The placement of the application depends a bit upon the topology of the network. If your organization uses a virtual...
private network (VPN) and volunteers will be required to connect to the VPN before using the application, place the application's Web front-end in the same location where the VPN terminates. If this is your internal network, it's fine to place the Web front-end there.
If you don't plan to require a VPN connection, however, the DMZ is definitely the right choice, since it ensures that those accessing the application from the public Internet -- including those who attempt to access it without authorization -- won't be able to gain access to other applications or network resources.
The level of access granted to remote users should fall back upon the principle of least privilege; grant them only the access they need to get their jobs done. If there is no business requirement for users to modify data while off-site, there's no need to grant them those permissions. On the other hand, if they do need read access, there are many examples of organizations that expose database-driven applications to external users. Just be sure that you've thought about Web application security as well, since there are a whole other set of concerns involved with properly securing a hosted application.
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