Rechargeable magnesium batteries have lately received great attention for large-scale energy storage systems due to their high volumetric capacities, low materials cost, and safe characteristic. However, the bivalency of Mg(2+) ions has made it challenging to find cathode materials operating at high voltages with decent (de)intercalation kinetics. In an effort to overcome this challenge, we adopt an unconventional approach of engaging crystal water in the layered structure of Birnessite MnO2 because the crystal water can effectively screen electrostatic interactions between Mg(2+) ions and the host anions. The crucial role of the crystal water was revealed by directly visualizing its presence and dynamic rearrangement using scanning transmission electron microscopy (STEM). Moreover, the importance of lowering desolvation energy penalty at the cathode-electrolyte interface was elucidated by working with water containing nonaqueous electrolytes. In aqueous electrolytes, the decreased interfacial energy penalty by hydration of Mg(2+) allows Birnessite MnO2 to achieve a large reversible capacity (231.1 mAh g(-1)) at high operating voltage (2.8 V vs Mg/Mg(2+)) with excellent cycle life (62.5% retention after 10000 cycles), unveiling the importance of effective charge shielding in the host and facile Mg(2+) ions transfer through the cathode's interface.
RAM (regulation of Ace2p transcription factor and polarized morphogenesis) is a conserved signaling network that regulates polarized morphogenesis in yeast, worms, flies, and humans. To investigate the role of the RAM network in cell polarity and hyphal morphogenesis of Candida albicans, each of the C. albicans RAM genes (CaCBK1, CaMOB2, CaKIC1, CaPAG1, CaHYM1, and CaSOG2) was deleted. All C. albicans RAM mutants exhibited hypersensitivity to cell-wall- or membrane-perturbing agents, exhibiting cell-separation defects, a multinucleate phenotype and loss of cell polarity. Yeast two-hybrid and in vivo functional analyses of CaCbk1p and its activator, CaMob2p, the key factors in the RAM network, demonstrated that the direct interaction between the SMA domain of CaCbk1p and the Mob1/phocein domain of CaMob2p was necessary for hyphal growth of C. albicans. Genome-wide transcription profiling of a Camob2 mutant suggested that the RAM network played a role in serum- and antifungal azoles-induced activation of ergosterol biosynthesis genes, especially those involved in the late steps of ergosterol biosynthesis, and might be associated, at least indirectly, with the Tup1p-Nrg1p pathway. Collectively, these results demonstrate that the RAM network is critically required for hyphal growth as well as normal vegetative growth in C. albicans.
The phase transition of layered manganese oxides to spinel phases is a well-known phenomenon in rechargeable batteries and is the main origin of the capacity fading in these materials. This spontaneous phase transition is associated with the intrinsic properties of manganese, such as its size, preferred crystal positions, and reaction characteristics, and it is therefore very difficult to avoid. The introduction of crystal water by an electrochemical process enables the inverse phase transition from spinel to a layered Birnessite structure. Scanning transmission electron microscopy can be used to directly visualize the rearrangement of lattice atoms, the simultaneous insertion of crystal water, the formation of a transient structure at the phase boundary, and layer-by-layer progression of the phase transition from the edge. This research indicates that crystal water intercalation can reverse phase transformation with thermodynamically favored directionality.
The addition of axial DW imaging to a conventional MR imaging protocol improved diagnostic accuracy in the differentiation of acute osteoporotic from malignant compression fractures by measuring ADCs in the solid portion with careful use of a small ROI.
We
developed a “nanobattery” consisting of LiMn2O4 nanowires, ionic liquid electrolyte, and Li4Ti5O12 crystals and performed in situ
transmission electron microscope observation during charge and discharge
cycles. The LiMn2O4 nanowire was found to be
changed into the tetragonal phase at the interface region with electrolyte
during the discharge process of the 4 V reaction (vs Li/Li+). This result is explained by the lithium accumulation due to the
different local lithium diffusion rates: the lithium ions were inserted
into the nanowire at a higher rate than they diffused toward the bulk
side of the nanowire. We also found that the LiMn2O4 nanowire cathode was restored to be cubic phase without any
fracture in the charge process. No fracture during the cubic-tetragonal
transition is promising for the long-lifetime battery with LiMn2O4 nanowire cathode.
Hydrated materials contain crystal
water within their crystal frameworks
and can exhibit extraordinary properties as a result. However, a detailed
understanding of the mechanism involved in the hydration process is
largely lacking, because the overall synthesis process is very difficult
to monitor. Here, we elucidate how the insertion of crystal water
mediates an anomalous spinel-to-Birnessite phase
transition during electrochemical cycling in aqueous media. We find
that, at the initial stage of the phase transition, crystal water
is inserted into the interlayer space between MnO6 layers
in the form of a hydronium ion (H3O+). The H3O+ insertion is chemically driven in the reverse
(reducing) direction to the applied anodic (oxidizing) electric field,
stabilizing the structure and recovering the charge balance following
the deinsertion of Mn2+. A comparative investigation using
various electrolyte solutions revealed that the H3O+ insertion competes with the insertion of other ionic charge
carriers (Li+, Na+, and Mg2+), and
the overall efficiency of the phase transition is determined by this
competition. This understanding of crystal water insertion offers
an insight into strategies to synthesize hydrated materials.
Macroautophagy (autophagy) is believed to maintain energy homeostasis by degrading unnecessary cellular components and molecules. Its implication in regulating cancer metabolism recently started to be uncovered. However, the precise roles of autophagy in cancer metabolism are still unclear. Here, we show that autophagy plays a critical role in glutamine metabolism, which is required for tumor survival. Pancreatic ductal adenocarcinoma (PDAC) cells require both autophagy and typical glutamine transporters to maintain intracellular glutamine levels. Glutamine deprivation, but not that of glucose, led to the activation of macropinocytosis-associated autophagy through TFEB induction and translocation into the nucleus. In contrast, glutamine uptake increased as a compensatory response to decreased intracellular glutamine levels upon autophagy inhibition. Moreover, autophagy inhibition and glutamine deprivation did not induce cell death, while glutamine deprivation dramatically activated apoptotic cell death upon autophagy inhibition. Interestingly, the addition of α-ketoglutarate significantly rescued the apoptotic cell death caused by the combination of the inhibition of autophagy with glutamine deprivation. Our data suggest that macropinocytosis-associated autophagy is a critical process providing glutamine for anaplerosis of the TCA cycle in PDAC. Thus, targeting both autophagy and glutamine metabolism to completely block glutamine supply may provide new therapeutic approaches to treat refractory tumors.
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