In this study, we present proof of concept applications of MQ-SC experiments on powdered and their respective vitrified solution species counterparts, along with a novel calcium phosphate time stabilized prenucleation system. We focus first on both discrete and extended 31 P dipolar coupled systems for spin counting studies, demonstrated respectively for molecular adenosine triphosphate (ATP), amorphous calcium phosphate (ACP) and crystalline hydroxyapatite (HAp) (Ca 5 (PO 4 ) 3 OH), where ACP is an amorphous precursor to HAp in the crystallization pathway of calcium phosphate 66 . We then discuss experiments with a modified simulated body fluid (mSBF) shown to contain calcium phosphate prenucleation clusters , which spontaneously phase transform and aggregate to form ACP . We have prepared our samples according to common dynamic nuclear polarization (DNP) sample preparation practices. DNP typically utilizes stable bi-radicals (in our study, AMUPol) by saturating the EPR resonance of a sub-population of the bi-radicals via microwave irradiation to transfer polarization to nuclear spins of the solvent, resulting in significant signal enhancements . All samples were prepared for vitrification in a solution of 6:3:1 parts by volume glycerol-d8, D 2 O, and H 2 O respectively with 10 mM (Figure and 2) / 6.67 mM (Figure ) AMUPol (referred to as DNP juice). Samples were first prepared in 100 % H For our study, we disregard the potential impact of the paramagnetic polarizing and glassing agents on the reaction pathway, given that the chemical shift between powdered and vitrified samples closely align for HAp, ACP, and ATP samples (Figure and). The effect of glycerol on the non-classical growth pathway to form ACP from modified simulated body fluid (mSBF) samples containing PNCs cannot be verified given that there is no powder sample for comparison. We found that glycerol can increase the solubility of ACP at lower calcium and phosphate concentrations (verified by DLS, solution NMR, and ssNMR not shown in this paper), but the systematic and mechanistic study of the role of glycerol in modulating the equilibrium or kinetics of the non-classical growth pathway of ACP is outside the scope of this study . Here, we only focus on the question whether DNP-enhanced NMR of manually plunge frozen mSBF samples, en route to ACP solids, can capture vitrified intermediate species in solution state and whether 31 P MQ-SC can identify one or more of these species to be PNC candidates.