Shadow glass transition as a thermodynamic signature of β relaxation in hyper-quenched metallic glasses

One puzzling phenomenon in glass physics is the so-called ‘shadow glass transition’ which is an anomalous heat-absorbing process below the real glass transition and influences glass properties. However, it has yet to be entirely characterized, let alone fundamentally understood. Conventional calorimetry detects it in limited heating rates. Here, with the chip-based fast scanning calorimetry, we study the dynamics of the shadow glass transition over four orders of magnitude in heating rates for 24 different hyper-quenched metallic glasses. We present evidence that the shadow glass transition correlates with the secondary (β) relaxation: (i) The shadow glass transition and the β relaxation follow the same temperature–time dependence, and both merge with the primary relaxation at high temperature. (ii) The shadow glass transition is more obvious in glasses with pronounced β relaxation, and vice versa; their magnitudes are proportional to each other. Our findings suggest that the shadow glass transition signals the thermodynamics of β relaxation in hyper-quenched metallic glasses.     

Au23(CR)14 nanocluster restores fibril Aβ’s unfolded state with abolished cytotoxicity and dissolves endogenous Aβ plaques

The misfolding of amyloid-β (Aβ) peptides from the natural unfolded state to β-sheet structure is a critical step, leading to abnormal fibrillation and formation of endogenous Aβ plaques in Alzheimer''s disease (AD). Previous studies have reported inhibition of Aβ fibrillation or disassembly of exogenous Aβ fibrils in vitro. However, soluble Aβ oligomers have been reported with increased cytotoxicity; this might partly explain why current clinical trials targeting disassembly of Aβ fibrils by anti-Aβ antibodies have failed so far. Here we show that Au₂₃(CR)₁₄ (a new Au nanocluster modified by Cys-Arg (CR) dipeptide) is able to completely dissolve exogenous mature Aβ fibrils into monomers and restore the natural unfolded state of Aβ peptides from misfolded β-sheets. Furthermore, the cytotoxicity of Aβ₄₀ fibrils when dissolved by Au₂₃(CR)₁₄ is fully abolished. More importantly, Au₂₃(CR)₁₄ is able to completely dissolve endogenous Aβ plaques in brain slices from transgenic AD model mice. In addition, Au₂₃(CR)₁₄ has good biocompatibility and infiltration ability across the blood–brain barrier. Taken together, this work presents a promising therapeutics candidate for AD treatment, and manifests the potential of nanotechnological approaches in the development of nanomedicines.     

Model-based orbital-scale precipitation δ18O variations and distinct mechanisms in Asian monsoon and arid regions

The past Asian precipitation δ¹⁸O (δ¹⁸O_p) records from stalagmites and other deposits have shown significant orbital-scale variations, but their climatic implications and regional differences are still not fully understood. This study, as the first attempt of a 300-kyr transient stable isotope-enabled simulation, investigated the characteristics and mechanisms of the orbital-scale δ¹⁸O_p variations in three representative regions of Asia: arid Central Asia (CA), monsoonal South Asia (SA) and monsoonal East Asia (EA). The modelling results showed that the variations in the CA, SA and EA annual δ¹⁸O_p exhibited significant but asynchronous 23-kyr precession cycles. Further analyses revealed that although the precession-induced insolation variation was the ultimate cause of the δ¹⁸O_p variation in all three regions, the dominant mechanisms and the involved physical processes were distinct among them. For the CA region, the rainy-season (November–March) temperature effect and water vapour transport by the westerly circulation were identified as the key precession-scale processes linking the October–February boreal mid-latitude insolation to the rainy-season or annual δ¹⁸O_p. In the SA region, the rainy-season (June–September) precipitation amount effect and upstream depletion of the monsoonal water vapour δ¹⁸O served as the main mechanisms linking the rainy-season or annual δ¹⁸O_p to the April–July insolation variation at the precession scale. For the EA region, however, the precession-scale annual δ¹⁸O_p was mainly controlled by the late-monsoon (August–September) and pre-monsoon (April–May) water vapour transport patterns, which were driven by the July–August insolation and the global ice volume, respectively. These results suggest that the climatic implications of the orbital-scale Asia δ¹⁸O_p variations are sensitive to their geographic locations as determined by the combined effects of insolation and regional circulation patterns associated with the respective rainy seasons. This study provides new insights into understanding the regional differences and formation mechanisms of the Asian orbital-scale δ¹⁸O_p variations.     

Paving the road toward the use of β-Fe2O3 in solar water splitting: Raman identification,phase transformation and strategies for phase stabilization

Although β-Fe₂O₃ has a high theoretical solar-to-hydrogen efficiency because of its narrow band gap, the study of β-Fe₂O₃ photoanodes for water splitting is elusive as a result of their metastable nature. Raman identification of β-Fe₂O₃ is theoretically and experimentally investigated in this study for the first time, thus clarifying the debate about its Raman spectrum in the literature. Phase transformation of β-Fe₂O₃ to α-Fe₂O₃ was found to potentially take place under laser and electron irradiation as well as annealing. Herein, phase transformation of β-Fe₂O₃ to α-Fe₂O₃ was inhibited by introduction of Zr doping, and β-Fe₂O₃ was found to withstand a higher annealing temperature without any phase transformation. The solar water splitting photocurrent of the Zr-doped β-Fe₂O₃ photoanode was increased by 500% compared to that of the pure β-Fe₂O₃ photoanode. Additionally, Zr-doped β-Fe₂O₃ exhibited very good stability during the process of solar water splitting. These results indicate that by improving its thermal stability, metastable β-Fe₂O₃ film is a promising photoanode for solar water splitting.