Composites with immobilized bioactive spirulina on an inorganic substrate (yellow clay, hydroxyapatite, SiO2, TiO2, ZnO).

In order to improve the structural properties of clays and composites of powdered spirulina, clay, nanosilica, hydroxyapatite, TiO2 and ZnO were used as an additive for mechanical processing. As a result, composites with natural nanostructured materials (NNM) are prepared with improved structural properties and bioactivity. The mixtures based on NNM with crystalline kaolinite, clays and admixtures were processed in a knife mill. The materials were characterized using FTIR spectroscopy, nitrogen adsorption and desorption, SEM release of bioactive components (anthocyanin 0,004 - 0,07 mg/g; chlorophyll 20 - 29 mg/g), composite toxicity level (below 25%), particle size measurement and surface charge density, zeta potential. Adsorption enthalpies during the formation of an intermolecular complex during the interactions of an anthocyanin molecule with the appropriate component of the composite were also calculated. There are regularities in the characteristics depending on the type of NNM, particle morphology and textural features of solids. The morphological and structural properties of the components changed slighty in the blends because the processing was conducted under relatively low mechanical stress. The morphological, textural and structural characteristics of the composites as well as the transformation to a nanostructured state, assume great bioactive activity of the composites, interesting for practical applications.

Assessment of Selected Surface and Electrochemical Properties of Boron and Strontium-Substituted Hydroxyapatites.

Tissue engineering is an interdisciplinary field of science that has been developing very intensively over the last dozen or so years. New ways of treating damaged tissues and organs are constantly being sought. A variety of porous structures are currently being investigated to support cell adhesion, differentiation, and proliferation. The selection of an appropriate biomaterial on which a patient's new tissue will develop is one of the key issues when designing a modern tissue scaffold and the associated treatment process. Among the numerous groups of biomaterials used to produce three-dimensional structures, hydroxyapatite (HA) deserves special attention. The aim of this paper was to discuss changes in the double electrical layer in hydroxyapatite with an incorporated boron and strontium/electrolyte solution interface. The adsorbents were prepared via dry and wet precipitation and low-temperature nitrogen adsorption and desorption methods. The specific surface area was characterized, and the surface charge density and zeta potential were discussed.

In situ synthesis of AgI on the nanosilica surface for potential application as a cloud seeding material.

A series of nanosilica/AgI composites was synthesized by in situ reactions between silver nitrate and ammonium iodide deposited on the nanosilica surface using the gas-phase solvate-stimulated mechanosorption modification (GSSMSM) under both dry and wet conditions. The characterization of the synthesized materials was performed by X-ray diffraction (XRD), SEM/EDX (Scanning Electron Microscopy-Energy Dispersive X-ray), thermogravimetric (TGA) and gas sorption methods. As a result of the mechanosorption modification of nanosilica, the bulk density of the samples synthesized in the dry and wet medium increases from 45 g/l for initial nanosilica to 249 g/l and 296 g/l for the modified samples, respectively. The specific surface area of the composites decreased in compared to the nanosilica precursor. The SEM data showed a denser aggregate structure of the nanocomposites compared to the initial nanosilica. The XRD, SEM/EDX and TEM/EDX data indicated the formation of AgI clusters. The AgI particle size was in the range of 6-45 nm. The ice-forming activity of the AgI-containing samples was examined as well. The sample with a smaller size of silver iodide on the surface exhibited superior ice-forming properties, and considering the quantity of utilized AgI, the prepared samples hold promise for application in this field.

Autophagy of Candida albicans cells after the action of earthworm Venetin-1 nanoparticle with protease inhibitor activity.

