Synchrotron Small-angle X-ray Scattering Research Articles

Highly Ordered Gyroid Nanostructured Polymers: Facile Fabrication by Polymerizable Pluronic Surfactants.

Highly ordered, network-nanostructured polymers offer compelling geometric features and application potential. However, their practical utilization is hampered by the restricted accessibility. Here, we address this challenge using commercial Pluronic surfactants with a straightforward modification of tethering polymerizable groups. By leveraging lyotropic self-assembly, we achieve facile production of double-gyroid mesophases, which are subsequently solidified via photoinduced cross-linking. The exceptionally ordered periodicities of Ia3d symmetry in the photocured polymers are unambiguously confirmed by synchrotron small-angle X-ray scattering (SAXS), which can capture single-crystal-like diffraction patterns. Electron density maps reconstructed from SAXS data complemented by transmission electron microscopy analysis further elucidate the real-space gyroid assemblies. Intriguingly, by tuning the cross-linking through thiol-acrylate chemistry, the mechanical properties of the polymer are modulated without compromising the integrity of Ia3d assemblies. The 3-D percolating gyroid nanochannels demonstrate an ionic conductivity that surpasses that of disordered structures, offering promising prospects for scalable fabrication.

Tooth acellular extrinsic fibre cementum incremental lines in humans are formed by parallel branched Sharpey’s fibres and not by its mineral phase

In humans, the growth pattern of the acellular extrinsic fibre cementum (AEFC) has been useful to estimate the age-at-death. However, the structural organization behind such a pattern remains poorly understood. In this study tooth cementum from seven individuals from a Mexican modern skeletal series were analyzed with the aim of unveiling the AEFC collagenous and mineral structure using multimodal imaging approaches. The organization of collagen fibres was first determined using: light microscopy, transmission electron microscopy (TEM), electron tomography, and plasma FIB scanning electron microscopy (PFIB-SEM) tomography. The mineral properties were then investigated using: synchrotron small-angle X-ray scattering (SAXS) for T-parameter (correlation length between mineral particles); synchrotron X-ray diffraction (XRD) for L-parameter (mineral crystalline domain size estimation), alignment parameter (crystals preferred orientation) and lattice parameters a and c; as well as synchrotron X-ray fluorescence for spatial distribution of calcium, phosphorus and zinc. Results show that Sharpey’s fibres branched out fibres that cover and uncover other collagen bundles forming aligned arched structures that are joined by these same fibres but in a parallel fashion. The parallel fibres are not set as a continuum on the same plane and when they are superimposed project the AEFC incremental lines due to the collagen birefringence. The orientation of the apatite crystallites is subject to the arrangement of the collagen fibres, and the obtained parameter values along with the elemental distribution maps, revealed this mineral tissue as relatively homogeneous. Therefore, no intrinsic characteristics of the mineral phase could be associated with the alternating AEFC incremental pattern.

Tailoring pore size of mesoporous silica and organosilica using biodegradable pentablock copolymer templates via EISA process

In this work, we have designed unique poly(lactic acid-co-glycolic acid)-b-poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)-b-poly(lactic acid-co-glycolic acid) pentablock copolymers using Pluronic F68 and F108 triblock copolymers as macroinitiators. The poly(lactic acid-co-glycolic acid) (PLGA) blocks were attached as glycolide and lactide monomers at the both ends of each F68 and F108 triblock copolymer. The molecular weights and the block fractions were confirmed by gel permeation chromatography (GPC) and proton nuclear magnetic resonance (1H NMR) for the four kinds of pentablock copolymers. Using these pentablock copolymers as templates, we synthesized mesoporous ethane-silicas as well as silicas by the evaporation-induced self-assembly (EISA) method. 1,2-bis(triethoxysily)ethane (BTEE) were used as an organosilica precursor. The mesoporous ethane-silica samples were characterized using synchrotron small angle X-ray scattering (SAXS), nitrogen sorption experiments, transmission electron microscopy (TEM), and solid-state 29Si CP-MAS NMR. Based on the experimental results, it was confirmed that the porosity and pore diameter can be varied with the PLGA weight fraction of the pentablock copolymer. It is due to the PLGA block in polymer forming the hydrophobic domain in micelles, which leads to the formation of increased pore size over 20 nm without any additive pore expander. In addition, it seems that as the organosilica precursor increases, the association number of block copolymers forming one micelle decreases, resulting in a decrease in pore size. In summary, the polymer template plays a vital part in tuning the structure of the mesoporous ethane-silica samples. Thus, the development of synthetic method of mesoporous organosilica materials using polymer templates with different topology is still challenging and can endow the unique structure and property for mesoporous organosilica for future applications.

