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SAM binds to this complex, and the reaction follows the kinetically preferred pathway.
The lack of a lag-phase at low decanoyl-ACP concentrations suggests that AHL synthesis proceeds via the preferred pathway.
Nevertheless, it is clear that the M06 calculations also support transmetallation as the energetically preferred pathway rather than β-hydride elimination.
Taken together these results support the hypothesis that transmetallation in the σ-alkyl complex is the energetically preferred pathway and proceeds starting from a Pd OH complex, aided by the associated BQ.
At higher butyryl-ACP or octanoyl-CoA concentrations, however, more of the acyl-donor substrate would bind to E shifting the AHL synthesis reaction coordinate toward the kinetically preferred pathway leading to the upward increase in the substrate velocity curve (top pathway in Scheme 1, Figure 5A,D).
If BmaI1 specifically recognizes octanoyl-ACP surface contour, then an altered recognition surface between BmaI1 and a non-native acyl-ACP substrate could potentially influence the rate of acyl-chain release, which could also affect the formation of a stable and productive E·acyl-ACP complex necessary to progress the AHL synthesis reaction along the kinetically preferred pathway.
Similar(35)
The most preferred pathway agrees with the experimentally determined TSE, while the two least preferred pathways differ significantly.
This information can be used to derive preferred pathways for assembling subunits into closed capsids.
Additionally, the motions may have generated preferred pathways in shallow soils for the carrier gas, such as cracks and connections between pores.
Furthermore, the complex structural geology has likely caused strong heterogeneities, e.g. along deep-seated faults that may provide preferred pathways for fluids and thus have locally strong effects on cementation and porosity.
In the Aegean's karstic landscape earthquake fault scarps act as limestone ramparts on which fortifications, citadels and acropoli were constructed, and underlying fault lines were preferred pathways for groundwater movement and egress.
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