Mudrocks, ubiquitous yet poorly understood sedimentary rocks with significant variations in composition and physical properties, form seals for geological carbon dioxide and energy (e.g., hydrogen and methane) storage, repositories for radioactive waste disposal, and reservoirs for natural gas. Understanding the controls on mudrock pore structure is essential for evaluating their porosity. The identification and quantification of controls depend on the nano-to micron scale pore network, which are the subject of this study. Small-angle (SANS) and very small-angle neutron scattering (VSANS) experiments were conducted on 13 diverse mudrock sets, charac-terised by differences in mineralogy, stratigraphy, maturity, and depositional environment. We performed multivariate statistics to systematically characterise the pore structure in 71 samples cross a 5 mu m-2 nm pore size range. Our results indicate a multivariate approach more effectively captures the complex controls on porosity rather than single parameters. Compaction and clay content emerge as key primary and secondary controls on mudrock porosity, respectively, upon which we introduce a new porosity classification. Our complementary experimental-statistical assessment involving SANS-derived multiscale porosity sheds new light on the influence of structural controls on storage or production capacity in mudrocks.

Herein, a single-ion polymer electrolyte is reported for high-voltage and low-temperature lithium-metal batteries that enables suppressing the growth of dendrites, even at high current densities of 2 mA cm-2. The nanostructured electrolyte was introduced into the cell by mechanically processing the polymer powder via an easily scalable process. Important for the potential application in commercial battery cells is the finding that it does not induce aluminum corrosion at high voltages and leads to low interfacial resistance with lithium metal. These beneficial characteristics, in combination with its high single-ion conductivity and its high anodic stability, allow for the stable cycling of state-of-the-art lithium-ion cathodes, such as NMC111 and NMC622, in combination with a lithium metal anode at 20 °C and even 0 °C for several hundred cycles.

A polymer acceptor, named PX-1, is designed and synthesized using a polymerization strategy with grafted small molecule acceptors. This design approach allows for the freedom of end groups while maintaining efficient terminal packing, enhancing & pi;-& pi; interactions, and facilitating charge transport. All-polymer organic solar cells based on PM6: PX-1 demonstrate a promising efficiency of 13.55%. The result presents an alternative pathway for the design of high-efficiency polymer acceptors through the careful regulation of small molecule acceptor monomers and linker units. A polymer acceptor, named PX-1, is designed and synthesized using a polymerization strategy with grafted small molecule acceptors. This design approach allows for the freedom of end groups while maintaining efficient terminal packing, enhancing & pi;-& pi; interactions, and facilitating charge transport. All-polymer organic solar cells based on PM6: PX-1 demonstrate a promising efficiency of 13.55%.image

The pore structure of mudrocks is a key characteristic to evaluate flow behavior through these rocks. Although significant advances have been made to resolve pore characteristics, porosity evolution, or pore connectivity, there is still insufficient knowledge linking porosity evolution to flow and transport in mudrocks. To better understand these links, we conducted very small-angle (VSANS) and small-angle neutron scattering (SANS) experiments on 13 sets of mudrocks from global locations, characterized by differences in composition, maturity, and depositional environment. Our results indicate that a homogeneous pore structure reflects a stable and low-energy depositional environment. Organic-lean mudrocks mainly contain pores <10 nm, which restricts flow and is beneficial for, e.g., caprock seal integrity. Increasing maturity as a result of increasing burial depth, and therefore, temperature leads to porosity evolution. In organic-rich mudrocks (ORMs), this happens through the generation of organic matter pores and pore preservation around diagenetically formed carbonates. ORMs mainly contain macropores (>50 nm), favoring production from, e.g., unconventional reservoirs. SANS-derived pore size distributions will help to better understand fluid imbibition and flow properties in mudrocks through comprehensive quantitative characterization of the nano- to micron scale pore network conduits and their relationships to burial diagenesis.

