Formation of poly-L-lysine monolayers on silica : modeling and experimental studies

Modification of solid substrates by poly-l-lysine (PLL) layers has been widely employed in order to improve their biocompatibility, for promoting protein and cell immobilization for fabrication of biosensor arrays and antibacterial coatings. However, despite many studies conducted in the literature, there is a deficiency in a quantitative description of PLL adsorption processes. It is postulated that this becomes feasible by applying direct experimental techniques combined with thorough theoretical modeling. In this work, the kinetics of PLL adsorption on silica for various ionic strengths was determined in situ under controlled flow conditions using the optical reflectometry and the streaming potential methods. Both the initial adsorption rates and longer time kinetic runs were acquired and quantitatively interpreted in terms of the convective diffusion and the random sequential adsorption theoretical modeling based on the coarse-grained Monte Carlo approach. This unique combination of experimental and theoretical approaches enabled us to gain new insight into the mechanism of macroion adsorption controlled by the electrostatic interactions, which affect both the molecule conformations and the blocking effects. Besides significance for basic science, the results obtained in this work can be exploited for developing reliable procedures for preparing stable PLL monolayers of well-controlled coverage and electrokinetic properties

Bubble motion in liquids and physocochemcal method of detection of surface-active pollutants in water

Motion of gas bubbles in aqueous phase (either clean water or solutions of surface-active substances) is a phenomenon of great practical importance. Gas/liquid contacting is one of the most common operations in the chemical and petrochemical industry and mineral processing In particular in mineral industry, for all kind of flotation processes it is the main act responsible for the success of the entire technology As a result, properties of the liquid/gas interfaces are considered as a one of the most important parameters, determining the outcome of industrial applications and engineering processes. These properties can be modified by surfactants which adsorption (molecules accumulation) at the interfaces leads to the decrease in the interfacial tension and modification of the hydrodynamic boundary conditions. Description of a single bubble motion in wide range of flow magnitude (Reynolds numbers) is not trivial and many attempts have been undertaken to quantify a bubble behavior in liquids. This paper presents a short overview of the current “state of arts” on physics of the bubble motion in liquids and the elaborated models, describing motion of the bubble formed in liquid phase. The comparison of the theoretical models predictions with the available experimental data is presented. It is shown, moreover, that the bubble velocity can be used as a very sensitive tool for detection of organic contaminations in environmental water samples

Particle Deposition to Silica Surfaces Functionalized with Cationic Polyelectrolytes

Positively charged water-solid interfaces are prepared by adsorption of a cationic polyelectrolyte poly(diallyldimethylammonium chloride) (PDADMAC) from aqueous solutions to planar silica substrates. These substrates are characterized by atomic force microscopy (AFM), optical reflectivity, and streaming current measurements. By tuning the amount of adsorbed polyelectrolyte, the surface charge of the substrate can be systematically varied. These substrates are further used to study deposition of sulfate latex nanoparticles, which is also accomplished by optical reflectivity. This deposition process is found to be consistent with an extension of the random sequential adsorption (RSA) model in a semi-quantitative fashion. Such deposition studies were further used to ascertain that the substrates obtained by in situ and ex situ functionalization behave in an identical fashion

Surface roughness in bubble attachment and flotation of highly hydrophobic solids in presence of frother – experiment and simulations

In this paper, the kinetic of the three-phase contact (TPC) formation and the flotation recovery of highly hydrophobic solids with different surface roughness were studied in pure water and aqueous solutions of n-octanol. The surface roughness varied between 1 to 100 μm. It was found that there was a strong influence of surface roughness on both kinetics of TPC formation and flotation. The time of three phase contact formation and flotation rate were much faster for rough surfaces in both water and aqueous solutions of frother. Irrespective of the surface roughness, at above a certain frother dose, the attachment time increased and the flotation rate decreased. It was related to the presence of air at the hydrophobic solid surfaces. The mechanism of this prolongation of the time of TPC formation at the solid surfaces with different roughness due to the frother overdosage was discussed, and the experimental data were confirmed by numerical simulations

Conformations of Poly- l -lysine Molecules in Electrolyte Solutions

Physicochemical properties of poly-l-lysine (PLL) hydrobromide were determined by molecular dynamics (MD) modeling and a variety of experimental techniques. Primarily, the density, the chain diameter, the monomer length, and the PLL molecule conformations were theoretically calculated. These results were applied for the interpretation of experimental data acquired for the PLL sample of average molar mass equal to 122 kg/mol. They comprised the diffusion coefficient, the hydrodynamic diameter, and the electrophoretic mobility of molecules determined for the ionic strength ranging from 2 × 10-5 to 0.15 M and pH 5.6. Using these data, the electrokinetic charge and the effective ionization degree of PLL molecules were determined as a function of ionic strength. Additionally, precise dynamic viscosity measurements for dilute PLL solutions were performed yielding the intrinsic viscosity, which decreased from 2420 to 120 for ionic strengths of 2 × 10-5 and 0.15 M, respectively. This confirmed that PLL molecules assume extended conformations in accordance with theoretical modeling. These data enabled to determine the molecule length, the chain diameter, and its effective molecule cross-section area for various ionic strengths. Therefore, it was concluded that the combined dynamic light scattering and viscosity measurements supplemented by MD modeling furnish reliable information about PLL macromolecule conformations in electrolyte solution. Besides the significance for basic science, the results obtained in this work can be exploited for precisely determining the molar mass of macroions.Peer reviewe

