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Computational chemistry

Anion–π contacts are common in the PDB

Lucas X, Bauzá A, Frontera A, et al. · Chemical science · 2016

Open access · cc by · source: Europe PMC

A PDB-wide search finds anion–π interactions in most protein structures, with Asp/Glu carboxylates packing on aromatics and frequent cation–π partners opposite.

Key findings

Thousands of anion–π contacts exist. 61.3% of 62 033 processed PDB structures contain them. Asp/Glu dominate with near-parallel carboxylates; His is the most common protein aromatic, but Tyr rises at interfaces. DNA vs RNA differ in Glu/Asp and base preferences. Opposite-face cation–π and stacking are common, implying cooperativity.

Methodology

Authors scanned the PDB for anion–π pairs among carboxylates, phosphates, and aromatic side chains/nucleobases, classified geometry, tested enrichment statistically, and looked for ternary anion–π–cation and anion–π–π contacts that could cooperate.

Limitations

This is a structural census, not a measured binding free energy for a designed host; predicted cooperativity is inferred from geometry, not from a new titration series.

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