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.
A simplified procedure to synthesize zwitterionic cellulose by means of N-protected aspartic anhydride under mild conditions was developed. The preparation of modified cellulose samples was carried out under heterogeneous, aqueous conditions by reacting NH4OH-activated cellulose with aspartic anhydrides N-protected with trifluoroacetyl (TFAc) and carbobenzyloxy (Cbz). Modified cellulose samples Cel-Asp-N-TFAc and Cel-Asp-N-Cbz were characterized by Fourier Transform Infrared (FTIR) and 13C solid state Nuclear Magnetic Resonance (NMR) spectroscopy. The functionalization degree of each cellulose sample was determined by the 13C NMR signal integration values corresponding to the cellulose C1 vs. the Cα of the aspartate residue and corroborated by elemental analysis. In agreement, both analytical methods averaged a grafting degree of 20% for Cel-Asp-N-TFAc and 16% for Cel-Asp-N-Cbz. Conveniently, Cel-Asp-N-TFAc was concomitantly partially N-deprotected (65%) as determined by the ninhydrin method. The zwitterion character of this sample was confirmed by a potentiometric titration curve and the availability of these amino acid residues on the cellulose was inspected by adsorption kinetics method with a 100 mg L−1 cotton blue dye solution. In addition, the synthesis reported in the present work involves environmentally related advantages over previous methodologies developed in our group concerning to zwitterionic cellulose preparation.
To design the properties of a copolymer using free radical polymerization, a semicontinuous process can be applied to vary the instantaneous copolymer composition along the conversion searching for a specific composition spectrum of copolymer chains, which can be termed as weight composition distribution (WCD) of copolymer chains. Here, the styrene-n-butyl acrylate (S/BA) system was polymerized by means of a semicontinuous emulsion process, varying the composition of the comonomer feed to obtain forced composition copolymers (FCCs). Five different feeding profiles were used, searching for a scheme to obtain chains rich in S (looking for considerable modulus), and chains rich in BA (looking for large deformation) as a technique to achieve synergy in copolymer properties; the mechanostatic and dynamic characterization discloses the correspondence between WCD and the bulk properties. 1H-nuclear magnetic resonance (1H-NMR) analysis enabled the determination of the cumulative copolymer composition characterization, required to estimate the WCD. The static test (stress-strain) and dynamic mechanical analysis (DMA) were performed following normed procedures. This is the first report that shows very diverse mechanostatic performances of copolymers obtained using the same chemical system and global comonomer composition, forming a comprehensive failure envelope, even though the tests were carried out at the same temperature and cross head speed. The principles for synergic performance can be applied to controlled radical copolymerization, designing the composition variation in individual molecules along the conversion.