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New hybrid hydrogel composites based on a mixture of natural polysaccharides (sodium alginate, κ-carrageenan, and chitosan) filled with the clay mineral of natural origin, montmorillonite (MMT), were studied. The structure of intercalated/flocculated MMT distribution in the interpenetrating network of polysaccharide matrix was characterized using FTIR, X-ray diffraction, and SEM techniques. Swelling kinetics was investigated using the weight analysis, whereas the phase transition of water in the composition of hybrid hydrogels, by DSC method. Their biosafety was estimated using the Nelyubov method, germination test on cress (L. sativum) seeds, and metabolic fingerprinting of microbial communities and dehydrogenase assay. The obtained results indicated promising water-retaining properties of the synthesized materials. The hydrogels had a good sorption affinity for cadmium (Cd) ions confining bioavailability of the selected toxic heavy metal. They were safe for soil microorganisms and did not generate metabolic stress for them. Moreover, they did not reduce the viability of pea seeds. Thus, the development of biosafe hybrid hydrogel composites with a comprehensive, good effect on the environment could be considered as successful., Competing Interests: Declaration of competing interest The authors declare that they have no competing interests., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Due to the extensive application of pesticides and their hazardous effects on organisms, there is an urgent need to remove them effectively from wastewater. Metal-incorporated carbon-mineral composites (Ni/Mn-CMC and Ni/Fe-CMC) described in this paper can certainly be applied for this purpose. They were synthesized by combining mechanochemical and pyrolytic processes and their physicochemical properties were investigated using numerous methods (SEM-EDS, N 2 adsorption/desorption, XRD, surface charge, FTIR). Adsorption capacity towards diuron and carboxin with and without impurities commonly detected in natural ecosystems, cadmium ions or arsenite, was measured. The obtained results indicated that Ni/Fe-CMC is more efficient adsorbent of pesticides due to its well-developed surface. It was able to bind 158.34 mg g -1 of diuron and 133.58 mg g -1 of carboxin in the solutions, where only one pesticide was present. In turn, these values for the Ni/Mn-CMC sample were 126.49 mg g -1 and 102.08 mg g -1 , respectively. It should be noted that the composites maintained their high adsorption capacity in the multicomponent solutions, i.e., containing both pesticide and metal ions. Then, the maximum reduction in pesticide adsorption was only 8.36. Ni/Mn-CMC and Ni/Fe-CMC were successfully regenerated with ethanol without changing their structure and adsorption capacity. Also, the extracts from investigated materials did not have negative impact on plant growth. This confirmed suitability of carbon-mineral composites for repeated multiple use without toxic effects to organisms., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

During multivalent ions insertion processes, intense electrostatic interaction between charge carriers and host makes the high-performance reversible Al 3+ storage remains an elusive target. On account of the strong electrostatic repulsion and poor robustness, Prussian Blue analogues (PBAs) suffer severely from the inevitable and large strain and phase change during reversible Al 3+ insertion. Herein, we demonstrate an entropy-driven strategy to realize ultralong life aqueous Al-ion batteries (AIBs) based on medium entropy PBAs (ME-PBAs) host. By multiple redox active centers introduction, the intrinsic poor conductivity can be enhanced simultaneously, resulting in outstanding capabilities of electrochemical Al 3+ storage. Meanwhile, the co-occupation at metal sites in PBA frameworks can also increase the M-N bond intensity, which is beneficial for constraining the phase change during consecutive Al 3+ reversible insertion, to realize an extended lifespan over 10,000 cycles. Based on the calculation at different operation states, the fluctuation of ME-PBA lattice parameters is only 1.2 %. Assembled with MoO 3 anodes, the full cells can also deliver outstanding electrochemical properties. The findings highlight that, the entropy regulation strategy could uncover the isochronous constraint on both strain and phase transition for long-term reversible Al 3+ storage, providing a promising design for advanced electrode materials for aqueous multivalent ions batteries., (© 2024 Wiley-VCH GmbH.)

