Recent studies have revealed two distinct pathways for the DNA overstretching transition near 65 pN: ‘unpeeling’ of one strand from the other, and a transition from B-DNA to an elongated double-stranded ‘S-DNA’ form. However, basic questions concerning the dynamics of these transitions, relative stability of the two competing overstretched states, and effects of nicks and free DNA ends on overstretching, remain open. In this study we report that: (i) stepwise extension changes caused by sequence-defined barriers occur during the strand-unpeeling transition, whereas rapid, sequence-independent extension fluctuations occur during the B to S transition; (ii) the secondary transition that often occurs following the overstretching transition is strand-unpeeling, during which the extension increases by 0.01–0.02 nm per base pair of S-DNA converted to single-stranded DNA at forces between 75 and 110 pN; (iii) even in the presence of nicks or free ends, S-DNA can be stable under physiological solution conditions; (iv) distribution of small GC-rich islands in a large DNA plays a key role in determining the transition pathways; and (v) in the absence of nicks or free ends, torsion-unconstrained DNA undergoes the overstretching transition via creation of S-DNA. Our study provides a new, high-resolution understanding of the competition between unpeeling and formation of S-DNA.
The
high energy density, low cost, and environmental friendliness
of lithium–sulfur (Li–S) batteries enable them to be
promising next-generation energy storage systems. However, the commercialization
of Li–S batteries is presently hindered by the bottlenecks,
such as the low conductivity of sulfur species, shuttle effect of
polysulfides, and poor conversion efficiency in discharging/charging
processes. Here, on the basis of first-principles calculations, we
predicted that the two-dimensional magnetic Fe3GeX2 (X = S, Se, and Te) monolayers are quite promising to overcome
the aforesaid problems. The Fe3GeX2 monolayer
has metallic electronic structures and moderate binding strength to
the soluble lithium polysulfides, which are expected to improve the
overall electric conductivity of sulfur species and anchor the soluble
lithium polysulfides to suppress the shuttle effect. Remarkably, Fe3GeX2 monolayers show bifunctional electrocatalytic
activity to the S reduction reaction and the Li2S decomposition
reaction, which improves the conversion efficiency in discharging
and charging processes. This finding may open up an avenue for the
development of high-performance Li–S batteries.
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