The elasticity of silicone-stabilized liposomes has no impact on their in vivo behavior.

BACKGROUND: The elastomechanical properties of nanocarriers have recently been discussed as important for the efficient delivery of various therapeutics. Some data indicate that optimal nanocarriers' elasticity can modulate in vivo nanocarrier stability, interaction with phagocytes, and uptake by target cells. Here, we presented a study to extensively analyze the in vivo behavior of LIP-SS liposomes that were modified by forming the silicone network within the lipid bilayers to improve their elastomechanical properties. We verified liposome pharmacokinetic profiles and biodistribution, including retention in tumors on a mouse model of breast cancer, while biocompatibility was analyzed on healthy mice. RESULTS: We showed that fluorescently labeled LIP-SS and control LIP-CAT liposomes had similar pharmacokinetic profiles, biodistribution, and retention in tumors, indicating that modified elasticity did not improve nanocarrier in vivo performance. Interestingly, biocompatibility studies revealed no changes in blood morphology, liver, spleen, and kidney function but indicated prolonged activation of immune response manifesting in increased concentration of proinflammatory cytokines in sera of animals exposed to all tested liposomes. CONCLUSION: Incorporating the silicone layer into the liposome structure did not change nanocarriers' characteristics in vivo. Further modification of the LIP-SS surface, including decoration with hydrophilic stealth polymers, should be performed to improve their pharmacokinetics and retention in tumors significantly. Activation of the immune response by LIP-SS and LIP-CAT, resulting in elevated inflammatory cytokine production, requires detailed studies to elucidate its mechanism.

Nanoscale surface defects of goethite governing DNA adsorption process and formation of the Goethite-DNA conjugates.

In urbanized areas, extracellular DNA (exDNA) is suspected of carrying genes with undesirable traits like virulence genes (VGs) or antibiotic resistance genes (ARGs), which can spread through horizontal gene transfer (HGT). Hence, it is crucial to develop novel approaches for the mitigation of exDNA in the environment. Our research explores the role of goethite, a common iron mineral with high adsorption capabilities, in exDNA adsorption processes. We compare well-crystalline, semi-crystalline, and nano goethites with varying particle sizes to achieve various specific surface areas (SSAs) (18.7-161.6 m2/g) and porosities. We conducted batch adsorption experiments using DNA molecules of varying chain lengths (DNA sizes: <11 Kb, <6 Kb, and <3 Kb) and assessed the impact of Ca2+ and biomacromolecules on the adsorption efficacy and mechanisms. Results show that porosity and pore structure significantly influence DNA adsorption capacity. Goethite with well-developed meso- and macroporosity demonstrated enhanced DNA adsorption. The accumulation of DNA on the goethite interface led to substantial aggregation in the system, thus the formation of DNA-goethite conjugates, indicating the bridging between mineral particles. DNA chain length, the presence of Ca2+, and the biomacromolecule matrix also affected the adsorption capacity and mechanism. Interactions between DNA and positively charged biomacromolecules or Ca2+ led to DNA compaction, allowing greater DNA accumulation in pores. However, a high concentration of biomacromolecules led to the saturation of the goethite surface, inhibiting DNA adsorption. AFM imaging of goethite particles after adsorption suggested the formation of the DNA multilayer. The study advances understanding of the environmental behavior of exDNA and its interaction with iron oxyhydroxides, offering insights into developing more effective methods for ARGs removal in wastewater treatment plants. By manipulating the textural properties of goethite, it's possible to enhance exDNA removal, potentially reducing the spread of biocontamination in urban and industrial environments.

Surface-grafted macromolecular nanowires with pedant fluorescein chromophores by dense non-aggregated nanoarchitectonics as versatile photoactive platforms.

In this paper, we present a facile method of synthesis and modification of poly(glycidyl methacrylate) brushes with 6-aminofluorescein (6AF) molecules. Polymer brushes were obtained using surface-grafted atom transfer radical polymerization (SI-ATRP) and functionalized in the presence of triethylamine (TEA) acting both as a reaction catalyst and an agent preventing aggregation of chromophores. Atomic force microscopy (AFM), FTIR, X-ray photoelectron spectroscopy (XPS) were used to study the structure and formation of obtained photoactive platforms. UV-Vis absorption and emission spectroscopy and confocal microscopy were conducted to investigate photoactivity of chromophores within the macromolecular matrix. Owing to the simplicity of fabrication and good ordering of the chromophore in a thin nanometric layer, the proposed method may open new opportunities for obtaining light sensors, photovoltaic devices, or other light-harvesting systems.