Partial substitution of V by other transition metals in Na 3 V 2 (PO 4 ) 3 (NVP) can improve the electrochemical performance of NVP as a cathode for sodium-ion batteries (SIBs). Herein, phosphate Na-V-Mn-Ni-containing composites based on NASICON (Natrium Super Ionic Conductor)-type structure have been fabricated by sol-gel method. The synchrotron-based X-ray study, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) studies show that manganese/nickel combinations successfully substitute the vanadium in its site within certain limits. Among the received samples, composite based on Na 3.83 V 1.17 Mn 0.58 Ni 0.25 (PO 4 ) 3 (VMN-0.5, 108.1 mAh g -1 at 0.2 C) shows the highest electrochemical ability. The cyclic voltammetry, galvanostatic intermittent titration technique, in situ XRD, ex situ XPS, and bond valence site energy calculations exhibit the kinetic properties and the sodium storage mechanism of VMN-0.5. Moreover, VMN-0.5 electrode also exhibits excellent electrochemical performance in quasi-solid-state sodium metal batteries with PVDF-HFP quasi-solid electrolyte membranes. The presented work analyzes the advantages of VMN-0.5 and the nature of the substituted metal in relation to the electrochemical properties of the NASICON-type structure, which will facilitate further commercialization of SIBs., (© 2023 Wiley-VCH GmbH.)

Two series of hydrogels based on acrylamide and its copolymers with acrylonitrile and acrylic acid were synthesized by two cross-linking methods - chemical (using N,N'-methylene bis-acrylamide) and physical (using montmorillonite (MMT)) ones. The structure of the gels was characterized by Fourier Transform Infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The swelling and sorption properties were analyzed as a function of both the monomer composition and the cross-linking method. The shift of the band corresponding to Si-O (995-1030 cm -1 ) confirmed the formation of intercalation structures for MMT-cross-linked gels. Moreover, physically cross-linked gels demonstrated a non-monotonic dependence of the swelling degree on the MMT concentration, and acrylamide-acrylic acid copolymer MMT-cross-linked gels showed pH sensitivity and the highest swelling degree of 150 g/g. The highest sorption capacity towards cadmium(II) ions was demonstrated by acrylamide-acrylic acid copolymer gels, both covalently cross-linked (30 mg/g) and MMT-cross-linked (8.9 mg/g)., (© 2024 Wiley-VCH GmbH.)

This review aims to provide a literature overview as well as the authors' personal account to the studies of Laponite® (Lap)/Polyethylene-oxide (PEO) based composite materials and their applications. These composites can be prepared over a wide range of their mutual concentrations, they are highly water soluble, and have many useful physico-chemical properties. To the readers' convenience, the contents are subdivided into different sections, related with consideration of PEO properties and its solubility in water, behavior of Lap systems(structure of Lap-platelets, properties of aqueous dispersions of Lap and aging effects in them), analyzing ofproperties LAP/PEO systems, Lap platelets-PEO interactions, adsorption mechanisms, aging effects, aggregation and electrokinetic properties. The different applications of Lap/PEO composites are reviewed. These applications include Lap/PEO based electrolytes for lithium polymer batteries, electrospun nanofibers, environmental, biomedical and biotechnology engineering. Both Lap and PEO are highly biocompatible with living systems and they are non-toxic, non-yellowing, and non-inflammable. Medical applications of Lap/PEO composites in bio-sensing, tissue engineering, drug delivery, cell proliferation, and wound dressings are also discussed., (© 2023 The Chemical Society of Japan & Wiley-VCH GmbH.)

Simultaneous study of magnetic and electrocatalytic properties of cobaltites under extreme conditions expands the understanding of physical and chemical processes proceeding in them with the possibility of their further practical application. Therefore, La 0.6 Sr 0.4 CoO 3 (LSCO) nanopowders were synthesized at different annealing temperatures t ann increases, the rhombohedral perovskite structure of the LSCO becomes more single-phase, whereas the average particle size and dispersion grow. Co t ann increases, the rhombohedral perovskite structure of the LSCO becomes more single-phase, whereas the average particle size and dispersion grow. Co 3+ and Co 4+ are the major components. It has been found that LSCO-900 shows two main Curie temperatures, T C1 and T C2 = 0.8 GPa, respectively. The increment of ⟨d P increases, average ⟨ T C1 > 50 K that can be used as one of the composite components, expanding its working temperature window. Moreover, all LSCO samples showed excellent electrocatalytic performance for the oxygen evolution reaction (OER) process (overpotentials of only 265-285 mV at a current density of 10 mA cm T C2 for LSCO-900. Based on the experimental data, it was concluded that the formation of a dense amorphous layer on the surface of the particles ensures high stability as a catalyst (at least 24 h) during electrolysis in 1 M KOH electrolyte.P = 0.8 GPa, respectively. The increment of ⟨d T C /d P ⟩ for the smaller and bigger particles is sufficiently high and equals 10 and 13 K/GPa, respectively. The magnetocaloric effect in the LSCO-900 nanopowder demonstrates an extremely wide peak δ T fwhm > 50 K that can be used as one of the composite components, expanding its working temperature window. Moreover, all LSCO samples showed excellent electrocatalytic performance for the oxygen evolution reaction (OER) process (overpotentials of only 265-285 mV at a current density of 10 mA cm -2 ) with minimal η 10 for LSCO-900. Based on the experimental data, it was concluded that the formation of a dense amorphous layer on the surface of the particles ensures high stability as a catalyst (at least 24 h) during electrolysis in 1 M KOH electrolyte.

