Co-delivery of paclitaxel and etoposide prodrug by human serum albumin and PLGA nanoparticles: synergistic cytotoxicity in brain tumour cells.

The aims of this study were to develop co-delivery systems of paclitaxel (PTX) and etoposide prodrug (4'-O-benzyloxycarbonyl-etoposide, ETP-cbz) based on non-cross-linked human serum albumin (HSA) and poly(lactide-co-glycolide) nanoparticles and to evaluate the synergistic potential of these drugs in vitro. The nanoformulations were prepared by the high-pressure homogenisation technique and characterised using DLS, TEM, SEM, AFM, HPLC, CZE, in-vitro release, and cytotoxicity in human and murine glioma cells. All nanoparticles had 90-150 nm in size and negative ζ-potentials. The Neuro2A cells were the most sensitive to both HSA- and PLGA-based co-delivery systems (IC50 0.024 µM and 0.053 µM, respectively). The drugs' synergistic effect (combination index < 0.9) was observed in the GL261 cells for both types of co-delivery formulations and in the Neuro2A cells for the HSA-based system. These nanodelivery systems may be useful to improve combination chemotherapy for brain tumour treatment. To our knowledge, this is the first report describing the non-cross-linked HSA-based co-delivery nanosuspension which was prepared using nab™ technology.

One-Step Interfacial Integration of Graphene Oxide and Organic Chromophores into Multicomponent Nanohybrids with Photoelectric Properties.

A one-step protocol for interfacial self-assembly of graphene oxide (GO), glutamine-substituted perylene diimide (PDI-glu), 10,12-pentacosadiynoic acid (PCDA), and zinc acetate into three- and four-component hybrid nanofilms through hydrogen and coordination bonding was developed. The hybrids deposited onto solid supports were studied after polymerization of PCDA by UV-vis absorption, fluorescence, and Raman spectroscopies, scanning electron microscopy (SEM), and atomic force microscopy (AFM). The results of spectroscopic studies suggest that the hybrids assembled through H-bonds can maintain the light-induced Förster energy transfer from the PDI-glu chromophore to the conjugated polymer and then to GO leading to fluorescence quenching. In the hybrids assembled through coordination bonding with zinc clusters, the energy transfer proceeds from PDI-glu to the PDA polymer, whereas the transfer from PDA to GO is quenched completely. Another important characteristic of these ultrathin hybrids is their stability with respect to photobleaching of chromophores due to the acceptor properties of GO. The as-assembled hybrid nanofilms were integrated with conventional photovoltaic planar architectures to study their photoelectric properties. The zinc-containing hybrids integrated with a hole transport layer exhibited photovoltaic properties. The cell with the integrated four-component hybrid comprising both PDI-glu and PDA showed a photocurrent/dark current ratio almost an order higher than that of the three-component hybrid assembled with PDA only. The supramolecular method based on the interfacial self-assembly can be extended to a wide variety of organic chromophores and polymerizable surfactants for integrating them into multicomponent functional GO-based nanohybrids with targeted properties for organic electronics.

An unexpected imidazole-induced porphyrinylphosphonate-based MOF-to-HOF structural transformation leading to the enhancement of proton conductivity.

Post-synthetic modification of proton-conducting metal-organic frameworks (MOFs) by loading small molecules capable of generating protons into pores is an efficient approach for developing a new type of material with improved ionic conductivity. Herein, the synthesis, characterization and proton conductivity of a novel electroneutral MOF based on palladium(II) meso-tetrakis(4-(phosphonatophenyl))porphyrinate, IPCE-1Pd, are reported. The exposure of the obtained framework to imidazole by the diffusion vapor method has surprisingly led to its complete crystal-to-crystal MOF-to-HOF transformation, resulting in the formation of a novel hydrogen-bonded organic framework (HOF) IPCE-1Pd_Im, which is the first example of such kind of structural change among all known MOFs. This modification has led to an almost 25-fold increase in the proton conductivity in comparison with the pristine MOF, reaching up to 6.54 × 10-3 S cm-1 at 85 °C and 95% relative humidity, which is one of the highest values among all known porphyrin-based HOFs.

An anionic porphyrinylphosphonate-based hydrogen-bonded organic framework: optimization of proton conductivity through the exchange of counterions.

