Time-Space-Resolved Chemical Deconvolution of Cementitious Colloidal Systems Using Raman Spectroscopy.

Concrete is one of the most used materials in the world, second only to water. One of the key advantages of this versatile material is its workability in the early stages before setting. Here, we use in situ underwater Raman microspectroscopy to investigate and visualize the early hydration kinetics of ordinary Portland cement (OPC) with submicron spatial and high temporal resolution. First, the spectral features of the C-S-H gel were analyzed in the hydroxyl stretching region to confirm the coexistence of Ca-OH and Si-OH bonds in a highly disordered C-S-H gel. Second, the disordered calcium hydroxide (Ca(OH)2) is experimentally identified for the first time in the mixture before setting, suggesting that Ca(OH)2 crystallization and growth are essential in the setting of cement paste. Finally, the phase transformations of clinker, C-S-H, and Ca(OH)2 are spatially and temporally resolved, and the hydration kinetics are studied by analyzing the spatial relationships of these phases using two-point correlation functions. The results quantitatively validate that the setting occurs as a percolation process, wherein the hydration products intersect and form an interconnected network. This time-space-resolved characterization method can map and quantitatively analyze the heterogeneous reaction of the cementitious colloidal system and thus provide potential application value in the field of cement chemistry and materials design more broadly.

Multiscale characterization of the mineral phase at skeletal sites of breast cancer metastasis.

Skeletal metastases, the leading cause of death in advanced breast cancer patients, depend on tumor cell interactions with the mineralized bone extracellular matrix. Bone mineral is largely composed of hydroxyapatite (HA) nanocrystals with physicochemical properties that vary significantly by anatomical location, age, and pathology. However, it remains unclear whether bone regions typically targeted by metastatic breast cancer feature distinct HA materials properties. Here we combined high-resolution X-ray scattering analysis with large-area Raman imaging, backscattered electron microscopy, histopathology, and microcomputed tomography to characterize HA in mouse models of advanced breast cancer in relevant skeletal locations. The proximal tibial metaphysis served as a common metastatic site in our studies; we identified that in disease-free bones this skeletal region contained smaller and less-oriented HA nanocrystals relative to ones that constitute the diaphysis. We further observed that osteolytic bone metastasis led to a decrease in HA nanocrystal size and perfection in remnant metaphyseal trabecular bone. Interestingly, in a model of localized breast cancer, metaphyseal HA nanocrystals were also smaller and less perfect than in corresponding bone in disease-free controls. Collectively, these results suggest that skeletal sites prone to tumor cell dissemination contain less-mature HA (i.e., smaller, less-perfect, and less-oriented crystals) and that primary tumors can further increase HA immaturity even before secondary tumor formation, mimicking alterations present during tibial metastasis. Engineered tumor models recapitulating these spatiotemporal dynamics will permit assessing the functional relevance of the detected changes to the progression and treatment of breast cancer bone metastasis.

Biomineralogical signatures of breast microcalcifications.

Microcalcifications, primarily biogenic apatite, occur in cancerous and benign breast pathologies and are key mammographic indicators. Outside the clinic, numerous microcalcification compositional metrics (e.g., carbonate and metal content) are linked to malignancy, yet microcalcification formation is dependent on microenvironmental conditions, which are notoriously heterogeneous in breast cancer. We interrogate multiscale heterogeneity in 93 calcifications from 21 breast cancer patients using an omics-inspired approach: For each microcalcification, we define a "biomineralogical signature" combining metrics derived from Raman microscopy and energy-dispersive spectroscopy. We observe that (i) calcifications cluster into physiologically relevant groups reflecting tissue type and local malignancy; (ii) carbonate content exhibits substantial intratumor heterogeneity; (iii) trace metals including zinc, iron, and aluminum are enhanced in malignant-localized calcifications; and (iv) the lipid-to-protein ratio within calcifications is lower in patients with poor composite outcome, suggesting that there is potential clinical value in expanding research on calcification diagnostic metrics to include "mineral-entrapped" organic matrix.

Black Drum Fish Teeth: Built for Crushing Mollusk Shells.

