Deposition of Human-Serum-Albumin-Functionalized Spheroidal Particles on Abiotic Surfaces: Reference Kinetic Results for Bioparticles.

Human serum albumin (HSA) corona formation on polymer microparticles of a spheroidal shape was studied using dynamic light scattering and Laser Doppler Velocimetry (LDV). Physicochemical characteristics of the albumin comprising the zeta potential and the isoelectric point were determined as a function of pH for various ionic strengths. Analogous characteristics of the polymer particles were analyzed. The adsorption of albumin on the particles was in situ monitored by LDV. The stability of the HSA-functionalized particle suspensions under various pHs and their electrokinetic properties were also determined. The deposition kinetics of the particles on mica, silica and gold sensors were investigated by optical microscopy, AFM and quartz microbalance (QCM) under diffusion and flow conditions. The obtained results were interpreted in terms of the random sequential adsorption model that allowed to estimate the range of applicability of QCM for determining the deposition kinetics of viruses and bacteria at abiotic surfaces.

Cu-Containing Faujasite-Type Zeolite as an Additive in Eco-Friendly Energetic Materials.

Regarding the current state of the art on the utilization of zeolites in industry, the application of zeolites as an additive to eco-friendly energetic materials indicates the innovative character of the present research. One of the most commonly used energetic materials in the mining industry (engineering works) is ANFO (ammonium nitrate fuel oil), due to its easy and cheap production procedure as well as its good energetic properties and vast possibilities for modification. In the present research, we investigated Cu-zeolite with a faujasite structure (Cu-FAU) as a modifier of ANFO-based energetic materials. Analysis of the results obtained from thermodynamic calculations of energetic performance led to the conclusion that the application of Cu-faujasite as an additive to ANFO resulted in a relevant reduction in the total emission of post-decomposition fumes, with simultaneous enhancement of the energetic properties of the energetic material, which corresponded with the changes in the status of the surface and the reduced thermal effect accompanying the ammonium nitrate's decomposition. From analysis of both the energetic performance and fumes, it may be concluded that our eco-friendly and enhanced energetic material can be used as a low-emission source of energy for the quarrying of raw materials.

Quartz Crystal Microbalance Frequency Response to Discrete Adsorbates in Liquids.

Quartz crystal microbalance with dissipation monitoring (QCM-D) has become a major tool enabling accurate investigation of the adsorption kinetics of nanometric objects such as DNA fragments, polypeptides, proteins, viruses, liposomes, polymer, and metal nanoparticles. However, in liquids, a quantitative analysis of the experimental results is often intricate because of the complex interplay of hydrodynamic and adhesion forces varying with the physicochemical properties of adsorbates and functionalized QCM-D sensors. In the present paper, we dissect the role of hydrodynamics for the analytically tractable case of stiff contact, whereas the adsorbed rigid particles oscillate with the resonator without rotation. Under the assumption of the low surface coverage, we theoretically study the excess shear force exerted on the resonator, which has two contributions: (i) the fluid-mediated force due to flow disturbance created by the particle and (ii) the force exerted on the particle by the fluid and transmitted to the sensor via contact. The theoretical analysis enables an accurate interpretation of the QCM-D impedance measurements. It is demonstrated inter alia that for particles of the size comparable with protein molecules, the hydrodynamic force dominates over the inertial force and that the apparent mass derived from QCM independently of the overtone is about 10 times the Sauerbrey (inertial) mass. The theoretical results show excellent agreement with the results of experiments and advanced numerical simulations for a wide range of particle sizes and oscillation frequencies.

Anisotropic Particle Deposition Kinetics from Quartz Crystal Microbalance Measurements: Beyond the Sphere Paradigm.

Deposition kinetics of polymer particles characterized by a prolate spheroid shape on gold sensors modified by the adsorption of poly(allylamine) was investigated using a quartz crystal microbalance and atomic force microscopy. Reference measurements were also performed for polymer particles of a spherical shape and the same diameter as the spheroid shorter axis. Primarily, the frequency and dissipation shifts for various overtones were measured as a function of time. These kinetic data were transformed into the dependence of the complex impedance, scaled up by the inertia impedance, upon the particle size to the hydrodynamic boundary layer ratio. The results obtained for low particle coverage were interpolated, which enabled the derivation of Sauerbrey-like equations, yielding the real particle coverage using the experimental frequency or dissipation (bandwidth) shifts. Experiments carried out for a long deposition time confirmed that, for spheroids, the imaginary and real impedance components were equal to each other for all overtones and for a large range of particle coverage. This result was explained in terms of a hydrodynamic, lubrication-like contact of particles with the sensor, enabling their sliding motion. In contrast, the experimental data obtained for spheres, where the impedance ratio was a complicated function of overtones and particle coverage, showed that the contact was rather stiff, preventing their motion over the sensor. It was concluded that results obtained in this work can be exploited as useful reference systems for a quantitative interpretation of bioparticle, especially bacteria, deposition kinetics on macroion-modified surfaces.