Lipid structural diversity strongly affects biomembrane chemico-physical and structural properties in addition to membrane-associated events. At high concentrations, cholesterol increases membrane order and rigidity, while polyunsaturated lipids are reported to increase disorder and flexibility. How these different tendencies balance in composite bilayers is still controversial. In this study, electron paramagnetic resonance spectroscopy, small angle neutron scattering, and neutron reflectivity were used to investigate the structural properties of cholesterol-containing lipid bilayers in the fluid state with increasing amounts of polyunsaturated omega-3 lipids. Either the hybrid 1-stearoyl-2-docosahexaenoyl-sn-glycero-3-phosphocholine or the symmetric 1,2-docosahexaenoyl-sn-glycero-3-phosphocholine were added to the mixture of the naturally abundant 1-palmitoyl-2-oleyl-sn-glycero-3-phosphocholine and cholesterol. Our results indicate that the hybrid and the symmetric omega-3 phospholipids affect the microscopic organization of lipid bilayers differently. Cholesterol does not segregate from polyunsaturated phospholipids and, through interactions with them, is able to suppress the formation of non-lamellar structures induced by the symmetric polyunsaturated lipid. However, this order/disorder balance leads to a bilayer whose structural organization cannot be ascribed to either a liquid ordered or to a canonical liquid disordered phase, in that it displays a very loose packing of the intermediate segments of lipid chains.

Small-angle scattering (SAS) experiments are a powerful method for studying self-assembly phenomena in nanoscopic materials because of the sensitivity of the technique to structures formed by interactions on the nanoscale. Numerous out-of-the-box options exist for analysing structures measured by SAS but many of these are underpinned by assumptions about the underlying interactions that are not always relevant for a given system. Here, a numerical algorithm based on reverse Monte Carlo simulations is described to model the intensity observed on a SAS detector as a function of the scattering vector. The model simulates a two-dimensional detector image, accounting for magnetic scattering, instrument resolution, particle polydispersity and particle collisions, while making no further assumptions about the underlying particle interactions. By simulating a two-dimensional image that can be potentially anisotropic, the algorithm is particularly useful for studying systems driven by anisotropic interactions. The final output of the algorithm is a relative particle distribution, allowing visualization of particle structures that form over long-range length scales (i.e. several hundred nanometres), along with an orientational distribution of magnetic moments. The effectiveness of the algorithm is shown by modelling a SAS experimental data set studying finite-length chains consisting of magnetic nanoparticles, which assembled in the presence of a strong magnetic field due to dipole interactions.

Amphiphilic polymers show a rich variety of self-assembly behavior in aqueous solutions. In experimental studies, statistical copolymer or block copolymer architectures are usually investigated because of their ease of synthesis or their structural analogy to surfactants. A copolymer structure that links the two architectures is an alternating copolymer, which is easily accessible by polycondensation reactions. Using alternating hydrophilic and hydrophobic building blocks with varying lengths allows a systematic variation between statistical and multiblock architectures. We synthesized alternating amphiphilic copolymers as polyesters using hydrophobic dicarboxylic acids (C-4-C-20) and hydrophilic poly(ethylene glycol) (PEG) units (EG(3)-EG(1000)). Copolymers with long EG units were made accessible with the help of a newly developed esterification process. The solution properties of amphiphilic copolymers feature a lower critical solution temperature (LCST) behavior in water, which can be systematically varied over a wide range from 3 to 83 degrees C by adjusting the lengths of the Cn and EG(m) units. We find that the transition temperature depends linearly on the hydrophobic unit length C-m and logarithmically on the hydrophilic length EG(n). In the one-phase region, PEG copolymer coils are more compact compared to the respective PEG homopolymers due to hydrophobic interactions between the hydrophobic units leading to loop formation. For shorter PEG units, the copolymers form micellar structures consisting only of a few copolymer chains. The micellar cores consist of hydrophobic regions containing only a few dicarboxylic acid units embedded in a PEG-rich and water-poor matrix. The cores are surrounded by a diluted corona of PEG chains. Further decreasing the PEG unit length leads to the formation of highly swollen gels consisting of networks of interconnected micelles. These can self-assemble to form highly ordered liquid crystalline cubic phases. The study demonstrates how the structure of alternating amphiphilic copolymers can be systematically varied to adjust the thermal solution properties such as the LCST over a wide range, as well as the self-assembly properties varying between single chains, micelles, gels, and highly ordered lyotropic liquid crystals.

