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Deep eutectic solvents (DESs) are an emerging class of materials that show promise for applications as inexpensive “designer” solvents with tunable properties. A detailed review of the current literature reveals a lack of predictive understanding of the microscopic mechanisms that govern the structure−property relationships in this class of solvents. They can dissolve both organic and inorganic compounds, including salts and metal oxides. Zinc oxide is used as a substrate for the synthesis of various task-specific materials, and has excellent antibacterial properties. In this work, both DES and a DES + ZnO combination were used for the first time as admixtures for cement composites, and were shown to improve the final properties of the cement matrix. The materials obtained exhibit good antibacterial properties, even with small amounts of zinc oxide, improved mechanical properties, and good durability when subjected to freezing–thawing cycles.

Paracetamol is one of the most commonly used painkillers. Its significant production and consumption result in its presence in the environment. For that reason, paracetamol has a negative impact on the organisms living in ecosystems. Therefore, it is necessary to develop effective methods to remove paracetamol from sewage. One of the methods is the bioaugmentation of activated sludge with organisms with increased degradation potential in relation to paracetamol. This study determined the effectiveness of paracetamol degradation by activated sludge augmented with a free or immobilised Pseudomonas moorei KB4. To immobilise the strain, innovative capsules made of cellulose acetate were used, the structure of which provides an optimal environment for the development of bacteria. Augmentation with both a free and immobilised strain significantly improves the efficiency of paracetamol biodegradation by activated sludge. Over a period of 30 days, examined systems allowed ten doses of paracetamol decomposition, while the unaugmented system degraded only four. At the same time, using the immobilised strain does not significantly affect the functioning of the activated sludge, which was reflected in the stability of processes such as nitrification. Due to the high stability of the preparation, it can become a valuable tool in wastewater treatment processes.

The skeletons of marine sponges are ancient biocomposite structures in which mineral phases are formed on 3D organic matrices. In addition to calcium- and silicate-containing biominerals, iron ions play an active role in skeleton formation in some species of bath sponges in the marine environment, which is a result of the biocorrosion of the metal structures on which these sponges settle. The interaction between iron ions and biopolymer spongin has motivated the development of selected extreme biomimetics approaches with the aim of creating new functional composites to use in environmental remediation and as adsorbents for heavy metals. In this study, for the first time, microporous 3D spongin scaffolds isolated from the cultivated marine bath sponge Hippospongia communis were used for electro-assisted deposition of iron oxides such as goethite [α-FeO(OH)] and lepidocrocite [γ-FeO(OH)]. The obtained iron oxide phases were characterized with the use of scanning electron microscopy, FTIR, and X-ray diffraction. In addition, mechanisms of electro-assisted deposition of iron oxides on the surface of spongin, as a sustainable biomaterial, are proposed and discussed.

Sponges (phylum Porifera) were among the first metazoans on Earth, and represent a unique global source of highly structured and diverse biosilica that has been formed and tested over more than 800 million years of evolution. Poriferans are recognized as a unique archive of siliceous multiscaled skeletal constructs with superficial micro-ornamentation patterned by biopolymers. In the present study, spicules and skeletal frameworks of selected representatives of sponges in such classes as Demospongiae, Homoscleromorpha, and Hexactinellida were desilicified using 10% HF with the aim of isolating axial filaments, which resemble the shape and size of the original structures. These filaments were unambiguously identified in all specimens under study as F-actin, using the highly specific indicators iFluor™ 594-Phalloidin, iFluor™ 488-Phalloidin, and iFluor™ 350-Phalloidin. The identification of this kind of F-actins, termed for the first time as silactins, as specific pattern drivers in skeletal constructs of sponges opens the way to the fundamental understanding of their skeletogenesis. Examples illustrating the biomimetic potential of sophisticated poriferan biosilica patterned by silactins are presented and discussed.

A novel UV-light-curable poly(ethylene glycol) diacrylate matrix composite material with unmodified and methacryloxyl-grafted TiO2 and TiO2-ZrO2 systems was developed and tested as a potential coating material for medical components. The main goal of the research was to evaluate how the addition of (un)modified inorganic oxide fillers affects the properties of the composition (viscosity, UV/Vis spectra), the kinetics of photocuring (photo-DSC), and the morphological (SEM), physicochemical, and thermal properties (DSC, TGA) of the resulting composites. The applied filler functionalization process decreased their polarity and changed their size, BET surface area, and pore volume, which influenced the viscosity and kinetics of the photocurable system. In addition, the addition of synthesized fillers reduced the polymer’s glass transition temperature and increased its thermal stability. It was also observed that additional UV irradiation of the tested composite changed its surface, resulting in hydrophobic properties (with the addition of 7 wt.% filler, an increase in the contact angle by more than 45% was observed).

Abstract CuO nanoparticles (NPs) were added to cement matrices in quantities of 0.25, 0.50 and 1.00 wt% to inhibit the growth of Gram-positive (Bacillus cereus, Staphylococcus aureus) and Gram-negative (Pseudomonas aeruginosa, Escherichia coli) bacteria. It was shown that CuO NPs, in all tested concentrations, improved the antibacterial properties of the cement matrix. Nevertheless, the best mechanical, structural and durability properties were obtained for cement composites doped with CuO NPs at 0.25 wt%. Larger amounts of NPs caused a decrease in all parameters relative to the reference mortar, which may be the result of a slight change in the porosity of the composite microstructure. For 0.50 wt% CuO NPs, a slight increase in the volume of micropores in the cement matrix was observed, and an increased number of larger pores was confirmed by non-invasive computed tomography (CT). The reduction in the mechanical parameters of composites with 0.50 and 1.00 wt% CuO NPs may also be due to the slower hydration of the cement binder, as confirmed by changes in the heat of hydration for these configurations, or agglomeration of NPs, especially for the 1.00 wt% concentration, which was manifested in a decrease in the plasticity of the mortars.

