Low Barrier Hydrogen Bonds: Getting Close, but Not Sharing...

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Low Barrier Hydrogen Bonds: Getting Close, but Not Sharing...

Hydrogen bonding represents one of the primary interactions controlling chemical structure and reactivity. The properties of H-bonds are predicted to vary with the distance between the H-donor and H-acceptor, Figure 1, from a canonical structure (>2.5 Å, Figure 1A), in which the proton resides within a double welled structure, to one in which the proton has become fully delocalized within a sin...

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Strong, low-barrier hydrogen bonds may be available to enzymes.

The debate over the possible role of strong, low-barrier hydrogen bonds in stabilizing reaction intermediates at enzyme active sites has taken place in the absence of an awareness of the upper limits to the strengths of low-barrier hydrogen bonds involving amino acid side chains. Hydrogen bonds exhibit their maximal strengths in isolation, i.e., in the gas phase. In this work, we measured the i...

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On the electronic nature of low-barrier hydrogen bonds in enzymatic reactions.

The electronic nature of low-barrier hydrogen bonds (LBHBs) in enzymatic reactions is discussed based on combined low temperature neutron and x-ray diffraction experiments and on high level ab initio calculations by using the model substrate benzoylacetone. This molecule has a LBHB, as the intramolecular hydrogen bond is described by a double-well potential with a small barrier for hydrogen tra...

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ژورنال

عنوان ژورنال: ACS Central Science

سال: 2015

ISSN: 2374-7943,2374-7951

DOI: 10.1021/acscentsci.5b00215