Advances in magnetic materials have enabled the development of new therapeutic agents that can be localized by external magnetic fields. These agents offer a potential means of improving treatment targeting and reducing the toxicity-related side effects associated with systemic delivery. Achieving sufficiently high magnetic fields at clinically relevant depths in vivo, however, remains a challenge. Similarly, there is a need for techniques for real-time monitoring that do not rely on magnetic resonance imaging (MRI). Here, we present a hand-held device to meet these requirements, combining an array of permanent magnets and a thin 64-element capacitive micromachined ultrasonic transducer (CMUT) interfaced to a real-time imaging system. Drug carrier localization was assessed by measuring the terminal velocity of magnetic microbubbles in a column of fluid above the magnetic array. It was found that the magnetic pull force was sufficient to overcome buoyancy at equivalent tissue depths of at least 35 mm and that the median terminal velocity ranged from 0.7 to 20 $\mu \text{m}$ /s over the distances measured. A Monte Carlo study was performed to estimate capture effectiveness in tumor microvessels over a range of different tissue depths and flow rates. Finally, B-mode and contrast-enhanced ultrasound (CEUS) imaging were demonstrated using a gel flow phantom containing a 1.6-mm diameter vessel. Real-time monitoring provided visual confirmation of retention of magnetic microbubbles along the vessel wall at a flow rate of 0.5 mL/min. These results indicate that the system can successfully retain and image magnetic microbubbles at tissue depths and flow rates relevant for clinical applications such as molecular ultrasound imaging of atherosclerosis, sonodynamic and antimetabolite cancer therapy, and clot dissolution via sonothrombolysis.

Abstract Magnetic nanoparticles (MNPs) are key elements in several biomedical applications, e.g., in cancer therapy. Here, the MNPs are remotely manipulated by magnetic fields from outside the body to deliver drugs or generate heat in tumor tissue. The efficiency and success of these approaches strongly depend on the spatial distribution and quantity of MNPs inside a body and interactions of the particles with the biological matrix. These include dynamic processes of the MNPs in the organism such as binding kinetics, cellular uptake, passage through cell barriers, heat induction and flow. While magnetic measurement methods have been applied so far to resolve the location and quantity of MNPs for therapy monitoring, these methods can be advanced to additionally access these particle–matrix interactions. By this, the MNPs can further be utilized as probes for the physical properties of their molecular environment. In this review, we first investigate the impact of nanoparticle–matrix interactions on magnetic measurements in selected experiments. With these results, we then advanced the imaging modalities magnetorelaxometry imaging and magnetic microsphere tracking to spatially resolve particle–matrix interactions.

Self-assembly of iron oxide nanoparticles (IONPs) into 1D chains is appealing, because of their biocompatibility and higher mobility compared to 2D/3D assemblies while traversing the circulatory passages and blood vessels for in vivo biomedical applications. In this work, parameters such as size, concentration, composition, and magnetic field, responsible for chain formation of IONPs in a dispersion as opposed to spatially confining substrates, are examined. In particular, the monodisperse 27 nm IONPs synthesized by an extended LaMer mechanism are shown to form chains at 4 mT, which are lengthened with applied field reaching 270 nm at 2.2 T. The chain lengths are completely reversible in field. Using a combination of scattering methods and reverse Monte Carlo simulations the formation of chains is directly visualized. The visualization of real-space IONPs assemblies formed in dispersions presents a novel tool for biomedical researchers. This allows for rapid exploration of the behavior of IONPs in solution in a broad parameter space and unambiguous extraction of ​the parameters of the equilibrium structures. Additionally, it can be extended to study novel assemblies formed by more complex geometries of IONPs.

Spherical iron oxide nanoparticles in dispersion are controlled by external magnetic fields to form flexible and reversible chains for biomedical applications. In article number 2008683, Mikhail Feygenson and co-workers combine the advanced scattering methods and reverse Monte Carlo simulations to directly visualize the chain formation in real space. This methodology paves the way for exploring novel assemblies of particles with a complex morphology in various liquid carriers.