Water Sorption and Structural Properties of Human Airway Mucus in Health and Muco-Obstructive Diseases.

Muco-obstructive diseases change airway mucus properties, impairing mucociliary transport and increasing the likelihood of infections. To investigate the sorption properties and nanostructures of mucus in health and disease, we investigated mucus samples from patients and cell cultures (cc) from healthy, chronic obstructive pulmonary disease (COPD), and cystic fibrosis (CF) airways. Atomic force microscopy (AFM) revealed mucin monomers with typical barbell structures, where the globule to spacer volume ratio was the highest for CF mucin. Accordingly, synchrotron small-angle X-ray scattering (SAXS) revealed more pronounced scattering from CF mucin globules and suggested shorter carbohydrate side chains in CF mucin and longer side chains in COPD mucin. Quartz crystal microbalance with dissipation (QCM-D) analysis presented water sorption isotherms of the three types of human airway mucus, where, at high relative humidity, COPD mucus had the highest water content compared to cc-CF and healthy airway mucus (HAM). The higher hydration of the COPD mucus is consistent with the observation of longer side chains of the COPD mucins. At low humidity, no dehydration-induced glass transition was observed in healthy and diseased mucus, suggesting mucus remained in a rubbery state. However, in dialyzed cc-HAM, a sorption-desorption hysteresis (typically observed in the glassy state) appeared, suggesting that small molecules present in mucus suppress the glass transition.

In Operando Analysis of Milk-Based Oral Formulations during Digestion Using Synchrotron Small-Angle X-ray Scattering Coupled to Low-Frequency Raman Spectroscopy.

A low-frequency Raman (LFR) probe was coupled to an in-line small-angle X-ray scattering (SAXS) beamline to test the capabilities of a combinatory approach for the determination of lipid and drug behavior during the enzymatic lipolysis of milk-based oral formulations. Cinnarizine was used as the model drug, and its solubilization dynamics as well as its potential impact on the supramolecular structures formed by the digestion products of bovine milk were evaluated from the perspective of both techniques. The SAXS data were superior in distinguishing various liquid crystalline assemblies formed during the digestion process, with LFR providing complementary information regarding the formation of calcium soaps. On the other hand, studying changes in the LFR domain allowed the differentiation of drug solubilization and precipitation; processes that were less clear from the X-ray scattering data. Given the relative simplicity of the combined experimental setup, these results highlight the advantages that the combination of the two techniques can provide for understanding and developing new lipid-based formulations and will help to translate the results obtained at synchrotron facilities to routine analysis procedures in laboratory/industry-based environments.

SAXS unveils porous anodes for potassium-ion batteries: dynamic evolution of pore structures in Fe@Fe2O3/PCNFs composite nanofibers.