One of the most important aspects of shaping the antibacterial properties of nano-mixed cementitious composites is the proper dispersion of nanoparticles (NPs) to ensure their sustainable application. Therefore, in the presented article special attention was paid to the method of mixing zinc oxide NPs with the cement matrix. A two-stage modification of the cement matrix was used; in the first stage, zinc oxide NPs were introduced directly in dry form into the cement binder or mixed mechanically, with ultrasound and combined mechanically and with ultrasound. Then, in the second stage, a superplasticizer was added to the mixing methods mentioned above. It was shown that the combined use of premixing and then mixing with superplasticizer influences better dispersion of zinc oxide in the cement matrix, which in turn translates into higher mechanical parameters, better microstructure compaction and resistance to microorganisms. The most homogeneous mixture was obtained with combined mechanical and ultrasonic mixing. On the other hand, better antimicrobial properties were exhibited by composites obtained only by mechanical mixing.

Abstract A mathematical description of the thermal degradation of spongin-based scaffolds is given. The Arrhenius integral was evaluated using the inverse problem approach, in which the unknown values were the activation energy E A , the pre-exponential factor A, and the model function f(α) characterizing the physical process. The form of f(α) was determined and the values of the parameters E A , A and T S were evaluated in detail. Moreover, the function f(α) assessed in this study was compared with classical solid-state model functions. Finally, the mean square minimization approach was used to solve the inverse problem with unknown function f(α) and pre-exponential constant A. Likewise, the approximation of f(α) with 6th- and 7th-degree polynomials was used to obtain numerical values of E A and A. This study evaluated the inverse problem approach for the Arrhenius equation. These investigations provide new insight into the description of the thermal degradation of spongin-based scaffolds.

Chitin, a ubiquitous biopolymer, holds paramount scientific and economic significance. Historically, it has been primarily isolated from marine crustaceans. However, the surge in demand for chitin and the burgeoning interest in biopolymers have necessitated the exploration of alternative sources. Among these methods, the mulberry silkworm (Bombyx mori) has emerged as a particularly intriguing prospect. To isolate chitin from Bombyx mori, a chemical extraction methodology was employed. This process involved a series of meticulously orchestrated steps, including Folch extraction, demineralization, deproteinization, and decolorization. The resultant chitin was subjected to comprehensive analysis utilizing techniques such as attenuated total reflectance–Fourier transform infrared spectroscopy (ATR-FTIR), 13C nuclear magnetic resonance (NMR) spectroscopy, and wide-angle X-ray scattering (WAXS). The obtained results allow us to conclude that the Bombyx mori represents an attractive alternative source of α-chitin.

Shape memory and self-healing polymer nanocomposites have attracted considerable attention due to their modifiable properties and promising applications. The incorporation of nanomaterials (polypyrrole, carboxyl methyl cellulose, carbon nanotubes, titania nanotubes, graphene, graphene oxide, mesoporous silica) into these polymers has significantly enhanced their performance, opening up new avenues for diverse applications. The self-healing capability in polymer nanocomposites depends on several factors, including heat, quadruple hydrogen bonding, π–π stacking, Diels–Alder reactions, and metal–ligand coordination, which collectively govern the interactions within the composite materials. Among possible interactions, only quadruple hydrogen bonding between composite constituents has been shown to be effective in facilitating self-healing at approximately room temperature. Conversely, thermo-responsive self-healing and shape memory polymer nanocomposites require elevated temperatures to initiate the healing and recovery processes. Thermo-responsive (TRSMPs), light-actuated, magnetically actuated, and Electrically actuated Shape Memory Polymer Nanocomposite are discussed. This paper provides a comprehensive overview of the different types of interactions involved in SMP and SHP nanocomposites and examines their behavior at both room temperature and elevated temperature conditions, along with their biomedical applications. Among many applications of SMPs, special attention has been given to biomedical (drug delivery, orthodontics, tissue engineering, orthopedics, endovascular surgery), aerospace (hinges, space deployable structures, morphing aircrafts), textile (breathable fabrics, reinforced fabrics, self-healing electromagnetic interference shielding fabrics), sensor, electrical (triboelectric nanogenerators, information energy storage devices), electronic, paint and self-healing coating, and construction material (polymer cement composites) applications.

In the presented study, a variety of hybrid and single nanomaterials of various origins were tested as novel platforms for horseradish peroxidase immobilization. A thorough characterization was performed to establish the suitability of the support materials for immobilization, as well as the activity and stability retention of the biocatalysts, which were analyzed and discussed. The physicochemical characterization of the obtained systems proved successful enzyme deposition on all the presented materials. The immobilization of horseradish peroxidase on all the tested supports occurred with an efficiency above 70%. However, for multi-walled carbon nanotubes and hybrids made of chitosan, magnetic nanoparticles, and selenium ions, it reached up to 90%. For these materials, the immobilization yield exceeded 80%, resulting in high amounts of immobilized enzymes. The produced system showed the same optimal pH and temperature conditions as free enzymes; however, over a wider range of conditions, the immobilized enzymes showed activity of over 50%. Finally, a reusability study and storage stability tests showed that horseradish peroxidase immobilized on a hybrid made of chitosan, magnetic nanoparticles, and selenium ions retained around 80% of its initial activity after 10 repeated catalytic cycles and after 20 days of storage. Of all the tested materials, the most favorable for immobilization was the above-mentioned chitosan-based hybrid material. The selenium additive present in the discussed material gives it supplementary properties that increase the immobilization yield of the enzyme and improve enzyme stability. The obtained results confirm the applicability of these nanomaterials as useful platforms for enzyme immobilization in the contemplation of the structural stability of an enzyme and the high catalytic activity of fabricated biocatalysts.

Due to the growing importance of synthesizing active pharmaceutical ingredients (APIs) in enantiomerically pure form, new methods of asymmetric synthesis are being sought. Biocatalysis is a promising technique that can lead to enantiomerically pure products. In this study, lipase from Pseudomonas fluorescens, immobilized on modified silica nanoparticles, was used for the kinetic resolution (via transesterification) of a racemic mixture of 3-hydroxy-3-phenylpropanonitrile (3H3P), where the obtaining of a pure (S)-enantiomer of 3H3P is a crucial step in the fluoxetine synthesis pathway. For additional stabilization of the enzyme and enhanced process efficiency, ionic liquids (ILs) were used. It was found that the most suitable IL was [BMIM]Cl; a process efficiency of 97.4 % and an enantiomeric excess (ee%) of 79.5 % were obtained when 1 % (w/v) of that IL in hexane was applied and the process was catalyzed by lipase immobilized on amine-modified silica.