Effect of Al Polishing Conditions on the Growth and Morphology of Porous Anodic Alumina Films.

The conditions applied during the electrochemical polishing of aluminum were found to be important parameters for the successive formation of nanoporous alumina films. First, a high-purity Al foil was electrochemically polished in an aqueous solution containing C2H5OH and HClO4 at various sets of conditions, such as applied potential (5-35 V), temperature (0-20 °C), and process duration (10-180 s). Extensive studies of the topography of Al after polishing by scanning electron microscopy and atomic force microscopy allow verification of the correlations between conditions applied during the substrate pretreatment and dimensions of the nanopatterns generated on the metal surface. Next, Al polished samples at two different sets of conditions were used as starting materials for anodization. Unpolished Al samples were also anodized for reference. It was confirmed that electropolishing conditions do not significantly affect the oxide growth rate during anodization and the efficiency of anodic film formation. On the contrary, it was proved that the dimensions of the surface texture formed during Al polishing significantly affect the morphology and pore order within the anodic film. Therefore, it can be stated that it is possible to tune to some extent the arrangement of nanochannels within anodic aluminum oxide films by simply changing conditions during the electropolishing procedure..

Improving the quality of multi-layer films based on furcellaran by immobilising active ingredients and impact assessment of the use of a new packaging material.

To improve the quality of multi-layer film, four-layer films based on furcellaran and active ingredients: gelatin hydrolysate, curcumin, capsaicin, montmorillonite and AgNPs, were produced in an innovative manner. The films were characterised by SEM and AFM analysis. Along with an increase in the concentration of active ingredients, the structure of the film becomes less homogeneous, which may affect the functional properties. The objective of the study was to analyse changes in the functional properties of the newly-obtained films and to verify their potential as packaging materials for fish products. With the increase in active ingredient concentration, water properties also improved, but there were no noticeable significant effects on mechanical properties. For antioxidant properties, the obtained values were within 1.04-2.74 mM Trolox/mg (FRAP) and 7.67-40.49% (DPPH). The obtained multi-layer films were examined with regard to the shelf-life of salmon. For this purpose, salmon fillets were packed in films having good antioxidant and functional properties. The films were effective in microorganism growth inhibition responsible for fillet spoilage during storage. The microorganism number in the active film-stored samples was lower by 0.13 log CFU/g on day 12 versus the control. However, film application did not retard lipid oxidation in the salmon fillets. Nonetheless, the films show great potential as active packaging materials, extending the shelf-life of the packed foods.

High-Entropy Perovskite Thin Film in the Gd-Nd-Sm-La-Y-Co System: Deposition, Structure and Optoelectronic Properties.

Multicomponent equimolar perovskite oxides (ME-POs) have recently emerged as a highly promising class of materials with unique synergistic effects, making them well-suited for applications in such areas as photovoltaics and micro- and nanoelectronics. High-entropy perovskite oxide thin film in the (Gd0.2Nd0.2La0.2Sm0.2Y0.2)CoO3 (RECO, where RE = Gd0.2Nd0.2La0.2Sm0.2Y0.2, C = Co, and O = O3) system was synthesized via pulsed laser deposition. The crystalline growth in an amorphous fused quartz substrate and single-phase composition of the synthesized film was confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Surface conductivity and activation energy were determined using a novel technique implementing atomic force microscopy (AFM) in combination with current mapping. The optoelectronic properties of the deposited RECO thin film were characterized using UV/VIS spectroscopy. The energy gap and nature of optical transitions were calculated using the Inverse Logarithmic Derivative (ILD) and four-point resistance method, suggesting direct allowed transitions with altered dispersions. The narrow energy gap of RECO, along with its relatively high absorption properties in the visible spectrum, positions it as a promising candidate for further exploration in the domains of low-energy infrared optics and electrocatalysis.

