Magnetothermally-responsive nanocarriers using confined phosphorylated halloysite nanoreactor for in situ iron oxide nanoparticle synthesis: A MW-assisted solvothermal approach

A family of easily recoverable magnetic and thermally responsive composite materials, with nanoscale dimensions, were synthesized by a rapid and simple solvothermal approach. The synthesis was thermally activated, accelerated, and controlled using a coaxial antenna to directly apply the microwave energy inside the solvothermal reactor. The composite materials were made up by a confined phosphorylated nanoreactor, namely halloysite nanotubes grafted on the inner lumen with phosphoric acid (HNTs-(H+-PO4)), that promoted the urea hydrolysis thus favoring the formation of a local alkaline environment to catalyze the homogeneous in situ precipitation of superparamagnetic iron oxide nanoparticles (IONs) selectively on their inner or outer surface. Two new MW-assisted solvothermal methodologies were used: 1) in the first the solvent is directly loaded into the MW-assisted reactor together with HNTs-(H+-PO4) mechanically preloaded with iron chloride and urea in the lumen 2) in the second the synthesis is preceded by a further pre-functionalization step of the iron salt with clove essential oil (EO) as a green functionalization agent. Structural, morphological, textural, and magnetic properties were assessed by TEM, N2 physisorption, TG-FTIR, ICP, XRD, magnetic and magnetic hyperthermia measurements. The MW-assisted solvothermal deposition of IONs was fully controlled using the phosphorylated nanoreactor, in short synthesis times, by a simple methodology following the principles of sustainable chemistry. IONs were selectively deposited on the outer surface or in the inner lumen of HNTs yielding easily recoverable superparamagnetic and thermally responsive nanocarriers suitable for applications like targeted hyperthermia therapy. [Display omitted] •in-situ urea hydrolysis and IONs deposition were promoted by HNTs-(H+-PO4) nanoreactor.•Selective deposition of magnetic IONs in the inner or outer surfaces of HNTs-(H+-PO4).•Good heating response of magnetic nanocomposites under a remotely applied magnetic field.•Green, fast and simple MW-assisted solvothermal deposition methodologies.•Magnetic and thermally responsive nanocarriers suitable for applications like targeted hyperthermia.