Abstract Novel alumina-based materials enriched with vanadia and lanthana were successfully synthesized via in situ modification using a mechanochemical method, and were applied in ammonia-induced selective catalytic reduction of nitrogen oxides (SCR process). The synthesis was optimized in terms of the ball milling time (3 or 5 h), vanadium content (0.5, 1 or 2 wt% in the final product), and lanthanum content (0.5 or 1 wt% in the final product). Vanadium (V) oxide was immobilized on an alumina support to provide catalytic activity, while lanthana was introduced to increase the affinity of nitrogen oxides and create more active adsorption sites. Mechanochemical synthesis successfully produced mesoporous materials with a large specific surface area of 279–337 m2/g and a wide electrokinetic potential range from 60 to (− 40) mV. Catalytic tests showed that the incorporation of vanadia resulted in a very large improvement in catalytic performance compared with pristine alumina, increasing its efficiency from 14 to 63% at 400 °C. The best SCR performance, a 75% nitrogen oxide conversion rate at a temperature of 450 °C, was obtained for alumina enriched with 2 and 0.5 wt% of vanadium and lanthanum, respectively, which may be considered as a promising result.

The structural biopolymer spongin in the form of a 3D scaffold resembles in shape and size numerous species of industrially useful marine keratosan demosponges. Due to the large-scale aquaculture of these sponges worldwide, it represents a unique renewable source of biological material, which has already been successfully applied in biomedicine and bioinspired materials science. In the present study, spongin from the demosponge Hippospongia communis was used as a microporous template for the development of a new 3D composite containing goethite [α-FeO(OH)]. For this purpose, an extreme biomimetic technique using iron powder, crystalline iodine, and fibrous spongin was applied under laboratory conditions for the first time. The product was characterized using SEM and digital light microscopy, infrared and Raman spectroscopy, XRD, thermogravimetry (TG/DTG), and confocal micro X-ray fluorescence spectroscopy (CMXRF). A potential application of the obtained goethite–spongin composite in the electrochemical sensing of dopamine (DA) in human urine samples was investigated, with satisfactory recoveries (96% to 116%) being obtained.

Abstract A novel chitin–ethylene glycol hybrid gel was prepared as a hydrogel electrolyte for electrical double-layer capacitors (EDLCs) using 1-butyl-3-methylimidazolium acetate [Bmim][Ac] as a chitin solvent. Examination of the morphology and topography of the chitin–EG membrane showed a homogeneous and smooth surface, while the thickness of the membrane obtained was 27 µm. The electrochemical performance of the chitin–EG hydrogel electrolyte was investigated by cyclic voltammetry and galvanostatic charge/discharge measurements. The specific capacitance value of the EDLC with chitin–EG hydrogel electrolyte was found to be 109 F g−1 in a potential range from 0 to 0.8 V. The tested hydrogel material was electrochemically stable and did not decompose even after 10,000 GCD cycles. Additionally, the EDLC test cell with chitin–EG hydrogel as electrolyte exhibited superior capacitance retention after 10,000 charge/discharge cycles compared with a commercial glass fiber membrane.

Abstract In this work, new MxOy/fucoidan hybrid systems were fabricated and applied in lipase immobilization. Magnesium (MgO) and zirconium (ZrO2) oxides were used as MxOy inorganic matrices. In the first step, the proposed oxides were functionalized with fucoidan from Fucus vesiculosus (Fuc). The obtained MgO/Fuc and ZrO2/Fuc hybrids were characterized by means of spectroscopic analyses, including Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and nuclear magnetic resonance. Additionally, thermogravimetric analysis was performed to determine the thermal stability of the hybrids. Based on the results, the mechanism of interaction between the oxide supports and fucoidan was also determined. Furthermore, the fabricated MxOy/fucoidan hybrid materials were used as supports for the immobilization of lipase from Aspergillus niger, and a model reaction (transformation of p-nitrophenyl palmitate to p-nitrophenol) was performed to determine the catalytic activity of the proposed biocatalytic system. In that reaction, the immobilized lipase exhibited high apparent and specific activity (145.5 U/gcatalyst and 1.58 U/mgenzyme for lipase immobilized on MgO/Fuc; 144.0 U/gcatalyst and 2.03 U/mgenzyme for lipase immobilized on ZrO2/Fuc). The immobilization efficiency was also confirmed using spectroscopic analyses (FTIR and XPS) and confocal microscopy.

Herein, we present a novel biosensor based on nature-inspired poly(caffeic acid) (PCA) grafted to magnetite (Fe3O4) nanoparticles with glucose oxidase (GOx) from Aspergillus niger via adsorption technique. The biomolecular corona was applied to the fabrication of a biosensor system with a screen-printed electrode (SPE). The obtained results indicated the operation of the system at a low potential (0.1 V). Then, amperometric measurements were performed to optimize conditions like various pH and temperatures. The SPE/Fe3O4@PCA-GOx biosensor presented a linear range from 0.05 mM to 25.0 mM, with a sensitivity of 1198.0 μA mM−1 cm−2 and a limit of detection of 5.23 μM, which was compared to other biosensors presented in the literature. The proposed system was selective towards various interferents (maltose, saccharose, fructose, L-cysteine, uric acid, dopamine and ascorbic acid) and shows high recovery in relation to tests on real samples, up to 10 months of work stability. Moreover, the Fe3O4@PCA-GOx biomolecular corona has been characterized using various techniques such as Fourier transform infrared spectroscopy (FTIR), high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and Bradford assay.

