Combustion Synthesis of Functionalized Carbonated Boron Nitride Nanoparticles and Their Potential Application in Boron Neutron Capture Therapy.

In this research, we developed boron-rich nanoparticles that can be used for boron neutron capture therapy as potential carriers for boron delivery to cancerous tissues. Functionalized carbonated boron nitride nanostructures (CBNs) were successfully synthesized in self-propagating combustion waves in mixtures of high-nitrogen explosives and boron compounds. The products' composition, morphology, and structural features were investigated using Fourier transform infrared spectroscopy, powder X-ray diffraction, low-temperature nitrogen sorption analysis, thermogravimetric analysis, high-resolution scanning electron microscopy, and high-resolution transmission electron microscopy. The extreme conditions prevailing in combustion waves favor the formation of nanosized CBN hollow grains with highly disordered structures that are properly functionalized on the surface and inside the particles. Therefore, they are characterized by high porosity and good dispersibility in water, which are necessary for medical applications. During biological tests, a concentration-dependent effect of the obtained boron nitride preparations on the viability of normal and neoplastic cells was demonstrated. Moreover, the assessment of the degree of binding of fluorescently labeled nanoparticles to selected cells confirmed the relationships between the cell types and the concentration of the preparation at different incubation time points.

Macrophages as carriers of boron carbide nanoparticles dedicated to boron neutron capture therapy.

BACKGROUND: The use of cells as carriers for the delivery of nanoparticles is a promising approach in anticancer therapy, mainly due to their natural properties, such as biocompatibility and non-immunogenicity. Cellular carriers prevent the rapid degradation of nanoparticles, improve their distribution, reduce cytotoxicity and ensure selective delivery to the tumor microenvironment. Therefore, we propose the use of phagocytic cells as boron carbide nanoparticle carriers for boron delivery to the tumor microenvironment in boron neutron capture therapy. RESULTS: Macrophages originating from cell lines and bone marrow showed a greater ability to interact with boron carbide (B4C) than dendritic cells, especially the preparation containing larger nanoparticles (B4C 2). Consequently, B4C 2 caused greater toxicity and induced the secretion of pro-inflammatory cytokines by these cells. However, migration assays demonstrated that macrophages loaded with B4C 1 migrated more efficiently than with B4C 2. Therefore, smaller nanoparticles (B4C 1) with lower toxicity but similar ability to activate macrophages proved to be more attractive. CONCLUSIONS: Macrophages could be promising cellular carriers for boron carbide nanoparticle delivery, especially B4C 1 to the tumor microenvironment and thus prospective use in boron neutron capture therapy.

Synthesis and Characterization of Boron Carbide Nanoparticles as Potential Boron-Rich Therapeutic Carriers.

Boron carbide is one of the hardest materials in the world which can be synthesized by various methods. The most common one is a carbothermic or magnesiothermic reduction of B2O3 performed at high temperatures, where the obtained powder still requires grinding and purification. The goal of this research is to present the possibility of synthesizing B4C nanoparticles from elements via vapor deposition and modifying the morphology of the obtained powders, particularly those synthesized at high temperatures. B4C nanoparticles were synthesized in the process of direct synthesis from boron and carbon powders heated at the temperature of 1650 °C for 2 h under argon and characterized by using scanning electron microscopy, transmission electron microscopy, atomic force microscopy, X-ray diffraction analysis, and dynamic light scattering measurements. The physicochemical characteristics of B4C nanoparticles were determined, including the diffusion coefficients, hydrodynamic diameter, electrophoretic mobilities, and zeta potentials. An evaluation of the obtained B4C nanoparticles was performed on several human and mouse cell lines, showing the relation between the cytotoxicity effect and the size of the synthesized nanoparticles. Assessing the suitability of the synthesized B4C for further modifications in terms of its applicability in boron neutron capture therapy was the overarching goal of this research.

Mechanism of Anti-Salmonella Rabbit Immunoglobulin Adsorption on Polymer Particles.