Aerogels based on cationically modified chitosan and poly(vinyl alcohol) for efficient capturing of viruses.

In this study, we developed a new filtering bioaerogel based on linear polyvinyl alcohol (PVA) and the cationic derivative of chitosan (N-[(2-hydroxy-3-trimethylamine) propyl] chitosan chloride, HTCC) with a potential antiviral application. A strong intermolecular network architecture was formed thanks to the introduction of linear PVA chains, which can efficiently interpenetrate the glutaraldehyde(GA)-crosslinked HTCC chains. The morphology of the obtained structures was examined using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The aerogels and modified polymers' elemental composition (including the chemical environment) was determined using X-ray photoelectron spectroscopy (XPS). New aerogels with more than twice as much developed micro- and mesopore space and BET-specific surface area were obtained concerning the starting sample chitosan aerogel crosslinked by glutaraldehyde (Chit/GA). The results obtained from the XPS analysis showed the presence of cationic 3-trimethylammonium groups on the surface of the aerogel, which can interact with viral capsid proteins. No cytotoxic effect of HTCC/GA/PVA aerogel was also observed on fibroblast cells of the NIH3T3 line. Furthermore, the HTCC/GA/PVA aerogel has been shown that efficiently traps mouse hepatitis virus (MHV) from suspension. The presented concept of aerogel filters for virus capture based on modified chitosan and polyvinyl alcohol has a high application potential.

Incorporation of curcumin extract with lemongrass essential oil into the middle layer of triple-layered films based on furcellaran/chitosan/gelatin hydrolysates - In vitro and in vivo studies on active and intelligent properties.

Triple-layered, pH-sensitive and active films based on furcellaran (FUR), chitosan (CHIT) and gelatin hydrolysates (HGEL) were obtained for the first time. Curcumin ethanol extract (CUR) enriched with lemongrass essential oil (LEO) in three concentrations was added to the middle layer of the film. SEM and AFM analysis confirmed the formation of 3 layers, and CUR-LEO was evenly dispersed in the 2nd layer. The addition of CUR-LEO influenced the color of the surface and improved the UV blocking properties of the film. However, the mechanical and water vapor barrier properties remained unchanged. The CUR-LEO demonstrated antibacterial properties against bacteria and fungi. The antioxidant activity of the films increased along with the increasing concentrations of CUR-LEO. The presented films were able to effectively extend the storage life of tomatoes. Moreover, the colored films had the monitoring freshness effect with a distinct color change during carp storage.

Double-Layered Films Based on Furcellaran, Chitosan, and Gelatin Hydrolysates Enriched with AgNPs in Yerba Mate Extract, Montmorillonite, and Curcumin with Rosemary Essential Oil.

Double-layered active films based on furcellaran (1st layer-FUR), chitosan, and gelatin hydrolysates (2nd layer-CHIT+HGEL) were successfully prepared. Bioactive ingredients were added to the 1st film layer: AgNPs, which were synthesized in situ with yerba mate extract; montmorillonite clay (MMT); and different loads of ethanolic curcumin (CUR) extract enriched with rosemary essential oil (REO). SEM images confirmed the presence of AgNPs with a size distribution of 94.96 ± 3.33 nm throughout the films, and AFM and SEM photos indicated that the higher substance concentrations had rougher and more porous film microstructures. However, the water vapor transmission rate was reduced only at the lowest load of this ingredient. Despite the tensile strength of the films having decreased, the incorporation of the compounds showed a tendency towards reducing the modulus of elasticity, resulting in a lower stiffness of the composites. The addition of CUR and AgNPs improved the UV light barrier properties of the materials. The presented films showed quick reactions to changes in the pH value (from orange to red along with an increase in pH from 2 to 10), which indicates their potential use as indicators for monitoring the freshness of food products. Composite No. 2 showed the highest antimicrobial potential, while none of the presented films showed an antifungal effect. Finally, the antioxidant activities of the films increased dramatically at higher AgNP and CUR loads, suggesting an outstanding potential for active food packaging applications.

Control of Specific/Nonspecific Protein Adsorption: Functionalization of Polyelectrolyte Multilayer Films as a Potential Coating for Biosensors.

