Behaviour of FITC-Labeled Polyallylamine in Polyelectrolyte Microcapsules

There are many studies devoted to the application of polyelectrolyte microcapsules (PMC) in various fields; however, there are significantly fewer studies devoted to the study of the polyelectrolyte microcapsules themselves. The study examined the mutual arrangement of the polyelectrolytes in 13-layered PMC capsules composed of (PAH/PSS)6PAH. The research showed that different layers of the polyelectrolyte microcapsules dissociate equally, as in the case of 13-layered PMC capsules composed of (PAH/PSS)6PAH with a well-defined shell, and in the case of 7-layered PMC capsules composed of (PAH/PSS)3PAH, where the shell is absent. The study showed that polyallylamine layers labeled with FITC migrate to the periphery of the microcapsule regardless of the number of layers. This is due to an increase in osmotic pressure caused by the rapid flow of ions from the interior of the microcapsule into the surrounding solution. In addition, FITC-polyallylamine has a lower charge density and less interaction with polystyrene sulfonate in the structure of the microcapsule. Meanwhile, the hydrophilicity of FITC-polyallylamine does not change or decreases slightly. The results suggest that this effect promotes the migration of labeled polyallylamine to a more hydrophilic region of the microcapsule, towards its periphery

A Study of the Buffer Capacity of Polyelectrolyte Microcapsules Depending on Their Concentration and the Number of Layers of the Polyelectrolyte Shell

Polyelectrolyte microcapsules are used in the development of new forms of targeted delivery systems, self-healing materials, sensors, and smart materials. Nevertheless, their buffer capacity has not been practically studied, although that characteristic makes it possible to estimate the change in the state of protonation of the entire polyelectrolyte system. This is necessary both for creating a buffer barrier system for pH-sensitive compounds (metals, enzymes, polyelectrolytes, drugs) and for the correct interpretation of the results of research and studying of the PMC structure. The buffer capacity of a PMC can be affected by the concentration of microcapsules in solution and the number of shell layers since the listed parameters affect other physicochemical properties of the PMC shell. This includes, for example, the electrical conductivity, permeability (of ions), osmotic pressure, charge density, etc. In this regard, we studied the change in the buffer capacity of polyelectrolyte microcapsules depending on their concentration and the number of shell layers. As a result, it was found that with an increasing concentration of microcapsules, the buffering capacity of the PMC increases, but at the same time, in the pH range from 4 to 5.5, the calculated buffering capacity of 1 billion capsules decreases with increasing their concentration. This effect may be associated with a decrease in the available -NH2 groups of the PMC’s shell. In addition, it was found that the main contribution to the buffer capacity of a PMC is made by the entire shell of the microcapsule and not just its surface. At the same time, the buffer capacity of the capsules has non-linear growth with an increase in the number of PMC shell layers. It is presumably associated either with a decrease in the polyelectrolyte layer with an increase in their number or with a decrease in the permeability of hydrogen protons

Sorption of Salts of Various Metals by Polyelectrolyte Microcapsules

Anthropogenic activity negatively affects the environment by polluting it with the salts of various metals. One of the ways to reduce this influence is to use water purification methods for the salts of various metals. Water purification methods based on nanomaterials are promising. In this regard, we proposed to study polyelectrolyte microcapsules (PMC) as a promising sorption agent for the salts of various metals. It was found that the polystyrene sulfonate-polyallylamine (PSS-PAH) polyelectrolyte complex and polyelectrolyte microcapsules of different compositions are not able to adsorb salts CuSO4, Pb(NO)3, FeCl3, and CuCl2. At the same time, it was found that all types of capsules, except for (PSS/PAH)2/PSS, are capable of sorbing about 420 µg of K3[Fe(CN)6] and about 500 µg of K4[Fe(CN)6] from solution. The adsorption of polyelectrolyte microcapsules has an electrostatic nature which is confirmed by increases in the sorption capacity of PMC of K3[Fe(CN)6] and K4[Fe(CN)6] with decreases in the pH of the solution. Also, It was confirmed that the sorption process of PMC of K3[Fe(CN)6] and K4[Fe(CN)6] is concentration dependent and has the limitation of the number of binding sites