The different variants of two-stage random sequential adsorption (RSA) models for packing of disks and discorectangles on a two-dimensional (2D) surface were investigated. In the SD (sticks+disks) model, the discorectangles were first deposited and then the disks were added. In the DS (disks+sticks) model, the disks were first deposited and then discorectangles were added. At the first stage the particles were deposited up to the selected concentration and at the final (second) stage the particles were deposited up to the saturated (jamming) state. The main parameters of the models were the concentration of particles deposited at the first stage, aspect ratio of the discorectangles ɛ (length to diameter of ratio ɛ=l/d) and disk diameter D. All distances were measured using the value of d as a unit of measurement of linear dimensions, the disk diameter was varied in the interval D∈[1-10], and the aspect ratio value was varied in the interval ɛ∈[1-50]. The dependencies of the jamming coverage of particles deposited at the second stage versus the parameters of the models were analyzed. The presence of first deposited particles for both models regulated the maximum possible disk diameter D_{max} (SD model) or the maximum aspect ratio ɛ_{max} (DS model). This behavior was explained by the deposition of particles in the second stage into triangular (SD model) or elongated (DS model) pores formed by particles deposited at the first stage. The percolation connectivity of disks (SD model) and discorectangles (DS model) for the particles with a hard core and a soft shell structure was analyzed. The disconnectedness was ensured by overlapping of soft shells. The dependencies of connectivity versus the parameters of SD and DS models were also analyzed.

In this work, a new material for in vitro plant rooting based on highly dispersed polyacrylamide hydrogel (PAAG) enriched with amber powder was synthesized and investigated. PAAG was synthesized by homophase radical polymerization with ground amber addition. Fourier transform infrared spectroscopy (FTIR) and rheological studies were used to characterize the materials. They showed that the synthesized hydrogels have physicochemical and rheological parameters similar to those of the standard agar media. The acute toxicity of PAAG-amber was estimated based on the influence of washing water on the viability of plant seeds (pea and chickpea) and Daphnia magna . It proved its biosafety after four washes. The impact on plant rooting was studied using the propagation of Cannabis sativa on synthesized PAAG-amber and compared with agar. The developed substrate stimulated the rooting of the plants to more than 98% in comparison to standard agar medium (95%). Additionally, the use of PAAG-amber hydrogel markedly enhanced metric indicators of seedlings: root length increased by 28%, stem length-by 26.7%, root weight-by 167%, stem weight-by 67%, root and stem length-by 27%, root and stem weight-by 50%. This means that the developed hydrogel significantly accelerates reproduction and allows obtaining a larger amount of plant material within a shorter period of time than the standard agar substrate.

The freshwater microalga Haematococcus pluvialis is well known as the cell factory for natural astaxanthin, which composes up to 4-7% of its total dry weight. The bioaccumulation of astaxanthin in H. pluvialis cysts seems to be a very complex process that depends on different stress conditions during its cultivation. The red cysts of H. pluvialis develop thick and rigid cell walls under stress growing conditions. Thus, the biomolecule extraction requires general cell disruption technologies to reach a high recovery rate. This short review provides an analysis of the different steps in H. pluvialis's up and downstream processing including cultivation and harvesting of biomass, cell disruption, extraction and purification techniques. Useful information on the structure of H. pluvialis's cells, biomolecular composition and properties and the bioactivity of astaxanthin is collected. Special emphasis is given to the recent progress in application of different electrotechnologies during the growth stages and for assistance of the recovery of different biomolecules from H. pluvialis .