The porous structure of composite nanofibers plays a key role in improving their electrochemical performance. However, the dynamic evolution of pore structures and their action during ion intercalation/extraction processes for negative electrodes are not clear. Herein, porous carbon composite nanofibers (Fe@Fe2O3/PCNFs) were prepared as negative electrode materials for potassium-ion batteries. Electrochemical test findings revealed that the composites had good electrochemical characteristics, and the porous structure endowed composite electrodes with pseudo-capacitive behaviors. After 1500 discharge/charge cycles at a current density of 1000 mA g-1, the specific capacity of the potassium-ion batteries was 144.8 mAh g-1. We innovatively used synchrotron small-angle X-ray scattering (SAXS) technique to systematically investigate the kinetic process of potassium formation in composites and showed that the kinetic process of potassium reaction in composites can be divided into four stages, and the pores with smaller average diameter distribution are more sensitive to changes in the reaction process. This work paves a new way to study the deposition kinetics of potassium in porous materials, which facilitates the design of porous structures and realizes the development of alkali metal ion-anode materials with high energies.

Investigation of the Microstructure of PAN Precursor Fibers Obtained at Various Processing Stages

The production of high-performance carbon fibers relies heavily on the structural transformations of polyacrylonitrile (PAN) fiber during processing. In this article differential scanning calorimetry (DSC), synchrotron small-angle X-ray scattering (SAXS), and synchrotron wide-angle X-ray diffraction (WAXD) were used to study the changes of the thermal properties, voids and crystal structure of the PAN precursor fibers on industrial lines during the continuous processing stages, i.e., after the treatment in the coagulation bath, after stretching in boiling water and after stretching in high-temperature steam. The findings of this study suggest that after boiling water stretching the molecular chain motion of the PAN precursor fiber weaken, resulting in the expansion of the voids. After high-temperature steam stretching the voids became elliptical and oriented in the stretching direction. Although the boiling water stretching process partially damaged the (100) crystal planes of the PAN precursor fibers, it does not hinder their overall crystalline structure. The high stretching ratio primarily affected the orientation of the molecular chains. This orientation, even in the context of partial crystal plane disruption, further promoted the crystallization of the (100) crystal planes in the fibers. These experiments explored the correlation between the processing technology and fiber structure transformation of PAN-based carbon fibers, resulting in producing a guide for the preparation of high-performance carbon fibers with fewer defects.

Pore Characterization of Sandy Silty Soil in Metro Surrounding Rock: A Synchrotron Small-Angle X-ray Scattering Experiment

Pore Characterization of Sandy Silty Soil in Metro Surrounding Rock: A Synchrotron Small-Angle X-ray Scattering Experiment

The influence of mannose-based esters on the mesophase behaviour of lyotropic liquid crystalline nanosystems as drug delivery vectors

Lyotropic Liquid Crystalline (LLC) nanoparticles represent an emerging class of smart, biocompatible, and biodegradable systems for the delivery of drugs. Among these, structures with complex 3D architectures such as cubosomes are of particular interest. These are non- lamellar assemblies having hydrophobic and hydrophilic portions able to carry drugs of different nature. They can further be modulated including suitable additives to control the release of the active payload, and to promote an active targeting. Starting from monoolein (GMO) cubic phase, different concentrations of mannose-based esters were added, and the eventual structural modifications were monitored to ascertain the effects of the presence of glycolipids. Moreover, the structural properties of these nanosystems loaded with Dexamethasone (DEX), a very well-known anti-inflammatory steroid, were also studied. Experiments were carried out by synchrotron Small Angle X-ray Scattering (SAXS), Raman Microspectroscopy (RMS) and Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) measurements. The drug delivery potential (i.e. entrapment efficiency and release properties) of the obtained nanoparticles was evaluated. Finally, in vitro cytocompatibility and anti-inflammatory activity studies of the prepared formulations were carried out. Inclusion of mannose-based surfactants up to 10 mol% influenced the structural parameters of Im3m cubic phase and swollen cubic phases were obtained with the different glycolipids with lattice parameters significantly higher than GMO. A complete cytocompatibility and an increased DEX activity were observed, thus suggesting the possibility to use GMO/glycolipids nanoparticles to formulate innovative drug delivery systems.

Heating-Induced Switching to Hierarchical Liquid Crystallinity Combining Colloidal and Molecular Order in Zwitterionic Molecules.