The introduction of “water-in-salt” electrolyte (WiSE) concept opens a new horizon to aqueous electrochemistry that is benefited from the formation of a solid-electrolyte interphase (SEI). However, such SEI still faces multiple challenges, including dissolution, mechanical damaging, and incessant reforming, which result in poor cycling stability. Here, we report a polymeric additive, polyacrylamide (PAM) that effectively stabilizes the interphase in WiSE. With the addition of 5 molar % PAM to 21 mol kg −1 LiTFSI electrolyte, a LiMn 2 O 4 ∥L-TiO 2 full cell exhibits enhanced cycling stability with 86 % capacity retention after 100 cycles at 1 C. The formation mechanism and evolution of PAM-assisted SEI was investigated using operando small angle neutron scattering and density functional theory (DFT) calculations, which reveal that PAM minimizes the presence of free water molecules at the anode/electrolyte interface, accelerates the TFSI − anion decomposition, and densifies the SEI.

Polyunsaturated omega-3 fatty acid docosahexaenoic acid (DHA) is found in very high concentrations in a few peculiar tissues, suggesting that it must have a specialized role. DHA was proposed to affect the function of the cell membrane and related proteins through an indirect mechanism of action, based on the DHA-phospholipid effects on the lipid bilayer structure. In this respect, most studies have focused on its influence on lipid-rafts, somehow neglecting the analysis of effects on liquid disordered phases that constitute most of the cell membranes, by reporting in these cases only a general fluidifying effect. In this study, by combining neutron reflectivity, cryo-transmission electron microscopy, small angle neutron scattering, dynamic light scattering and electron paramagnetic resonance spectroscopy, we characterize liquid disordered bilayers formed by the naturally abundant 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine and different contents of a di-DHA glycero-phosphocholine, 22:6-22:6PC, from both a molecular/microscopic and supramolecular/mesoscopic viewpoint. We show that, below a threshold concentration of about 40% molar percent, incorporation of 22:6-22:6PC in the membrane increases the lipid dynamics slightly but sufficiently to promote the membrane deformation and increase of multilamellarity. Notably, beyond this threshold, 22:6-22:6PC disfavours the formation of lamellar phases, leading to a phase separation consisting mostly of small spherical particles that coexist with a minority portion of a lipid blob with water-filled cavities. Concurrently, from a molecular viewpoint, the polyunsaturated acyl chains tend to fold and expose the termini to the aqueous medium. We propose that this peculiar tendency is a key feature of the DHA-phospholipids making them able to modulate the local morphology of biomembranes.

The performance characteristics of magnetic nanoparticles toward application, e.g., in medicine and imaging or as sensors, are directly determined by their magnetization relaxation and total magnetic moment. In the commonly assumed picture, nanoparticles have a constant overall magnetic moment originating from the magnetization of the single-domain particle core surrounded by a surface region hosting spin disorder. In contrast, this work demonstrates the significant increase of the magnetic moment of ferrite nanoparticles with an applied magnetic field. At low magnetic field, the homogeneously magnetized particle core initially coincides in size with the structurally coherent grain of 12.8(2) nm diameter, indicating a strong coupling between magnetic and structural disorder. Applied magnetic fields gradually polarize the uncorrelated, disordered surface spins, resulting in a magnetic volume more than 20% larger than the structurally coherent core. The intraparticle magnetic disorder energy increases sharply toward the defect-rich surface as established by the field dependence of the magnetization distribution. In consequence, these findings illustrate how the nanoparticle magnetization overcomes structural surface disorder. This new concept of intraparticle magnetization is deployable to other magnetic nanoparticle systems, where the in-depth knowledge of spin disorder and associated magnetic anisotropies are decisive for a rational nanomaterials design.

Poly(N-isopropylmethacrylamide) (PNIPMAM) is a thermoresponsive polymer, exhibiting lower critical solution temperature (LCST) behavior in an aqueous solution. We investigate the temperature-dependent phase behavior of PNIPMAM solutions in D2O using turbidimetry, differential scanning calorimetry (DSC), small-angle and very small angle neutron scattering (SANS and VSANS), and Raman spectroscopy, covering a large concentration range, and compare the results from PNIPMAM with the findings from its analogue poly(N-isopropylacrylamide) (PNIPAM). We find that the PNIPMAM chains only dehydrate 2-3 degrees C above the macroscopic cloud point temperature, T-CP. Even in the one-phase state, loosely packed, large-scale inhomogeneities and physical cross-links are observed, and the chain conformation of PNIPMAM is more compact than the one of PNIPAM. This is attributed to the attractive intermolecular interactions between the hydrophobic moieties. The phase transition of PNIPMAM is broader than the one of PNIPAM. Upon heating to the two-phase state, the PNIPMAM chains collapse and form mesoglobules. These are larger and more hydrated than those for PNIPAM. This is attributed to the steric hindrance caused by the additional methyl groups, which weaken the intrapolymer interactions in the two-phase state. Thus, the methyl groups in the backbone of the PNIPMAM chains have a significant impact on the hydration and the structural behavior around the phase transition.