A two-dimensional Monte Carlo simulation of dead-end diafiltration of bidispersed particle suspensions was performed. The diafiltration process involves separation of components based on their size by using a permeable membrane. The continuous model was applied to study separation of mixture of disks with diameter d and D (D>d). It was assumed that the membrane at the bottom was permeable to the particles of the smaller diameter d, and impermeable to the particles of the larger diameter D. The process of vertical filtration was accompanied by the simultaneous Brownian motion of the particles and downward movement of the piston. The mixtures with different numerical concentrations of particles, diameter ratio, and initial size of the systems in the vertical direction L_{y} have been studied. The time dependencies of the rejection coefficient k and relative height of suspension h/L_{y} revealed the presence of complete and incomplete separation regimes. The presence of filtration and diffusion-driven stratification of the disks in the vertical direction was observed. The phenomenon of incomplete separation was explained by the formation of an impenetrable barrier from larger particles at the bottom of the deposit.

Prospects for the use of manganites in various areas of modern technologies require comprehensive studies of their physical and chemical properties. La 0.9 Mn 1.1 O 3 (LMO) ceramics have been synthesized at an annealing temperature t of 1150 °C with further post-annealing at 1250, 1350, and 1450 °C. As ann increases, the structure symmetry changes, and both the crystallite size and chemical defects increase. The post-annealing, on one hand, leads to a dramatic reduction of the magnetocaloric effect (MCE) |-Δ t ann increases, the structure symmetry changes, and both the crystallite size and chemical defects increase. The post-annealing, on one hand, leads to a dramatic reduction of the magnetocaloric effect (MCE) |-Δ S maxM| from 3.50 to 0.75 J (kg K) -1 at 2 T and a Curie temperature T works oppositely enhancing ferromagnetic interactions. The saturation of -Δ C from 227 to 113 K with increasing t ann of ≈ 0.4 GPa. LMO-1150 exhibits the best magnetocaloric characteristics compared with other studied samples. Moreover, the electrochemical characteristics of the LMO materials as electrocatalysts for overall water splitting (OER process) and features of their transformation in different 0.5 M K P works oppositely enhancing ferromagnetic interactions. The saturation of -Δ S maxM and T C is already achieved at a relatively low P of ≈ 0.4 GPa. LMO-1150 exhibits the best magnetocaloric characteristics compared with other studied samples. Moreover, the electrochemical characteristics of the LMO materials as electrocatalysts for overall water splitting (OER process) and features of their transformation in different 0.5 M K 2 SO 4 electrolytes have been studied thoroughly. After electrocatalysis of LMO, the magnetization 2 HPO 4 remains, which makes it possible to control the depletion of electrodes and predict their working time based on the magnetic measurements. All samples show the best OER activity in the 0.5 M K 2 B 4 media. The obtained results demonstrate the ways for controlling the MCE of LMO under changing internal and external conditions, and an evaluation of the possibilities for their OER applications in electrocatalysts.7 electrolytes have been studied thoroughly. After electrocatalysis of LMO, the magnetization M decreases and T C remains, which makes it possible to control the depletion of electrodes and predict their working time based on the magnetic measurements. All samples show the best OER activity in the 0.5 M K 2 HPO 4 media. The obtained results demonstrate the ways for controlling the MCE of LMO under changing internal and external conditions, and an evaluation of the possibilities for their OER applications in electrocatalysts.

The effects of acid activation of Laponite RD (Lap) on the structure and properties of activated Lap nanoparticles (aLap) and the properties of polyNIPAA m hydrogels physically cross-linked by aLap have been studied. The acid activation of Lap by the sulfuric acid was done using the concentration of sulfuric acid within the interval C a ≤ 1.25 wt %), the significant increase of the specific surface area (by ≈1.56 times) was accompanied with a significant decrease in both the values of the specific heat of immersion in water and C -decane. However, the hydrophilic properties of all samples S a ≤ 1.25 wt %), the significant increase of the specific surface area (by ≈1.56 times) was accompanied with a significant decrease in both the values of the specific heat of immersion in water and n were still observed. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) data, Fourier transform infrared (FTIR) spectra, and X-ray diffraction (XRD) patterns demonstrated that the acid activation resulted in the destruction of the crystal lattice of Lap, leaching of magnesium and lithium, and formation of the amorphous phases. Moreover, the acid activation significantly affected aggregation and negative surface charges of the aLap faces in aqueous suspension. The effects of aLap on the swelling properties and cooperativity in the phase transitions of polyNIPAA 0 -S 5 resulted in a significant increase in the equilibrium degree of swelling of the hydrogels and a decrease in the hydrogel phase-transition temperature from the swollen phase to the shrunken phase.m hydrogels cross-linked by aLap are also discussed. It was demonstrated that an increase in C a resulted in a significant increase in the equilibrium degree of swelling of the hydrogels and a decrease in the hydrogel phase-transition temperature from the swollen phase to the shrunken phase.

