Direct Raman measurement of an elevated base pKa in the active site of a small ribozyme in a precatalytic conformation
作者： Man Guo , Robert C. Spitale , Rosaria Volpini , Jolanta Krucinska , Gloria Cristalli
DOI: 10.1021/JA9060883
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摘要: Catalytic RNA molecules can achieve rate acceleration by shifting base pKa values toward neutrality. Prior evidence has suggested that A38 of the hairpin ribozyme plays an important role in phosphoryl transfer, possibly functioning as a general acid, or orienting specific water molecule for proton transfer. To address A38, we used Raman spectroscopy to measure directly N1-imino moiety context crystals representative “precatalytic” conformation. The results revealed is shifted 5.46 ± 0.05 relative 3.68 0.06 derived from reference solution nucleotide AMP. elevated correlates well with first titration point macroscopic pH−rate profile and strongly supports acid catalyst bond scission. confirm protonated before transition state, which would promote phosphorane development. Overall, establish ...
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