Hierarchical self-assemblies of soft matter involving triggerable or switchable structures at different length scales have been pursued toward multifunctional behaviors and complexity inspired by biological matter. They require several and balanced competing attractive and repulsive interactions, which provide a grand challenge in particular in the "bulk" state, i.e., in the absence of plasticizing solvents. Here, we disclose that zwitterionic bis-n-tetradecylphosphobetaine, as a model compound, shows a complex thermally switchable hierarchical self-assembly in the solvent-free state. It shows polymorphism and heating-induced reversible switching from low-temperature molecular-level assemblies to high-temperature hierarchical self-assemblies, unexpectedly combining colloidal and molecular self-assemblies, as inferred by synchrotron small-angle X-ray scattering (SAXS). The high-temperature phase sustains birefringent flow, indicating a new type of hierarchical thermotropic liquid crystallinity. The high-temperature colloidal-level SAXS reflections suggest indexation as a 2D oblique pattern and their well-defined layer separation in the perpendicular direction. We suggest that the colloidal self-assembled motifs are 2D nanoplatelets formed by the lateral packing of the molecules, where the molecular packing frustration between the tightly packed zwitterionic moieties and the coiled alkyl chains demanding more space limits the lateral platelet growth controlled by the alkyl stretching entropy. An indirect proof is provided by the addition of plasticizing ionic liquids, which relieve the ionic dense packings of zwitterions, thus allowing purely smectic liquid crystallinity without the colloidal level order. Thus, molecules with a simple chemical structure can lead to structural hierarchy and tunable complexity in the solvent-free state by balancing the competing long-range electrostatics and short-range nanosegregations.

Research on Improving the Pre‐Oxidation Process of the Excellent Mechanical Strength Carbon Fiber

AbstractThis study uses synchrotron wide‐angle X‐ray diffraction (WAXD) and synchrotron small angle X‐ray scattering (SAXS) to carry out an in situ study of the pre‐oxidation process of polyacrylonitrile (PAN) fibers with two different preparation processes. Through analysis of 2D WAXD/SAXS data, this study divides the evolution of PAN fiber's crystal and microporous structures during pre‐oxidation into three and two stages, respectively. The evolution of PAN fiber's crystal structure during pre‐oxidation can be divided into three stages: 1) Initial stage: small‐sized crystals melt, crystal orientation decreases, and no cyclization reactions occur. 2) Intermediate stage: cyclization reactions happen in the amorphous region, leading to increased crystal size, crystal orientation, and crystallinity. 3) Final stage: cyclization reactions occur in the crystal region, resulting in reduced crystal size and orientation. The evolution of microporous structure can be divided into two stages: microporous shrinkage stage and microporous expansion stage. These features are analyzed using 2D WAXD/SAXS techniques. This study provides valuable references and guidance for the industrial production of PAN fibers by exploring the mechanism of the pre‐oxidation process in‐depth.

Small-Angle X-ray Scattering for PEGylated Liposomal Doxorubicin Drugs: An Analytical Model Comparison Study.

Liposomal delivery systems are recognized as efficient and safe platforms for chemotherapeutic agents, with doxorubicin-loaded liposomes being the most representative nanopharmaceuticals. Characterizing the structure of liposomal nanomedicines in high spatial and temporal resolution is critical to analyze and evaluate their stability and efficacy. Small-angle X-ray scattering (SAXS) is a powerful tool increasingly used to investigate liposomal delivery systems. In this study, we chose a Doxil-like PEGylated liposomal doxorubicin (PLD) as an example and characterized the liposomal drug structure using synchrotron SAXS. Classical analytical models, including the spherical-shell or flat-slab geometries with Gaussian or uniform electron density profiles, were used to model the internal structure of the liposomal membrane. A cylinder model was applied to fit the scattering from the drug crystal loaded in the liposomes. The high-resolution structures of the original drug, Caelyx, and a similar research drug prepared in our laboratory were characterized using these analytical models. The structural parameters of PLDs, including the thickness of the liposomal membrane and morphology of the drug crystal, were further compared. The results demonstrated that both spherical-shell and flat-slab geometries with Gaussian electron density distribution were suitable to elucidate the structural features of the liposomal membrane under a certain range of scattering vectors, while models with uniform electron density distribution exhibited poor fitting performance. This study highlights the technical features of SAXS, which provides structural information at the nanoscale for liposomal drugs. The demonstrated methods are reliable and easy-to-use for the structural analysis of liposomal drugs, which are helpful for a broader application of SAXS in the production and regulation of nanopharmaceuticals.

