Preparation of novel molecularly imprinted magnetic graphene oxide and their application for quercetin determination.

In this work, quercetin (Que) molecular imprinted polymer (MIP) material decorated on magnetic graphene oxide (MGO) with high performance was prepared for the first time using a surface-imprinting technique. Magnetic graphene oxide was synthesized using the solvothermal route. Methacrylic acid (MAA) was used as functional monomer, ethylene glycol dimethyl acrylate (EGDMA) as cross-linker; Que. was used as template, for the decoration with MIP. The prepared nanocomposite was examined by different characterization methods including fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), vibrating sample magnetometer (VSM). The adsorption performance was investigated. MGO-MIP was found to have high loading (369 mg g-1) and selective capacity making the nanomaterial more performant than previous similar reported nanomaterials. The determination of Que. was carried out by mean of magnetic solid phase extraction method coupled with high-performance liquid chromatography (HPLC) and the extraction conditions studies were also performed out. Under the optimized conditions, MGO-MIP showed great performance for the extraction, separation and determination of Que. in green tea and serum samples, compared to the flavonoid analogs luteolin (Lut) and rutin (Rut) in the same matrix samples.

Preparation of multifunctional PEG-graft-Halloysite Nanotubes for Controlled Drug Release, Tumor Cell Targeting, and Bio-imaging.

With the intent of enhancing the loading capacity and controlled the release of a low-water soluble drug (quercetin), 6 ar ms (Poly-Ethylene-Glycol)-amine was grafted in the external surface of halloysite nanotubes. The grafted halloysite nanotubes (HNTs-g-PEG) were decorated with carbon quantum dots for additive fluorescents properties. Conjointly, biotin was conjugated to PEG's free amine groups for precise targeting of tumor tissue and higher cellular uptake. The obtained nanoparticles were characterized by the FTIR, TEM, XRD, zeta potential and TGA analysis. The photoluminescence (PL) properties were investigated by firstly, observing under UV-light at 365 nm; then, the fluorescence spectra of modified HNTs at different levels of preparation were obtained and showed a suitable blue fluorescence. Furthermore, the fluorescent properties were demonstrated by the optical image of HNTs-g-PEG-CDs-Biotin obtained from the confocal microscope, which could be interesting for both in vitro and in vivo imaging. Besides, the prepared NPs showed a superior loading capacity of Que (278.36 mg/g) at optimal adsorption conditions comparing to pristine HNTs. The in vitro drug release from these NPs was relatively sustained and pH sensitive. The incubation of the prepared HNTs-g-PEG-CDs-Biotin NPs with HeLa cells showed a low toxicity and a suitable biocompatibility. The MTT assay of the Que-loaded NPs possesses enhanced antitumor activity over the free Que.

QbD approach by computer aided design and response surface methodology for molecularly imprinted polymer based on magnetic halloysite nanotubes for extraction of norfloxacin from real samples.

This article describes the development, optimization, and evaluation of a novel composite imprinted polymer, on the basis of magnetic halloysite nanotubes (MHNTs-MIPs) using "Quality by Design (QbD)" approach combining computer simulation and response surface methodology. Norfloxacin, methacrylic acid, and ethylene glycol dimethacrylate were used as template, functional monomer and cross-linker, respectively. As a comparison, two MHNTs-MIPs have been prepared with the most suitable functional monomer methacrylic acid (MAA) along with acrylamide (AM). To explain the adsorption behavior, adsorption kinetics and isotherms were studied. Magnetic halloysite nanotubes molecularly imprinted polymers prepared from MAA (MHNTs-MIP1) displayed a high adsorption capacity (349 µg mg-1) toward NOR. A magnetic imprinting solid phase extraction method coupled with high performance liquid chromatography (MHNTs-MISPE-HPLC-UV) was developed for the determination of NOR in serum and water samples, by applying MHNTs-MIP as a sorbent. The recoveries from 83.76% to 103.30% in water and from 90.46% to 99.78% in serum were obtained. Besides remarquable mechanical properties and specific recognition of MHNTs-MIP toward template molecule. It could be also collected and separated fastly by external magnetic field. Moreover, MHNTs-MIPs could be reused for several cycles with the recovery range from 83.25% to 100.96% for water sample and from 85.65% to 100.33% for serum sample. These analytical results of serum and water samples showed that the proposed method based on MHNTs-MIPs is applicable for fast and selective extraction of therapeutic agents from biological fluids and environmental water.

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.