The selection and material properties update in the Enscape Materials window - this is not a problem. However there are a couple of minor details that can make it confusing:
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The list of materials should scroll so that the current selection is in the middle of the (visible) list: currently you have to scroll to see it (admittedly it is highlighted when you find it)
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When the material list is filtered and the results exclude the current material I think that the current selection should be included, perhaps as an italic entry?
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Similarly, if a new material selection is made from the native application and it does not match the current filter, it will not be seen in the list of materials: I think it should be an exception to the filter and be included.
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After clearing the filter, the list of materials re-populates but in doing so it can (again) hide the current selection out-with the visible list.
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If you are on any of the additional texture tabs (albedo, transparency, bump, reflection) and select another texture in the native application without that tab, you get a confusing blank/empty tab rather than jumping to the General tab for that texture. (It jumps to General if another texture is selected from the pick-list within the dialogue)