The present studies show the effect of the Venetin-1 protein-polysaccharide complex obtained from the coelomic fluid of the earthworm Dendrobaena veneta on Candida albicans cells. They are a continuation of research on the mechanisms of action, cellular targets, and modes of cell death. After the action of Venetin-1, a reduced survival rate of the yeast cells was noted. The cells were observed to be enlarged compared to the controls and deformed. In addition, an increase in the number of cells with clearly enlarged vacuoles was noted. The detected autophagy process was confirmed using differential interference contrast, fluorescence microscopy, and transmission electron microscopy. Autophagic vesicles were best visible after incubation of fungus cells with the Venetin-1 complex at a concentration of 50 and 100 µg mL-1. The changes in the vacuoles were accompanied by changes in the size of mitochondria, which is probably related to the previously documented oxidative stress. The aggregation properties of Venetin-1 were characterized. Based on the results of the zeta potential at the Venetin-1/KCl interface, the pHiep = 4 point was determined, i.e. the zeta potential becomes positive above pH = 4 and is negative below this value, which may affect the electrostatic interactions with other particles surrounding Venetin-1.

Selected Textural and Electrochemical Properties of Nanocomposite Fillers Based on the Mixture of Rose Clay/Hydroxyapatite/Nanosilica for Cosmetic Applications.

In order to improve the properties and characteristics of rose clay composites with acai, hydroxyapatite (HA), and nanosilica, the systems were mechanically treated. This treatment provides the preparation of better nanostructured composites with natural and synthetic nanomaterials with improved properties. The materials were characterized using XRD, nitrogen adsorption and desorption, particle sizing, zeta potential, and surface charge density measurements. For the systems tested in the aqueous media, the pH value of the point of zero charge (pHPZC) ranges from 8 to 9.9. However, the isoelectric point (pHIEP) values for all composites are below pH 2. This large difference between pHPZC and pHIEP is due to the complexity of the electrical double layer (EDL) and the relation of these points to different layers of the EDL. The tested samples as composite/electrolyte solutions are colloidally unstable. The toxicity level of the ingredients and release of anthocyanins as bioactive substances from acai in the composites were determined. The composites demonstrate an enhanced release of anthocyanins. There are some regularities in the characteristics depending on the type of components, morphology, and textural features of solids. The morphological, electrochemical, and structural characteristics of the components have changed in composites. The release of anthocyanins is greater for the composites characterized by minimal confined space effects in comparison with rose clay alone. The morphological, electrochemical, and structural characteristics allow us to expect high efficiency of composites as bioactive systems that are interesting for practical applications in cosmetics.

Adsorption of Ag (I) Ions at the Zirconium Phosphate/KNO3 Aqueous Solution Interface.

The paper presented the mechanical (MChT), microwave (MWT), and hydrothermal (HTT) methods of zirconium phosphate samples modification in order to improve its adsorption affinity for the Ag (I) ions. The FTIR studies proved that the modification of both gel and xerogel samples with the ultrasonic microwaves causes an increase in the concentration of phosphate groups on the surface of MWT-modified zirconium phosphate: the isoelectric point pHiep = 2.2-2.9 for these samples against 3.9 for the initial sample and pKa2 values were 4.7-5.6 and 6.3, respectively. As resulting from the Ag+ ion adsorption studies, the MWT treatment of zirconium phosphate samples caused the greatest affinity of Ag+ ions for the surface of MWT zirconium phosphate. Compared with the initial ZrP sample, the shift of the Ag (I) ion adsorption edge towards lower pH values was observed, e.g., with adsorption of Ag (I) ions from the solution with the initial concentration of 1 µmol/dm3 for the initial ZrP sample pH50% = 3.2, while for the sample MWT ZrPxero pH50% = 2.6.

Synthesis of Hydroxyapatite/Iron Oxide Composite and Comparison of Selected Structural, Surface, and Electrochemical Properties.

