I don't think polysaccharides should smell bad. Did they smell bad at first? If not, then they have probably been contaminated by bacteria. Maybe include some sodium azide, antibacterials or filter sterilize them next time, whichever is most appropriate for your application.
A bad smell indicates a possible bacterial contamination which also indicates that your polysaccaride isolates are already denatured. It is not therefore advisable to use isolates with with that characteristic. On the safer side, you should keep your samples below 4 degrees
Yea. its contaminated, because they are polysaccharides they will be easily contaminated. I think you need to store them -20 or -80 after precipitation. it depends what you want to do with them now, you will have some polysaccharides introduced from the micro-organism.