Quantifying Nanoparticle Layer Topography: Theoretical Modeling and Atomic Force Microscopy Investigations.

A comprehensive method consisting of theoretical modeling and experimental atomic force microscopy (AFM) measurements was developed for the quantitative analysis of nanoparticle layer topography. Analytical results were derived for particles of various shapes such as cylinders (rods), disks, ellipsoids, hemispheres (caps), etc. It was shown that for all particles, their root-mean-square (rms) parameter exhibited a maximum at the coverage about 0.5, whereas the skewness was a monotonically decreasing function of the coverage. This enabled a facile determination of the particle coverage in the layer, even if the shape and size were not known. The validity of the analytical results was confirmed by computer modeling and experimental data acquired by AFM measurements for polymer nanoparticle deposition on mica and silica. The topographical analysis developed in this work can be exploited for a quantitative characterization of self-assembled layers of nano- and bioparticles, e.g., carbon nanotubes, silica and noble metal particles, DNA fragments, proteins, vesicles, viruses, and bacteria at solid surfaces. The acquired results also enabled a proper calibration, in particular the determination of the measurement precision, of various electron and scanning probe microscopies, such as AFM.

Mimicking Pseudo-Virion Interactions with Abiotic Surfaces: Deposition of Polymer Nanoparticles with Albumin Corona.

Adsorption of human serum albumin (HSA) molecules on negatively charged polystyrene microparticles was studied using the dynamic light scattering, the electrophoretic and the solution depletion methods involving atomic force microscopy. Initially, the physicochemical characteristics of the albumin comprising the hydrodynamic diameter, the zeta potential and the isoelectric point were determined as a function of pH. Analogous characteristics of the polymer particles were acquired, including their size and zeta potential. The formation of albumin corona on the particles was investigated in situ by electrophoretic mobility measurements. The size, stability and electrokinetic properties of the particles with the corona were also determined. The particle diameter was equal to 125 nm, which coincides with the size of the SARS-CoV-2 virion. The isoelectric point of the particles appeared at a pH of 5. The deposition kinetics of the particles was determined by atomic force microscopy (AFM) under diffusion and by quartz microbalance (QCM) under flow conditions. It was shown that the deposition rate at a gold sensor abruptly vanished with pH following the decrease in the zeta potential of the particles. It is postulated that the acquired results can be used as useful reference systems mimicking virus adsorption on abiotic surfaces.

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.

QCM-D Investigations of Anisotropic Particle Deposition Kinetics: Evidences of the Hydrodynamic Slip Mechanisms.

Deposition kinetics of positively charged polymer microparticles, characterized by prolate spheroid shape, at silica and gold sensors was investigated using the quartz microbalance (QCM) technique. Reference measurements were also performed for positively charged polymer particles of spherical shape and the same mass as the spheroids. Primarily, the frequency and bandwidth shifts for various overtones were measured as a function of time. It is shown that the ratio of these signals is close to unity for all overtones. These results were converted to the dependence of the frequency shift on the particle coverage, directly determined by atomic force microscopy and theoretically interpreted in terms of the hydrodynamic model. A quantitative agreement with experiments was attained considering particle slip relative to the ambient oscillating flow. In contrast, the theoretical results pertinent to the rigid contact model proved inadequate. The particle deposition kinetics derived from the QCM method was compared with theoretical modeling performed according to the random sequential adsorption approach. This allowed to assess the feasibility of the QCM technique to furnish proper deposition kinetics for anisotropic particles. It is argued that the hydrodynamic slip effect should be considered in the interpretation of QCM kinetic results acquired for bioparticles, especially viruses.

Nanoparticle and bioparticle deposition kinetics.

