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It's not possible to say based on our current knowledge. It is likely that the earliest forms of life replicated using RNA rather than DNA.

In glass vessels in the Lab we have, not all that easily, combined substances that produced Rna particles capable of, if not self-replication, then the replication of other Rna strands in the same solution.

With DNA being as fragile as a strand of fiberglass, and as such it cannot exist without being wound around histone proteins, this shows that Rna Way came first.

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