Investigation of Adsorption Behavior of Anticancer Drug on Zinc Oxide Nanoparticles: A Solid State NMR and Cyclic...

The present study aims to comprehend the adsorption behavior of a set of anticancer drugs namely 5-fluorouracil (5-FU), doxorubicin and daunorubicin on ZnO nanoparticles (ZnO NPs) proposed as drug delivery systems employing solid state (ss) NMR, FTIR and Cyclic Voltammetry (CV) analysis. FTIR and ¹H MAS ssNMR data recorded for bare ZnO nanoparticle confirmed the presence of adsorbed -OH groups on the surface. ¹³C CP-MAS NMR spectra recorded for free and ZnO surface adsorbed drug samples exhibited considerable line broadening and chemical shift changes that complemented our earlier report on UV-DRS and XRD data of surface adsorption in case of 5-FU. Moreover, a remarkable enhancement of ¹³C signal intensity in case of loaded 5-FU was observed. This clearly indicated rigid nature of the drug on the surface allowing efficient transfer of ¹H polarization from the hetero nitrogen of 5-FU to ZnO to form surface hydroxyl (-OH) groups and the same has been observed in the quantum chemical calculations. To further analyze the motional dynamics of the surface adsorbed 5-FU, longitudinal relaxation times (T₁) were quantified employing Torchia method that revealed significant enhancement of ¹³C relaxation rate of adsorbed 5-FU. The enhanced rate suggested an effective role of quadrupolar contribution from ⁶⁷Zn to the ¹³C relaxation mechanism of ZnO_5-FU. The heterogeneous rate constant (k_het), average free energy of activation (∆G^≠) and point of zero charge (PZC) measured for free and drug loaded ZnO NPs samples using CV further support the SS-NMR results.