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For an example showing you how to find the information you need to work with assemblies, see:
For detailed information, see:
If MATLAB® does not automatically load your assembly, use the NET.addAssembly function. The syntax is:
asmInfo = NET.addAssembly('assemblyName');
You need to know if the assembly is global or private, as explained in What is an Assembly? Your vendor documentation has this information.
You cannot unload an assembly from MATLAB.