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Chemistry |
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Authors: Sosale Chandrasekhar
The titled concept has not been broached so far, and arises from the fact that bond angle strain increases as the square of the concerned angle (torsional strain also behaving similarly). Macrocyclic systems can thus accumulate less overall strain than smaller systems, whether in the ground state or transition state. Although strain delocalisation is generally overridden by forbidding entropic barriers in macrocyclization reactions, strain delocalisation may well be important in enzyme catalysis. This is because entropic effects are largely minimised within the organized interior of an enzyme molecule, so that preferred reaction trajectories are more easily achieved. (Strain delocalisation would also play a role in duplex formation in nucleic acids.)
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[v1] 2020-06-17 10:59:00
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