After updating to NX11.01, I am seeing new dialog for part boundary creation. But where is "Remove last Member" button?. If we select a wrong edge while selecting part boundary there seems no way to deselect that.
Expand all groups of the new dialog and check the one that lists the boundary members, there you can select the member to delete, if I remember correctly.
The boundary dialogs are now the same for all boundaries, in NX 10 only the boundary dialogs for planar milling operations were the only old ones.
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I tried to deselect with "shift" key .. and it works. But must be aktive Select Curve (orange beckground). After deselecting member it sometimes jumps to member dialog. So try it.
I worked with planar mill operation, select part boundary, curve selection method
The boudary dialog uses standard NX selection, so in addition to shift-select, be sure to pay attention to the selection filters and intent rules on the selction bar.