| Summary: | The salt-dependent polymorphs of glycine crystals formed from bulk solutions have been a longstanding riddle. In this study, in order to shed fresh light, we studied the effects of seven common salts on primary nucleation of the metastable α-glycine and the stable γ-glycine. Our nucleation experiments and in-depth data analyses enabled us to reveal that (NH<sub>4</sub>)<sub>2</sub>SO<sub>4</sub>, NaCl and KNO<sub>3</sub>, in general, promote γ-glycine primary nucleation very significantly while simultaneously inhibiting α-glycine primary nucleation, thereby explaining why these three salts induce γ-glycine readily. In comparison, Ca(NO<sub>3</sub>)<sub>2</sub> and MgSO<sub>4</sub> also promote γ-glycine and inhibit α-glycine primary nucleation but not sufficiently to induce γ-glycine. More interestingly, Na<sub>2</sub>SO<sub>4</sub> and K<sub>2</sub>SO<sub>4</sub> promote not only γ-glycine but also α-glycine primary nucleation, which is unexpected and presents a rare case where a single additive promotes the nucleation of both polymorphs. As a result, the promoting effects of Na<sub>2</sub>SO<sub>4</sub> and K<sub>2</sub>SO<sub>4</sub> on γ-glycine do not enable γ-glycine nucleation to be more competitive than α-glycine nucleation, with γ-glycine failing to appear. These observations help us to better understand salt-governed glycine polymorphic selectivity.
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