The adsorption of anti-Salmonella rabbit immunoglobulin (IgaR) on negatively charged polymer particles leading to the formation of immunolatex was studied using various techniques comprising atomic force microscopy (AFM) and laser Doppler velocimetry (LDV). Initially, the basic physicochemical properties of IgaR molecules and the particles, inter alia their electrophoretic mobilities, the zeta potentials and hydrodynamic diameters, were determined under different ionic strengths and pHs. Applying AFM, single immunoglobulin molecules adsorbed on mica were also imaged, which allowed to determine their size. The adsorption of the IgaR molecules on the particles leading to changes in their electrophoretic mobility was monitored in situ using the LDV method. The obtained results were interpreted applying a general electrokinetic model which yielded quantitative information about the molecule coverage on the particles. The obtained immunolatex was thoroughly characterized with respect to its acid-base properties and its stability upon storage. Notably, the developed procedure demonstrated better efficiency compared to commercially applied methods, characterized by a higher immunoglobulin consumption.

Physicochemical Nature of SARS-CoV-2 Spike Protein Binding to Human Vimentin.

Vimentin, a protein that builds part of the cytoskeleton and is involved in many aspects of cellular function, was recently identified as a cell surface attachment site for the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2). The present study investigated the physicochemical nature of the binding between the SARS-CoV-2 S1 glycoprotein receptor binding domain (S1 RBD) and human vimentin using atomic force microscopy and a quartz crystal microbalance. The molecular interactions of S1 RBD and vimentin proteins were quantified using vimentin monolayers attached to the cleaved mica or a gold microbalance sensor as well as in its native extracellular form present on the live cell surface. The presence of specific interactions between vimentin and S1 RBD was also confirmed using in silico studies. This work provides new evidence that cell-surface vimentin (CSV) functions as a site for SARS-CoV-2 virus attachment and is involved in the pathogenesis of Covid-19, providing a potential target for therapeutic countermeasures.

Silver nanoparticles affect wheat (Triticum aestivum L.) germination, seedling blight and yield.

The aim of the study was to evaluate the effect of two types of negatively charged quasi-spherical silver nanoparticles (AgNPs) at concentrations of 10, 20 and 30mgL-1 and silver ions at a concentration of 30mgL-1 on the growth, selected physiological aspects and yielding of wheat (Triticum aestivum L.) cv. Tybalt, and on plant resistance to seedling blight. Seed germination, α-amylase activity in seeds, morphology and infestation of seedlings by pathogens were assessed in a hydroponic treatment. Growth rate, PSII efficiency, heading and yield of the same plants were then analysed in pot culture. Results showed that the AgNPs and silver ions had a negative effect on roots, but reduced seedling blight and improved leaf area compared to the control. In addition, the AgNPs reduced with sodium borohydride in the presence of trisodium citrate at concentrations of 10 and 20mgL-1 stimulated germination, α-amylase activity and shoot length, which was not observed in the case of silver ions and the AgNPs reduced with sodium hypophosphite in the presence of sodium hexametaphosphate. In a pot experiment, the AgNPs improved plant growth, PSII efficiency, accelerated heading and increased yield-related parameters compared with the control. Results revealed the interaction strength in the following order: TCSB-AgNPs>SHSH-AgNPs>silver ions. TCSB-AgNPs in the lowest concentration had the most favourable effect, indicating their great potential for use in improving wheat cultivation.

Biocidal Activity of Tannic Acid-Prepared Silver Nanoparticles towards Pathogens Isolated from Patients with Exacerbations of Chronic Rhinosinusitis.

The microbiome's significance in chronic rhinosinusitis (CRS) is unclear. Antimicrobials are recommended in acute exacerbations of the disease (AECRS). Increasing rates of antibiotic resistance have stimulated research on alternative therapeutic options, including silver nanoparticles (AgNPs). However, there are concerns regarding the safety of silver administration. The aim of this study was to assess the biological activity of tannic acid-prepared AgNPs (TA-AgNPs) towards sinonasal pathogens and nasal epithelial cells (HNEpC). The minimal inhibitory concentration (MIC) for pathogens isolated from patients with AECRS was approximated using the well diffusion method. The cytotoxicity of TA-AgNPswas evaluated using an MTT assay and trypan blue exclusion. A total of 48 clinical isolates and 4 reference strains were included in the study (Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli, Klebsiella pneumoniae, Klebsiellaoxytoca, Acinetobacter baumannii, Serratia marcescens, Enterobacter cloacae). The results of the studies revealed that the MIC values differed between isolates, even within the same species. All the isolates were sensitive to TA-AgNPs in concentrations non-toxic to human cells during 24 h exposition. However, 48 h exposure to TA-AgNPs increased toxicity to HNEpC, narrowing their therapeutic window and enabling 19% of pathogens to resist the TA-AgNPs' biocidal action. It was concluded that TA-AgNPs are non-toxic for the investigated eukaryotic cells after short-term exposure and effective against most pathogens isolated from patients with AECRS, but sensitivity testing may be necessary before application.

