Solvent Cavitation during Ambient Pressure Drying of Silica Aerogels.

Ambient-pressure drying of silica gels stands out as an economical and accessible process for producing monolithic silica aerogels. Gels experience significant deformations during drying due to the capillary pressure generated at the liquid-vapor interface in submicron pores. Proper control of the gel properties and the drying rate is essential to enable reversible drying shrinkage without mechanical failure. Recent in operando microcomputed X-ray tomography (µCT) imaging revealed the kinetics of the phase composition during drying and spring-back. However, to fully explain the underlying mechanisms, spatial resolution is required. Here we show evidence of evaporation by hexane cavitation during the ambient-pressure drying of silylated silica gels by spatially resolved quantitative analysis of µCT data supported by wide-angle X-ray scattering measurements. Cavitation consists of the rupture of the pore liquid put under tension by capillary pressure, creating vapor bubbles within the gels. We found the presence of a homogeneously distributed vapor-air phase in the gels well ahead of the maximum shrinkage. The onset of this vapor/air phase corresponded to a pore volume shrinkage of ca. 50 vol % that was attributed to a critical stiffening of the silica skeleton enabling cavitation. Our results provide new aspects of the relation between the shape changes of silica gels during drying and the evaporation mechanisms. We conclude that stress release by cavitation may be at the origin of the resistance of the silica skeleton to drying stresses. This opens the path toward producing larger monolithic silica aerogels by fine-tuning the drying conditions to exploit cavitation.

Microporous Sulfur-Carbon Materials with Extended Sodium Storage Window.

Developing high-performance carbonaceous anode materials for sodium-ion batteries (SIBs) is still a grand quest for a more sustainable future of energy storage. Introducing sulfur within a carbon framework is one of the most promising attempts toward the development of highly efficient anode materials. Herein, a microporous sulfur-rich carbon anode obtained from a liquid sulfur-containing oligomer is introduced. The sodium storage mechanism shifts from surface-controlled to diffusion-controlled at higher synthesis temperatures. The different storage mechanisms and electrode performances are found to be independent of the bare electrode material's interplanar spacing. Therefore, these differences are attributed to an increased microporosity and a thiophene-rich chemical environment. The combination of these properties enables extending the plateau region to higher potential and achieving reversible overpotential sodium storage. Moreover, in-operando small-angle X-ray scattering (SAXS) reveals reversible electron density variations within the pore structure, in good agreement with the pore-filling sodium storage mechanism occurring in hard carbons (HCs). Eventually, the depicted framework will enable the design of high-performance anode materials for sodium-ion batteries with competitive energy density.

Springback effect of ambient-pressure-dried silica aerogels: nanoscopic effects of silylation revealed by in situ synchrotron X-ray scattering.

Ambient pressure drying (APD) allows for synthesizing aerogels without expensive and sophisticated equipment for achieving supercritical conditions. Since APD does not eliminate the capillary stress that is induced by the liquid/vapour phase boundary, the shrinkage during drying needs to be prevented or reversed. The re-expansion of the silylated silica gels during drying is commonly referred to as the springback effect (SBE). The SBE is not only important for producing aerogels via APD, but is also a fascinating phenomenon, since it is accompanied by a significant volume change unusual for rigid ceramics. Synchrotron X-ray scattering has proven to be especially effective for the investigation of the volume change of these fractal silica structures on different length scales. In this work, we follow the drying, shrinkage, and (partial) re-expansion of various monolithic samples in situ to explore the occurrence of the SBE. For this purpose, various silylation agents, i.e., hexamethyldisilazane, trimethylchlorosilane, and triethylchlorosilane were used to investigate different shrinkage and re-expansion behavior. A scattering model was used to extract additional information of the evolving primary particle size, correlation length, fractal dimension, and other intensity contributions of the silica network and the hexane. While the primary particles pointed towards a relaxation at near molecular size, they were likely not involved in the SBE. However, structures near the size of the correlation length could be essential for the occurrence of this phenomenon. These findings may lead to the origin of this interesting phenomenon, as well as a better understanding of the production of APD aerogels.

Invasive mussels fashion silk-like byssus via mechanical processing of massive horizontally acquired coiled coils.