Mechanisms and kinetic of particle deposition at solid surfaces leading to the formation of self-assembled layers of controlled structure and density were reviewed. In the first part theoretical aspects were briefly discussed, comprising limiting analytical solutions for the linear transport under flow and diffusion. Methods of the deposition kinetics analysis for non-linear regimes affected by surface blocking were also considered. Characteristic monolayer formation times under diffusion and flow for the nanoparticle size range were calculated. In the second part illustrative experimental results obtained for micro- and nanoparticles were discussed. Deposition at planar substrates was analyzed with emphasis focused on the stability of layers and the release kinetics of silver particles. Applicability of the quartz microbalance measurements (QCM) for quantitative studies of nanoparticle deposition kinetic was also discussed. Except for noble metal and polymer particles, representative results for virus deposition at abiotic surfaces were analyzed. Final part of the review was devoted to nanoparticle corona formation at polymer carrier particles investigated by combination of the concentration depletion, AFM, SEM and the in situ electrokinetic method. It is argued that the results obtained for colloid particles can be used as reliable reference systems for interpretation of protein and other bioparticle deposition, confirming the thesis that simple is universal.

Nanoparticle and Bioparticle Deposition Kinetics: Quartz Microbalance Measurements.

Controlled deposition of nanoparticles and bioparticles is necessary for their separation and purification by chromatography, filtration, food emulsion and foam stabilization, etc. Compared to numerous experimental techniques used to quantify bioparticle deposition kinetics, the quartz crystal microbalance (QCM) method is advantageous because it enables real time measurements under different transport conditions with high precision. Because of its versatility and the deceptive simplicity of measurements, this technique is used in a plethora of investigations involving nanoparticles, macroions, proteins, viruses, bacteria and cells. However, in contrast to the robustness of the measurements, theoretical interpretations of QCM measurements for a particle-like load is complicated because the primary signals (the oscillation frequency and the band width shifts) depend on the force exerted on the sensor rather than on the particle mass. Therefore, it is postulated that a proper interpretation of the QCM data requires a reliable theoretical framework furnishing reference results for well-defined systems. Providing such results is a primary motivation of this work where the kinetics of particle deposition under diffusion and flow conditions is discussed. Expressions for calculating the deposition rates and the maximum coverage are presented. Theoretical results describing the QCM response to a heterogeneous load are discussed, which enables a quantitative interpretation of experimental data obtained for nanoparticles and bioparticles comprising viruses and protein molecules.

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.

Adaptation of the Marine Bacterium Shewanella baltica to Low Temperature Stress.

Marine bacteria display significant versatility in adaptation to variations in the environment and stress conditions, including temperature shifts. Shewanella baltica plays a major role in denitrification and bioremediation in the marine environment, but is also identified to be responsible for spoilage of ice-stored seafood. We aimed to characterize transcriptional response of S. baltica to cold stress in order to achieve a better insight into mechanisms governing its adaptation. We exposed bacterial cells to 8 °C for 90 and 180 min, and assessed changes in the bacterial transcriptome with RNA sequencing validated with the RT-qPCR method. We found that S. baltica general response to cold stress is associated with massive downregulation of gene expression, which covered about 70% of differentially expressed genes. Enrichment analysis revealed upregulation of only few pathways, including aminoacyl-tRNA biosynthesis, sulfur metabolism and the flagellar assembly process. Downregulation was observed for fatty acid degradation, amino acid metabolism and a bacterial secretion system. We found that the entire type II secretion system was transcriptionally shut down at low temperatures. We also observed transcriptional reprogramming through the induction of RpoE and repression of RpoD sigma factors to mediate the cold stress response. Our study revealed how diverse and complex the cold stress response in S. baltica is.

Hydrodynamic Solvent Coupling Effects in Quartz Crystal Microbalance Measurements of Nanoparticle Deposition Kinetics.

Hydrodynamic coupling effects pertinent to quartz crystal microbalance (QCM) investigation of nanoparticle adsorption kinetics were evaluated using atomic force microscopy and the theoretical modeling. Monodisperse polymer particles of the size between 26 and 140 nm and the density of 1.05 g cm-3 were used. The ζ-potential of particles was opposite to the substrate ζ-potential that promoted their irreversible adsorption on the silica sensor. The experimental kinetic data were interpreted in terms of theoretical calculations derived from the hybrid random sequential adsorption model. This allowed us to determine the amount of hydrodynamically coupled solvent (electrolyte) for the absolute particle coverage range up to 0.5. The coupling function representing the ratio of the solvent to the particle volumes was also determined and used to explicitly calculate the solvent level in particle monolayers. It is shown that the solvent level abruptly increases with the particle coverage attaining values comparable with the particle size. One can expect that these results can serve as useful reference data for the interpretation of protein adsorption kinetics on rough surfaces where the presence of stagnant solvent is inevitable.

