly developing formulations based on water-insoluble oils, water, and alcohols.

We combine the recently proposed spherical harmonic expansion (SHE) method [Phys. Rev. X 2017, 7, 031003] with a modified network model to analyze the small-angle neutron scattering (SANS) spectra ...

The phase transition from swollen chains to polymer mesoglobules of an aqueous solution of poly(N-isopropylacrylamide) is investigated with kinetic small-angle neutron scattering with 50 ms time resolution in conjunction with millisecond pressure jumps across the coexistence line. The time-resolved study evidenced three distinct regimes: fractal clusters form during the first second and transform into compact mesoglobules. During the following ∼20 s, these grow by diffusion-limited coalescence. The final step consists of a slow growth characterized by an energy barrier of several kBT. The method opens opportunities for kinetic structural studies of multicomponent systems over wide length and time scales and gives a structural picture spanning from the chain collapse to mesoscopic phase separation.

The stability of biofuels toward oxidation is currently one of the major challenges for its widespread use. In fact, insoluble deposits issued from biofuels degradation can cause several types of d...

Highly purified hydrogenous ring poly(4-trimethylsilylstyrene) (h-PT) and deuterated ring polyisoprene (d-PI) samples as well as their linear counterparts were prepared, and the miscibility of three kinds of polymer blends, i.e., linear–linear, ring–linear, and ring–ring, denoted as L–L, R–L, and R–R, respectively, with all 50/50 vol % was evaluated by small angle neutron scattering (SANS) measurements. PT and PI are known as a miscible polymer pair with lower critical solution temperature (LCST) type phase diagram. At low-q regime of the scattering profiles, R–R blend exhibits much higher scattering intensity than L–L and R–L, while the latter two show similar profiles. Moreover, from Zimm’s analysis, the spinodal temperature of R–R was estimated to be about 100 °C lower than the other two blends, L–L and R–L. These results suggest that the miscibility of R–R is considerably lower than the other two blends, which is a clear manifestation of the topological effect on the phase behavior of the present blend.

Results of oedometric consolidation experiments linked with small-angle neutron scattering (SANS) measurements are presented, using SWy-2 Wyoming bentonite clay in dry and water-bearing N2 and CO2 atmospheres. Oedometric SANS involves deforming a porous sample under uniaxial strain conditions with applied axial force and internal pore pressure control, and combines with SANS for in situ observation of pore structure evolution and interaction. Scattering from both interlayer (clay intra-aggregate) and free (interaggregate) pores is observed, showing decreasing pore size with dry consolidation and interactions between interlayer and free pore types with swelling and consolidation. Introduction of dry liquid CO2 at zero effective stress (axial stress minus pore pressure) produces large shifts in interlayer scatterers, but is reversible back to pre-CO2 levels upon decreasing pore pressure and increasing effective stress. Introduction of wet liquid CO2, conversely, produces large but irreversible changes in in...

Small-angle neutron scattering (SANS) was used to examine dilute solutions of a poly(quinoxaline-2,3-diyl) (PQX) with (R)-2-octyloxymethyl side chains in deuterated THF or a mixture of deuterated 1,1,2-TCE and THF (8/2, v/v), in which the PQX adopts pure P- and M-helical structures. The structures of the PQX that were obtained based on the SANS experiments in combination with theoretical calculations suggest that in THF, the chiral side chains of the P-helical PQX are extended, whereas in the 1,1,2-TCE/THF mixture, the side chains of the M-helical PQX are folded. Consequently, P-helical structures should be preferred in good solvents such as THF, which solvate the extended side chains, whereas M-helical structures should be preferred in poor solvents such as 1,1,2-TCE, wherein the side chains adopt shrunken conformations with maximized van der Waals interactions between the side chains. This study thus reveals the first example for fully determined nuanced conformations of the side chains of synthetic polymers in solution based on SANS experiments and theoretical calculations.