The paper presents the synthesis of a hydroxyapatite/iron oxide composite utilizing the wet chemical method, as well as the comparison of several selected material characteristics. As follows from the literature reports, hydroxyapatite is a common mineral possessing numerous significant properties. Nowadays, there is an increase in the amount of research on possible modifications of this compound. The promising way to improve hydroxyapatite features is its combination with iron oxide. Particularly, there can be two forms that are distinguished, namely Fe3O4 and γ-Fe2O3. These oxides exhibit valuable properties, particularly magnetism. A combination of the mentioned materials leads to multifunctional composite formation with many potential applications, as follows from several studies. However, this area of science is not fully developed. There are still many aspects to be examined. The synthesized composite and its components were analyzed by employing the following methods. The X-ray diffraction analysis revealed formation of hydroxyapatite and Fe2O3 crystalline phases. Moreover, porosimetry proved a larger specific area for the composite sample in comparison with other materials. The results obtained using the SEM method confirmed an external layer of hydroxyapatite and spherical shapes of internal Fe2O3 particles. Furthermore, the X-ray photoelectron spectroscopy data presented characteristic peaks of Fe, Ca, P, and O atoms in all samples. The Fourier Transform Infrared spectra displayed all the specific vibrations typical of the analyzed materials. What is more, the Vibrating Sample Magnetometer method confirmed the paramagnetic nature of the samples. It could be concluded that the synthesized composite has intermediate properties between the components used in the formation process. The results suggest that these composites are superparamagnetic. This type of material architecture would be well suited for biomedical applications.

The co-occurrence of Zn-and Cu-based engineered nanoparticles in soils: The metal extractability vs. toxicity to Folsomia candida.

The presence of engineered nanoparticles (ENPs) in soil gradually increases, among others due to the nano-agrochemicals application. So far, the co-existence of different ENPs in soil is poorly examined. Here, the metal extractability and toxicity of soils spiked (300 mg kg-1) singly and jointly with Zn- and Cu-based ENPs or metal salts were tested. The samples were aged for 1 and 90 days. The predicting available metal component of ENPs concentrations were determined by different methods including soil pore water collection and batch extractions with H2O, CaCl2 or DTPA. Survival and reproduction of Folsomia candida were also evaluated. The combined effect of ENPs on the extractability of metals was mainly found with DTPA characterized by the highest leaching capacity among the used extractants. In fresh soil, the mixtures of ENPs differentiated only DTPA-extractable Cu level, while aging resulted in changes in both Zn and Cu concentrations leached by CaCl2 or DTPA. However, the character of the combined effect was an ENPs- and soil type-dependent, whereas the mixtures of metal salts mostly provided higher Zn and Cu recovery than the individual compounds. The pattern of co-toxicity of metal-oxide ENPs was also time-dependent: the antagonistic and synergistic effect was observed in the samples after 1 and 90 days, respectively. However, the toxicity was weakly related with extractable concentrations in both single and joint treatment of metal compounds. The distinct joint effect patterns of ENPs imply the need for more in-depth investigation of mechanisms of activity of ENPs mixtures in soil.

Adsorption of the Tartrate Ions in the Hydroxyapatite/Aqueous Solution of NaCl System.

The research on the interaction of tartrate ions with the surface of hydroskyapatite was presented, including the measurements of the kinetics of tartrate ion adsorption and tartrate ion adsorption as a function of pH. The adsorption of tartrate ions was calculated from the loss of tartrate concentration in the solution as measured by a radioisotope method using C-14 labeled tartaric acid. In order to explain the mechanism of interaction of tartrate ions with hydroxyapatite, supplementary measurements were carried out, i.e., potentiometric measurements of the balance of released/consumed ions in the hydroxyapatite/electrolyte solution system, zeta potential measurements, FTIR spectrophotometric measurements and the hydroxyapatite crystal structure and particle size distribution were characterized. It was found that the adsorption of tartrate ions occurs as a result of the exchange of these ions with hydroxyl, phosphate and carbonate ions. Replacing the ions with the abovementioned tartrate ions leads to the appearance of a negative charge on the surface of the hydroxapatite. On the basis of XRD study and particle size distribution, a decrease in the size of crystallites and the diameter of hydroxyapatite particles in contact with a solution of 0.001 mol/dm3 of tartaric acid was found.

Hydroxyapatite with magnetic core: Synthesis methods, properties, adsorption and medical applications.

