One of the main differences between VB6 and VB.NET is that VB.NET is fully object-oriented. Plan on putting some effort into learning object-oriented theory and design to truly take advantage of .NET. Much of what you need to learn is about the .NET Framework, rather than specifically about VB.NET. The syntax in VB.NET will be familiar, but the way to accomplish various tasks is new. Study the .NET Framework. A significant new feature, although it is not strictly a part of .NET, is Web services. You will want to learn about Web services and what they can do for you.
Dig deeper on WCF (Windows Communication Foundation)
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