Relaxation of the packing of elongated particles (discorectangles) aligned on a line was studied numerically. The aspect ratio (length-to-width ratio) for the discorectangles was varied within the range ɛ∈[1;50]. The initial jamming (saturated) state was produced using the basic variant of the random sequential adsorption model with random positions and orientations of particles. The relaxation was performed by allowing rotational and translational diffusion motions of the particles while their centers remained located on the line. The effects of the aspect ratio ɛ on the kinetics of relaxation, the orientation order parameter, and the distribution function of the distances between nearest-neighbor discorectangles were analyzed. The transport properties of the resulting one-dimensional systems were also analyzed by using the diffusion of a tracer particle (random walker) between the nearest-neighbor discorectangles. In the relaxed states the anomalous diffusion was observed having a hopping exponent d_{w}>2 dependent upon ɛ.

Single crystals of the langbeinite-type phosphates K 1.65 Na 0.35 TiFe(PO 4 ) 3 and K 0.97 Na 1.03 Ti 1.26 Fe 0.74 (PO 4 ) 3 were grown by crystallization from high-temperature self-fluxes in the system Na 2 O-K 2 O-P 2 O 5 -TiO 2 -Fe 2 O 3 using fixed molar ratios of (Na+K):P = 1.0, Ti:P = 0.20 and Na:K = 1.0 or 2.0 over the temperature range 1273-953 K. The three-dimensional framework of the two isotypic phosphates are built up from [(Ti/Fe) 2 (PO 4 ) 3 ] structure units containing two mixed [(Ti/Fe)O 6 ] octa-hedra (site symmetry 3) connected via three bridging PO 4 tetra-hedra. The potassium and sodium cations share two different sites in the structure that are located in the cavities of the framework. One of these sites has nine and the other twelve surrounding O atoms., (© Zatovsky et al. 2021.)

Cubic crystals of tripotassium aluminium (or gallium) nitridotriphosphate, K 3 M III (PO 3 = Al, Ga), were grown by application of the self-flux method. In their isostructural crystal structures, all metal cations and the N atom occupy special positions with site symmetry 3, while the P and O atoms are situated in general positions. The three-dimensional framework of these oxidonitridophosphates is built up from [ 3 N ( M III = Al, Ga), were grown by application of the self-flux method. In their isostructural crystal structures, all metal cations and the N atom occupy special positions with site symmetry 3, while the P and O atoms are situated in general positions. The three-dimensional framework of these oxidonitridophosphates is built up from [ M III O 6 N tetra-hedra sharing a common N atom. The coordination environments of the three potassium cations are represented by two types of polyhedra, via (PO 3 ) 3 N for the other two cations. An unusual tetra-dentate type of coordination for the latter potassium cations by the (PO 3 N tetra-hedra sharing a common N atom. The coordination environments of the three potassium cations are represented by two types of polyhedra, viz . KO 9 for one and KO 9 N for the other two cations. An unusual tetra-dentate type of coordination for the latter potassium cations by the (PO 3 ) 3 N 6- anion is observed. These K 3 M III (PO 3 ) 3 N ( M III = Al, Ga) compounds are isostructural with the Na 3 M III (PO 3 ) 3 N ( M III = Al, V, Ti) compounds., (© Zatovsky et al. 2021.)

The behavior of a system of two-dimensional elongated particles (discorectangles) packed in a slit between the two parallel walls was analyzed using a simulation approach. The packings were produced using the random sequential adsorption model with continuous positional and orientational degrees of freedom. The aspect ratio (length-to-width ratio, ɛ=l/d) of the particles was varied within the range ɛ∈[1;32] while the distance between the walls was varied within the range h/d∈[1;80]. The properties of deposits in jammed state [the coverage, the order parameter, and the long-range (percolation) connectivity between particles] were studied numerically. The values of ɛ and h significantly affected the structure of the packings and the percolation connectivity. Particularly, the observed nontrivial dependencies of the jamming coverage φ(ɛ) or φ(h) were explained by the interplay of the different geometrical factors related to confinement, particle orientation degrees of freedom and excluded volume effects.