This review presents the actual state of knowledge and recent research results on the magnetic composite synthesized from iron oxide (γ-Fe2O3 or Fe3O4) and hydroxyapatite. It can be obtained applying some methods, i.e. chemical precipitation, hydrothermal, sol-gel, and biomimetic or combined techniques which exhibit characteristic properties affecting the form of the prepared product. More specific details are discussed in this paper. A comparison of the discussed synthesis methods is presented. On the basis of selected publications, a comparison of the results of the analysis by XRD, FTIR, SEM and EDX methods for hydroxyapatite with a magnetic core was also presented. Moreover, the characteristics large adsorption capacity and specific area allow employing nanocomposites as adsorbents particularly in removal of toxic metal ions. Nowadays this issue is extremely vital due to large amounts of pollutants in the environment and greater ecological awareness of people. Moreover, magnetic hydroxyapatite can be also applied as a catalyst in various syntheses or oxidation reactions as well as in medicine in magnetic resonance imaging, hyperthermia treatment, drug delivery and release, bone regeneration or cell therapy.

Adsorption of Uranyl Ions at the Nano-hydroxyapatite and Its Modification.

Nano-hydroxyapatite and its modification, hydroxyapatite with the excess of phosphorus (P-HAP) and hydroxyapatite with the carbon ions built into the structure (C-HAP), were prepared by the wet method. They were studied by means of XRD, accelerated surface area and porosimetry (ASAP), and SEM. The size of crystallites computed using the Scherrer method was nano-hydroxyapatite (HAP) = 20 nm; P-HAP-impossible to determine; C-HAP = 22 nm; nano-HAP/U(VI) = 13.7 nm; P-HAP/U(VI)-impossible to determine, C-HAP/U(VI) = 11 nm. There were determined basic parameters characterizing the double electrical layer at the nano-HAP/electrolyte and P-HAP/electrolyte, C-HAP/electrolyte inter faces: density of the surface charge and zeta potential. The adsorption properties of nano-HAP sorbent in relation to U(VI) ions were studied by the batch technique. The adsorption processes were rapid in the first 60 min and reached the equilibrium within approximately 120 min (for P-HAP) and 300 min (for C-HAP and nano-HAP). The adsorption process fitted well with the pseudo-second-order kinetics. The Freundlich, Langmuir-Freundlich, and Dubinin-Radushkevich models of isotherms were examined for their ability to the equilibrium sorption data. The maximum adsorption capabilities (q m ) were 7.75 g/g for P-HAP, 1.77 g/g for C-HAP, and 0.8 g/g for HAP at 293 K.

Toxicity of combined mixtures of nanoparticles to plants.

An increasing production and using of nanoproducts results in releasing and dispersing nanoparticles (NPs) in the environment. Being released into various environment components, NPs may interact with numerous pollutants, including other NPs. This research aimed at assessing toxicity of combined binary mixtures of NPs. The study focused on assessing mixtures of NPs believed to be toxic (nano-ZnO+nano-CuO) and nano-ZnO/nano-CuO with the ones that are insignificantly toxic or non-toxic NPs (nano-TiO2/nano-Cr2O3/nano-Fe2O3). Toxicity of combined mixtures proved comparable to toxicity of individual mixtures of NPs (the sum of effects triggered by individual types of NPs comprising respective mixtures). Toxicity evaluation was based on two parameters: seed germination and inhibition of root growth with respect to four plant species: Lepidium sativum, Linum utisassimmum, Cucumis sativus and Triticum aestivum. The findings showed combined mixtures of NPs to be significantly less toxic in comparison to individual mixtures, irrespective of their components. Within the scope of concentrations used, greatest differences between the toxicity of mixtures were reported at the 100mgL-1 concentration. Toxicity levels of combined and individual mixtures might have been determined by a lower total concentration of Zn and Cu metals and a greater aggregation of particles in combined mixtures than in individual mixtures.

Synthesis, Structural, and Adsorption Properties and Thermal Stability of Nanohydroxyapatite/Polysaccharide Composites.