Zebra and quagga mussels (Dreissena spp.) are invasive freshwater biofoulers that perpetrate devastating economic and ecological impact. Their success depends on their ability to anchor onto substrates with protein-based fibers known as byssal threads. Yet, compared to other mussel lineages, little is understood about the proteins comprising their fibers or their evolutionary history. Here, we investigated the hierarchical protein structure of Dreissenid byssal threads and the process by which they are fabricated. Unique among bivalves, we found that threads possess a predominantly ß-sheet crystalline structure reminiscent of spider silk. Further analysis revealed unexpectedly that the Dreissenid thread protein precursors are mechanoresponsive α-helical proteins that are mechanically processed into ß-crystallites during thread formation. Proteomic analysis of the byssus secretory organ and byssus fibers revealed a family of ultrahigh molecular weight (354 to 467 kDa) asparagine-rich (19 to 20%) protein precursors predicted to form α-helical coiled coils. Moreover, several independent lines of evidence indicate that the ancestral predecessor of these proteins was likely acquired via horizontal gene transfer. This chance evolutionary event that transpired at least 12 Mya has endowed Dreissenids with a distinctive and effective fiber formation mechanism, contributing significantly to their success as invasive species and possibly, inspiring new materials design.

Evidence for liquid-liquid phase separation during the early stages of Mg-struvite formation.

The precipitation of struvite, a magnesium ammonium phosphate hexahydrate (MgNH4PO4 · 6H2O) mineral, from wastewater is a promising method for recovering phosphorous. While this process is commonly used in engineered environments, our understanding of the underlying mechanisms responsible for the formation of struvite crystals remains limited. Specifically, indirect evidence suggests the involvement of an amorphous precursor and the occurrence of multi-step processes in struvite formation, which would indicate non-classical paths of nucleation and crystallization. In this study, we use synchrotron-based in situ x-ray scattering complemented by cryogenic transmission electron microscopy to obtain new insights from the earliest stages of struvite formation. The holistic scattering data captured the structure of an entire assembly in a time-resolved manner. The structural features comprise the aqueous medium, the growing struvite crystals, and any potential heterogeneities or complex entities. By analysing the scattering data, we found that the onset of crystallization causes a perturbation in the structure of the surrounding aqueous medium. This perturbation is characterized by the occurrence and evolution of Ornstein-Zernike fluctuations on a scale of about 1 nm, suggesting a non-classical nature of the system. We interpret this phenomenon as a liquid-liquid phase separation, which gives rise to the formation of the amorphous precursor phase preceding actual crystal growth of struvite. Our microscopy results confirm that the formation of Mg-struvite includes a short-lived amorphous phase, lasting >10 s.

Origin of the Springback Effect in Ambient-Pressure-Dried Silica Aerogels: The Effect of Surface Silylation.

Ambient pressure drying (APD) can prospectively reduce the costs of aerogel fabrication and processing. APD relies solely on preventing shrinkage or making it reversible. The latter, i.e., the aerogel re-expansion after drying (so-called springback effect-SBE), needs to be controlled for reproducible aerogel fabrication by APD. This can be achieved by an appropriate surface functionalization of aerogel materials (e.g., SiO2). This work addresses the fabrication of monolithic SiO2 aerogels and xerogels by APD. The effect of several silylation agents, i.e., trimethylchlorosilane, triethylchlorosilane, and hexamethyldisilazane on the SBE is studied in detail, applying several complementary experimental techniques, allowing the evaluation of the macroscopic and microscopic morphology as well as the composition of SiO2 aerogels. Here, we show that some physical properties, e.g., the bulk density, the macroscopic structure, and pore sizes/volumes, were significantly affected by the re-expansion. However, silylation did not necessarily lead to full re-expansion. Therefore, similarities in the molecular composition could not be equated to similarities in the SBE. The influences of steric hindrance and reactivity are discussed. The impact of silylation is crucial in tailoring the SBE and, as a result, the APD of monolithic aerogels.

The complex structure of Fomes fomentarius represents an architectural design for high-performance ultralightweight materials.

High strength, hardness, and fracture toughness are mechanical properties that are not commonly associated with the fleshy body of a fungus. Here, we show with detailed structural, chemical, and mechanical characterization that Fomes fomentarius is an exception, and its architectural design is a source of inspiration for an emerging class of ultralightweight high-performance materials. Our findings reveal that F. fomentarius is a functionally graded material with three distinct layers that undergo multiscale hierarchical self-assembly. Mycelium is the primary component in all layers. However, in each layer, mycelium exhibits a very distinct microstructure with unique preferential orientation, aspect ratio, density, and branch length. We also show that an extracellular matrix acts as a reinforcing adhesive that differs in each layer in terms of quantity, polymeric content, and interconnectivity. These findings demonstrate how the synergistic interplay of the aforementioned features results in distinct mechanical properties for each layer.

