See PInvoke.net for more detail
   [DllImport("urlmon.dll", CharSet = CharSet.Unicode, ExactSpelling = true, SetLastError = false)]
    static extern int FindMimeFromData(IntPtr pBC,
          [MarshalAs(UnmanagedType.LPWStr)] string pwzUrl,
         [MarshalAs(UnmanagedType.LPArray, ArraySubType=UnmanagedType.I1, SizeParamIndex=3)] 
        byte[] pBuffer,
          int cbSize,
             [MarshalAs(UnmanagedType.LPWStr)]  string pwzMimeProposed,
          int dwMimeFlags,
          out IntPtr ppwzMimeOut,
          int dwReserved);
Sample usage:
  public string MimeTypeFrom(byte[] dataBytes, string mimeProposed) {
   if (dataBytes == null)
     throw new ArgumentNullException("dataBytes");
   string mimeRet = String.Empty;
   IntPtr suggestPtr = IntPtr.Zero, filePtr = IntPtr.Zero, outPtr = IntPtr.Zero;
   if (mimeProposed != null && mimeProposed.Length > 0) {
     //suggestPtr = Marshal.StringToCoTaskMemUni(mimeProposed); // for your experiments ;-)
     mimeRet = mimeProposed;
   }
   int ret = FindMimeFromData(IntPtr.Zero, null, dataBytes, dataBytes.Length, mimeProposed, 0, out outPtr, 0);
   if (ret == 0 && outPtr != IntPtr.Zero) {
    //todo: this leaks memory outPtr must be freed
     return Marshal.PtrToStringUni(outPtr);
   }
   return mimeRet;
}
// call it this way:
Trace.Write("MimeType is " + MimeTypeFrom(Encoding.ASCII.GetBytes("%PDF-"), "text/plain"));
Another example:
/// <summary>
/// Ensures that file exists and retrieves the content type 
/// </summary>
/// <param name="file"></param>
/// <returns>Returns for instance "images/jpeg" </returns>
public static string getMimeFromFile(string file)
{
    IntPtr mimeout;
    if (!System.IO.File.Exists(file))
    throw new FileNotFoundException(file + " not found");
    int MaxContent = (int)new FileInfo(file).Length;
    if (MaxContent > 4096) MaxContent = 4096;
    FileStream fs = File.OpenRead(file);
    byte[] buf = new byte[MaxContent];        
    fs.Read(buf, 0, MaxContent);
    fs.Close();
    int result = FindMimeFromData(IntPtr.Zero, file, buf, MaxContent, null, 0, out mimeout, 0);
    if (result != 0)
    throw Marshal.GetExceptionForHR(result);
    string mime = Marshal.PtrToStringUni(mimeout);
    Marshal.FreeCoTaskMem(mimeout);
    return mime;
}