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Award ID contains: 1710049

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  1. Abstract Calcium oxalate (CaOx) is the major phase in kidney stones and the primary calcium storage medium in plants. CaOx can form crystals with different lattice types, water contents, and crystal structures. However, the conditions and mechanisms leading to nucleation of particular CaOx crystals are unclear. Here, liquid‐cell transmission electron microscopy and atomistic molecular dynamics simulations are used to study in situ CaOx nucleation at different conditions. The observations reveal that rhombohedral CaOx monohydrate (COM) can nucleate via a classical pathway, while square COM can nucleate via a non‐classical multiphase pathway. Citrate, a kidney stone inhibitor, increases the solubility of calcium by forming calcium‐citrate complexes and blocks oxalate ions from approaching calcium. The presence of multiple hydrated ionic species draws additional water molecules into nucleating CaOx dihydrate crystals. These findings reveal that by controlling the nucleation pathways one can determine the macroscale crystal structure, hydration state, and morphology of CaOx. 
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  2. Abstract Understanding the behavior of confined matter within Van der Waals (VdW) materials is complicated due to the interplay of various factors, including the VdW interaction between the interlayers, the layer interaction with the matter, and the bending strain energy of the layers to accommodate encapsulation. Herein, new insight on the magnitude of pressure and density of water entrapped within confined spaces in VdW materials is provided. This is accomplished by studying the plasmon excitation of water encapsulated between two sheets of graphene membranes in an aberration‐corrected scanning transmission electron microscope. The results indicate ≈12% maximum increase in the density of water under tight graphene encasement, where pressure as high as 400 MPa is expected. The pressure estimation from theoretical analysis considering the effect of VdW forces, Laplace pressure, and strain energy is in agreement with the experimental results. The findings of this work open new opportunities to explore the local physical state of not only water but also other liquid materials under high pressure with imaging and analytical resolutions never achieved before. 
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  3. Abstract Imaging materials and biological structures in a liquid environment pose a significant challenge for conventional transmission electron microscopy (TEM) due to stringent requirement of ultrahigh vacuum design in the microscope column. The most recent liquid‐cell TEM technique, graphene liquid‐cell (GLC) microscopy, employs only layers of graphene to encapsulate liquid specimens. Recent efforts with GLC–TEM have demonstrated superior imaging resolution of beam‐sensitive specimens. Herein, the parameters that affect the quality of GLC analysis, including the graphene transfer onto TEM grids, are reviewed. Several important factors that affect the in situ TEM imaging of specimens, including the variations in GLC geometries and capillary pressure are discussed. The interaction between the electron beam and the liquid along with the possibility for artifacts or the formation of radical ions is also highlighted in this review. The scientific discoveries enabled by GLC–TEM in the areas of nucleation and growth of crystals, corrosion, battery science, as well as high‐resolution imaging of organelles and proteins are also briefly discussed. Finally, possible future research directions of GLC–TEM and the associated challenges are discussed. The synergistic effort to accomplish the proposed research directions has the potential to yield new discoveries in both materials and life sciences. 
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  4. Abstract The direct observation of amorphous barium carbonate (ABC), which transforms into a previously unknown barium carbonate hydrate (herewith named gortatowskite) within a few hundred milliseconds of formation, is described. In situ X‐ray scattering, cryo‐, and low‐dose electron microscopy were used to capture the transformation of nanoparticulate ABC into gortatowskite crystals, highly anisotropic sheets that are up to 1 μm in width, yet only about 10 nm in thickness. Recrystallization of gortatowskite to witherite starts within 30 seconds. We describe a bulk synthesis and report a first assessment of the composition, vibrational spectra, and structure of gortatowskite. Our findings indicate that transient amorphous and crystalline precursors can play a role in aqueous precipitation pathways that may often be overlooked owing to their extremely short lifetimes and small dimensions. However, such transient precursors may be integral to the formation of more stable phases. 
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  5. Commercial poly methyl methacrylate (PMMA)-based cement is currently used in the field of orthopedics. However, it suffers from lack of bioactivity, mechanical weakness, and monomer toxicity. In this study, a PMMA-based cement nanocomposite reinforced with hydroxyapatite (HA) nanofibers and two-dimensional (2D) magnesium phosphate MgP nanosheets was synthesized and optimized in terms of mechanical property and cytocompatibility. The HA nanofibers and the MgP nanosheets were synthesized using a hydrothermal homogeneous precipitation method and tuning the crystallization of the sodium-magnesium-phosphate ternary system, respectively. Compressive strength and MTT assay tests were conducted to evaluate the mechanical property and the cytocompatibility of the PMMA-HA-MgP nanocomposites prepared at different ratios of HA and MgP. To optimize the developed nanocomposites, the standard response surface methodology (RSM) design known as the central composite design (CCD) was employed. Two regression models generated by CCD were analyzed and compared with the experimental results, and good agreement was observed. Statistical analysis revealed the significance of both factors, namely, the HA nanofibers and the MgP nanosheets, in improving the compressive strength and cell viability of the PMMA-MgP-HA nanocomposite. Finally, it was demonstrated that the HA nanofibers of 7.5% wt and the MgP nanosheets of 6.12% wt result in the PMMA-HA-MgP nanocomposite with the optimum compressive strength and cell viability. 
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