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.

Mechanisms of Fibrinogen Adsorption on Silica Sensors at Various pHs: Experiments and Theoretical Modeling.

The adsorption kinetics of human serum fibrinogen at silica substrates was studied using optical waveguide lightmode spectroscopy (OWLS) and quartz crystal microbalance (QCM) techniques. Measurements were performed at pH 3.5, 4, and 7.4 for various ionic strengths. The experimental data were interpreted in terms of a hybrid random sequential adsorption model. This allowed the mass transfer rate coefficient for the OWLS cell and maximum coverages to be determined at various pHs. The appearance of different, pH-dependent mechanisms of fibrinogen adsorption on silica substrates was confirmed. At pH 3.5 the molecules mostly adsorb in the side-on orientation that produces a low maximum coverage of ca. 1 mg m-2. At this pH, the kinetics derived from the OWLS measurements agree with those theoretically predicted using the convective-diffusion theory. In consequence, a comparison of the OWLS and QCM results allows the water factor and the dynamic hydration of fibrinogen molecules to be determined. At pH 7.4, the OWLS method gives inaccurate kinetic data for the low coverage range. However, the maximum coverage that was equal to ca. 4 mg m-2 agrees with the QCM results and with previous literature results. It is postulated that the limited accuracy of the OWLS method for lower coverage stems from a heterogeneous structure of fibrinogen monolayers, which consist of side-on and end-on adsorbed molecules. One can expect that the results acquired in this work allow development of a robust procedure for preparing fibrinogen monolayers of well-controlled coverage and molecule orientation, which can be exploited for efficient immunosensing purposes.

Human Serum Albumin Adsorption Kinetics on Silica: Influence of Protein Solution Stability.

Adsorption kinetics of human serum albumin (HSA) on silica substrates was studied using optical waveguide lightmode spectroscopy (OWLS) and quartz microbalance (QCM) techniques. Measurements were performed at pH 3.5, 5.6, and 7.4 for various bulk suspension concentrations and ionic strengths. The diffusion coefficient measurements showed that for pH 3.5 the HSA molecules are stable for NaCl concentrations from 10-3 to 0.15 M. This allowed us to precisely determine the mass transfer rate coefficients for the OWLS and QCM cells. The experimental data were adequately interpreted in terms of a hybrid random sequential adsorption model. The OWLS maximum coverage of HSA at pH 3.5, which is equal to 1.3 mg m-2, agrees with the QCM result and with previous results derived from streaming potential measurements. Thus, the results obtained at pH 3.5 served as reference data for the analysis of adsorption kinetics at higher pHs. In this way, it was confirmed that the adsorption kinetics of HSA molecules at pH 5.6 and 7.4 was considerably slower than at pH 3.5. This effect was attributed to aggregation of HSA solutions and interpreted in terms of a theoretical model combining the Smoluchowski aggregation theory with the convective diffusion mass transfer theory. New analytical equations were derived that can be used for the interpretation of other protein adsorption from unstable solutions.

Kinetics of human serum albumin adsorption at silica sensor: Unveiling dynamic hydration function.

Adsorption kinetics of human serum albumin (HSA) at a silica substrate was studied using the QCM-D and AFM methods. Measurements were performed at pH 3.5 for various bulk suspension concentrations and ionic strengths. The QCM experimental data were compared with the dry coverage of HSA derived from AFM and from the solution of the mass transfer equation. In this way, the dynamic hydration functions and water factors of HSA monolayers were quantitatively evaluated as a function of dry coverage for various ionic strengths. Using the hydration functions, the HSA adsorption runs derived from QCM-D measurements were converted to the dry coverage vs. the time relationships. In this way, the maximum coverage of irreversibly bound HSA molecules was determined. It was equal to 0.35 and 1.4 mg m-2 for NaCl concentration of 0.001 and 0.15 M, respectively. These results agree with previous experimental data derived by streaming potential measurements for mica and with theoretical modeling. Therefore, the side-on mechanism of HSA adsorption at silica sensor at pH 3.5 was confirmed. Also, a quantitative analysis of the desorption runs allowed one to calculate the binding energy of the reversibly bound HSA fraction. Beside significance to basic science, these results enable to develop a robust technique of preparing HSA monolayers at silica sensor of well-controlled coverage and molecule orientation.