Crystal-Chemical and Biological Controls of Elemental Incorporation into Magnetite Nanocrystals.

Magnetite nanoparticles possess numerous fundamental, biomedical, and industrial applications, many of which depend on tuning the magnetic properties. This is often achieved by the incorporation of trace and minor elements into the magnetite lattice. Such incorporation was shown to depend strongly on the magnetite formation pathway (i.e., abiotic vs biological), but the mechanisms controlling element partitioning between magnetite and its surrounding precipitation solution remain to be elucidated. Here, we used a combination of theoretical modeling (lattice and crystal field theories) and experimental evidence (high-resolution inductively coupled plasma-mass spectrometry and X-ray absorption spectroscopy) to demonstrate that element incorporation into abiotic magnetite nanoparticles is controlled principally by cation size and valence. Elements from the first series of transition metals (Cr to Zn) constituted exceptions to this finding, as their incorporation appeared to be also controlled by the energy levels of their unfilled 3d orbitals, in line with crystal field mechanisms. We finally show that element incorporation into biological magnetite nanoparticles produced by magnetotactic bacteria (MTB) cannot be explained by crystal-chemical parameters alone, which points to the biological control exerted by the bacteria over the element transfer between the MTB growth medium and the intracellular environment. This screening effect generates biological magnetite with a purer chemical composition in comparison to the abiotic materials formed in a solution of similar composition. Our work establishes a theoretical framework for understanding the crystal-chemical and biological controls of trace and minor cation incorporation into magnetite, thereby providing predictive methods to tailor the composition of magnetite nanoparticles for improved control over magnetic properties.

Primary radiation damage in bone evolves via collagen destruction by photoelectrons and secondary emission self-absorption.

X-rays are invaluable for imaging and sterilization of bones, yet the resulting ionization and primary radiation damage mechanisms are poorly understood. Here we monitor in-situ collagen backbone degradation in dry bones using second-harmonic-generation and X-ray diffraction. Collagen breaks down by cascades of photon-electron excitations, enhanced by the presence of mineral nanoparticles. We observe protein disintegration with increasing exposure, detected as residual strain relaxation in pre-stressed apatite nanocrystals. Damage rapidly grows from the onset of irradiation, suggesting that there is no minimal 'safe' dose that bone collagen can sustain. Ionization of calcium and phosphorous in the nanocrystals yields fluorescence and high energy electrons giving rise to structural damage that spreads beyond regions directly illuminated by the incident radiation. Our findings highlight photoelectrons as major agents of damage to bone collagen with implications to all situations where bones are irradiated by hard X-rays and in particular for small-beam mineralized collagen fiber investigations.

Characterization of lipid bilayers adsorbed to functionalized air/water interfaces.

Lipid bilayers immobilized in planar geometries, such as solid-supported or "floating" bilayers, have enabled detailed studies of biological membranes with numerous experimental techniques, notably X-ray and neutron reflectometry. However, the presence of a solid support also has disadvantages as it complicates the use of spectroscopic techniques as well as surface rheological measurements that would require surface deformations. Here, in order to overcome these limitations, we investigate lipid bilayers adsorbed to inherently soft and experimentally well accessible air/water interfaces that are functionalized with Langmuir monolayers of amphiphiles. The bilayers are characterized with ellipsometry, X-ray scattering, and X-ray fluorescence. Grazing-incidence X-ray diffraction reveals that lipid bilayers in a chain-ordered state can have significantly different structural features than regular Langmuir monolayers of the same composition. Our results suggest that bilayers at air/water interfaces may be well suited for fundamental studies in the field of membrane biophysics.

Gradients of Orientation, Composition, and Hydration of Proteins for Efficient Light Collection by the Cornea of the Horseshoe Crab.