Ageing response and strengthening mechanisms in a new Al-Mn-Ni-Cu-Zr alloy designed for laser powder bed fusion

Aluminum alloys designed for laser powder bed fusion (L-PBF) often show a bimodal grain structure and a strong out-of-equilibrium character with heterogeneities developing at scales ranging from the melt pool, i.e. several hundred microns, down to sub-nanometer. When subjected to post-fabrication heat treatments, microstructural evolutions arise at all scales. Herein are established the relationships between microstructure and mechanical properties at room temperature of a novel Al-4Mn-3Ni-2Cu-1Zr alloy, designed for L-PBF and subjected to direct ageing. On the basis of a multiscale microstructural study using scanning-electron microscopy (SEM), automated orientation mapping in the transmission-electron microscope (TEM-ACOM), atom probe tomography (APT), and synchrotron small-angle X-ray scattering (SAXS), we discuss and weigh the role of multiple strengthening mechanisms to the high strength of the material. In the stress-relieved conditions (300 °C/4 h), the yield strength is about 320 MPa and solid solution strengthening accounts for nearly two third of the yield strength (∼200 MPa) thanks to a very high content of Mn retained in solid solution (> 1.5 at.%) and, to a lesser extent, grain boundary strengthening. After ageing at 400 °C/1 h, the yield strength reaches 410 MPa. The additional contribution is brought by precipitation strengthening by L12-ordered Al3Zr, and to a lesser extent, Mn-rich precipitates. The composite effect due to the large fraction of relatively fine (< 1 μm) intermetallic particles (∼20%) is highlighted and cannot be neglected. This work provides guidelines to further optimize the mechanical properties and thermal stability of Al-alloys designed for L-PBF.

Realizing the AF4-UV-SAXS on-line coupling on protein and antibodies using high flux synchrotron radiation at the CoSAXS beamline, MAX IV.

In this paper, we demonstrate the coupling of synchrotron small angle X-ray scattering (SAXS) to asymmetrical flow-field flow fractionation (AF4) for protein characterization. To the best of our knowledge, this is the first time AF4 is successfully coupled to a synchrotron for on-line measurements on proteins. This coupling has potentially high impact, as it opens the possibility to characterize individual constituents of sensitive and/or complex samples, not suited for separation using other techniques, and for low electron density samples where high X-ray flux is required, e.g., biomolecules and biologics. AF4 fractionates complex samples in native or close to native environment, with low shear forces and system surface area. Many orders of magnitude in size can be fractionated in one measurement, without having to reconfigure the experimental setup. We report AF4 fractionations with correlated UV and statistically adequate SAXS data of bovine serum albumin and a monoclonal antibody and evaluate SAXS data recorded for the two protein systems.

Lysozyme-Sucrose Interactions in the Solid State: Glass Transition, Denaturation, and the Effect of Residual Water.

