Previous work identified deoxyribozymes that simultaneously require both Zn2+ and Mn2+ to hydrolyze DNA (1012 rate enhancement). Here we show that in vitro selection in the presence of 10 �M lanthanide ion (Ce3+, Eu3+, or Yb3+) along with 1 mM Zn2+ leads to numerous DNA-hydrolyzing deoxyribozymes that strictly require the lanthanide ion and Zn2+ for catalysis. These DNA catalysts have a range of lanthanide dependences, including some deoxyribozymes that strongly favor one particular lanthanide ion. Intriguingly, two of the Yb3+-dependent deoxyribozymes function well with Yb3+ alone (Kd,app ~10 �M, without Zn2+). In contrast, new selections with Zn2+ or Mn2+ alone, or Zn2+ with Mg2+/Ca2+, led primarily to deoxyribozymes that cleave DNA by deglycosylation and �-elimination rather than hydrolysis. Lanthanide ions warrant consideration as cofactors when identifying new nucleic acid catalysts, especially for applications in which high concentrations of polyvalent metal ion cofactors are undesirable.

Lanthanide ions as required cofactors for DNA catalysts

244th National Meeting (2012)

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