Marine sponges of the subclass Keratosa originated on our planet about 900 million years ago and represent evolutionarily ancient and hierarchically structured biological materials. One of them, proteinaceous spongin, is responsible for the formation of 3D structured fibrous skeletons and remains enigmatic with complex chemistry. The objective of this study was to investigate the interaction of spongin with iron ions in a marine environment due to biocorrosion, leading to the occurrence of lepidocrocite. For this purpose, a biomimetic approach for the development of a new lepidocrocite-containing 3D spongin scaffold under laboratory conditions at 24 °C using artificial seawater and iron is described for the first time. This method helps to obtain a new composite as “Iron-Spongin”, which was characterized by infrared spectroscopy and thermogravimetry. Furthermore, sophisticated techniques such as X-ray fluorescence, microscope technique, and X-Ray diffraction were used to determine the structure. This research proposed a corresponding mechanism of lepidocrocite formation, which may be connected with the spongin amino acids functional groups. Moreover, the potential application of the biocomposite as an electrochemical dopamine sensor is proposed. The conducted research not only shows the mechanism or sensor properties of “Iron-spongin” but also opens the door to other applications of these multifunctional materials.

A novel catechol-based PCA@MWCNT-Ni(OH)2 hybrid material was prepared and used to construct a non-enzymatic glucose biosensor. In this synthesis, MWCNTs were covered with a poly(caffeic acid) coating and then subjected to a straightforward electrochemical process to decorate the hybrid material with Ni(OH)2 particles. The physicochemical properties and morphology of the nanomaterial were characterized using high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), and atomic force microscopy (AFM). Amperometry and cyclic voltammetric studies demonstrated the enhanced redox properties of a GC/PCA@MWCNT-Ni(OH)2 electrode and its electrocatalytic activity in glucose detection, with a low detection limit (0.29 μM), a selectivity of 232.7 μA mM−1 cm−2, and a linear range of 0.05–10 mM, with good stability (5 months) and reproducibility (n = 8). The non-enzymatic sensor was also used for glucose determination in human serum and human blood, with recovery values ranging from 93.3% to 98.2%. In view of the properties demonstrated, the described GC/PCA@MWCNT-Ni(OH)2 sensor represents a facile synthesis method of obtaining the hybrid nanomaterial and a low-cost approach to electrochemical glucose measurement in real samples (human serum, human blood).

In this study, lignin-based spherical particles (Lig-IL) with the use of 1-(propoxymethyl)-1H-imidazolium hydrogen sulfate were prepared in different biopolymer and ionic liquid (IL) weight ratios. The application of IL during the preparation of spherical particles is an innovative method, which may be beneficial for further applications. The particles were obtained with the use of the soft-templating method and their chemical, structural and morphological characterization was performed. The spherical shape of products and their size (91–615 nm) was confirmed with the use of scanning electron microscopy (SEM) images and the particle size distribution results. The attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectra were analyzed to identify functional groups of all precursors and produced material and it was confirmed, that all materials exhibit characteristic hydroxyl and carboxylic groups, but the presence of carbonyl group was detected. Moreover, the zeta potential analysis was performed to evaluate the electrokinetic behavior of obtained materials. It was confirmed, that all materials are colloidally stable in pH above 4. Produced lignin-based spherical particles were used for evaluation of their antibacterial properties. Particles were tested against Staphylococcus aureus (S. aureus), a gram-positive bacterium, and Escherichia coli (E. coli), a gram-negative one. It was observed, that only the material with the highest addition of IL showed the antibacterial properties against both strains. A reduction of 50% in the number of microorganisms was observed for particles with the addition of hydrogen sulfate ionic liquid in a 1:1 ratio after 1 h. However, all prepared materials exhibited the antibacterial activity against a gram-positive bacterium.

γ-Alumina with incorporated metal oxide species (including Fe, Cu, Zn, Bi, and Ga) was synthesized by liquid-assisted grinding—mechanochemical synthesis, applying boehmite as the alumina precursor and suitable metal salts. Various contents of metal elements (5 wt.%, 10 wt.%, and 20 wt.%) were used to tune the composition of the resulting hybrid materials. The different milling time was tested to find the most suitable procedure that allowed the preparation of porous alumina incorporated with selected metal oxide species. The block copolymer, Pluronic P123, was used as a pore-generating agent. Commercial γ−alumina (SBET = 96 m2·g−1), and the sample fabricated after two hours of initial grinding of boehmite (SBET = 266 m2·g−1), were used as references. Analysis of another sample of γ-alumina prepared within 3 h of one-pot milling revealed a higher surface area (SBET = 320 m2·g−1) that did not increase with a further increase in the milling time. So, three hours of grinding time were set as optimal for this material. The synthesized samples were characterized by low-temperature N2 sorption, TGA/DTG, XRD, TEM, EDX, elemental mapping, and XRF techniques. The higher loading of metal oxide into the alumina structure was confirmed by the higher intensity of the XRF peaks. Samples synthesized with the lowest metal oxide content (5 wt.%) were tested for selective catalytic reduction of NO with NH3 (NH3-SCR). Among all tested samples, besides pristine Al2O3 and alumina incorporated with gallium oxide, the increase in reaction temperature accelerated the NO conversion. The highest NO conversion rate was observed for Fe2O3-incorporated alumina (70%) at 450 °C and CuO-incorporated alumina (71%) at 300 °C. The CO2 capture was also studied for synthesized samples and the sample of alumina with incorporated Bi2O3 (10 wt.%) gave the best result (1.16 mmol·g−1) at 25 °C, while alumina alone could adsorb only 0.85 mmol·g−1 of CO2. Furthermore, the synthesized samples were tested for antimicrobial properties and found to be quite active against Gram-negative bacteria, P. aeruginosa (PA). The measured Minimum Inhibitory Concentration (MIC) values for the alumina samples with incorporated Fe, Cu, and Bi oxide (10 wt.%) were found to be 4 µg·mL−1, while 8 µg·mL−1 was obtained for pure alumina.

Abstract Actin is a fundamental member of an ancient superfamily of structural intracellular proteins and plays a crucial role in cytoskeleton dynamics, ciliogenesis, phagocytosis, and force generation in both prokaryotes and eukaryotes. It is shown that actin has another function in metazoans: patterning biosilica deposition, a role that has spanned over 500 million years. Species of glass sponges (Hexactinellida) and demosponges (Demospongiae), representatives of the first metazoans, with a broad diversity of skeletal structures with hierarchical architecture unchanged since the late Precambrian, are studied. By etching their skeletons, organic templates dominated by individual F‐actin filaments, including branched fibers and the longest, thickest actin fiber bundles ever reported, are isolated. It is proposed that these actin‐rich filaments are not the primary site of biosilicification, but this highly sophisticated and multi‐scale form of biomineralization in metazoans is ptterned.