The freeze-drying of proteins, along with excipients, offers a solution for increasing the shelf-life of protein pharmaceuticals. Using differential scanning calorimetry, thermogravimetric analysis, sorption calorimetry, and synchrotron small-angle X-ray scattering (SAXS), we have characterized the properties at low (re)hydration levels of the protein lysozyme, which was freeze-dried together with the excipient sucrose. We observe that the residual moisture content in these samples increases with the addition of lysozyme. This results from an increase in equilibrium water content with lysozyme concentration at constant water activity. Furthermore, we also observed an increase in the glass transition temperature (Tg) of the mixtures with increasing lysozyme concentration. Analysis of the heat capacity step of the mixtures indicates that lysozyme does not participate in the glass transition of the sucrose matrix; as a result, the observed increase in the Tg of the mixtures is the consequence of the confinement of the amorphous sucrose domains in the interstitial space between the lysozyme molecules. Sorption calorimetry experiments demonstrate that the hydration behavior of this formulation is similar to that of the pure amorphous sucrose, while the presence of lysozyme only shifts the sucrose transitions. SAXS analysis of amorphous lysozyme-sucrose mixtures and unfolding of lysozyme in this environment show that prior to unfolding, the size and shape of lysozyme in a solid sucrose matrix are consistent with its native state in an aqueous solution. The results obtained from our study will provide a better understanding of the low hydration behavior of protein-excipient mixtures and support the improved formulation of biologics.

Investigating the mechanism of action of DNA-loaded PEGylated lipid nanoparticles

PEGylated lipid nanoparticles (LNPs) are commonly used to deliver bioactive molecules, but the role of PEGylation in DNA-loaded LNP interactions at the cellular and subcellular levels remains poorly understood. In this study, we investigated the mechanism of action of DNA-loaded PEGylated LNPs using gene reporter technologies, dynamic light scattering (DLS), synchrotron small angle X-ray scattering (SAXS), and fluorescence confocal microscopy (FCS). We found that PEG has no significant impact on the size or nanostructure of DNA LNPs but reduces their zeta potential and interaction with anionic cell membranes. PEGylation increases the structural stability of LNPs and results in lower DNA unloading. FCS experiments revealed that PEGylated LNPs are internalized intact inside cells and largely shuttled to lysosomes, while unPEGylated LNPs undergo massive destabilization on the plasma membrane. These findings can inform the design, optimization, and validation of DNA-loaded LNPs for gene delivery and vaccine development.

Effect of bacterial surfactants on the phase behavior of miscible pollutants in water

Rhamnolipids are bacterial amphiphiles. In addition to emulsifying hydrophobic solvents, they affect the phase behaviour of miscible solvents. In mixtures of toluene and water, rhamnolipids mediate the migration of metal ions (e.g., iron and copper) from the water to the toluene phase. Also, rhamnolipids phase separate the miscible solvent tetrahydrofuran (THF) from water, yielding emulsions even in the absence of toluene. This is because they compete with THF for hydrogen (H) bonding with similar water species. Water is an ensemble of species, including single donors (SD) or double (DD) donors, and single acceptors (SA) or double (DA) acceptors. In pure water, SD-SA and DD-DA have similar abundance and are dominant, as shown by attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR). With 50–200 g/L rhamnolipids, a water species intermediate between SD-SA and DD-DA is dominant, indicating that rhamnolipid-water interactions mainly occur through this species. This same species primarily interacts with THF, at 50–80% THF. At lower THF percentages, a similar (albeit not identical) species dominates, namely DD-DA, explaining separation. Emulsions are THF in water, as demonstrated by synchrotron mid-infrared spectro-microscopy and confocal microscopy using a hydrophobic dye. Synchrotron small angle X-ray scattering (SAXS) showed that rhamnolipids self- assemble into micelles, which contain THF. These findings have potential implications for miscible pollutant migration in groundwater, and their toxicity to rhamnolipid-secreting bacteria.

The elasto-plastic nano- and microscale compressive behaviour of rehydrated mineralised collagen fibres.