The internal morphology of temperature-responsive degradable poly(N-isopropylacrylamide) (PNIPAM) microgels formed via an aqueous self-assembly process based on hydrazide and aldehyde-functionalized PNIPAM oligomers is investigated. A combination of surface force measurements, small angle neutron scattering (SANS), and ultrasmall angle neutron scattering (USANS) was used to demonstrate that the self-assembled microgels have a homogeneously cross-linked internal structure. This result is surprising given the sequential addition process used to fabricate the microgels, which was expected to result in a densely cross-linked shell-diffuse core structure. The homogeneous internal structure identified is also significantly different than conventional microgels prepared via precipitation polymerization, which typically exhibit a diffuse shell-dense core structure. The homogeneous structure is hypothesized to result from the dynamic nature of the hydrazone cross-linking chemistry used to couple with the assembly conditions chosen that promote polymer interdiffusion. The lack of an internal cross-linking gradient within these degradable and monodisperse microgels is expected to facilitate more consistent drug release over time, improved optical properties, and other potential application benefits.

Nanoparticle dispersions open up an ecofriendly route toward printable organic solar cells. They can be formed from a variety of organic semiconductors by using miniemulsions that employ surfactants to stabilize the nanoparticles in dispersion and to prevent aggregation. However, whenever surfactant-based nanoparticle dispersions have been used to fabricate solar cells, the reported performances remain moderate. In contrast, solar cells from nanoparticle dispersions formed by precipitation (without surfactants) can exhibit power conversion efficiencies close to those of state-of-the-art solar cells processed from blend solutions using chlorinated solvents. In this work, we use small-angle neutron scattering measurements and transient absorption spectroscopy to investigate why surfactant-free nanoparticles give rise to efficient organic solar cells. We show that surfactant-free nanoparticles comprise a uniform distribution of small semiconductor domains, similar to that of bulk-heterojunction films formed using traditional solvent processing. This observation differs from surfactant-based miniemulsion nanoparticles that typically exhibit core-shell structures. Hence, the surfactant-free nanoparticles already possess the optimum morphology for efficient energy conversion before they are assembled into the photoactive layer of a solar cell. This structural property underpins the superior performance of the solar cells containing surfactant-free nanoparticles and is an important design criterion for future nanoparticle inks.

Herein, we comprehensively investigate the internal morphology of fully injectable interpenetrating networks (IPNs) prepared via coextrusion of functionalized precursor polymer solutions based on thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) and nonthermoresponsive poly(vinyl pyrrolidone) (PVP) by reactive mixing using kinetically orthogonal hydrazone and thiosuccinimide cross-linking mechanisms. Small-angle neutron scattering, probing both the full IPN as well as the individual constituent networks of the IPN using index-matching, suggests a partially mixed internal structure characterized by PNIPAM-rich domains entrapped in a clustered PVP-rich phase. This interpretation is supported by super-resolution fluorescence microscopy (direct stochastic optical reconstruction microscopy) measurements on the same gels on a different length scale, which show both the overall phase segregation typical of an IPN as well as moderate mixing of PNIPAM into the PVP-rich phase. Such a morphology is consistent with the kinetics of both gelation and phase separation in this in situ gelling system, in which gelation effectively traps a fraction of the PNIPAM in the PVP phase prior to full phase separation; by contrast, such interphase mixing is not observed in semi-IPN control hydrogels. This knowledge has significant potential for the design of an injectable hydrogel with internal morphologies optimized for particular biomedical applications.

