The crystallinity of freeze/thaw poly(vinyl alcohol) (PVA) hydrogels, either fresh or aged or
obtained by dipping dried freeze/thaw gel samples in water immediately after their preparation, was
investigated by using different techniques. Free induction decays obtained from 1H NMR experiments
provide the most accurate measurement of the degree of crystallinity of these systems. Values thus
obtained are in a good agreement with data obtained by X-ray diffraction for all the samples under study.
The degrees of crystallinity, determined by using differential scanning calorimetry (DSC), instead, are
lower than those obtained by the other two methods, for all the gel samples, but the aged gels. This
result is due to the occurrence of the gel−sol transition during the heating scan which is characterized
by the endothermic melting of the crystallites and the exothermic solubilization and solvation of PVA
chains in water. In as-prepared and rehydrated gels, the endothermic and exothermic effects overlap,
which leads to an underestimated value of the degree of crystallinity. For aged samples, the crystallites
are larger and more perfect; the corresponding melting endotherms are narrower and shifted toward
higher temperatures, which permits the separation of the endothermic and exothermic effects and leads
to a more accurate measurement of the degree of crystallinity. Thus, the comparative analysis of the
degree of crystallinity in PVA hydrogels measured by different techniques provides indirect information
concerning their complex structure.
Cancer stem cells (CSC) constitute a cell subpopulation in solid tumors that is responsible for resistance to conventional chemotherapy, metastasis and cancer relapse. The natural product Salinomycin can selectively target this cell niche by directly interacting with lysosomal iron, taking advantage of upregulated iron homeostasis in CSC. Here, inhibitors of the divalent metal transporter 1 (DMT1) have been identified that selectively target CSC by blocking lysosomal iron translocation. This leads to lysosomal iron accumulation, production of reactive oxygen species and cell death with features of ferroptosis. DMT1 inhibitors selectively target CSC in primary cancer cells and circulating tumor cells, demonstrating the physiological relevance of this strategy. Taken together, this opens up opportunities to tackle unmet needs in anti‐cancer therapy.
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