Kinetics of Human Serum Albumin Adsorption on Polycation Functionalized Silica

The adsorption kinetics of human serum albumin (HSA) on bare and poly-L-arginine (PARG)-modified silica substrates were investigated using reflectometry and atomic force microscopy (AFM). Measurements were carried out at various pHs, flow rates and albumin concentrations in the 10 and 150 mM NaCl solutions. The mass transfer rate constants and the maximum protein coverages were determined for the bare silica at pH 4.0 and theoretically interpreted in terms of the hybrid random sequential adsorption model. These results were used as reference data for the analysis of adsorption kinetics at larger pHs. It was shown that the adsorption on bare silica rapidly decreased with pH and became negligible at pH 7.4. The albumin adsorption on PARG-functionalized silica showed an opposite trend, i.e., it was negligible at pH 4 and attained maximum values at pH 7.4 and 150 mM NaCl, the conditions corresponding to the blood serum environment. These results were interpreted as the evidence of a significant role of electrostatic interactions in the albumin adsorption on the bare and PARG-modified silica. It was also argued that our results can serve as useful reference data enabling a proper interpretation of protein adsorption on substrates functionalized by polyelectrolytes

Bubble Formation and Motion in Liquids—A Review

In flotation, a bubble acts as a carrier for attached particles. The properties of the gas–liquid interface of the bubble are one of the main factors determining the bubble motion and flotation efficiency. Monitoring of the bubble motion may deliver interesting information about the state of the gas–liquid interface. In the case of pure liquids, a bubble surface is fully mobile, while the presence of surface-active substances (e.g., surfactants) causes diminishing bubble velocity due to the retardation of the interface fluidity. The theoretical prediction of the terminal velocity value for the bubble has been investigated for over a century, delivering a number of various models describing bubble motion in a liquid. This narrative review is devoted to the motion of the bubble in stagnant liquids and is divided into three main sections describing: (i) experimental techniques for tracking bubble motion, (ii) bubble motion and shape deformation in clean water, and (iii) bubble motion in solutions of surface-active substances

Poly-L-arginine molecule properties in simple electrolytes : molecular dynamic modeling and experiments

Physicochemical properties of poly-L-arginine (P-Arg) molecules in NaCl solutions were determined by molecular dynamics (MD) modeling and various experimental techniques. Primarily, the molecule conformations, the monomer length and the chain diameter were theoretically calculated. These results were used to interpret experimental data, which comprised the molecule secondary structure, the diffusion coefficient, the hydrodynamic diameter and the electrophoretic mobility determined at various ionic strengths and pHs. Using these data, the electrokinetic charge and the effective ionization degree of P-Arg molecules were determined. In addition, the dynamic viscosity measurements for dilute P-Arg solutions enabledto determine the molecule intrinsic viscosity, which was equal to 500 and 90 for ionic strength of 10(−5) and 0.15 M, respectively. This confirmed that P-Arg molecules assumed extended conformations and approached the slender body limit at the low range of ionic strength. The experimental data were also used to determine the molecule length and the chain diameter, which agreed with theoretical predictions. Exploiting these results, a robust method for determining the molar mass of P-Arg samples, the hydrodynamic diameter, the radius of gyration and the sedimentation coefficient was proposed

Thickness of the particle-free layer near charged interfaces in suspensions of like-charged nanoparticles

When a suspension of charged nanoparticles is in contact with a like-charged water–solid interface, next to this interface a particle-free layer is formed. The present study provides reliable measurements of the thickness of this particle-free layer with three different techniques, namely optical reflectivity, quartz crystal microbalance (QCM), and direct force measurements with atomic force microscopy (AFM). Suspensions of negatively charged nanoparticles of different size and type are investigated. When the measured layer thickness is normalized to the particle size, one finds that this normalized thickness shows universal inverse square root dependence on the particle volume fraction. This universal dependence can be also derived from Poisson–Boltzmann theory for highly asymmetric electrolytes, whereby one has to assume that the nanoparticles represent the multivalent coions

Formation of Polyllysine Monolayers on Silica: Modeling and Experimental Studies

Modification of solid substrates by poly-l-lysine (PLL) layers has been widely employed in order to improve their biocompatibility, for promoting protein and cell immobilization for fabrication of biosensor arrays and antibacterial coatings. However, despite many studies conducted in the literature, there is a deficiency in a quantitative description of PLL adsorption processes. It is postulated that this becomes feasible by applying direct experimental techniques combined with thorough theoretical modeling. In this work, the kinetics of PLL adsorption on silica for various ionic strengths was determined in situ under controlled flow conditions using the optical reflectometry and the streaming potential methods. Both the initial adsorption rates and longer time kinetic runs were acquired and quantitatively interpreted in terms of the convective diffusion and the random sequential adsorption theoretical modeling based on the coarse-grained Monte Carlo approach. This unique combination of experimental and theoretical approaches enabled us to gain new insight into the mechanism of macroion adsorption controlled by the electrostatic interactions, which affect both the molecule conformations and the blocking effects. Besides significance for basic science, the results obtained in this work can be exploited for developing reliable procedures for preparing stable PLL monolayers of well-controlled coverage and electrokinetic properties