To enable a renewable energy future, electro- chemical energy storage remains as one of the main challenges of today’s society. Lithium-ion batteries have been shown to be of great potential in that respect, but they still suffer from safety instabilities arising from the use of flammable liquid electrolytes. Solid electrolytes are an interesting alternative that provide the required safety properties. We introduce a highly stable solid single-ion diblock copolymer electrolyte poly(deuterated styrene)- block-poly(poly(ethylene glycol) methyl ether styrene-co-lithium styrene sulfonyl(trifluoromethane sulfonyl)imide), denoted PS(d)-b-P(SPEG-co-STFSILi). Lithium metal batteries based on PS(d)-b-P(SPEG-co-STFSILi) are probed in operando with small-angle neutron scattering in order to investigate their suitability as safe batteries using lithium metal anodes. We compare cell operation when cycling at 0.5 C at 80 °C to 0.7 C at 90 °C, which represent severe working conditions for the battery. More than 200 cycles are performed, showing the inflation of the ionic pathways through cycling at 0.7 C, whereas at 0.5 C and 80 °C, battery performance and morphology remain unchanged.

The infinite dilution radii of gyration (Rg,0) for five different molecular weights (10–250 kg/mol) of perdeuterated poly(ethylene oxide) (d-PEO) have been determined at 80 °C in the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]) using small-angle neutron scattering (SANS). The results establish the dependence of Rg,0 on polymer molecular weight as Rg,0 ∼ Mw0.55. An excluded volume exponent of ν ≈ 0.55 indicates that [BMIM][BF4] is a moderately good solvent and that PEO remains a flexible random coil in this ionic liquid. These results clarify the uncertainty surrounding PEO coil dimensions in this ionic liquid, as computer simulations at various levels of complexity have led to conflicting results, and prior experimental results also do not present a completely consistent picture.

Using molecular dynamics simulations, small-angle neutron scattering, and a variety of spectroscopic techniques, we evaluated the ion solvation and transport behaviors in aqueous electrolytes containing bis(trifluoromethanesulfonyl)imide. We discovered that, at high salt concentrations (from 10 to 21 mol/kg), a disproportion of cation solvation occurs, leading to a liquid structure of heterogeneous domains with a characteristic length scale of 1 to 2 nm. This unusual nano-heterogeneity effectively decouples cations from the Coulombic traps of anions and provides a 3D percolating lithium-water network, via which 40% of the lithium cations are liberated for fast ion transport even in concentration ranges traditionally considered too viscous. Due to such percolation networks, superconcentrated aqueous electrolytes are characterized by a high lithium-transference number (0.73), which is key to supporting an assortment of battery chemistries at high rate. The in-depth understanding of this transport mechanism establishes guiding principles to the tailored design of future superconcentrated electrolyte systems.

R67 dihydrofolate reductase (DHFR) is a homotetramer with a single active site pore and no sequence or structural homology with chromosomal DHFRs. The R67 enzyme provides resistance to trimethoprim, an active site-directed inhibitor of Escherichia coli DHFR. Sixteen to twenty N-terminal amino acids are intrinsically disordered in the R67 dimer crystal structure. Chymotrypsin cleavage of 16 N-terminal residues results in an active enzyme with a decreased stability. The space sampled by the disordered N-termini of R67 DHFR was investigated using small angle neutron scattering. From a combined analysis using molecular dynamics and the program SASSIE (http://www.smallangles.net/sassie/SASSIE_HOME.html), the apoenzyme displays a radius of gyration (Rg) of 21.46 ± 0.50 Å. Addition of glycine betaine, an osmolyte, does not result in folding of the termini as the Rg increases slightly to 22.78 ± 0.87 Å. SASSIE fits of the latter SANS data indicate that the disordered N-termini sample larger regions of space and remain disordered, suggesting they might function as entropic bristles. Pressure perturbation calorimetry also indicated that the volume of R67 DHFR increases upon addition of 10% betaine and decreased at 20% betaine because of the dehydration of the protein. Studies of the hydration of full-length R67 DHFR in the presence of the osmolytes betaine and dimethyl sulfoxide find around 1250 water molecules hydrating the protein. Similar studies with truncated R67 DHFR yield around 400 water molecules hydrating the protein in the presence of betaine. The difference of ∼900 waters indicates the N-termini are well-hydrated.