Is 1.8V the only permissible VCCIO on the PS Banks? Can this be changed to 3.3V after power up?

In G57M - Versal AI Edge SOM, PMIC’s BUCK 3 cannot be changed to 3.3V since this is also used to power other on-SOM interfaces which are fixed to 1.8V.

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Please find the detailed product information here:
Versal™ AI Edge System on Module