Concept of Sustainable Demolition Process for Brickwork Buildings with Expanded Polystyrene Foam Insulation Using Mealworms of Tenebrio molitor.

The traditional demolition process for brickwork buildings results in a significant volume of mixed debris. The debris consists of ceramic bricks (and other wall elements), mortar, thermal insulation (usually expanded polystyrene or rockwool), smaller steel elements, pieces of wood, and glass. Such mixed debris is difficult to recycle. Separating thermal insulation that is "glued" by cement mortar to brickwork is probably the most difficult and time-consuming task in processing mixed debris. This task can be performed in a very different and fully "automatized" manner using Tenebrio molitor mealworms. The mealworms remove expanded polystyrene from brickwork surfaces and transform it into frass. In the paper, a research program aiming to prove the concept of using the mealworms of Tenebrio molitor for processing mixed debris is presented. The tests were conducted using two models of a three-layered brickwork wall, which is very common in Europe. The proposed approached was successful. Both types of used expanded polystyrene foam (EPS) were fully removed from multilayer wall specimens. The possibilities and limitations of the proposed processing method were discussed and analyzed. The conducted research proved that it is feasible to clean brickwork debris from the EPS using Tenebrio molitor mealworms. Differences in the speed of cleaning process regarding the type of EPS were noted. More research is needed to scale the process, and to find the best method for using frass. By using Tenebrio molitor mealworms, one can make the demolition process much cleaner.

SARS-CoV-2 Spike Protein (RBD) Subunit Adsorption at Abiotic Surfaces and Corona Formation at Polymer Particles.

The adsorption kinetics of the SARS-CoV-2 spike protein subunit with the receptor binding domain at abiotic surfaces was investigated. A combination of sensitive methods was used such as atomic force microscopy yielding a molecular resolution, a quartz microbalance, and optical waveguide lightmode spectroscopy. The two latter methods yielded in situ information about the protein adsorption kinetics under flow conditions. It was established that at pH 3.5-4 the protein adsorbed on mica and silica surfaces in the form of compact quasi-spherical aggregates with an average size of 14 nm. The maximum coverage of the layers was equal to 3 and 1 mg m-2 at pH 4 and 7.4, respectively. The experimental data were successfully interpreted in terms of theoretical results derived from modeling. The experiments performed for flat substrates were complemented by investigations of the protein corona formation at polymer particles carried out using in situ laser Doppler velocimetry technique. In this way, the zeta potential of the protein layers was acquired as a function of the coverage. Applying the electrokinetic model, these primary data were converted to the dependence of the subunit zeta potential on pH. It was shown that a complete acid-base characteristic of the layer can be acquired only using nanomolar quantities of the protein.

Variously Prepared Zeolite Y as a Modifier of ANFO.

In the presented research, we investigated Ammonium Nitrate Fuel Oil (ANFO), with the addition of variously modified zeolite Y as an attractive explosive. Analysis of both blasting tests and thermodynamic models of blasting properties led to the conclusion that the addition of zeolite Y enhanced the detonation properties of such prepared ANFO via the growth of the detonation pressure, temperature, compression energy, and heat of the explosion. Generally, the modification of ANFO with variously prepared zeolite Y also reduced the volume of (COx + NOx) post-blast fumes. Furthermore, it was found that the ANFO's velocity of detonation (VOD) could be controlled by the choice of the way of zeolite Y modification. Namely, for zeolite Y without Mg, as well as Mg-Y prepared via the impregnation method, the VOD rose. The opposite effect was observed when ANFO was modified with Mg-Y, obtained from the deposition of Mg over zeolite Y via the ultrasonic-assisted procedure.