Control of nonspecific/specific protein adsorption is the main goal in the design of novel biomaterials, implants, drug delivery systems, and sensors. The specific functionalization of biomaterials can be achieved by proper surface modification. One of the important strategies is covering the materials with functional coatings. Therefore, our work aimed to functionalize multilayer coating to control nonspecific/specific protein adsorption. The polyelectrolyte coating was formed using a layer-by-layer technique (LbL) with biocompatible polyelectrolytes poly-L-lysine hydrobromide (PLL) and poly-L-glutamic acid (PGA). Nonspecific protein adsorption was minimized/eliminated by pegylation of multilayer films, which was achieved by adsorption of pegylated polycations (PLL-g-PEG). The influence of poly (ethylene glycol) chain length on eliminating nonspecific protein adsorption was confirmed. Moreover, to achieve specific protein adsorption, the multilayer film was also functionalized by immobilization of antibodies via a streptavidin bridge. The functional coatings were tested, and the adsorption of the following proteins confirmed the ability to control nonspecific/specific adsorption: human serum albumin (HSA), fibrinogen (FIB), fetal bovine serum (FBS), carcinoembryonic antigen human (CEA) monitored by quartz crystal microbalance with dissipation (QCM-D). AFM imaging of unmodified and modified multilayer surfaces was also performed. Functional multilayer films are believed to have the potential as a novel platform for biotechnological applications, such as biosensors and nanocarriers for drug delivery systems.

Utilisation of Carp Skin Post-Production Waste in Binary Films Based on Furcellaran and Chitosan to Obtain Packaging Materials for Storing Blueberries.

The aim of the study was to develop and characterise an innovative three-component biopolymer film based on chitosan (CHIT), furcellaran (FUR) and a gelatin hydrolysate from carp skins (Cyprinus carpio) (HGEL). The structure and morphology were characterised using the Fourier transform infrared spectroscopy (FT-IR) and atomic force microscopy (AFM). The FT-IR test showed no changes in the matrix after the addition of HGEL, which indicates that the film components were compatible. Based on the obtained AFM results, it was found that the addition of HGEL caused the formation of grooves and cracks on the surface of the film (reduction by ~21%). The addition of HGEL improved the antioxidant activity of the film (improvement by up to 2.318% and 444% of DPPH and FRAP power, respectively). Due to their properties, the tested films were used as active materials in the preservation of American blueberries. In the active films, the blueberries lost mass quickly compared to the synthetic film and were characterised by higher phenol content. The results obtained in this study create the opportunity to use the designed CHIT-FUR films in developing biodegradable packaging materials for food protection, but it is necessary to test their effectiveness on other food products.

Composite biopolymer films based on a polyelectrolyte complex of furcellaran and chitosan.

The aim of research was to develop biopolymer films based on natural polysaccharides. For the first time, biodegradable films were obtained on the basis of a furcellaran-chitosan polyelectrolyte complex. The conditions for its formation were determined by measuring the zeta potential as a function of colloid pH, the size of pure components and their mixtures. The structure and morphology of the prepared films were characterised by FT-IR and AFM analysis. The lowest WVTR values were observed for the FUR and the CHIT-FUR films at the ratio of 9:1. The mechanical, water and rheological properties depend on the weight ratio of furcellaran to chitosan in the mixture. The thermal stability has been improved in CHIT-FUR films at the 9:1 ratio. The results obtained create the possibility of successfully using CHIT-FUR films in the development of biodegradable packaging materials.

Tuning the Surface Properties of Poly(Allylamine Hydrochloride)-Based Multilayer Films.