The lateral eyes of the horseshoe crab, Limulus polyphemus, are the largest compound eyes within recent Arthropoda. The cornea of these eyes contains hundreds of inward projecting elongated cuticular cones and concentrate light onto proximal photoreceptor cells. Although this visual system has been extensively studied before, the precise mechanism allowing vision has remained controversial. Correlating high-resolution quantitative refractive index (RI) mapping and structural analysis, it is demonstrated how gradients of RI in the cornea stem from structural and compositional gradients in the cornea. In particular, these RI variations result from the chitin-protein fibers architecture, heterogeneity in protein composition, and bromine doping, as well as spatial variation in water content resulting from matrix cross-linking on the one hand and cuticle porosity on the other hand. Combining the realistic cornea structure and measured RI gradients with full-wave optical modeling and ray tracing, it is revealed that the light collection mechanism switches from refraction-based graded index (GRIN) optics at normal light incidence to combined GRIN and total internal reflection mechanism at high incident angles. The optical properties of the cornea are governed by different mechanisms at different hierarchical levels, demonstrating the remarkable versatility of arthropod cuticle.

Cellulose lattice strains and stress transfer in native and delignified wood.

Small specimens of spruce wood with different degrees of delignification were studied using in-situ tensile tests and simultaneous synchrotron X-ray diffraction to reveal the effect of delignification and densification on their tensile properties at relative humidities of 70-80 %. In addition to mechanical properties, these analyses yield the ratio of strains in the cellulose crystals and in the bulk, which reflects the stress-transfer to crystalline cellulose. While the specific modulus of elasticity slightly increases from native wood by partial or complete delignification, the lattice strain ratio does not show a significant change. This could indicate a compensatory effect from the decomposition of the amorphous matrix by delignification and from a tighter packing of cellulose crystals that would increase the stress transfer. The reduced strain to failure and maximum lattice strain of delignified specimens suggests that the removal of lignin affects the stress-strain behavior with fracture at lower strain levels.

Springback effect and structural features during the drying of silica aerogels tracked by in-situ synchrotron X-ray scattering.

The springback effect during ambient pressure drying of aerogels is an interesting structural phenomenon, consisting of a severe shrinkage followed by almost complete re-expansion. The drying of gels causes shrinkage, whereas re-expansion is believed to be linked to repelling forces on the nanoscale. A multi-scale structural characterization of this significant volume change is key in controlling aerogel processing and properties. In this work, hydrophobic, monolithic silica aerogels with high specific surface areas were synthesized by modification with trimethylchlorosilane and ambient pressure drying. Here, we report a multi-method approach focusing on in-situ X-ray scattering to observe alterations of the nanostructured material during the drying of surface-modified and unmodified silica gels. Both show a porous fractal nanostructure, which partially collapses during drying and only recovers in surface-modified samples during the springback effect. Distinct changes of the X-ray scattering data were reproducibly associated with the shrinkage, re-expansion and drying of the gel network. Our findings may contribute to tailor aerogels with specific functionality, as the springback effect has a direct influence on properties (e.g., porosity, pore size distribution), which is directly affected by the degree of re-expansion.

Order vs. Disorder: Cholesterol and Omega-3 Phospholipids Determine Biomembrane Organization.

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.

Mineralization generates megapascal contractile stresses in collagen fibrils.

During bone formation, collagen fibrils mineralize with carbonated hydroxyapatite, leading to a hybrid material with excellent properties. Other minerals are also known to nucleate within collagen in vitro. For a series of strontium- and calcium-based minerals, we observed that their precipitation leads to a contraction of collagen fibrils, reaching stresses as large as several megapascals. The magnitude of the stress depends on the type and amount of mineral. Using in-operando synchrotron x-ray scattering, we analyzed the kinetics of mineral deposition. Whereas no contraction occurs when the mineral deposits outside fibrils only, intrafibrillar mineralization generates fibril contraction. This chemomechanical effect occurs with collagen fully immersed in water and generates a mineral-collagen composite with tensile fibers, reminiscent of the principle of reinforced concrete.

Formation Mechanism of a Nano-Ring of Bismuth Cations and Mono-Lacunary Keggin-Type Phosphomolybdate.