Human Vimentin Layers on Solid Substrates: Adsorption Kinetics and Corona Formation Investigations.

Adsorption kinetics of human vimentin on negatively charged substrates (mica, silica, and polymer particles) was analyzed using atomic force microscopy (AFM), quartz microbalance (QCM), and the laser doppler velocimetry (LDV) method. AFM studies realized under diffusion conditions proved that the adsorbed protein layer mainly consisted of aggregates in the form of compact tetramers and hexamers of a size equal to 11-12 nm. These results were consistent with vimentin adsorption kinetics under flow conditions investigated by QCM. It was established that vimentin aggregates efficiently adsorbed on the negatively charged silica sensor at pH 3.5 and 7.4, forming compact layers with the coverage reaching 3.5 mg m-2. Additionally, the formation of the vimentin corona at polymer particles was examined using the LDV method and interpreted in terms of the electrokinetic model. This allowed us to determine the zeta potential of the corona as a function of pH and the electrokinetic charge of aggregates, which was equal to -0.7 e nm-2 at pH 7.4 in a 10 mM NaCl solution. The anomalous adsorption of aggregates exhibiting an average negative charge on the negatively charged substrates was interpreted as a result of a heterogeneous charge distribution. These investigations confirmed that it is feasible to deposit stable vimentin layers both at planar substrates and at carrier particles with well-controlled coverage and zeta potential. They can be used for investigations of vimentin interactions with various ligands including receptors of the innate immune system, immunoglobulins, bacterial virulence factors, and spike proteins of viruses.

Kinetics of Immunolatex Deposition at Abiotic Surfaces under Flow Conditions: Towards Quantitative Agglutination Assays.

Physicochemical properties of immunolatex, prepared by incubation of negatively charged polystyrene microparticles with polyclonal rabbit IgGs, were determined by a variety of experimental techniques. These comprised dynamic light scattering (DLS), laser Doppler velocimetry (LDV) and atomic force microscopy (AFM). The particle diffusion coefficient, the hydrodynamic diameter, the electrophoretic mobility, the zeta potential and the suspension stability were determined as a function of pH for different ionic strengths. The deposition of the immunolatex on bare and polyallylamine (PAH) functionalized mica was investigated using the microfluidic oblique impinging-jet cell, with an in situ, real-time image analysis module. The particle deposition kinetics was acquired by a direct particle enumeration procedure. The measurements enabled us to determine the range of pH where the specific deposition of the immunolatex on these substrates was absent. We argue that the obtained results have practical significance for conducting efficient flow immunoassays governed by specific antigen/antibody interactions.

Antibacterial and Antifungal Properties of Silver Nanoparticles-Effect of a Surface-Stabilizing Agent.

The biocidal properties of silver nanoparticles (AgNPs) prepared with the use of biologically active compounds seem to be especially significant for biological and medical application. Therefore, the aim of this research was to determine and compare the antibacterial and fungicidal properties of fifteen types of AgNPs. The main hypothesis was that the biological activity of AgNPs characterized by comparable size distributions, shapes, and ion release profiles is dependent on the properties of stabilizing agent molecules adsorbed on their surfaces. Escherichia coli and Staphylococcus aureus were selected as models of two types of bacterial cells. Candida albicans was selected for the research as a representative type of eukaryotic microorganism. The conducted studies reveal that larger AgNPs can be more biocidal than smaller ones. It was found that positively charged arginine-stabilized AgNPs (ARGSBAgNPs) were the most biocidal among all studied nanoparticles. The strongest fungicidal properties were detected for negatively charged EGCGAgNPs obtained using (-)-epigallocatechin gallate (EGCG). It was concluded that, by applying a specific stabilizing agent, one can tune the selectivity of AgNP toxicity towards desired pathogens. It was established that E. coli was more sensitive to AgNP exposure than S. aureus regardless of AgNP size and surface properties.