Over recent years, silica and silica-based materials have become some of the most frequently used materials worldwide [...]

Lignin-based spherical particles have recently gained popularity due to their characteristic and the usage of biopolymeric material. In this study, lignin-based spherical particles were prepared using choline chloride at different pH values, ranging from 2 to 10. Their dispersive, microstructural, and physicochemical properties were studied by a variety of techniques, including scanning electron microscopy, Fourier transform infrared spectroscopy, and zeta potential analysis. The best results were obtained for the particles prepared at pH 5 and 7, which had a spherical shape without a tendency to form aggregates and agglomerates. The lignin-based spherical particles were used for the immobilization of lipase, a model enzyme capable of catalyzing a wide range of transformations. It was shown that the highest relative activity of immobilized lipase was obtained after 24 h of immobilization at 30 °C and pH 7, using 100 mg of the support. Moreover, the immobilized lipase exhibited enhanced stability under harsh process conditions, and demonstrated high reusability, up to 87% after 10 cycles, depending on the support used. In the future, the described approach to enzyme immobilization based on lignin spheres may play a significant role in the catalytic synthesis of organic and fine chemicals, with high utility value.

Oxidized mesoporous carbon CSBA-15, obtained by the hard method, was applied to remove rhodamine B from the aqueous system. The process of carbon oxidation was performed using 0.5 and 5 M of nitric (V) acid solution at 70 and 100 °C. Functionalization of mesoporous carbon with HNO3 solutions led to reduction in the surface area, pore volume, and micropore area, however, it also led to an increased number of oxygen functional groups of acidic character. The functional groups probably are located at the entrance of micropores, in this way, reducing the values of textural parameters. Isotherms of rhodamine B adsorption indicate that the oxidation of mesoporous carbons resulted in an increase in the effectiveness of the removal of this dye from aqueous solutions. The influence of temperature, pH, and contact time of mesoporous material/rhodamine B on the effectiveness of dye removal was tested. The process of dye adsorption on the surfaces of the materials studied was established to be most effective at pH 12 and at 60 °C. Kinetic studies of the process of adsorption proved that the equilibrium state between the dye molecules and mesoporous carbon materials is reached after about 1 h. The adsorption kinetics were well fitted using a pseudo-second-order model. The most effective in rhodamine B removal was the sample CSBA-15-5-100, containing the greatest number of oxygen functional groups of acidic character. The Langmuir model best represented equilibrium data.

The kinetic parameters of thermal degradation of 3D skeletal biopolymer spongin - isolated from the marine demosponge Hippospongia communis, using thermogravimetric analysis (TG) were evaluated. The kinetic parameters of the pyrolysis in a nitrogen atmosphere were calculated using standard methods, including a model-fitting approach (Coats–Redfern method) and the model-free iso-conversional Friedman, Kissinger–Akahira–Sunose (KAS) and Ozawa–Flynn–Wall (OFW) methods. Based on the kinetic parameters obtained from the respective equations, the changes of entropy (ΔS), enthalpy (ΔH), and free Gibbs energy (ΔG) were evaluated using the theory of the active complex of the reagent. It was found that the chemical reaction model best describes the experimental data. The activation energies calculated by the Coats–Redfern method were in the range 39.3–48.7 kJ/mol. The calculated values of kinetics parameters are slightly lower than for the commercial polyurethane foams. Nevertheless, this study provides a comprehensive insight into the pathway, mechanism, and outcomes of pyrolysis of spongin-based scaffolds with the relation to the physicochemical characteristics of finally obtained carbon materials. Moreover, a critical discussion of the obtained results is given, with regard to the physical meaning of the applied approximations.

Noninvasive, continuous glucose detection can provide some insights into daily fluctuations in blood glucose levels, which can help us balance diet, exercise, and medication. Since current commercially available glucose sensors can barely provide real-time glucose monitoring and usually imply different invasive sampling, there is an extraordinary need to develop new harmless methods for detecting glucose in non-invasive body fluids. Therefore, it is crucial to design (bio)sensors that can detect very low levels of glucose (down to tens of µM) normally found in sweat or tears. Apart from the selection of materials with high catalytic activity for glucose oxidation, it is also important to pay considerable attention to the electrode functionalization process, as it significantly contributes to the overall detection efficiency. In this study, the (ZnO tetrapods) ZnO TPs-based electrodes were functionalized with Nafion and chitosan polymers to compare their glucose detection efficiency. Cyclic voltammetry (CV) measurements have shown that chitosan-modified ZnO TPs require a lower applied potential for glucose oxidation, which may be due to the larger size of chitosan micelles (compared to Nafion micelles), and thus easier penetration of glucose through the chitosan membrane. However, despite this, both ZnO TPs modified with chitosan and Nafion membranes, provided quite similar glucose detection parameters (sensitivities, 7.5 µA mM−1 cm−1 and 19.2 µA mM−1 cm−1, and limits of detection, 24.4 µM and 22.2 µM, respectively). Our results show that both electrodes have a high potential for accurate real-time sweat/tears glucose detection.

In this study, lipase from Aspergillus niger immobilized by physical immobilization by the adsorption interactions and partially interfacial activation and mixed physical immobilization via interfacial activation and ion exchange was used in the kinetic resolution of the ketoprofen racemic mixture. The FTIR spectra of samples after immobilization of enzyme-characteristic signals can be seen, and an increase in particle size diameters upon immobilization is observed, indicating efficient immobilization. The immobilization yield was on the level of 93% and 86% for immobilization unmodified and modified support, respectively, whereas activity recovery reached around 90% for both systems. The highest activity of immobilized biocatalysts was observed at pH 7 and temperature 40 °C and pH 8 and 20 °C for lipase immobilized by physical immobilization by the adsorption interactions and partially interfacial activation and mixed physical immobilization via interfacial activation and ion exchange, respectively. It was also shown that over a wide range of pH (from 7 to 10) and temperature (from 20 to 60 °C) both immobilized lipases retained over 80% of their relative activity, indicating improvement of enzyme stability. The best solvent during kinetic resolution of enantiomers was found to be phosphate buffer at pH 7, which obtained the highest efficiency of racemic ketoprofen methyl ester resolution at the level of over 51%, followed by enantiomeric excess 99.85% in the presence of biocatalyst obtained by physical immobilization by the adsorption interactions and partially interfacial activation.