With an exclusive diet of hard-shelled mollusks, the black drum fish (Pogonias cromis) exhibits one of the highest bite forces among extant animals. Here we present a systematic microstructural, chemical, crystallographic, and mechanical analysis of the black drum teeth to understand the structural basis for achieving the molluscivorous requirements. At the material level, the outermost enameloid shows higher modulus (Er = 126.9 ± 16.3 GPa, H = 5.0 ± 1.4 GPa) than other reported fish teeth, which is attributed to the stiffening effect of Zn and F doping in apatite crystals and the preferential co-alignment of crystallographic c-axes and enameloid rods along the biting direction. The high fracture toughness (Kc = 1.12 MPa⋅m1/2) of the outer enameloid also promotes local yielding instead of fracture during crushing contact with mollusk shells. At the individual-tooth scale, the molar-like teeth, high density of dentin tubules, enlarged pulp chamber, and specialized dentin-bone connection, all contribute to the functional requirements, including confinement of contact compressive stress in the stiff enameloid, enhanced energy absorption in the compliant dentin, and controlled failure of tooth-bone composite under excessive loads. These results show that the multi-scale structures of black drum teeth are adapted to feed on hard-shelled mollusks. STATEMENT OF SIGNIFICANCE: The black drum fish feeds on hard-shelled mollusks, which requires strong, tough, and wear-resistant teeth. This study presents a comprehensive multiscale material and mechanical analysis of the black drum teeth in achieving such remarkable biological function. At microscale, the fluoride- and zinc-doped apatite crystallites in the outer enameloid region are aligned perpendicular to the chewing surface, representing one of the stiffest biomineralized materials found in nature. In the inner enameloid region, the apatite crystals are arranged into intertwisted rods with crystallographic misorientation for increased crack resistance and toughness. At the macroscale, the molariform geometry, the two-layer design based on the outer enameloid and inner dentin, enlarged pulp chamber and the underlying strong bony toothplate work synergistically to contribute to the teeth's crushing resistance.

Anti-fatigue-fracture hydrogels.

The emerging applications of hydrogels in devices and machines require hydrogels to maintain robustness under cyclic mechanical loads. Whereas hydrogels have been made tough to resist fracture under a single cycle of mechanical load, these toughened gels still suffer from fatigue fracture under multiple cycles of loads. The reported fatigue threshold for synthetic hydrogels is on the order of 1 to 100 J/m2. We propose that designing anti-fatigue-fracture hydrogels requires making the fatigue crack encounter and fracture objects with energies per unit area much higher than that for fracturing a single layer of polymer chains. We demonstrate that the controlled introduction of crystallinity in hydrogels can substantially enhance their anti-fatigue-fracture properties. The fatigue threshold of polyvinyl alcohol (PVA) with a crystallinity of 18.9 weight % in the swollen state can exceed 1000 J/m2.

Mapping and Profiling Lipid Distribution in a 3D Model of Breast Cancer Progression.

Aberrant lipid accumulation and marked changes in cellular lipid profiles are related to breast cancer metabolism and disease progression. In vitro, these phenomena are primarily studied using cells cultured in monolayers (2D). Here, we employ multicellular spheroids, generated using the MCF10A cell line series of increasing malignancy potential, to better recapitulate the 3D microenvironmental conditions that cells experience in vivo. Breast cancer cell lipid compositions were assessed in 2D and 3D culture models as a function of malignancy using liquid chromatography coupled with mass spectrometry. Further, the spatial distribution of lipids was examined using Raman chemical imaging and lipid staining. We show that with changes in the cellular microenvironment when moving from 2D to 3D cell cultures, total lipid amounts decrease significantly, while the ratio of acylglycerols to membrane lipids increases. This ratio increase could be associated with the formation of large lipid droplets (>10 µm) that are spatially evident throughout the spheroids but absent in 2D cultures. Additionally, we found a significant difference in lipid profiles between the more and less malignant spheroids, including changes that support de novo sphingolipid production and a reduction in ether-linked lipid fractions in the invasive spheroids. These differences in lipid profiles as a function of cell malignancy and microenvironment highlight the importance of coupled spatial and lipidomic studies to better understand the connections between lipid metabolism and cancer.