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Surprisingly, both experiments and simulations show that while intracellular concentrations may be insufficient for global phase separation, sequestering protein ligands to slowly diffusing nucleation centers can move the cell into a different region of the phase diagram, resulting in localized phase separation.
The physical aging effects result preferentially from global phase separation in As S glass system due to high localization of covalent bonding and local demixing on neighboring As2Sem+1 and As2Sem−1 nanoclusters in As Se system.
Interestingly, the minimal barriers in global phase separation ΔE(2) for both As S/Se ChG roughly coincide with the center of compositional domains ascribed to the TM-DSC-defined RW [5 8].
But with further tending towards stoichiometry, the As−S ChG becomes resistant to global phase separation in respect to reaction (2), this transition being revealed abruptly just near Z = 2.25.
The examined As2(S/Se m network-forming nanoclusters show similar oscillating character in tendency to local chemical decomposition but obvious step-like behavior in preference to global phase separation on boundary chemical compounds.
Despite energetic barriers of global phase separation ΔE(2) in this system attain only negative values, this parameter clearly shows threshold-like behavior in a vicinity of Z = 2.22 2.25 (Fig. 1d).
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