Sensitive systems with controlled release of drugs or diagnostic markers are attractive for solving the problems of biomedicine and antitumor therapy. In this study, new decasubstituted pillar[5]arene derivatives containing L-Tryptophan and L-Phenylalanine residues have been synthesized as pH-responsive drug nanocarriers. Fluorescein dye (Fluo) was loaded into the pillar[5]arene associates and used as a spectroscopic probe to evaluate the release in buffered solutions with pH 4.5, 7.4, and 9.2. The nature of the substituents in the pillar[5]arene structure has a huge influence on the rate of delivering. When the dye was loaded into the associates based on pillar[5]arene derivatives containing L-Tryptophan, the Fluo release occurs in the neutral (pH = 7.4) and alkaline (pH = 9.2) buffered solutions. When the dye was loaded into the associates based on pillar[5]arene with L-Phenylalanine fragments, the absence of release was observed in every pH evaluated. This happens as the result of different packing of the dye in the structure of the associate. This fact was confirmed by different fluorescence mechanisms (aggregation-caused quenching and aggregation-induced emission) and association constants. It was shown that the macrocycle with L-Phenylalanine fragments binds the dye more efficiently (lgK_a = 3.92). The experimental results indicate that the pillar[5]arene derivatives with amino acids fragments have a high potential to be used as a pH-responsive drug delivery devices, especially for promoting the intracellular delivering, due to its nanometric size. Full article

Nanoplatforms applied for the loading of anticancer drugs is a cutting-edge approach for drug delivery to tumors and reduction of toxic effects on healthy cells. In this study, we describe the synthesis and compare the sorption properties of four types of potential doxorubicin-carriers, in which iron oxide nanoparticles (IONs) are functionalized with cationic (polyethylenimine, PEI), anionic (polystyrenesulfonate, PSS), and nonionic (dextran) polymers, as well as with porous carbon. The IONs are thoroughly characterized by X-ray diffraction, IR spectroscopy, high resolution TEM (HRTEM), SEM, magnetic susceptibility, and the zeta-potential measurements in the pH range of 3–10. The degree of doxorubicin loading at pH 7.4, as well as the degree of desorption at pH 5.0, distinctive to cancerous tumor environment, are measured. Particles modified with PEI were shown to exhibit the highest loading capacity, while the greatest release at pH 5 (up to 30%) occurs from the surface of magnetite decorated with PSS. Such a slow release of the drug would imply a prolonged tumor-inhibiting action on the affected tissue or organ. Assessment of the toxicity (using Neuro2A cell line) for PEI- and PSS-modified IONs showed no negative effect. In conclusion, the preliminary evaluation of the effects of IONs coated with PSS and PEI on the rate of blood clotting was carried out. The results obtained can be taken into account when developing new drug delivery platforms. Full article

Biocompatible luminophores based on organic dyes, which have fluorescence characteristics that are highly sensitive to the properties of the solvating medium, are of particular interest as highly sensitive, selective, and easy-to-use analytical agents. We found that BODIPY dimers (2,2′-, 2,3′-3,3′-CH₂-bis(BODIPY) (1–3)) demonstrate fluorescence characteristics with a high sensitivity to the presence of polar solvents. The intense fluorescence of 1–3 in nonpolar/low-polarity solvents is dramatically quenched in polar media (acetone, DMF, and DMSO). It has been established that the main reason for CH₂-bis(BODIPY) fluorescence quenching is the specific solvation of dyes by electron-donating molecules (Solv) with the formation of stable supramolecular CH₂-bis(BODIPY)·2Solv structures. Using steady-state absorption and fluorescence spectroscopy, time-resolved fluorescence spectroscopy, and computational modeling, the formation mechanism, composition, and structure of CH₂-bis(BODIPY)·2Solv supramolecular complexes have been substantiated, and their stability has been evaluated. The results show the promise of developing fluorescent probes based on CH₂-bis(BODIPY)s for detecting toxic N/O-containing compounds in solutions. Full article

Chitosan or its derivatives exhibit lyotropic liquid crystalline mesophases under certain conditions due to its semi-rigid structures. This work describes the development of chitosan-based biocompatible systems that include new components: lactic acid and non-ionic surfactants. Polarized optical microscopy studies revealed that these systems are capable of forming gels or lyotropic liquid crystals (LLCs) in a certain range of chitosan and lactic acid concentrations. According to the viscosity studies, the rheological flow of the LLCs can be accurately described by the Casson flow model. The intermolecular interactions of the LLC components were studied by FTIR spectroscopy. According to the FTIR data, hydrogen bonding is supposed to be responsible for the formation of the LLCs. In the studied systems, this LLC complex exists as the [ChitH⁺·CH₃-CH(OH)-COO⁻] ion pair. The studied gel and LLCs were shown to possess the most prolonged release capabilities for riboflavin among similar binary LLC systems. The supramolecular organization and rheological characteristics of the studied chitosan-based systems were found to affect the release of riboflavin. Full article