A new hetero-bimetallic polyoxometalate (POM) nano-ring was synthesized in a one-pot procedure. The structure consists of tetrameric units containing four bismuth-substituted monolacunary Keggin anions including distorted [BiO8 ] cubes. The nano-ring is formed via self-assembly from metal precursors in aqueous acidic medium. The compound (NH4 )16 [(BiPMo11 O39 )4 ] ⋅ 22 H2 O; (P4 Bi4 Mo44 ) was characterized by single-crystal X-ray diffraction, extended X-ray absorption fine structure spectroscopy (EXAFS), Raman spectroscopy, matrix-assisted laser desorption/ionisation-time of flight mass spectrometry (MALDI-TOF), and thermogravimetry/differential scanning calorimetry mass spectrometry (TG-DSC-MS). The formation of the nano-ring in solution was studied by time-resolved in situ small- and wide-angle X-ray scattering (SAXS/WAXS) and in situ EXAFS measurements at the Mo-K and the Bi-L3 edge indicating a two-step process consisting of condensation of Mo-anions and formation of Bi-Mo-units followed by a rapid self-assembly to yield the final tetrameric ring structure.

Multiscale X-ray study of Bacillus subtilis biofilms reveals interlinked structural hierarchy and elemental heterogeneity.

Biofilms are multicellular microbial communities that encase themselves in an extracellular matrix (ECM) of secreted biopolymers and attach to surfaces and interfaces. Bacterial biofilms are detrimental in hospital and industrial settings, but they can be beneficial, for example, in agricultural as well as in food technology contexts. An essential property of biofilms that grants them with increased survival relative to planktonic cells is phenotypic heterogeneity, the division of the biofilm population into functionally distinct subgroups of cells. Phenotypic heterogeneity in biofilms can be traced to the cellular level; however, the molecular structures and elemental distribution across whole biofilms, as well as possible linkages between them, remain unexplored. Mapping X-ray diffraction across intact biofilms in time and space, we revealed the dominant structural features in Bacillus subtilis biofilms, stemming from matrix components, spores, and water. By simultaneously following the X-ray fluorescence signal of biofilms and isolated matrix components, we discovered that the ECM preferentially binds calcium ions over other metal ions, specifically, zinc, manganese, and iron. These ions, remaining free to flow below macroscopic wrinkles that act as water channels, eventually accumulate and may possibly lead to sporulation. The possible link between ECM properties, regulation of metal ion distribution, and sporulation across whole, intact biofilms unravels the importance of molecular-level heterogeneity in shaping biofilm physiology and development.

Seeds of imperfection rule the mesocrystalline disorder in natural anhydrite single crystals.

In recent years, we have come to appreciate the astounding intricacies associated with the formation of minerals from ions in aqueous solutions. In this context, a number of studies have revealed that the nucleation of calcium sulfate systems occurs nonclassically, involving the aggregation and reorganization of nanosized prenucleation species. In recent work, we have shown that this particle-mediated nucleation pathway is actually imprinted in the resultant micrometer-sized CaSO4 crystals. This property of CaSO4 minerals provides us with the unique opportunity to search for evidence of nonclassical nucleation pathways in geological environments. In particular, we focused on large anhydrite crystals extracted from the Naica Mine in Mexico. We were able to shed light on this mineral's growth history by mapping defects at different length scales. Based on this, we argue that the nanoscale misalignment of the structural subunits, observed in the initial calcium sulfate crystal seeds, propagates through different length scales both in morphological, as well as in strictly crystallographic aspects, eventually causing the formation of large mesostructured single crystals of anhydrite. Hence, the nonclassical nucleation mechanism introduces a "seed of imperfection," which leads to a macroscopic "single" crystal whose fragments do not fit together at different length scales in a self-similar manner. Consequently, anisotropic voids of various sizes are formed with very well-defined walls/edges. However, at the same time, the material retains in part its single crystal nature.

Investigating the Conformation of Surface-Adsorbed Proteins with Standing-Wave X-ray Fluorescence.

Protein adsorption to surfaces is at the heart of numerous technological and bioanalytical applications, but sometimes, it is also associated with medical risks. To deepen our insights into processes involving layers of surface-adsorbed proteins, high-resolution structural information is essential. Here, we use standing-wave X-ray fluorescence (SWXF) in combination with an optimized liquid-cell setup to investigate the underwater conformation of the random-coiled phosphoprotein ß-casein adsorbed to hydrophilic and hydrophobized solid surfaces. The orientation of the protein, as determined through the distributions of sulfur and phosphorus, is found to be sensitive to the chemical nature of the substrate. While no preferred orientations are observed on hydrophobized surfaces, on hydrophilic Al oxide, ß-casein is adsorbed as a diblock copolymer with the phosphorylated domain I attached to the surface. Our results demonstrate that targeting biologically relevant chemical elements with SWXF enables a detailed investigation of biomolecular layers under near-physiological conditions.