Deposition of Polymer Particles with Fibrinogen Corona at Abiotic Surfaces under Flow Conditions.

The deposition kinetics of polymer particles with fibrinogen molecule coronas at bare and poly-L-lysine (PLL) modified mica was studied using the microfluid impinging-jet cell. Basic physicochemical characteristics of fibrinogen and the particles were acquired using dynamic light scattering and the electrophoretic mobility methods, whereas the zeta potential of the substrates was determined using streaming potential measurements. Subsequently, an efficient method for the preparation of the particles with coronas, characterized by a controlled fibrinogen coverage, was developed. This enabled us to carry out measurements, which confirmed that the deposition kinetics of the particles at mica vanished at pH above 5. In contrast, the particle deposition of PLL modified mica was at maximum for pH above 5. It was shown that the deposition kinetics could be adequately analyzed in terms of the mean-field approach, analogously to the ordinary colloid particle behavior. This contrasts the fibrinogen molecule behavior, which efficiently adsorbs at negatively charged substrates for the entire range pHs up to 9.7. These results have practical significance for conducting label-free immunoassays governed by the specific antigen/antibody interactions.

Applicability of QCM-D for Quantitative Measurements of Nano- and Microparticle Deposition Kinetics: Theoretical Modeling and Experiments.

A new theoretical model is formulated for the quantitative analysis of quartz crystal microbalance (QCM) response for heterogeneous loads consisting of nano- and microparticles. The influence of particle coverage and structure is described using a universal correction function in an ab initio manner. Explicit analytical expressions for the frequency and dissipation shifts are derived for the entire range of particle size under the rigid contact regime. The solvent coupling functions are also calculated to determine the dry coverage using the QCM measurements. These expressions furnish the upper limit of the QCM signal, which can be attained for a sensor providing perfect adhesion of particles. Correction functions accounting for the finite adhesion strength (soft contact regime) are also derived. The theoretical results are confronted with QCM and atomic force microscopy measurements of positively charged polymer particle deposition on silica sensors. The main features of the theoretical model are confirmed, especially the abrupt decrease in the QCM wet mass with the particle coverage and the overtone number. The latter effect is especially pronounced for microparticles under the soft contact regime, where the higher-number overtones produce a negligible QCM signal. These results represent a useful reference data for the interpretation of protein and bioparticles, for example, virus and bacteria attachment processes to various substrates.

Mechanism of fibrinogen /microparticle complex deposition on solid substrates: Role of pH.

Deposition kinetics of fibrinogen/polystyrene particle complexes on mica and the silicon/silica substrates was studied using the direct optical and atomic force microscopy. Initially, basic physicochemical characteristics of fibrinogen and the microparticles were acquired using the dynamic light scattering and the electrophoretic mobility methods, whereas the zeta potential of the substrates was determined using the streaming potential measurements. Subsequently an efficient method for the preparation of fibrinogen/polymer microparticle complexes characterized by controlled coverage and molecule orientation was developed. It was demonstrated that for a lower suspension concentration the complexes are stable for pH range 3-9 and for a large concentration for pH below 4.5 and above 5.5. This enabled to carry out thorough pH cycling experiments where their isoelectric point was determined to appear at pH 5. Kinetic measurements showed that the deposition rate of the complexes vanished at pH above 5, whereas the kinetics of the positively charged amidine particles, used as control, remained at maximum for pH up to 9. These results were theoretically interpreted using the hybrid random sequential adsorption model. It was confirmed that the deposition kinetics of the complexes can be adequately analyzed in terms of the mean-field approach, analogously to the ordinary colloid particle behavior. This is in contrast to the fibrinogen molecule behavior, which efficiently adsorb on negatively charged substrates for the entire range pHs up to 9.7. These results have practical significance for conducting efficient immunoassays governed by the specific antigen/antibody interactions.

Silver nanoparticle/fibrinogen bilayers - Mechanism of formation and stability determined by in situ electrokinetic measurements.