The development of novel hemostatic agents is related to the fact that severe blood loss due to hemorrhage continues to be the leading cause of preventable death of patients with military trauma and the second leading cause of death of civilian patients with injuries. Herein we assessed the hemostatic properties of porous sponges based on biocompatible hydrophilic polymer, poly(vinyl formal) (PVF), which meets the main requirements for the development of hemostatic materials. A series of composite hemostatic materials based on PVF sponges with different porosities and fillers were synthesized by acetalization of poly(vinyl alcohol) with formaldehyde. Nano-sized aminopropyl silica, micro-sized calcium carbonate, and chitosan hydrogel were used to modify PVF matrixes. The physicochemical properties (pore size, elemental composition, functional groups, hydrophilicity, and acetalization degree) of the synthesized composite sponges were studied by gravimetrical analysis, optical microscopy, scanning electron microscopy combined with energy dispersive x-ray spectroscopy, infrared spectroscopy, and nuclear magnetic resonance. Hemostatic properties of the materials were assessed using a model of parenchymal bleeding from the liver of white male Wistar rat with a gauze bandage as a control. All investigated PVF-based porous sponges showed high hemostatic activity: upon the application of PVF-samples the bleeding decreased within 3 min by 68.4-94.4% (р < 0.001). The bleeding time upon the application of PVF-based composites decreased by 78.3-90.4% (p < 0.001) compared to the application of well-known commercial product Celox™., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Connectedness percolation phenomena in the two-dimensional packing of elongated particles (discorectangles) were studied numerically. The packings were produced using random sequential adsorption off-lattice models with preferential orientations of the particles along a given direction. The partial ordering was characterized by the order parameter S, with S=0 for completely disordered films (random orientation of particles) and S=1 for completely aligned particles along the horizontal direction x. The aspect ratio (length-to-width ratio) of the particles was varied within the range ɛ∈[1;100]. Analysis of connectivity was performed assuming a core-shell structure of the particles. The value of S affected the structure of the packings, the formation of long-range connectivity, and the behavior of the electrical conductivity. The effects can be explained by taking accounting of the competition between the particles' orientational degrees of freedom and excluded volume effects. For aligned deposition, anisotropy in the electrical conductivity was observed with the values along the alignment direction σ&#95;{x} being larger than the values in the perpendicular direction σ&#95;{y}. Anisotropy in the localization of the percolation threshold was also observed in finite-sized packings, but it disappeared in the limit of infinitely large systems.

A computer simulation was used to study the random sequential adsorption of identical discorectangles onto a continuous plane. The problem was analyzed for a wide range of discorectangle aspect ratios (ɛ∈[1;100]). We studied the anisotropic deposition, i.e., the orientations of the deposited particles were uniformly distributed within some interval such that the particles were preferentially aligned along a given direction. The kinetics of the changes in the packing fraction found at different values of such the alignment are discussed. Partial ordering of the discorectangles significantly affected the packing fraction at the jamming state, φ&#95;{j}, and shifted the cusps in the φ&#95;{j}(ɛ) dependencies. The structure of the jammed state was analyzed using the adsorption of disks of different diameters into the porous space between the deposited discorectangles. The analysis of the connectivity between the discorectangles was performed assuming a core-shell structure of particles.

The random sequential adsorption (RSA) of identical elongated particles (discorectangles) on a line ("Paris car parking problem") was studied numerically. An off-lattice model with continuous positional and orientational degrees of freedom was considered. The possible orientations of the discorectanles were restricted between θ∈[-θ&#95;{m};θ&#95;{m}] while the aspect ratio (length-to-width ratio) for the discorectangles was varied within the range ɛ∈[1;100]. Additionally, the limiting case ɛ=∞ (i.e., widthless sticks) was considered. We observed that the RSA deposition for the problem under consideration was governed by the formation of rarefied holes (containing particles oriented along a line) surrounded by comparatively dense stacks (filled with almost parallel particles oriented in the vertical direction). The kinetics of the changes of the order parameter and the packing density are discussed. Partial ordering of the discorectangles significantly affected the packing density at the jamming state, φ&#95;{j}, and shifted the cusps in the φ&#95;{j}(ɛ) dependencies. This can be explained by the effects on the competition between the particles' orientational degrees of freedom and the excluded volume effects.

