Mesoporous Networks of N-Vinylpyrrolidone with (di)Methacrylates as Precursors of Ecological Molecular Imprinted Polymers

Abstract

Mesoporous polymer networks were prepared via the cross-linking radical copolymerization of non-toxic hydrophilic N-vinylpyrrolidone (VP) with triethylene glycol dimethacrylate (TEGDM) and poly(ethylene glycol) methyl ester methacrylate (PEGMMA) in bulk, using appropriate soluble and thermodynamically compatible macromolecular additives with a branched structure as porogens. The branched copolymers of various monomer compositions were obtained by radical copolymerization in toluene, controlled by 1-decanethiol, and these materials were characterized by a wide set of physical chemical methods. The specific surface areas and surface morphology of the polymer networks were determined by nitrogen low-temperature adsorption or Rose Bengal (RB) sorption, depending on the copolymer compositions and scanning electron microscopy. The electrochemical properties of RB before and after its encapsulation into a branched VP copolymer were studied on a glassy carbon electrode and the interaction between these substances was observed. Quantum chemical modeling of RB-VP or RB-copolymer complexes has been carried out and sufficiently strong hydrogen bonds were found in these systems. The experimental and modeling data demonstrate the high potency of such mesoporous polymer networks as precursors of molecularly imprinted polymers for the recognition of fluorescent dyes as nanomarkers for biomedical practice.

New Nanosized Systems Doxorubicin—Amphiphilic Copolymers of N-Vinylpyrrolidone and (Di)methacrylates with Antitumor Activity

“…When the components of a working solution and electrodes were introduced into the cell, as well as during the electrochemical measurements, a slight excess argon pressure (~20 mbar) was maintained above the solutions. The standard Schlenk procedure [44,[53][54][55] was used for it. All the experiments were performed at a room temperature in PBS with pH 7.24, and the range of the potential scan rate was 10-2000 mV•s -1 .…”

“…Therefore, we added one more stage into the electrode preparation before experiments, namely, its cleaning with H 2 SO 4 /H 2 O 2 admixture followed by an ethyl alcohol washing. A detailed description of the CVA experiments can be found elsewhere [44,53,57].…”

“…The branched nature of the VP-MAA-TEGDM copolymer was demonstrated in [52] through an analysis of the dependence of M w on the eluent volume V r and root-mean-square radii of gyration on M w values and comparison with those for linear PVP. The VP-TEGDM copolymer was characterized by IR spectroscopy and NMR spectroscopy [53]. In the VP-MAA-TEGDM spectrum, absorption bands at wavenumbers ~1720 and ~1665 cm −1 , respectively, corresponding to the stretching vibrations of C=O groups in (di)methacrylate and VP units were observed (Figure 3a).…”

“…Molecular electrochemistry now is closely interfaced with medicinal chemistry, especially in the case of quinones [72]. Voltammetry allows obtaining additional information about the properties of nanosystems as encapsulated into (co)polymer electrochemical active compounds [44,45,53,57,73], especially if their free (molecular) and encapsulated forms differ substantially with energetic characteristics, see, e.g., [45,52,57].…”

“…Figure 2. TEM image of VP-TEGDM copolymer[53]. It was obtained from the aqueous solution (0.1 mg mL −1 ) using Leo 912 AB equipment (Leo Electron, Oberkochen, Germany).…”