The kinetics of negatively charged silver nanoparticle (AgNP) deposition on the supporting fibrinogen monolayers of well-characterized coverage was determined by the atomic force microscopy (AFM). The kinetics was quantitatively interpreted in terms of the hybrid random sequential adsorption model. The electrokinetic properties of the fibrinogen monolayers and fibrinogen/AgNP bilayers were thoroughly characterized in situ by the streaming potential measurements. These results were interpreted in terms of the general electrokinetic model expressing the particle coverage in terms of the zeta potential of the bilayers. This allowed one to determine the adsorption constants and the binding energy of AgNPs, which was equal to -20.8 and -21.3 kT for pH 3.5 and 7.4, respectively. These results confirmed the end-on mechanism of fibrinogen adsorption and the presence of positively charged spots at its molecule at pH 7.4 where it exhibits an average negative charge. Besides significance to basic science, the obtained results can be exploited for developing a procedure for producing AgNP monolayers of well-defined coverage and controlled particle release profile.

Spheroidal Microparticle Monolayers Characterized by Streaming Potential Measurements.

An efficient method was developed enabling the synthesis of spheroidal polymer microparticles. Thorough physicochemical characteristics of the particles were acquired comprising the size, shape, electrophoretic mobility, and the diffusion coefficient. The particles were monodisperse, and their shape was well-fitted by prolate spheroids having the axis ratio equal to 4.17. Knowing the diffusion coefficient, their hydrodynamic diameter of 449 nm was calculated, which matched the value derived from Brenner's analytical expression. Particle deposition kinetics on mica and silicon/silica substrates, modified by poly(allylamine hydrochloride) (PAH) adsorption, was studied by optical microscopy and AFM imaging. The validity of the random sequential adsorption model was confirmed. Additionally, monolayers of the particles on these substrates were thoroughly characterized in situ by the streaming potential measurements for different ionic strengths. These measurements confirmed that the ζ potential change with the spheroidal particle coverage is less abrupt than for spheres and agrees with theoretical predictions. Exploiting these results, a useful analytical expression was derived that allows one to calculate the spheroidal particle coverage in situ via the streaming potential measurements. This expression, especially accurate for low coverage range, can be used for a quantitative interpretation of adsorption and desorption kinetics of anisotropic macromolecules, e.g., proteins on solid substrates.

Monolayers of immunoglobulin G on polystyrene microparticles and their interactions with human serum albumin.

The adsorption of mouse monoclonal immunoglobulin G (IgG) on negatively charged polystyrene microparticles was studied by the laser Doppler velocimetry (LDV) electrophoretic mobility measurements. The dependence of the electrophoretic mobility of microparticles on the IgG concentration in the suspension was determined for different ionic strengths and pHs (3.5, 7.4). The increase in the electrophoretic mobility was quantitatively interpreted in terms of the 3D electrokinetic model. The maximum coverage of IgG on latex was determined by the depletion method aided by AFM imaging. It was shown by monitoring the electrophoretic mobility and hydrodynamic dimeter of IgG covered microparticles over prolonged time periods that IgG adsorption was irreversible. The acid-base properties of the IgG monolayers were also determined in pH cycling experiments. It was also confirmed that the adsorption of human serum albumin (HSA) on saturated IgG monolayers, often referred to as blocking, was negligible at pH 7.4.

Fibrinogen: a journey into biotechnology.

Fibrinogen has been known since the mid-nineteenth century. Although initially its interest had been within the field of physiology over time its study has spread to new disciplines such as biochemistry, colloids and interfaces or biotechnology. First, we will describe the bulk properties of the molecule as well as its supramolecular assembly with different ligands by using different techniques and theoretical models. In the next step we will analyze the interfacial properties, an important topic because fibrinogen is considered to be a major inhibitor of lung surfactants' function at the lining layer of alveoli. The final step will be devoted to its main application in biotechnology. Thus, the adsorption of fibrinogen at solid/electrolyte interfaces and at carrier particles will be discussed. The reversibility of adsorption, fibrinogen molecule orientation, and maximum coverage will be thoroughly discussed. The stability of fibrinogen monolayers formed at these surfaces with respect to pH and ionic strength cyclic changes will also be presented. Based on the physicochemical data, adsorption kinetics and colloid particle deposition measurements, probable adsorption mechanisms of fibrinogen on solid/electrolyte interfaces will be defined.