Recently, considering the potential applications of hydrogel nanocomposites in biomedical engineering, there has been a growing interest in the synthesis of hydrogels with improved mechanical properties. Among magnetic materials, iron oxides are of particular interest due to their magnetic properties and biocompatibility. At the same time, LAPONITE®, a synthetic clay, can be used to improve the mechanical properties of polymer-based nanocomposites. In this study we report the effects of hydrogel composition and structure on its thermoresponsive properties and hydrogel sorption and release of a model anticancer drug - 5-fluorouracil. Using one-step coprecipitation method we synthesized magnetic LAPONITE® (LAM) nanoparticles with magnetite-to-LAPONITE® weight ratios from 2 : 1 to 1 : 8. With increase in magnetite concentration the ferrofluidic properties of LAM nanoparticles are getting improved, while fluorouracil absorptivity - decreases. Exfoliation of the clay is observed when the magnetite content exceeds the LAPONITE® content. Physical crosslinking of poly(N-isopropylacrylamide) with LAM nanoparticles yields magnetic thermosensitive hydrogel nanocomposites with controllable temperature-induced drug release. All hydrogel nanocomposites have a distinct volume phase transition from a swollen state to a collapsed state upon heating within the physiologically acceptable temperature range of 33-36 °C.

The aqueous suspensions of Laponite RD (Lap) platelets demonstrate rich phase diagrams. Both poly(ethylene oxide) (PEO) and cetyltrimethylammonium bromide (CTAB) molecules competitively adsorb on the surface of Lap, and strong interactions between PEO and CTAB exist. The stability of ternary systems Lap + PEO + CTAB can be finely regulated by changing the balance of these interactions. The electrokinetic technique was used to study 0.065 and 2% wt Lap suspensions in the presence of different amounts of PEO of various molecular masses M (400-20,000 g/mol) and CTAB (0-1 mM). For 0.065% wt Lap suspension, the additives of PEO did not affect the position of the isoelectric point (IEP), but the impact of PEO in the regions below or above the IEP was significant, especially for a large w . The observed effects were explained, accounting the model for the adsorption of PEO in the form of loops and tails as well as for the changes in the packing balance of CTAB and PEO on the surface of Lap. For 2% wt suspension, the strong effects of M on the ζ-potential and aggregation of particles were explained by screening the repulsive double layers by PEO chains, by bridging the Lap particles via PEO molecules, and by the impact of CTAB molecules on the bridging between Lap aggregates.w . The observed effects were explained, accounting the model for the adsorption of PEO in the form of loops and tails as well as for the changes in the packing balance of CTAB and PEO on the surface of Lap. For 2% wt suspension, the strong effects of M w on the ζ-potential and aggregation of particles were explained by screening the repulsive double layers by PEO chains, by bridging the Lap particles via PEO molecules, and by the impact of CTAB molecules on the bridging between Lap aggregates.

Two-step procedure with the initial aqueous extraction from raw microalgae Nannochloropsis oculata and secondary organic solvent extraction from vacuum dried (VD) microalgae were applied for selective recovery of bio-molecules. The effects of preliminary aqueous washing and high voltage electrical discharges (HVED, 40 kV/cm, 4 ms pulses) were tested. The positive effects of HVED treatment and washing on selectivity of aqueous extraction of ionics and other water-soluble compounds (carbohydrates, proteins and pigments) were observed. Moreover, the HVED treatment allowed improving the kinetic of vacuum drying, and significant effects of HVED treatment on organic solvent extraction of chlorophylls, carotenoids and lipids were determined. The proposed two-step procedure combining the preliminary washing, HVED treatment and aqueous/organic solvents extraction steps are useful for selective extraction of different bio-molecules from microalgae biomass., Competing Interests: Declaration of competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The principles and mechanisms of adsorption of Ni(ii) ions by well characterized pristine and oxidized N-doped multi-walled carbon nanotubes (N-CNTs) are described and discussed. The samples were synthesized by CCVD method using n -butylamine as the carbon source and Ni(NO 3 ) 2 + MgO as the catalyst and purified by treatment with HCl. The surface functionalization was performed using oxidation with a mixture of concentrated H 2 SO 4 and HNO 3 . The morphology, nature and charge of surface groups were characterized by HRTEM, XPS, FTIR and micro-electrophoresis methods. It has been shown that: adsorption of Ni(ii) reaches an equilibrium value within 20-30 min; the degree of extraction of nickel ions from the solution increases with its dilution; adsorption of Ni(ii) results in an insufficient decrease in the suspension pH for pristine N-CNTs (0.5-0.6 pH unit) and considerable lowering of the pH for the oxidized sample (up to 2.5 pH unit); the adsorption isotherms are described by the Langmuir equation; the plateau amounts of adsorption (35-40 mg g -1 ) are almost the same for both as-prepared and oxidized samples; at pH 8 and higher a sharp increase in adsorption is observed which is caused by nickel hydroxide precipitation. The spectroscopic, adsorption, electrophoretic and pH measurement data testify that below pH 8 the major mechanism of adsorption by as-prepared N-CNTs is the donor-acceptor interaction between the free electron pair of N atoms incorporated into the nanotube lattice and vacant d-orbital of the adsorbing Ni(ii) ions. For the oxidized N-CNTs ion-exchange processes with a release of H + play a decisive role., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Electrochemical enzyme-based biosensors are one of the largest and commercially successful groups of biosensors. Integration of nanomaterials in the biosensors results in significant improvement of biosensor sensitivity, limit of detection, stability, response rate and other analytical characteristics. Thus, new functional nanomaterials are key components of numerous biosensors. However, due to the great variety of available nanomaterials, they should be carefully selected according to the desired effects. The present review covers the recent applications of various types of nanomaterials in electrochemical enzyme-based biosensors for the detection of small biomolecules, environmental pollutants, food contaminants, and clinical biomarkers. Benefits and limitations of using nanomaterials for analytical purposes are discussed. Furthermore, we highlight specific properties of different nanomaterials, which are relevant to electrochemical biosensors. The review is structured according to the types of nanomaterials. We describe the application of inorganic nanomaterials, such as gold nanoparticles (AuNPs), platinum nanoparticles (PtNPs), silver nanoparticles (AgNPs), and palladium nanoparticles (PdNPs), zeolites, inorganic quantum dots, and organic nanomaterials, such as single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), carbon and graphene quantum dots, graphene, fullerenes, and calixarenes. Usage of composite nanomaterials is also presented., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Relaxation in a two-dimensional suspensions containing rods was studied by using dynamic Monte Carlo simulations. An off-lattice model with continuous positional and orientational degrees of freedom was considered. The initial state was produced by using a random sequential adsorption model. During the relaxation, the rods underwent translational and rotational Brownian motions. The simulations were run at different values of number density ρ (the number of rods per unit area) and of the initial orientation order parameter S&#95;{i}. The rods were assumed to have core-shell structures. The evolutions of both the connectivity and the order parameter have revealed different relaxation behavior.