The occurrence of 17α-ethinylestradiol (EE2) in the environment and its removal have drawn special attention from the scientific community in recent years, due to its hazardous effects on human and wildlife around the world. Therefore, the aim of this study was to produce an efficient enzymatic system for the removal of EE2 from aqueous solutions. For the first time, commercial silica nanopowder and 3D fibrous chitinous scaffolds from Aplysina fistularis marine sponge were used as supports for horseradish peroxidase (HRP) immobilization. The effect of several process parameters onto the removal mechanism of EE2 by enzymatic conversion and adsorption of EE2 were investigated here, including system type, pH, temperature and concentrations of H2O2 and EE2. It was possible to fully remove EE2 from aqueous solutions using system SiO2(HRP)–chitin(HRP) over a wide investigated pH range (5–9) and temperature ranges (4–45 °C). Moreover, the most suitable process conditions have been determined at pH 7, temperature 25 °C and H2O2 and EE2 concentrations equaling 2 mM and 1 mg/L, respectively. As determined, it was possible to reuse the nanoSiO2(HRP)–chitin(HRP) system to obtain even 55% EE2 degradation efficiency after five consecutive catalytic cycles.

Removal of toxic contaminants such as Pb(II) from waste solutions is environmentally requested. Therefore, in this paper, for potential novel sorbents, mesoporous ionic liquid-functionalized silicas were synthesized and tested for the removal of Pb(II) from aqueous solutions. The successful synthesis of the adsorbents was proved by nuclear magnetic resonance (29Si and 13C NMR), Fourier transform infrared spectroscopy (FTIR), and elemental analysis. The structural and textural properties were determined using scanning electron microscopy (SEM), X-ray diffraction (XRD), high-resolution transmission electron microscopy (TEM), and low-temperature N2 sorption, and the result showed that the applied procedure made it possible to obtain highly ordered particles with a two-dimensional mesostructure. The effects of several parameters including initial pH, contact time, adsorption temperature, and Pb(II) concentration were studied in detail and were discussed to evaluate the adsorption properties of the fabricated materials towards Pb(II). The obtained results confirmed a very high potential of the sorbents; however, the adsorption properties depend on the structure and amounts of the functional group onto fabricated materials. The sample ILS-Ox3-40 showed fast kinetics (equilibrium reached within 10 min) and capacity of 172 mg/g, and that makes it a promising sorbent for the cleanup of water contaminated by lead. It was also indicated that, regardless on structure of the tested materials, the Pb(II) removal was spontaneous and exothermic. The fabricated mesoporous silicas exhibited that they were easy to regenerate and had excellent reusability.

Enzymatic conversion of pharmaceutically active ingredients (API), using immobilized enzymes should be considered as a promising industrial tool due to improved reusability and stability of the biocatalysts at harsh process conditions. Therefore, in this study horseradish peroxidase was immobilized into sodium alginate capsules and then trapped into poly(vinyl chloride) electrospun fibers to provide additional enzyme stabilization and protection against the negative effect of harsh process conditions. Due to encapsulation immobilization, 100% of immobilization yield was achieved leading to loading of 25 μg of enzyme in 1 mg of the support. Immobilized in such a way, enzyme showed over 80% activity retention. Further, only slight changes in kinetic parameters of free (Km = 1.54 mM) and immobilized horseradish peroxidase (Km = 1.83 mM) were noticed, indicating retention of high catalytic properties and high substrate affinity by encapsulated biocatalyst. Encapsulated horseradish peroxidase was tested in biodegradation of two frequently occurring in wastewater API, sulfamethoxazole (antibiotic) and carbamazepine (anticonvulsant). Over 80% of both pharmaceutics was removed by immobilized enzyme after 24 h of the process from the solution at a concentration of 1 mg/L, under optimal conditions, which were found to be pH 7, temperature 25 °C and 2 mM of H2O2. However, even from 10 mg/L solutions, it was possible to remove over 40% of both pharmaceuticals. Finally, the reusability and storage stability study of immobilized horseradish peroxidase showed retention of over 60% of initial activity after 20 days of storage at 4 °C and after 10 repeated catalytic cycles, indicating great practical application potential. By contrast, the free enzyme showed less than 20% of its initial activity after 20 days of storage and exhibited no recycling potential.

The TiO2-Eu and TiO2-La systems were successfully synthesized using the microwave method. Based on the results of X-ray diffraction analysis, it was found that regardless of the analyzed systems, two crystal structures were noted for the obtained samples: anatase and rutile. The analysis, such as XPS and EDS, proved that the doped lanthanum and europium nano-particles are present only on the TiO2 surface without disturbing the crystal lattice. In the synthesized systems, there were no significant changes in the bandgap energy. Moreover, all the obtained systems were characterized by high thermal stability. One of the key objectives of the work, and a scientific novelty, was the introduction of UV-LED lamps into the metronidazole photo-oxidation pathway. The results of the photo-oxidation study showed that the obtained TiO2 systems doped with selected lanthanides (Eu or La) show high efficiency in the removal of metronidazole, and at the same consuming nearly 10 times less electricity compared to conventional UV lamps (high-pressure mercury lamp). Liquid-chromatography mass-spectrometry (LC-MS) analysis of an intermediate solution showed the presence of fragments of the degraded molecule by m/z 114, 83, and 60, prompting the formulation of a plausible photodegradation pathway for metronidazole.