The layer-by-layer (LbL) method of polyelectrolyte multilayer (PEM) fabrication is extremely versatile. It allows using a pair of any oppositely charged polyelectrolytes. Nevertheless, it may be difficult to ascribe a particular physicochemical property of the resulting PEM to a structural or chemical feature of a single component. A solution to this problem is based on the application of a polycation and a polyanion obtained by proper modification of the same parent polymer. Polyelectrolyte multilayers (PEMs) were prepared using the LbL technique from hydrophilic and amphiphilic derivatives of poly(allylamine hydrochloride) (PAH). PAH derivatives were obtained by the substitution of amine groups in PAH with sulfonate, ammonium, and hydrophobic groups. The PEMs were stable in 1 M NaCl and showed three different modes of thickness growth: exponential, mixed exponential-linear, and linear. Their surfaces ranged from very hydrophilic to hydrophobic. Root mean square (RMS) roughness was very variable and depended on the PEM composition, sample environment (dry, wet), and the polymer constituting the topmost layer. Atomic force microscopy (AFM) imaging of the surfaces showed very different morphologies of PEMs, including very smooth, porous, and structured PEMs with micellar aggregates. Thus, by proper choice of PAH derivatives, surfaces with different physicochemical features (growth type, thickness, charge, wettability, roughness, surface morphology) were obtained.

Coacervate Thermoresponsive Polysaccharide Nanoparticles as Delivery System for Piroxicam.

Low water solubility frequently compromises the therapeutic efficacy of drugs and other biologically active molecules. Here, we report on coacervate polysaccharide nanoparticles (CPNs) that can transport and release a model hydrophobic drug, piroxicam, to the cells in response to changes in temperature. The proposed, temperature-responsive drug delivery system is based on ionic derivatives of natural polysaccharides-curdlan and hydroxypropyl cellulose. Curdlan was modified with trimethylammonium groups, while the anionic derivative of hydroxypropyl cellulose was obtained by the introduction of styrenesulfonate groups. Thermally responsive nanoparticles of spherical shape and average hydrodynamic diameter in the range of 250-300 nm were spontaneously formed in water from the obtained ionic polysaccharides as a result of the coacervation process. Their morphology was visualized using SEM and AFM. The size and the surface charge of the obtained objects could be tailored by adjusting the polycation/polyanion ratio. Piroxicam (PIX) was effectively entrapped inside the nanoparticles. The release profile of the drug from the CPNs-PIX was found to be temperature-dependent in the range relevant for biomedical applications.

Tailoring cellular microenvironments using scaffolds based on magnetically-responsive polymer brushes.

A variety of polymeric scaffolds with the ability to control cell detachment has been created for cell culture using stimuli-responsive polymers. However, the widely studied and commonly used thermo-responsive polymeric substrates always affect the properties of the cultured cells due to the temperature stimulus. Here, we present a different stimuli-responsive approach based on poly(3-acrylamidopropyl)trimethylammonium chloride) (poly(APTAC)) brushes with homogeneously embedded superparamagnetic iron oxide nanoparticles (SPIONs). Neuroblastoma cell detachment was triggered by an external magnetic field, enabling a non-invasive process of controlled transfer into a new place without additional mechanical scratching and chemical/biochemical compound treatment. Hybrid scaffolds obtained in simultaneous surface-initiated atom transfer radical polymerization (SI-ATRP) were characterized by atomic force microscopy (AFM) working in the magnetic mode, secondary ion mass spectrometry (SIMS), and X-ray photoelectron spectroscopy (XPS) to confirm the magnetic properties and chemical structure. Moreover, neuroblastoma cells were cultured and characterized before and after exposure to a neodymium magnet. Controlled cell transfer triggered by a magnetic field is presented here as well.

Stabilization of liposomes with silicone layer improves their elastomechanical properties while not compromising biological features.

The liposomes are among the most promising types of drug delivery systems but low stability significantly limits their application. Some approaches proposed to overcome this drawback may affect the liposomes toxicity profile. It is assumed that developed by us and presented here stabilization method involving formation of silicone network within the liposomal bilayer will improve elastomechanical properties of vesicles while not deteriorating their biocompatibility. The silicone-stabilized liposomes were prepared by base-catalyzed polycondensation process of the 1,3,5,7-tetramethylcyclotetrasiloxane (D4H) within the liposomal bilayer. The systematic biological in vitro studies of vesicles obtained were carried out. Moreover, the elastomechanical features investigation employing atomic force microscopy (AFM) measurements was performed. These properties of the liposome membrane are of great importance since they define the nanocarriers' stability as well as play a significant role in their cellular uptake via endocytosis. Applying the Derjaguin-Muller-Toporov (DMT) model, the elastic modulus of the silicone-stabilized liposomes was determined and compared to that characteristic for the pristine liposomes. The in vitro biological evaluation of silicone-stabilized liposomes demonstrated that these vesicles are not toxic for blood cells isolated from healthy donors and they do not induce oxidative stress in HepG2 cells. AFM results confirmed the stabilizing effect of silicone and revealed that the silicone network improves the elastomechanical properties of the resulted liposomes. This is the first report demonstrating that the silicone-stabilized liposomes retain biocompatibility of pristine liposomes' while acquire significantly better elastomechanical features.