A series of composites based on nanohydroxyapatite (nHAp) and natural polysaccharides (PS) (nHAp/agar, nHAp/chitosan, nHAp/pectin FB300, nHAp/pectin APA103, nHAp/sodium alginate) was synthesized by liquid-phase two-step method and characterized using nitrogen adsorption-desorption, DSC, TG, FTIR spectroscopy, and SEM. The analysis of nitrogen adsorption-desorption data shows that composites with a nHAp: PS ratio of 4:1 exhibit a sufficiently high specific surface area from 49 to 82 m2/g. The incremental pore size distributions indicate mainly mesoporosity. The composites with the component ratio 1:1 preferably form a film-like structure, and the value of S BET varies from 0.3 to 43 m2/g depending on the nature of a polysaccharide. Adsorption of Sr(II) on the composites from the aqueous solutions has been studied. The thermal properties of polysaccharides alone and in nHAp/PS show the influence of nHAp, since there is a shift of characteristic DSC and DTG peaks. FTIR spectroscopy data confirm the presence of functional groups typical for nHAp as well as polysaccharides in composites. Structure and morphological characteristics of the composites are strongly dependent on the ratio of components, since nHAp/PS at 4:1 have relatively large S BET values and a good ability to adsorb metal ions. The comparison of the adsorption capacity with respect to Sr(II) of nHAp, polysaccharides, and composites shows that it of the latter is higher than that of nHAp (per 1 m2 of surface).

Silica-Supported Titania-Zirconia Nanocomposites: Structural and Morphological Characteristics in Different Media.

A series of TiO2-ZrO2/SiO2 nanocomposites were synthesized using a liquid-phase method and characterized by various techniques, namely, nitrogen adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, high-resolution transmission electron microscopy, and photon correlation spectroscopy (PCS). It was revealed that the component ratio and calcination temperature affect the phase composition of nanocomposites. Composites TiZrSi1 (TiO2:ZrO2:SiO2 = 3:10:87) and TiZrSi2 (10:10:80) calcined at 1100 °Ð¡ demonstrate the presence of t-ZrO2 crystallites in TiZrSi1 and ZrTiO4 phase in TiZrSi2. The samples calcined at 550 °Ð¡ were amorphous as it was found from XRD data. According to the Raman spectra, the bands specific for anatase are observed in TiZrSi2. According to XPS data, Zr and Ti are in the highest oxidation state (+4). Textural analysis shows that initial silica is mainly meso/macroporous, but composites are mainly macroporous. The particle size distributions in aqueous media showed a tendency of increasing particle size with increasing TiO2 content in the composites.

Electrokinetic Properties of the Pristine and Oxidized MWCNT Depending on the Electrolyte Type and Concentration.

Electrostatic stabilization is reduced in its efficiency in an electrolyte-containing environment. The effect of electrolyte concentration is mostly described as negative factor for dispersion stabilization. Usually, zeta potential and physical stability decrease at increasing electrolyte concentration. The purpose of the present study was to measure the surface properties of nanotubes in aqueous solution of monovalent electrolytes at different concentration. Characteristics such as size distribution, surface chemistry, surface charge, and dispersability in aqueous phase have been identified. Hydrodynamic size and zeta potential in aqueous multiwalled carbon nanotube (MWCNT) suspensions were determined at different pH with the desired concentrations of electrolyte of the cationic group (NaCl, KCl, CsCl) and the anionic group (NaClO4). The correlations between the response of the surface functionality of pristine and oxidized multiwalled carbon nanotubes and electrical double layer (EDL) forming at different ionic environments in the vicinity of a nanotube surface were determined. The nanotube dispersion stabilization was found to be more affected by ion size and pH medium then electrolyte concentration. The data obtained confirms the predominant role of surface reactions. The most stable dispersion of nanotubes was achieved in KCl electrolyte solution at less negative charge of the surface.

Surfactants decrease the toxicity of ZnO, TiO2 and Ni nanoparticles to Daphnia magna.