A TiO2/ZnO oxide system was proposed as a support for the immobilization of laccase from Trametes versicolor (LTV). The obtained TiO2/ZnO/LTV biocatalytic system was then applied in the decolorization/degradation of C.I. Reactive Black 5 and C.I. Acid Green 25 dyes. The efficiency of immobilization was evaluated based on catalytic properties (Bradford method, oxidation reaction of 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)) and physicochemical (spectroscopic, porous, electrokinetic) analysis. The immobilization process was carried out with high performance (99.4%). Immobilized laccase retained about 40% of its activity in the whole analyzed temperature range and after 10 reaction cycles. Immobilization efficiency was also indirectly confirmed by the presence of characteristic functional groups (–C–H and –C–O), nitrogen and carbon on the TiO2/ZnO/LTV biocatalytic surface, identified by spectroscopic analyses. The increase in the surface area to 126 m2/g, change of isoelectric point (2.0) and zeta potential ranges (from +12.0 to −20.0 mV) after the immobilization process were also observed. The results show that the designed biocatalytic system enables the removal of acid dyes (C.I. Reactive Black 5 and C.I. Acid Green 25) with high efficiency (99% and 70%, respectively). Mass spectroscopy analysis indicated possible degradation products formed by the cleavage of N=N and C–N bonds.

The main goal of the study was the hydrothermal-assisted synthesis of TiO2-ZnO systems and their subsequent use in photoactive processes. Additionally, an important objective was to propose a method for synthesizing TiO2-ZnO systems enabling the control of crystallinity and morphology through epitaxial growth of ZnO nanowires. Based on the results of X-ray diffraction analysis, in the case of materials containing a small addition of ZnO (≥5 wt.%), no crystalline phase of wurtzite was observed, proving that a high amount of modified titanium dioxide can inhibit the crystallization of ZnO. The transmission electron microscopy (TEM) results confirmed the formation of ZnO nanowires for systems containing ≥ 5% ZnO. Moreover, for the synthesized systems, there were no significant changes in the band gap energy. One of the primary purposes of this study was to test the TiO2-ZnO system in the photodegradation process of 4-chlorophenol using low-power UV-LED lamps. The results of photo-oxidation studies showed that the obtained binary systems exhibit good photodegradation and mineralization efficiency. Additionally, it was also pointed out that the dye-sensitized solar cells can be a second application for the synthesized TiO2-ZnO binary systems.

The elimination of antibiotics occurring in the natural environment has become a great challenge in recent years. Among other techniques, the photocatalytic degradation of this type of pollutant seems to be a promising approach. Thus, the search for new photoactive materials is currently of great importance. The present study concerns the sol–gel synthesis of mono, binary and ternary TiO2-based materials, which are used as active photocatalysts. The main goal was to evaluate how the addition of selected components—zirconium dioxide (ZrO2) and/or zinc oxide (ZnO)—during the synthesis of TiO2-based materials and the temperature of thermal treatment affect the materials’ physicochemical and photocatalytic properties. The fabricated mixed oxide materials underwent detailed physicochemical analysis, utilizing scanning-electron microscopy (SEM), X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), energy-dispersive X-ray spectroscopy (EDS), low-temperature N2 sorption (BET model), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). The synthesized mixed oxide materials were used as photocatalysts in the heterogeneous photodegradation of tetracycline (TC). The physicochemical properties of the fabricated photocatalysts, including morphology, crystalline and textural structure, as well as the pH of the reaction system in the photocatalytic tests, were taken into account in determining their photo-oxidation activity. LC–MS/MS analysis was used to identify the possible degradation products of the selected antibiotic.

Biotechnological use of probiotic microorganisms involves providing them with appropriate conditions for growth, but also protection against environmental changes caused by an exchange of the medium, isolation of metabolites, etc. Therefore, the research on effective immobilization of probiotic microorganisms should be focused in this direction. The present study aimed to evaluate the effectiveness of an innovative hybrid immobilization system based on electrospun nanofibers and alginate hydrogel. The analyses carried out included the study of properties of the initial components, the evaluation of the degree and durability of cell immobilization in the final material, and their survival under stress conditions. Effective binding of microorganisms to the hydrogel and nanofibers was confirmed, and the collected results proved that the proposed biocomposite is an efficient method of cell protection. In addition, it was shown that immobilization on electrospun nanofibers leads to the preservation of the highest cell activity and the least cell growth restriction as compared to free or lyophilized cells only. The completed research opens new perspectives for the effective immobilization of microorganisms of significant economic importance.

As part of the present work, polymer composites used in 3D printing technology, especially in Melted and Extruded Manufacturing (MEM) technology, were obtained. The influence of modified fillers such as alumina modified silica, quaternary ammonium bentonite, lignin/silicon dioxide hybrid filler and unmodified multiwalled carbon nanotubes on the properties of polycarbonate (PC) composites was investigated. In the first part of the work, the polymer and its composites containing 0.5–3 wt.% filler were used to obtain a filament using the proprietary technological line. The moldings for testing functional properties were obtained with the use of 3D printing and injection molding techniques. In the next part of the work, the rheological properties—mass flow rate (MFR) and mechanical properties—Rockwell hardness, Charpy impact strength and static tensile strength with Young’s modulus were examined. The structure of the obtained composites was also described and determined using scanning electron microscopy (SEM). The porosity, roughness and dimensional stability of samples obtained by 3D printing were also determined. On the other hand, the physicochemical properties were presented on the basis of the research results using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), wide angle X-ray scattering analysis (WAXS) and Fourier Transform infrared spectroscopy (FT-IR). Additionally, the electrical conductivity of the obtained composites was investigated. On the basis of the obtained results, it was found that both the amount and the type of filler significantly affected the functional properties of the composites tested in the study.

Biologically induced and controlled mineralization of metals promotes the development of protective structures to shield cells from thermal, chemical, and ultraviolet stresses. Metal biomineralization is widely considered to have been relevant for the survival of life in the environmental conditions of ancient terrestrial oceans. Similar behavior is seen among extremophilic biomineralizers today, which have evolved to inhabit a variety of industrial aqueous environments with elevated metal concentrations. As an example of extreme biomineralization, we introduce the category of “forced biomineralization”, which we use to refer to the biologically mediated sequestration of dissolved metals and metalloids into minerals. We discuss forced mineralization as it is known to be carried out by a variety of organisms, including polyextremophiles in a range of psychrophilic, thermophilic, anaerobic, alkaliphilic, acidophilic, and halophilic conditions, as well as in environments with very high or toxic metal ion concentrations. While much additional work lies ahead to characterize the various pathways by which these biominerals form, forced biomineralization has been shown to provide insights for the progression of extreme biomimetics, allowing for promising new forays into creating the next generation of composites using organic-templating approaches under biologically extreme laboratory conditions relevant to a wide range of industrial conditions.

