Halloysite nanotubes in analytical sciences and in drug delivery: A review.

Halloysite (HNT) is a natural inorganic mineral that has many applications in manufacturing. This review (with 192 references) covers (a) the chemical properties of halloysites, (b) the effects of alkali and acid etching on the loading capacity and the release behavior of halloysites, (c) the use of halloysite nanotubes in analytical sciences and drug delivery, and (d) recent trends in the preparation of magnetic HNTs. Synthetic methods such as co-precipitation, thermal decomposition, and solvothermal method are discussed, with emphasis on optimal magnetization. In the analytical field, recent advancements are summarized in terms of applications of HNT-nanocomposites for extraction and detection of heavy metal ions, dyes, organic pollutants, and biomolecules. The review also covers methods for synthesizing molecularly imprinted polymer-modified HNTs and magnetic HNTs. With respect to drug delivery, the toxicity, techniques for drug loading and the various classes of drug-halloysite nanocomposites are discussed. This review gives a general insight on the utilization of HNT in analytical determination and drug delivery systems which may be useful for researchers to generate new ideas. Graphical abstract Schematic presentation of the structure of halloysite nanotubes, selected examples of modifications and functionalization, and represetative field of applications.

Simple and Efficient Detection Approach of Quercetin from Biological Matrix by Novel Surface Imprinted Polymer Based Magnetic Halloysite Nanotubes Prepared by a Sol-Gel Method.

Molecular imprinted polymers coated magnetic halloysite nanotubes (MHNTs-MIPs) were prepared through sol-gel method by using quercetin (Que), APTES and TEOS as template, monomer and cross-linker agent, respectively. The synthesized MHNTs-MIPs were characterized by fourier transform infrared, scanning electron microscope, transmission electron microscope, XRD and vibrating sample magnetometer. Various parameters influencing the binding capacity of the MHNTs-MIPs were investigated with the help of response surface methodology. Selectivity experiments showed that the MHNTs-MIPs exhibited the maximum selective rebinding to Que. Therefore, the MHNTs-MIPs was applied as a solid-phase extraction adsorbent for the extraction and preconcentration of quercetin and luteolin in serum and urine samples. The limits of detection for quercetin and luteolin range from 0.51 to 1.32 ng mL-1 in serum and from 0.23 to 1.05 ng mL-1 in urine, the recoveries are between 95.20 and 103.73% with the RSD less than 5.77%. While the recovery hardly decreased after several cycles. The designed MHNTs-MIP with high affinity, sensitivity and maximum selectivity toward Que in SPE might recommend a novel method for the extraction of flavonoids in other samples like natural products.

Folic acid-conjugated chitosan oligosaccharide-magnetic halloysite nanotubes as a delivery system for camptothecin.

In this research, to achieve enhanced intracellular uptake of anticancer drug carriers for efficient chemotherapy, folic acid conjugated chitosan oligosaccharides assembled magnetic halloysite nanotubes (FA-COS/MHNTs) have been tailored as multitask drug delivery system towards camptothecin (CPT). Besides magnetic targeting, the nanocomposites have been reacted with folate complex in order to selectively target cancer cells over expressing the folic acid receptor. HNTs showed to have a high storage capacity of CPT. In vitro, the release results indicated that CPT outflow from the nanocarriers at pH 5 was much greater than that at both pH 6.8 and 7.4. MTT assays showed that the CPT-loaded nanocarriers exhibited stronger cell growth inhibitory against colon cancer cell. Furthermore, nanocarriers gained specificity to target cancer cells because of the enhanced cell uptake mediated by FA moiety and presence of COS. Therefore, the rational designed HNTs nanocarrier for chemotherapy drug showed great potential as tumor-targeted drug delivery carrier.