Herein, we report the functionalization of carbon nano-onions (CNOs) with the hydroxyaryl group and subsequent modifications with resins: resorcinol–formaldehyde using porogenic Pluronic F-127, resorcinol–formaldehyde-melamine, benzoxazine made of bisphenol A and triethylenetetramine, and calix[4]resorcinarene-derived using F-127. Following the direct carbonization, extensive physicochemical analysis was carried out, including Fourier transform infrared, Raman and X-ray photoelectron spectroscopy, scanning and transmission electron microscopy, and adsorption–desorption of N2. The addition of CNO to the materials significantly increases the total pore volume (up to 0.932 cm3 g−1 for carbonized resorcinol–formaldehyde resin and CNO (RF-CNO-C) and 1.242 cm3 g−1 for carbonized resorcinol–formaldehyde-melamine resin and CNO (RFM-CNO-C)), with mesopores dominating. However, the synthesized materials have poorly ordered domains with some structural disturbance; the RFM-CNO-C composite shows a more ordered structure with amorphous and semi-crystalline regions. Subsequently, cyclic voltammetry and galvanostatic charge–discharge method studied the electrochemical properties of all materials. The influence of resins' compositions, CNO content, and amount of N atoms in carbonaceous skeleton on the electrochemical performance was studied. In all cases, adding CNO to the material improves its electrochemical properties. The carbon material derived from CNO, resorcinol and melamine (RFM-CNO-C) showed the highest specific capacitance of 160 F g−1 at a current density of 2 A g−1, which is stable after 3000 cycles. The RFM-CNO-C electrode retains approximately 97% of its initial capacitive efficiency. The electrochemical performance of the RFM-CNO-C electrode results from the hierarchical porosity's stability and the presence of nitrogen atoms in the skeleton. This material is an optimal solution for supercapacitor devices.
A series of 6,6-dihalo-2-azabicyclo[3.1.0]hexane and 7,7-dihalo-2-azabicyclo[4.1.0]heptane compounds were prepared by the reaction of dihalocarbene species with N-Boc-2,3-dihydro-1H-pyrroles or -1,2,3,4-tetrahydropyridines. Monochloro substrates were synthesised as well, using a chlorine-to-lithium exchange reaction. The behaviour of several aldehydes and ketones under reductive amination conditions with deprotected halogenated secondary cyclopropylamines was investigated, showing that this transformation typically triggers cyclopropane ring cleavage to give access to interesting nitrogen-containing ring-expanded products.
Background: In recent years, targeted drug delivery strategies have received special attention from the scientific world due to advantages such as more effective therapy and reduction of side effects. The principle of operation is delayed excretion from the bloodstream of the drug delivery system compared to the drug itself, as well as facilitated penetration into diseased cells thanks to the use of ligands recognized by appropriate receptors. Particularly interesting drug carriers are amphiphilic copolymers that form nano-sized micelles with a drug, which can release the drug at a specific place in the body under the influence of appropriate stimuli. Results: We describe the synthesis of the diblock polymer, poly(2-hydroxyethyl acrylate)-b-poly(N-vinylcaprolactam) using RAFT/MADIX (Reversible Addition-Fragmentation chain Transfer/MAcromolecular Design by Interchange of Xanthate) controlled polymerization affording polymers with good dispersity according to SEC (Size-Exclusion Chromatography). Some post-modifications of the polymer with folic acid were then performed as evidenced by NMR (Nuclear Magnetic Resonance), UV–Vis (UltraViolet–Visible) and FT-IR (Fourier-Transform Infrared) spectroscopy, and TGA (ThermoGravimetric Analysis). The formation of stable micellar systems from polymers with and without the drug, 5-fluorouracil, was confirmed by DLS (Dynamic Light Scattering) and zeta potential measurements, and TEM (Transmission Eelectron Microscopy) imaging. Finally, the cloud point of the polymers was investigated, which turned out to be close to the temperature of the human body. Most importantly, these micellar systems have been explored as a drug delivery system against colon cancer, showing increased cytotoxicity compared to the drug alone. This effect was achieved due to the easier cellular uptake by the interaction of folic acid and its receptors on the surface of cancer cells. Conclusions: The presented results constitute a solid foundation for the implementation of a nano-sized drug delivery system containing folic acid for practical use in the treatment of drug-resistant cancer, as well as more effective therapy with fewer side effects. Graphical