Tissue engineering (TE) is a field of regenerative medicine that has been experiencing a special boom in recent years. Among various materials used as components of 3D scaffolds, naturally formed chitinous materials seem to be especially attractive because of their abundance, non-toxic and eco-friendly character. In this study, chitinous skeleton isolated from the marine sponge Aplysina fistularis (phylum: Porifera) was used for the first time as a support for the cultivation of murine fibroblasts (Balb/3T3), human dermal fibroblasts (NHDF), human keratinocyte (HaCaT), and human neuronal (SH-SY5Y) cells. Characterization techniques such as ATR FTIR, TGA, and μCT, clearly indicate that an interconnected macro-porous, thermostable, pure α-chitin scaffold was obtained after alkali–acid treatment of air-dried marine sponge. The biocompatibility of the naturally formed chitin scaffolds was confirmed by cell attachment and proliferation determined by various microscopic methods (e.g., SEM, TEM, digital microscopy) and specific staining. Our observations show that fibroblasts and keratinocytes form clusters on scaffolds that resemble a skin structure, including the occurrence of desmosomes in keratinocyte cells. The results obtained here suggest that the chitinous scaffold from the marine sponge A. fistularis is a promising biomaterial for future research about tissues regeneration.

The presented study deals with the fabrication of highly stable and active nanobiocatalysts based on Candida antarctica lipase B (CALB) immobilization onto pristine and poly(dimethylsiloxane) modified MWCNTs. The MWCNTs/PDMS nanocomposites, containing 40 wt.% of the polymer with two molecular weights, were successfully synthesized via adsorption modification. The effect of PDMS chains length on the textural/structural properties of produced materials was studied by means of the nitrogen adsorption–desorption technique, Raman spectroscopy, and attenuated total reflectance Fourier transform infrared spectroscopy. P-MWCNTs and MWCNTs/PDMS nanocomposites were tested as supports for lipase immobilization. Successful deposition of the enzyme onto the surface of P-MWCNTs and MWCNTs/PDMS nanocomposite materials was confirmed mainly using ATR-FTIR spectroscopy. The immobilization efficiency, stability, and catalytic activity of the immobilized enzyme were studied, and the reusability of the produced biocatalytic systems was examined. The presented results demonstrate that the produced novel biocatalysts might be considered as promising materials for biocatalytic applications.

In this study, MgO-lignin (MgO-L) dual phase fillers with varying amounts of lignin as well as pristine lignin and magnesium oxide were used as effective bio-fillers to increase the ultraviolet light protection and enhance the barrier performance of low density polyethylene (LDPE) thin sheet films. Differential scanning calorimetry (DSC) was used to check the crystalline structure of the studied samples, and scanning electron microscopy (SEM) was applied to determine morphological characteristics. The results of optical spectrometry in the range of UV light indicated that LDPE/MgO-L (1:5 wt/wt) composition exhibited the best protection factor, whereas LDPE did not absorb ultraviolet waves. Moreover, the addition of hybrid filler decreased the oxygen permeability factor and water vapor transmission compared with neat LDPE and its composites with pristine additives, such as lignin and magnesium oxide. The strong influence of the microstructure on thin sheet films was observed in the DSC results, as double melting peaks were detected only for LDPE compounded with inorganic-organic bio-fillers: LDPE/MgO-L.

Silicon dioxide, in the form of nanoparticles, possesses unique physicochemical properties (size, shape, and a large surface to volume ratio). Therefore, it is one of the most promising materials used in biomedicine. In this paper, we compare the biological effects of both mesoporous silica nanoparticles extracted from Urtica dioica L. and pyrogenic material. Both SEM and TEM investigations confirmed the size range of tested nanoparticles was between 6 and 20 nanometers and their amorphous structure. The cytotoxic activity of the compounds and intracellular ROS were determined in relation to cells HMEC-1 and erythrocytes. The cytotoxic effects of SiO2 NPs were determined after exposure to different concentrations and three periods of incubation. The same effects for endothelial cells were tested under the same range of concentrations but after 2 and 24 h of exposure to erythrocytes. The cell viability was measured using spectrophotometric and fluorimetric assays, and the impact of the nanoparticles on the level of intracellular ROS. The obtained results indicated that bioSiO2 NPs, present higher toxicity than pyrogenic NPs and have a higher influence on ROS production. Mesoporous silica nanoparticles show good hemocompatibility but after a 24 h incubation of erythrocytes with silica, the increase in hemolysis process, the decrease in osmotic resistance of red blood cells, and shape of erythrocytes changed were observed.

One of the directions of development in the textiles industry is the search for new technologies for producing modern multifunctional products. New solutions are sought to obtain materials that will protect humans against the harmful effects of the environment, including such factors as the activity of microorganisms and UV radiation. Products made of natural cellulose fibers are often used. In the case of this type of material, it is very important to perform appropriate pretreatment before subsequent technological processes. This treatment has the aim of removing impurities from the surface of the fibers, which results in the improvement of sorption properties and adhesion, leading directly to the better penetration of dyes and chemical modifiers into the structure of the materials. In this work, linen fabrics were subjected to a new, innovative treatment being a combination of bio-pretreatment using laccase from Cerrena unicolor and modification with CuO-SiO2 hybrid oxide microparticles by a dip-coating method. To compare the effect of alkaline or enzymatic pretreatment on the microstructure of the linen woven fabrics, SEM analysis was performed. The new textile products obtained after this combined process exhibit very good antimicrobial activity against Candida albicans, significant antibacterial activity against the Gram-negative Escherichia coli and the Gram-positive Staphylococcus aureus, as well as very good UV protection properties (ultraviolet protection factor (UPF) > 40). These innovative materials can be used especially for clothing or outdoor textiles for which resistance to microorganisms is required, as well as to protect people who are exposed to long-term, harmful effects of UV radiation.