The interactions of DNA with lysozyme in the surface layer were studied by performing infrared reflection–absorption spectroscopy (IRRAS), ellipsometry, surface tensiometry, surface dilational rheology, and atomic force microscopy (AFM). A concentrated DNA solution was injected into an aqueous subphase underneath a spread lysozyme layer. While the optical properties of the surface layer changed fast after DNA injection, the dynamic dilational surface elasticity almost did not change, thereby indicating no continuous network formation of DNA/lysozyme complexes, unlike the case of DNA interactions with a monolayer of a cationic synthetic polyelectrolyte. A relatively fast increase in optical signals after a DNA injection under a lysozyme layer indicates that DNA penetration is controlled by diffusion. At low surface pressures, the AFM images show the formation of long strands in the surface layer. Increased surface compression does not lead to the formation of a network of DNA/lysozyme aggregates as in the case of a mixed layer of DNA and synthetic polyelectrolytes, but to the appearance of some folds and ridges in the layer. The formation of more disordered aggregates is presumably a consequence of weaker interactions of lysozyme with duplex DNA and the stabilization, at the same time, of loops of unpaired nucleotides at high local lysozyme concentrations in the surface layer. Full article

Novel monosubstituted pillar[5]arenes containing both amide and carboxyl functional groups were synthesized. Solid lipid nanoparticles based on the synthesized macrocycles were obtained. Formation of spherical particles with an average hydrodynamic diameter of 250 nm was shown for pillar[5]arenes containing N-(amidoalkyl)amide fragments regardless of their concentration. It was established that pillar[5]arene containing N-alkylamide fragments can form spherical particles with two different sizes (88 and 223 nm) depending on its concentration. Mixed solid lipid nanoparticles based on monosubstituted pillar[5]arenes and surfactant (dodecyltrimethylammonium chloride) were obtained for the first time. The surfactant made it possible to level the effect of the macrocycle concentration. It was found that various types of aggregates are formed depending on the macrocycle/surfactant ratio. Changing the macrocycle/surfactant ratio allows to control the charge of the particles surface. This controlled property will lead to the creation of molecular-scale porous materials that selectively interact with various types of substrates, including biopolymers. Full article

Antimicrobial, membranotropic and cytotoxic properties of dicationic imidazolium surfactants of n-s-n (Im) series with variable length of alkyl group (n = 8, 10, 12, 14, 16) and spacer fragment (s = 2, 3, 4) were explored and compared with monocationic analogues. Their activity against a representative range of Gram-positive and Gram-negative bacteria, and also fungi, is characterized. The relationship between the biological activity and the structural features of these compounds is revealed, with the hydrophobicity emphasized as a key factor. Among dicationic surfactants, decyl derivatives showed highest antimicrobial effect, while for monocationic analogues, the maximum activity is observed in the case of tetradecyl tail. The leading compounds are 2–4 times higher in activity compared to reference antibiotics and prove effective against resistant strains. It has been shown that the antimicrobial effect is not associated with the destruction of the cell membrane, but is due to specific interactions of surfactants and cell components. Importantly, they show strong selectivity for microorganism cells while being of low harm to healthy human cells, with a SI ranging from 30 to 100. Full article

Photocatalytic green hydrogen (H₂) production through water electrolysis is deemed as green, efficient, and renewable fuel or energy carrier due to its great energy density and zero greenhouse emissions. However, developing efficient and low-cost noble-metal-free photocatalysts remains one of the daunting challenges in low-cost H₂ production. Porous graphitic carbon nitride (gCN) nanostructures have drawn broad multidisciplinary attention as metal-free photocatalysts in the arena of H₂ production and other environmental remediation. This is due to their impressive catalytic/photocatalytic properties (i.e., high surface area, narrow bandgap, and visible light absorption), unique physicochemical durability, tunable electronic properties, and feasibility to synthesize in high yield from inexpensive and earth-abundant resources. The physicochemical and photocatalytic properties of porous gCNs can be easily optimized via the integration of earth-abundant heteroatoms. Although there are various reviews on porous gCN-based photocatalysts for various applications, to the best of our knowledge, there are no reviews on heteroatom-doped porous gCN nanostructures for the photocatalytic H₂ evolution reaction (HER). It is essential to provide timely updates in this research area to highlight the research related to fabrication of novel gCNs for large-scale applications and address the current barriers in this field. This review emphasizes a panorama of recent advances in the rational design of heteroatom (i.e., P, O, S, N, and B)-doped porous gCN nanostructures including mono, binary, and ternary dopants for photocatalytic HERs and their optimized parameters. This is in addition to H₂ energy storage, non-metal configuration, HER fundamental, mechanism, and calculations. This review is expected to inspire a new research entryway to the fabrication of porous gCN-based photocatalysts with ameliorated activity and durability for practical H₂ production. Full article