# Polarity-Driven Selective Adsorption of Quercetin on Kaolinite: An Integrated DFT and Monte Carlo Study

## TL;DR

This study explores how quercetin, a poorly soluble drug, selectively binds to different surfaces of kaolinite clay, offering insights for better drug delivery systems.

## Contribution

The first atomistic comparison of quercetin adsorption on kaolinite surfaces using DFT and Monte Carlo methods.

## Key findings

- Quercetin strongly binds to the hydrophilic (001) surface of kaolinite via hydrogen bonds.
- The hydrophobic (00-1) surface shows weaker adsorption dominated by van der Waals forces.
- Charge transfer is significantly higher on the hydrophilic surface, explaining the polarity-driven selectivity.

## Abstract

Quercetin’s therapeutic potential is limited by its poor water solubility and rapid degradation. Natural clay minerals such as kaolinite present sustainable platforms for drug delivery, yet the molecular mechanisms of drug encapsulation are not fully understood. Specifically, the role of kaolinite’s structural polarity, its hydrophilic aluminol (001) and hydrophobic siloxane (00-1) basal surfaces, in selective drug adsorption remains unexplored. This study combines Monte Carlo sampling and Density Functional Theory (DFT) to provide the first quantitative, atomistic comparison of quercetin adsorption on both kaolinite surfaces. The results demonstrate a pronounced polarity-driven selectivity. Strong, exothermic adsorption (−206.65 kJ mol−1) occurs on the hydrophilic (001) surface, stabilized by a network of five hydrogen bonds. In contrast, the hydrophobic (00-1) surface exhibits significantly weaker sorption (−147.16 kJ mol−1), dominated by van der Waals interactions. Charge-transfer analysis shows that the hydrophilic (001) surface exhibits a net charge transfer of −0.198 e, approximately 2.4 times greater than that of the hydrophobic (00-1) surface (−0.083 e), consistent with differential electron density maps and partial density of states. By linking hydrogen bonding and charge transfer to adsorption energy, these results elucidate how surface polarity dictates drug encapsulation. This work establishes a predictive framework for designing kaolinite-based nanocarriers with optimized stability, bioavailability, and controlled release, guiding the development of sustainable drug delivery systems. It is noted that this DFT study models adsorption at 0 K using periodic slab models in a vacuum.