[Treatment of ischemic stroke with mechanical trombectomy systems]. / Leczenie udaru niedokrwiennego mózgu z zastosowaniem systemów do trombektomii mechanicznej.

The implementation of ischemic stroke therapy has created new opportunities for clinical improvement and the reversal of adverse prognosis in patients with ischemic stroke. Mechanical thrombectomy has become the recommended treatment for acute stroke in a select group of patients and in highly specialized centres with experience in endovascular therapy. AIM: The aim of the study was to evaluate of the efficacy and safety of mechanical thrombectomy in patients with acute ischemic stroke within the first six hours of illness was reported. MATERIALS AND METHODS: 34 patients previously hospitalized in the Department of Neurology due to ischemic stroke were included in the study during the first six hours of illness. Short-term efficacy and safety (1 month after surgery) and long-term (3 months) were evaluated based on the assessment of early mortality, functional status and neurological status. Factors that increase the risk of death were also analyzed. RESULTS: In the study group, the recanalization of the vessel was obtained in 52% of patients, which was associated with a significant improvement of functional status. Improvements in functional and neurological status were obtained in most of the patients (63%), including very good functional status (mRS 0-1) in 7 (20%) patients upon discharge from the hospital. CONCLUSIONS: In the study group, the recanalization of the vessel was obtained in 52% of patients, which was associated with a significant improvement of functional status. Improvements in functional and neurological status were obtained in most of the patients (63%), including very good functional status (mRS 0-1) in 7 (20%) patients upon discharge from the hospital.

Formation mechanism of human serum albumin monolayers on positively charged polymer microparticles.

Human serum albumin (HSA) adsorption on positively and negatively charged polystyrene microparticles was studied at various pHs and NaCl concentrations. Thorough electrophoretic mobility measurements were carried out that enabled to monitor in situ the progress of protein adsorption. The maximum coverage of irreversibly adsorbed HSA on microparticles was determined by different concentration depletion methods, one of them involving AFM imaging of residual molecules. An anomalous adsorption of HSA on the positive microparticles was observed at pH 3.5 where the maximum coverage attained 1.0mgm-2 for NaCl concentrations of 0.05M despite that the molecules were on average positively charged. For comparison, the maximum coverage of HSA on negatively charged microparticles was equal to 1.3mgm-2 at this pH and NaCl concentration. At pH 7.4 the maximum coverage on positive microparticles was equal to 2.1mgm-2 for 0.05M NaCl concentration. On the other hand, for negative microparticles, negligible adsorption of HSA was observed at pH 7.4 and 9.7. These experimental data were adequately interpreted in terms of the random sequential adsorption approach exploiting the bead model of the HSA molecule. Different orientations of adsorbed molecules, inert alia, the edge-on orientation prevailing for positively charged microparticles at pH 7.4, were confirmed. This was explained in terms of a heterogeneous charge distribution over the HSA molecule prevailing for a wide range of pHs.

Formation of hematite nanoparticle monolayers of controlled coverage and structure at polymeric microparticles.

The deposition of hematite nanoparticles (22nm and 29nm in diameter) on negatively charged polystyrene microspheres (820nm in diameter) was studied by micro-electrophoretic measurements and AFM. The influence of ionic strength, varied between 10-4 and 10-2M, was determined. Initially, the electrophoretic mobility change of microspheres upon the addition of controlled amount of hematite nanoparticles were measured. These dependencies were quantitatively interpreted in terms of the general electrokinetic model. This allowed to determine the coverage of nanoparticles on microspheres under in situ conditions, which increased with ionic strength attaining 0.35 for the ionic strength of 10-2M and 29 in diameter hematite particles. This effect, attributed to the decreasing range of lateral electrostatic repulsion among deposited particles, was accounted for by the random sequential adsorption model. However, the coverages attained for lower ionic strength exceeded the theoretical predictions. This effect was interpreted in terms of an additional electrostatic screening due to polymeric chains present at the microparticle surface. The acid base properties of the hematite monolayers were also acquired by applying thorough micro-electrophoretic measurements. The obtained results confirmed a feasibility of preparing hematite nanoparticle monolayers on polymeric carrier microspheres having well-defined coverage and structure.