Hydrogen-bonded organic frameworks (HOFs) possessing high crystallinity, simple synthetic procedure and easy regeneration provide high efficiency as multifunctional systems, including applications as proton conductors. Porphyrinylphosphonates having acidic moieties, which can form multiple hydrogen bonds, together with tunable physical-chemical properties of a macrocycle may significantly improve the proton conductivity of such materials. Herein, the synthesis, characterization and proton-conducting properties of a novel anionic HOF based on a new complex of palladium(II) with meso-tetrakis(4-(phosphonatophenyl))porphyrin, HOF-IPCE-1Pd, are reported. Directed structural transformation of the framework by the exchange of dimethylammonium counterions for ammonium cations along with the absorption of ammonia and water molecules led to the formation of a more hydrolytically stable structure of HOF-IPCE-1Pd-NH3, demonstrating the proton conductivity of 1.27 × 10-3 S cm-1 at 85 °C and 85% RH, which is one of the highest among all known HOFs based on porphyrins. It is noteworthy that the reversible absorbance of water/ammonia molecules preserves the crystal structure of HOF-IPCE-1Pd-NH3.

Formation Kinetics and Antimicrobial Activity of Silver Nanoparticle Dispersions Based on N-Reacetylated Oligochitosan Solutions for Biomedical Applications.

The paper presents the results of the synthesis, a detailed kinetics study, and an investigation of the biological activity of silver nanoparticles (AgNPs) in aqueous solutions of N-reacetylated oligochitosan hydrochloride. UV-visible spectrophotometry and dynamic light scattering were employed to control silver ion reduction. The process was observed to follow a pseudo-first-order law. Transmission and scanning electron microscopy demonstrated that AgNPs ranging in size from 10 to 25 nm formed aggregates measuring 60 to 90 nm, with the aggregate surface coated by a 2-4 nm chitosan shell. X-ray microanalysis and powder X-ray diffractometry were used to study the phase composition, identifying two crystalline phases, nanocrystalline silver and AgCl, present in the dispersions. The antibacterial effect was assessed using the serial dilution method for dispersions with varying degrees of Ag+ conversion. Nanodispersions exhibited significant activity against Escherichia coli, Pseudomonas aeruginosa, Bacillus cereus, and Staphylococcus aureus. Interestingly, the activity did not appear to be heavily influenced by the presence of the AgCl phase or the concentration of Ag+ ions. These synthesized dispersions hold promise for the development of materials tailored for biomedical applications.

Modification of Polydiallyldimethylammonium Chloride with Sodium Polystyrenesulfonate Dramatically Changes the Resistance of Polymer-Based Coatings towards Wash-Off from Both Hydrophilic and Hydrophobic Surfaces.

Polymer coatings based on polycations represent a perspective class of protective antimicrobial coatings. Polydiallyldimethylammonium chloride (PDADMAC) and its water-soluble complexes with sodium polystyrenesulfonate (PSS) were studied by means of dynamic light-scattering, laser microelectrophoresis and turbidimetry. It was shown that addition of six mol.% of polyanion to polycation results in formation of interpolyelectrolyte complex (IPEC) that was stable towards phase separation in water-salt media with a concentration of salts (NaCl, CaCl2, Na2SO4, MgSO4) up to 0.5 M. Most of the polyelectrolyte coatings are made by layer-by-layer deposition. The utilization of water-soluble IPEC for the direct deposition on the surface was studied. The coatings from the PDADMAC and the PSS/PDADMAC complex were formed on the surfaces of hydrophilic glass and hydrophobic polyvinylchloride. It was found that formation IPEC allows one to increase the stability of the coating towards wash-off with water in comparison to individual PDADMAC coating on both types of substrates. The visualization of the coatings was performed by atomic force microscopy and scanning electron microscopy.

Structuring of Surface Films Formed on Magnesium in Hot Chlorobenzotriazole Vapors.

Chamberprotection of metals from atmospheric corrosion is a variety of vapor-phase inhibition. It is based on the effect of adsorption films formed in the vapors of low-volatile corrosion inhibitors at elevated temperatures. The paper analyzes the specific features of the chamber protection of a magnesium alloy with chlorobenzotriazole. It has been found that the protective properties of surface films formed in hot vapors of this compound increase upon exposure of the metal to air. The processes of structuring of protective films that occur in this case have been studied by a set of corrosion, electrochemical and physical methods. It has been shown that chamber treatment of the alloy is accompanied by chlorobenzotriazole adsorption and uniform thickening of the surface oxide-hydroxide layer. In this case, the corrosion processes slow down by a factor of up to 10. Prolonged exposure of the samples in air after the chamber treatment results in additional oxidation of magnesium and hydroxylation of the oxide. However, the oxide-hydroxide layer does not grow on the entire surface, but as separate islets. Such a change in the structure of the surface films results in an additional 10-fold increase in the corrosion resistance of the magnesium alloy.