Effect of Pollyallylamine on Alcoholdehydrogenase Structure and Activity

In this article, the effect of polyallylamine (PAA) on the structure and catalytic characteristics of alcohol dehydrogenase (ADH) was studied. For this research, we used methods of stationary kinetics and fluorescence spectroscopy. It has been shown that PAA non-competitively inhibits ADH activity while preserving its quaternary structure. It was established that 0.1 M ammonium sulfate removes the inhibitory effect of PAA on ADH, which is explained by the binding of sulfate anion (NH4)2SO4 with polyallylamine amino groups. As a result, the rigidity of the polymer chain increases and the ability to bind to the active loop of the enzyme increases. It is also shown that sodium chloride removes the inhibitory effect of PAA on ADH due to an electrostatic screening of the enzyme from polyelectrolyte. The method of encapsulating ADH in polyelectrolyte microcapsules was adapted to the structure and properties of the enzyme molecule. It was found that the best for ADH is its encapsulation by adsorption into microcapsules already formed on CaCO3 particles. It was shown that the affinity constant of encapsulated alcohol dehydrogenase to the substrate is 1.7 times lower than that of the native enzyme. When studying the affinity constant of ADH in a complex with PAA to ethanol, the effect of noncompetitive inhibition of the enzyme by polyelectrolyte was observed

A Study of the Buffer Capacity of Polyelectrolyte Microcapsules Depending on Their Ionic Environment and Incubation Temperature

Polyelectrolyte microcapsules (PMCs) are used in the development of new forms of drugs, coatings and diagnostic systems. Their buffer capacity, depending on the conditions of the medium, has not been practically studied, although it can affect the structure of both the capsule itself and the encapsulated agents. In this connection, we studied the buffer capacity of polyelectrolyte microcapsules of the composition (polystyrene sulfonate/polyallylamine)3 ((PSS/PAH)3) depending on the concentration and the type of salt in solution, as well as the microcapsule incubation temperature. It was found that the buffer capacity of microcapsules in the presence of mono- and di-valent salts of the same ionic strength did not differ practically. Increasing the NaCl concentration to 1 M led to an increase of buffer capacity of PMCs at pH ≥ 5, and an increase in NaCl concentration above 1 M did not change buffer capacity. The study of the buffer capacity of pre-heated PMCs showed that buffer capacity decreased with increasing incubation temperature, which was possibly due to the compaction of the PMCs and an increase in the number of compensated PAH sites. The addition of 1 M sodium chloride to heated PMCs presumably reversed the process described above, since an increase in the ionic strength of the solution led to an increase of the buffer capacity of the PMCs. The effects described above confirm the hypothesis put forward that the buffer properties of microcapsules are determined by uncompensated PAH regions in their composition

Sorption of Salts of Various Metals by Polyelectrolyte Microcapsules

Anthropogenic activity negatively affects the environment by polluting it with the salts of various metals. One of the ways to reduce this influence is to use water purification methods for the salts of various metals. Water purification methods based on nanomaterials are promising. In this regard, we proposed to study polyelectrolyte microcapsules (PMC) as a promising sorption agent for the salts of various metals. It was found that the polystyrene sulfonate-polyallylamine (PSS-PAH) polyelectrolyte complex and polyelectrolyte microcapsules of different compositions are not able to adsorb salts CuSO4, Pb(NO)3, FeCl3, and CuCl2. At the same time, it was found that all types of capsules, except for (PSS/PAH)2/PSS, are capable of sorbing about 420 µg of K3[Fe(CN)6] and about 500 µg of K4[Fe(CN)6] from solution. The adsorption of polyelectrolyte microcapsules has an electrostatic nature which is confirmed by increases in the sorption capacity of PMC of K3[Fe(CN)6] and K4[Fe(CN)6] with decreases in the pH of the solution. Also, It was confirmed that the sorption process of PMC of K3[Fe(CN)6] and K4[Fe(CN)6] is concentration dependent and has the limitation of the number of binding sites

Determination of Phenol with Peroxidase Immobilized on CaCO₃

Phenols are widely used in industries despite their toxicity, which requires governments to limit their concentration in water to 5 mg/L before discharge to the city sewer. Thus, it is essential to develop a rapid, simple, and low-cost detection method for phenol. This study explored two pathways of peroxidase immobilization to develop a phenol detection system: peroxidase encapsulation into polyelectrolyte microcapsules and peroxidase captured by CaCO3. The encapsulation of peroxidase decreased enzyme activity by 96%; thus, this method cannot be used for detection systems. The capturing process of peroxidase by CaCO3 microspherulites did not affect the maximum reaction rate and the Michaelis constant of peroxidase. The native peroxidase—Vmax = 109 µM/min, Km = 994 µM; CaCO3–peroxidase—Vmax = 93.5 µM/min, Km = 956 µM. Ultimately, a reusable phenol detection system based on CaCO3 microparticles with immobilized peroxidase was developed, capable of detecting phenol in the range of 700 ng/mL to 14 µg/mL, with an error not exceeding 5%, and having a relatively low cost and production time. The efficiency of the system was confirmed by determining the content of phenol in a paintwork product