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Most likely, you are saving as a PNG-8 (which has a maximum of 256 colors) and not PNG-24.
When you save for web with photoshop, make sure the dialog that comes up is set to PNG-24.
Based on your screen capture... I think you may be able to use PNG-8 but your current settings are restricting it to too few colours... or you have web-snap set to 100%
Try those and let me know...
Mike.
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