This kind of role requires a mix of theoretical and architectural understanding so, in your interviewer's shoes I would be asking you about:
- Design patterns
- UML
- Front-end architecture
- N-Tier considerations (difference between a business layer and a data layer, say)
- Database schema concepts (e.g. normalisation)
I would also expect the TA to know the tech inside out so for a web TA I would ask about how AJAX worked both from a theoretical viewpoint and practically given the techs being used (e.g. ASP.NET AJAX Toolkit or Prototype), how the latest techs have helped make a TA's job easier and how they saw the techs improving over the next 2-3 years.
In terms of tools, I would expect a TA to know Visio pretty well but tools like Axure RP Pro are now a much better alternative and you might get brownie points for implementing it.
Have fun!

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