The hierarchical design of bio-based nanostructured materials such as bone enables them to combine unique structure-mechanical properties. As one of its main components, water plays an important role in bone's material multiscale mechanical interplay. However, its influence has not been quantified at the length-scale of a mineralised collagen fibre. Here, we couple in situ micropillar compression, and simultaneous synchrotron small angle X-ray scattering (SAXS) and X-ray diffraction (XRD) with a statistical constitutive model. Since the synchrotron data contain statistical information on the nanostructure, we establish a direct connection between experiment and model to identify the rehydrated elasto-plastic micro- and nanomechanical fibre behaviour. Rehydration led to a decrease of 65%-75% in fibre yield stress and compressive strength, and 70% in stiffness with a 3x higher effect on stresses than strains. While in agreement with bone extracellular matrix, the decrease is 1.5-3x higher compared to micro-indentation and macro-compression. Hydration influences mineral more than fibril strain with the highest difference to the macroscale when comparing mineral and tissue levels. The effect of hydration seems to be strongly mediated by ultrastructural interfaces while results provide insights towards mechanical consequences of reported water-mediated structuring of bone apatite. The missing reinforcing capacity of surrounding tissue for an excised fibril array is more pronounced in wet than dry conditions, mainly related to fibril swelling. Differences leading to higher compressive strength between mineralised tissues seem not to depend on rehydration while the lack of kink bands supports the role of water as an elastic embedding influencing energy-absorption mechanisms. STATEMENT OF SIGNIFICANCE: Characterising structure-property-function relationships in hierarchical biological materials helps us to elucidate mechanisms that enable their unique properties. Experimental and computational methods can advance our understanding of their complex behaviour with the potential to inform bio-inspired material development. In this study, we close a gap for bone's fundamental mechanical building block at micro- and nanometre length scales. We establish a direct connection between experiments and simulations by coupling in situ synchrotron tests with a statistical model and quantify the behaviour of rehydrated single mineralised collagen fibres. Results suggest a high influence of hydration on structural interfaces, and the role of water as an elastic embedding by outlining important differences between wet and dry elasto-plastic properties of mineral nanocrystals, fibrils and fibres.

Dielectric relaxation processes observed in hydroxypropyl Cellulose − Ethanol solutions

We performed dielectric measurements of hydroxypropyl cellulose (HPC) − ethanol solutions with various HPC concentrations at various temperatures. A symmetric primary relaxation process reflecting the motion of ethanol molecules was observed in the high-temperature range. Below 250 K, additional relaxation processes appeared on the low-frequency side of the primary process observed at high temperatures. The molecular mechanism of this separation behavior of the relaxation processes can be explained in terms of the fragmentation of the hydrogen bonding network of ethanol molecules caused by the impregnation of HPC molecules into the hydrogen bonding network of the ethanol molecules. Below 250 K, each fragment forms a larger fragment through hydrogen bonding with the HPC molecules, and the motion of these large fragments leads to an additional low-frequency relaxation process. In addition, the obtained dielectric parameters were compared with the spatial scale of the liquid crystal structure obtained by synchrotron small-angle X-ray scattering (SAXS) measurements.

Evidence and importance of intermediate nanostructures in the journey from molecular precursors to allophane and imogolite nanocrystals

Nanoparticles often-called proto-imogolites have been identified as an intermediate in the formation process of imogolite nanotubes as early as 1979. Their composition and structure are now well documented in the case of synthetic imogolite. One specific characteristic of proto-imogolite is that they have a curved shape with a local structure close to the one of imogolite. During a growth stage, they evolve toward nanocrystals (allophane, imogolite). Their thorough characterization has so far been difficult. Using synchrotron Small Angle X-ray Scattering coupled with Raman spectroscopy, we observe that proto-imogolites form during the initial stage of the co-precipitation of aluminum and silicon molecular precursors thanks to a reorganization process. The shape of the initial proto-imogolites, before the growth stage, depends on the synthesis conditions and controls the characteristics of the final product. We show using cryo-TEM images that, at the end of the growth stage, non-tubular nanostructures continue to coexist with nanotubes. Protocols to quantify remaining non-tubular nano-objects and purify the samples are discussed.