The objective of the study was the estimation of the effect of surfactants on the toxicity of ZnO, TiO2 and Ni nanoparticles (ENPs) towards Daphnia magna. The effect of hexadecyltrimethylammonium bromide (CTAB), triton X-100 (TX100) and 4-dodecylbenzenesulfonic acid (SDBS) was tested. The Daphtoxkit F test (conforming to OECD Guideline 202 and ISO 6341) was applied for the toxicity testing. Both the surfactants and the ENPs were toxic to D. magna. The addition of ENPs to a solution of the surfactants caused a significant reduction of toxicity of ENPs. The range of reduction of the toxicity of the ENPs depended on the kind of the ENPs and their concentration in the solution, and also on the kind of surfactant. For nano-ZnO the greatest reduction of toxicity was caused by CTAB, while for nano-TiO2 the largest drop of toxicity was observed after the addition of TX100. In the case of nano-Ni, the effect of the surfactants depended on its concentration. Most probably the reduction of toxicity of ENPs in the presence of the surfactants was related with the formation of ENPs aggregates that inhibited the availability of ENPs for D. magna.

Influence of the Modifier Type and its Concentration on Electroosmotic Flow of the Mobile Phase in Pressurized Planar Electrochromatography.

The aim of this work was to find a relationship between electroosmotic flow (EOF) velocity of the mobile phase in pressurized planar electrochromatography (PPEC) and physicochemical properties like zeta potential, dielectric constant, and viscosity of the mobile phase as well as its composition. The study included different types of organic modifiers (acetonitrile, methanol, ethanol, acetone, formamide, N-methylformamide and N,N-dimethylformamide) in the full concentration range. In all experiments, chromatographic glass plates HPTLC RP-18 W from Merck (Darmstadt) were used as a stationary phase. During the study we found that there is no linear correlation between EOF velocity of the mobile phase and single variables such as zeta potential or dielectric constant or viscosity. However, there is quite strong linear correlation between EOF velocity of the mobile phase and variable obtained by multiplying zeta potential of the stationary phase-mobile phase interface, by dielectric constant of the mobile phase solution and dividing by viscosity of the mobile phase. Therefore, it could be concluded that the PPEC system fulfilled the Helmholtz-Smoluchowski equation.

Effect of zeta potential value on bacterial behavior during electrophoretic separation.

The aggregation and/or adhesion of bacterial cells is a serious disadvantage of electrophoretic separations. In this study, physicochemical surface characteristics of bacteria were measured to establish their role in bacterial adhesion and aggregation on the basis of electrophoretic behavior of different clinical strains of Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli bacteria. The number and the shape of peaks obtained on the electropherograms were connected with the zeta potential measurements and in-line microscope observation using specially designed CE fluorescence stereomicroscope setup. These results suggest that the lower the zeta potential, the higher the number of smaller peaks detected. The direct microscopic observation of electrophoretic movement proved the presence of many small aggregates originating from individual or clustered bacterial cells. On the other hand, lower zeta potential was also observed for dead bacterial cells, which suggested that some of the peaks can be attributed to viable cells while the other to the dead ones.

Effect of adsorption of Pb(II) and Cd(II) ions in the presence of EDTA on the characteristics of electrical double layers at the ion exchanger/NaCl electrolyte solution interface.

The main propose of this work was to describe the basic parameters of electrical double layer structures of the ion exchanger/NaCl before and after the sorption process of Pb(II) and Cd(II) ions from aqueous solutions in the presence of the complexing agent EDTA (ethylenediaminetetraacetic acid). In the studies the following ion exchangers were used: cation exchangers Micro-ionex (in the H(+) and NH(+)(4) forms), Dowex 50W x 4 (in the H(+) form), and Dowex 50W x 12 (in the H(+) form); anion exchangers Dowex 1 x 4 (in the Cl(-) form) and Dowex 1 x 8 (in the Cl(-) form). Study of the physicochemical properties of the sample surface was carried out. The influence of ionic strength, pH, and solution interface was investigated. Electrophoretic mobility, surface charge density, and parameters for different concentrations of the electrolytes under question were presented. pH was changed from 3 to 10. The studies were carried out for the M(II)-EDTA = 1:1 system. The effects of the concentration of the solution containing the above-noted complexes and of the ion exchange/solution phase contact time on sorption capacities of the ion exchangers under consideration were studied. Kinetic parameters of the sorption process were also determined.