Synthesis of Poly(L-lactide)-poly(ε-caprolactone)-poly(ethylene glycol) Terpolymer Grafted onto Partially Oxidized Carbon Nanotube Nanocomposites for Drug Delivery.

Nanocomposites prepared with a terpolymer of poly(L-lactide) (PLLA)-poly(ε-caprolactone) (PCL)-poly(ethylene glycol) (PEG) and partially oxidized carbon nanotubes (CNTspo) were synthesized and characterized to evaluate their ability to act as an effective nanocarrier of the anticancer drug methotrexate. The homopolymers of PLLA and PCL were synthesized through ring-opening polymerization (ROP) and characterized through gel permeation chromatography (GPC). The PLLA-PCL-PEG terpolymers were synthesized through a four-step chemical route using oxalyl chloride as a linker agent and analyzed with 1H-NMR, 13C-NMR, and FTIR spectroscopies. Additionally, the nanocomposites were characterized through FTIR, and X-ray photoelectron spectroscopy (XPS), as well as the differential scanning calorimetry (DSC) technique. XPS analysis revealed that PLLA-PCL-PEG terpolymer chains are grafted onto CNTspo. Moreover, evaluations through FTIR and DSC strongly suggest that the PCL-rich domains are preferentially oriented toward CNTspo. The release tests exhibited a "burst effect" profile, which was more evident in the terpolymers than in the nanocomposites. Five models were used to assess methotrexate's in vitro release. For the nanocomposites, the best fit to the experimental data was obtained using the first-order model, whereas the results obtained from the Korsmeyer-Peppas model indicated that Fickian diffusion drives methotrexate's release.

Synthesis and Evaluation of Antifungal and Antibacterial Abilities of Carbon Nanotubes Grafted to Poly(2-hydroxyethyl methacrylate) Nanocomposites.

Developing nanomaterials with the capacity to restrict the growth of bacteria and fungus is of current interest. In this study, nanocomposites of poly(2-hydroxyethyl methacrylate) (PHEMA) and carbon nanotubes (CNTs) functionalized with primary amine, hydroxyl, and carboxyl groups were prepared and characterized. An analysis by Fourier-transform infrared (FT-IR) spectroscopy showed that PHEMA chains were grafted to the functionalized CNTs. X-ray photoelectron spectroscopy suggested that the grafting reaction was viable. The morphology of the prepared nanocomposites studied by field-emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) showed significant changes with respect to the observed for pure PHEMA. The thermal behavior of the nanocomposites studied by differential scanning calorimetry (DSC) revealed that the functionalized CNTs strongly affect the mobility of the PHEMA chains. Tests carried out by thermogravimetric analysis (TGA) were used to calculate the degree of grafting of the PHEMA chains. The ability of the prepared nanocomposites to inhibit the growth of the fungus Candida albicans and the bacteria Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli was evaluated. A reduced antifungal and antibacterial capacity of the prepared nanocomposites was determined.

Semi-Continuous Heterophase Polymerization to Synthesize Poly(methacrylic acid)-Based Nanocomposites for Drug Delivery.

The design of nanocomposites with the potential for drug delivery is a topic of great interest. In this work, the synthesis of nanocomposites of poly(methacrylic acid) (PMAA) grafted onto carbon nanotubes (CNTs) functionalized with poly(amidoamine) (PAMAM) dendrimer by semicontinuous heterophase polymerization SHP, at three different methacrylic acid (MAA) dosing rates, is reported. SHP is a polymerization technique poorly used to prepare nanocomposites containing CNTs and has the potential to produce more ordered alkyl methacrylic polymer chains, which could favor the obtaining of a homogenous nanocomposite. For the nanocomposites synthesized, a lowest addition rate monomer-starved condition was reached. Analysis by X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TGA) demonstrate that functionalized CNTs are grafted onto the PMAA matrix. The ability of prepared nanocomposites to deliver hydrocortisone was evaluated by ultraviolet-visible spectroscopy (UV-Vis). The hydrocortisone release profiles of pure PMAA and of their nanocomposites prepared at the lowest monomer fed rate were fitted with Higuchi and Korsmeyer-Peppas models, successfully. Functionalized CNTs have a crucial role to induce an effective release of hydrocortisone from the prepared nanocomposites.

Synthesis of Poly(methacrylic acid-co-butyl acrylate) Grafted onto Functionalized Carbon Nanotube Nanocomposites for Drug Delivery.

Design of a smart drug delivery system is a topic of current interest. Under this perspective, polymer nanocomposites (PNs) of butyl acrylate (BA), methacrylic acid (MAA), and functionalized carbon nanotubes (CNTsf) were synthesized by in situ emulsion polymerization (IEP). Carbon nanotubes were synthesized by chemical vapor deposition (CVD) and purified with steam. Purified CNTs were analyzed by FE-SEM and HR-TEM. CNTsf contain acyl chloride groups attached to their surface. Purified and functionalized CNTs were studied by FT-IR and Raman spectroscopies. The synthesized nanocomposites were studied by XPS, 13C-NMR, and DSC. Anhydride groups link CNTsf to MAA-BA polymeric chains. The potentiality of the prepared nanocomposites, and of their pure polymer matrices to deliver hydrocortisone, was evaluated in vitro by UV-VIS spectroscopy. The relationship between the chemical structure of the synthesized nanocomposites, or their pure polymeric matrices, and their ability to release hydrocortisone was studied by FT-IR spectroscopy. The hydrocortisone release profile of some of the studied nanocomposites is driven by a change in the inter-associated to self-associated hydrogen bonds balance. The CNTsf used to prepare the studied nanocomposites act as hydrocortisone reservoirs.