When I want to run my python applications from commandline (under ubuntu) I have to be in the directory where is the source code app.py and run the application with command
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Probably you want to symlink to your file location instead of adding another location to the path
chmod +x app.py
ln ~app.py /opt/local/bin/app
...assuming that /opt/local/bin is already in your path,.
Also, do not forget to add the shebang line to the first line of your script:
#!/usr/bin/env python