The thermoresponsive behavior of two molecular brushes having poly(propylene oxide)-poly(ethylene oxide) copolymer side chains is investigated in aqueous solution, where the side chains have longer contour lengths than the backbone. The brushes differ in the side-chain architecture; they are either a diblock (PbE) or a random copolymer (PrE). For both types of brushes, an overall rodlike shape at room temperature is revealed by cryo-electron microscopy. A polymer-rich central part and a water-rich outer part are identified by small-angle neutron scattering (SANS). Upon heating up to the cloud point, the shell of PbE weakly dehydrates, while the one of PrE severely dehydrates along with a cylinder-to-disk transformation. Moreover, the aggregates formed above the cloud points feature significantly different inner structures: PbE aggregates are composed of strongly interpenetrating brushes, while PrE aggregates consist of loosely packed brushes. These differences indicate the important role of the side-chain architecture in the thermal dehydration behavior and the associated structural changes.

The technological performance of magnetic nanoparticles is dominated by finite size and disorder effects. However, it is often difficult to isolate intrinsic effects such as magnetic disorder at the particle surface. Despite numerous efforts and advanced techniques, the three-dimensional magnetism of spin disorder and its nanoscale distribution within magnetic nanoparticles remains a key challenge. Here we present the spatially resolved, non-correlated surface spin disorder in isolated, spherical cobalt ferrite nanoparticles, derived by a combination of polarized small-angle neutron scattering and micromagnetic analysis. The field-dependence of the coherently magnetized particle volume, which is not accessible with conventional integral measurement techniques, illustrates how the nanoparticle magnetization overcomes structural surface disorder. Our results allow to estimate the magnetic disorder energy, which is required to polarize gradually the surface spins, with spatial resolution within the nanoparticles. Such unprecedented knowledge of the intraparticle spin disorder and associated anisotropies will be decisive for a rational nanomaterials development.

The self-assembly of the two anomeric forms of n-hexadecyl-d-maltopyranoside (denoted α-C16G2 and β-C16G2) has been studied in dilute aqueous solution by means of surface tension measurements, scattering methods (dynamic light scattering, static light scattering, and small-angle X-ray and neutron scattering), and cryo-transmission electron microscopy at different surfactant concentrations and temperatures. Surface tension measurements demonstrate differences in the surfactant adsorption at the air-water interface, where α-C16G2 shows a lower CMC than β-C16G2. Similarly, micelle morphology was found to profoundly depend on anomerism. β-C16G2 preferentially forms very elongated micelles with large persistence lengths, whereas α-C16G2 assembles into smaller micelles for which the structure varies with concentration and temperature. The differences between the two surfactant anomers in terms of self-assembly can be attributed to the interaction between neighboring headgroups. Specifically, β-C16G2 allows for a closer packing in the palisade layer, hence reducing the micelle curvature and promoting the formation of more elongated micelles. Strong intermolecular headgroup interactions may also account for the observed rigidity of the micelles.

Summary The pore structure of organic rich mudrocks is associated with both inorganic and organic constituents. The contribution of organic matter to the pore structure has been investigated on Posidonia and Bossier Shale samples having different organic carbon content and thermal maturity. Development and distribution of organic matter pores were studied by using small angle neutron scattering technique at a broad pore scale size investigation, from 2 nm to 2 µm. The pore structure of the mudrocks studied is highly complicated at which total pore volume and specific surface area are not significantly affected by thermal maturation, however, the maturity attribute contributes to different pore size distribution on meso- and macro-pores. Thermal maturation is likely to be the factor of amalgamating small organic matter pores into larger pores in overmature organic rich mudrocks, potentially causing an increase in pore volume at macroscale pores. Although not considerably, the increased macroporosity can enhance the permeability of pore network for viscous gas flow in organic rich mudrocks.