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.
While titanium is the metal of choice for most prosthetics and inner body devices due to its superior biocompatibility, the discovery of Ti-containing species in the adjacent tissue as a result of wear and corrosion has been associated with autoimmune diseases and premature implant failures. Here, we utilize the in situ liquid cell transmission electron microscopy (TEM) in a liquid flow holder and graphene liquid cells (GLCs) to investigate, for the first time, the in situ nano-bio interactions between titanium dioxide nanoparticles and biological medium. This imaging and spectroscopy methodology showed the process of formation of an ionic and proteic bio-camouflage surrounding Ti dioxide (anatase) nanoparticles that facilitates their internalization by bone cells. The in situ understanding of the mechanisms of the formation of the bio-camouflage of anatase nanoparticles may contribute to the definition of strategies aimed at the manipulation of these NPs for bone regenerative purposes.
In the modern construction industry, large gypsum (CaSO4·2H2O) boards are manufactured through a two-step procedure, which features the heating of fine gypsum powders to form the intermediate plaster of Paris (bassanite, CaSO4·0.5H2O) followed by hydration of the intermediate phase to form the final formed product. Here, we explore a novel pathway toward the fabrication of gypsum microneedles that bypasses formation of the intermediate bassanite phase. Using in situ liquid transmission electron microscopy, the dynamic behavior of fine gypsum powders in a calcium sulfate solution is investigated at the nanoscale and in real time. An oriented-attachment mechanism is found to dominate the direct transformation of gypsum nanoparticles to gypsum microneedles, where no intermediate phases are involved. Our experimental results advance the fundamental understanding of the dynamic interactions between gypsum and water. The proposed nanoscale pathway for gypsum evolution could potentially revolutionize the construction industry rooted in gypsum board manufacturing by promising a time- and energy-efficient mass production procedure. In addition, this work can inspire research efforts associated with geology, archeology, and biology, where historical significance is frequently deduced from gypsum-related discoveries.
Water is ubiquitous in natural systems, ranging from the vast oceans to the nanocapillaries in the earth crust or cellular organelles. In bulk or in intimate contact with solid surfaces, water molecules arrange themselves according to their hydrogen (H) bonding, which critically affects their short-and long-range molecular structures. Formation of Hbonds among water molecules designates the energy levels of certain nonbonding molecular orbitals of water, which are quantifiable by spectroscopic techniques. While the molecular architecture of water in nanoenclosures is of particular interest to both science and industry, it requires fine spectroscopic probes with nanometer spatial resolution and sub-eV energy sensitivity. Graphene liquid cells (GLCs), which feature opposing closely spaced sheets of hydrophobic graphene, facilitate high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) measurements of attoliter water volumes encapsulated tightly in the GLC nanovessels. We perform in situ TEM and EELS analysis of water encased in thin GLCs exposed to room and cryogenic temperatures to examine the nanoscale arrangement of the contained water molecules. Simultaneous quantification of GLC thickness leads to the conclusion that H-bonding strengthens under increased water confinement. The present results demonstrate the feasibility of nanoscale chemical characterization of aqueous fluids trapped in GLC nanovessels and offer insights on water molecule arrangement under high-confinement conditions.
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