Colorectal cancer is the fourth most common cancer worldwide and the third most frequently diagnosed form of cancer associated with high mortality rates. Recently, targeted drug delivery systems have been under increasing attention owing to advantages such as high therapeutic effectiveness with a significant depletion in adverse events. In this report, we describe the biocompatible and thermoresponsive FA-conjugated PHEA-b-PNIPAAm copolymers as nanocarriers for the delivery of 5-FU. The block copolymers were obtained using RAFT (Reversible Addition–Fragmentation chain Transfer) polymerization and were characterized by methods such as SEC (Size Exclusion Chromatography), NMR (Nuclear Magnetic Resonance), UV–Vis (Ultraviolet–Visible), FT-IR (Fourier Transform Infrared) spectroscopy, and TGA (Thermogravimetric Analysis). Nanoparticles were formed from polymers with and without the drug-5-fluorouracil, which was confirmed using DLS (Dynamic Light Scattering), zeta potential measurements, and TEM (Transmission Electron Microscopy) imaging. The cloud points of the polymers were found to be close to the temperature of the human body. Eventually, polymeric carriers were tested as drug delivery systems for the safety, compatibility, and targeting of colorectal cancer cells (CRC). The biological evaluation indicated high compatibility with the representative host cells. Furthermore, it showed that proposed nanosystems might have therapeutic potential as mitigators for 5-FU-induced monocytopenia, cardiotoxicity, and other chemotherapy-associated disorders. Moreover, results show increased cytotoxicity against cancer cells compared to the drug, including a line with a drug resistance phenotype. Additionally, the ability of synthesized carriers to induce apoptosis and necrosis in treated CRC cells has been confirmed. Undoubtedly, the presented aspects of colorectal cancer therapy promise future solutions to overcome the conventional limitations of current treatment regimens for this type of cancer and to improve the quality of life of the patients.
The organization of specific pores in carbonaceous three-dimensional networks is crucial for efficient electrocatalytic processes and electrochemical performance. Therefore, the synthesis of porous materials with ordered and well-defined pores is required in this field. The incorporation of carbon nanostructures into polymers can create material structures that are more ordered in comparison to those of the pristine polymers. In this study we applied polymer-templated methods of carbon material preparation, in which outer blocks of the star copolymers form the carbon skeleton, while the core part is pore-forming. Well-defined 6-star-(poly(methyl acrylate)-b-poly(4-acetoxystyrene)) dendrimers were synthesized by reversible addition–fragmentation chain-transfer polymerization. They were then transformed into poly(4-vinylphenol) derivatives (namely 6-star-(poly(methyl acrylate)-b-poly(4-vinylphenol)), subjected to polycondensation with formaldehyde, and pyrolyzed at 800 °C. Cross-linking of phenolic groups provides a polymer network that does not depolymerize by pyrolysis, unlike poly(methyl acrylate) chains. The selected star polymers were attached to carbon nano-onions (CNOs) to improve the organization of the polymer chains. Herein, the physicochemical properties of CNO-polymer hybrids, including the textural and the electrochemical properties, were compared with those of the pristine pyrolyzed polymers obtained under analogous experimental conditions. For these purposes, we used several experimental and theoretical methods, such as infrared, Raman, and X-ray photoelectron spectroscopy, nitrogen adsorption/desorption measurements, scanning and transmission electron microscopy, and electrochemical studies, including cyclic voltammetry. All of the porous materials were evaluated for use as supercapacitors.
Catalysis of the cyclotrimerisation of alkynes with the Ti(OiPr) 4 / n BuLi system was studied, leading to the development of a particularly convenient and reliable protocol.