The ultrasound (US) assisted purification of polyphenols of apple skins by adsorption/desorption on the poly-aromatic Amberlite adsorbent XAD-16 was studied. The adsorption steps were done at different temperatures (T = 25-40 °C) with application of US at different intensities (P = 0-400 W). The desorption steps were tested in aqueous ethanol solution at different concentrations of ethanol (C et  = 0-96%). The isotherm of polyphenol adsorption was well described using the Freundlich model. The data on adsorption kinetics and static isotherm evidenced the presence of adsorption on heterogeneous surface with broad distribution of adsorption times that can depend on content of polyphenols in the solutions and applied power of sonication. The studies of desorption revealed the optimum desorption efficiency of polyphenols at 50% concentration of ethanol. The desorption ratio was positively affected by the sonication during the adsorption step. The highest adsorption/desorption efficiency (recovery) was observed for polyphenols as compared with proteins and soluble matter content and it reached of ≈30.6% (0 W) and 68.9% (50 W) in absence and presence of sonication, respectively. The effects of high US power on the damage of XAD-16 were discussed. The obtained data evidenced on good perspective of application of adsorption/desorption procedure assisted by sonication for purification of polyphenols from apple skin extracts., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The sedimentation of a two-dimensional suspension containing rods was studied by means of Monte Carlo (MC) simulations. An off-lattice model with continuous positional and orientational degrees of freedom was considered. The initial state before sedimentation was produced using a model of random sequential adsorption. During such sedimentation, the rods undergo translational and rotational Brownian motions. The MC simulations were run at different initial number densities (the numbers of rods per unit area), ρ&#95;{i}, and sedimentation rates, u. For sediment films, the spatial distributions of the rods, the order parameters, and the electrical conductivities were examined. Different types of sedimentation-driven self-assembly and anisotropy of the electrical conductivity were revealed inside the sediment films. This anisotropy can be finely regulated by changes in the values of ρ&#95;{i} and u.

The ultrasound (US) assisted extraction of bio-compounds from different fruit skins (apples, bananas and persimmons) was studied. The aqueous suspensions of skins were treated by US with different energy inputs (0.033-0.299 kW·h/kg) and total time of aqueous extraction was up to 2700 s. The ionic, Z i , and total polyphenol, Z p , extraction indexes of the liquid extracts were analyzed. From microscopic images the cell wall disintegration index, Z m , was determined. Increase in US energy input caused the increase of values of Z i , Z p and Z m . The correlations between extraction parameters and the disintegration index, Z m , were discussed., (Copyright © 2018 Elsevier B.V. All rights reserved.)