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Phosphorothioated DNA acts as an antioxidant in bacteria;moreover,the endogenously chemical modification is of sequence-selectivity and stereo-specificity.For example,all observed phosphorothioations are of Rp-configuration in the DNA phosphate linkages,which may relate to stereochemistry of the enzymes or special structural needs for biological functions,or both.We have extensively investigated conformational space of the non-bridging phosphorothioation in the phosphate diesters.