Structural evolution of supported lipid bilayers intercalated with quantum dots.

HYPOTHESIS: Supported lipid bilayers (SLBs) embedded with hydrophobic quantum dots (QDs) undergo temporal structural rearrangement. EXPERIMENTS: Synchrotron X-ray reflectivity (XRR) was applied to monitor the temporal structural changes over a period of 24 h of mixed SLBs of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) / 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-ethanolamine (POPE) intercalated with 4.9 nm hydrophobic cadmium sulphide quantum dots (CdS QDs). The QD-embedded SLBs (QD-SLBs) were formed via rupture of the mixed liposomes on a positively charged polyethylene imine (PEI) monolayer. Atomic force microscopy (AFM) imaging provided complementary characterization of the bilayer morphology. FINDINGS: Our results show time-dependent perturbations in the SLB structure due to the interaction upon QD incorporation. Compared to the SLB without QDs, at 3 h incubation time, there was a measurable decrease in the bilayer thickness and a concurrent increase in the scattering length density (SLD) of the QD-SLB. The QD-SLB then became progressively thicker with increasing incubation time, which - along with the fitted SLD profile - was attributed to the structural rearrangement due to the QDs being expelled from the inner leaflet to the outer leaflet of the bilayer. Our results give unprecedented mechanistic insights into the structural evolution of QD-SLBs on a polymer cushion, important to their potential biomedical and biosensing applications.

Nanohydrogels Based on Self-Assembly of Cationic Pullulan and Anionic Dextran Derivatives for Efficient Delivery of Piroxicam.

A cationic derivative of pullulan was obtained by grafting reaction and used together with dextran sulfate to form polysaccharide-based nanohydrogel cross-linked via electrostatic interactions between polyions. Due to the polycation-polyanion interactions nanohydrogel particles were formed instantly and spontaneously in water. The nanoparticles were colloidally stable and their size and surface charge could be controlled by the polycation/polyanion ratio. The morphology of the obtained particles was visualized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM). The resulting structures were spherical, with hydrodynamic diameters in the range of 100-150 nm. The binding constant (Ka) of a model drug, piroxicam, to the cationic pullulan (C-PUL) was determined by spectrophotometric measurements. The value of Ka was calculated according to the Benesi-Hildebrand equation to be (3.6 ± 0.2) × 103 M-1. After binding to cationic pullulan, piroxicam was effectively entrapped inside the nanohydrogel particles and released in a controlled way. The obtained system was efficiently taken up by cells and was shown to be biocompatible.

Homogeneous Embedding of Magnetic Nanoparticles into Polymer Brushes during Simultaneous Surface-Initiated Polymerization.

Here we present a facile and efficient method of controlled embedding of inorganic nanoparticles into an ultra-thin (<15 nm) and flat (~1.0 nm) polymeric coating that prevents unwanted aggregation. Hybrid polymer brushes-based films were obtained by simultaneous incorporation of superparamagnetic iron oxide nanoparticles (SPIONs) with diameters of 8⁻10 nm into a polycationic macromolecular matrix during the surface initiated atom transfer radical polymerization (SI-ATRP) reaction in an ultrasonic reactor. The proposed structures characterized with homogeneous distribution of separated nanoparticles that maintain nanometric thickness and strong magnetic properties are a good alternative for commonly used layers of crosslinked nanoparticles aggregates or bulk structures. Obtained coatings were characterized using atomic force microscopy (AFM) working in the magnetic mode, secondary ion mass spectrometry (SIMS), and X-ray photoelectron spectroscopy (XPS).