Exploring the antimicrobial and antioxidant potential of bacterial cellulose-cerium oxide nanoparticles hydrogel: Design, characterization and biomedical properties.

Bacterial cellulose (BC) is a promising natural polymer prized for its biocompatibility, microporosity, transparency, conformability, elasticity, and ability to maintain a moist wound environment while absorbing exudates. These attributes make BC an attractive material in biomedical applications, particularly in skin tissue repair. However, its lack of inherent antimicrobial activity limits its effectiveness. In this study, BC was enhanced by incorporating cerium (IV)-oxide (CeO2) nanoparticles, resulting in a series of bacterial cellulose-CeO2 (BC-CeO2) composite materials. Characterization via FESEM, XRD, and FTIR confirmed the successful synthesis of the composites. Notably, BC-CeO2-1 exhibited no cytotoxic or genotoxic effects on peripheral blood lymphocytes, and it additionally protected cells from genotoxic and cytotoxic effects in H2O2-treated cultures. Redox parameters in blood plasma samples displayed concentration and time-dependent trends in PAB and LPP assays. The incorporation of CeO2 nanoparticles also bolstered antimicrobial activity, expanding the potential biomedical applications of these composites.

The Roles of Impurities and Surface Area on Thermal Stability and Oxidation Resistance of BN Nanoplatelets.

This study considers the influence of purity and surface area on the thermal and oxidation properties of hexagonal boron nitride (h-BN) nanoplatelets, which represent crucial factors in high-temperature oxidizing environments. Three h-BN nanoplatelet-based materials, synthesized with different purity levels and surface areas (~3, ~56, and ~140 m2/g), were compared, including a commercial BN reference. All materials were systematically analyzed by various characterization techniques, including gas pycnometry, scanning electron microscopy, X-ray diffraction, Fourier-transform infrared radiation, X-ray photoelectron spectroscopy, gas sorption analysis, and thermal gravimetric analysis coupled with differential scanning calorimetry. Results indicated that the thermal stability and oxidation resistance of the synthesized materials were improved by up to ~13.5% (or by 120 °C) with an increase in purity. Furthermore, the reference material with its high purity and low surface area (~4 m2/g) showed superior performance, which was attributed to the minimized reactive sites for oxygen diffusion due to lower surface area availability and fewer possible defects, highlighting the critical roles of both sample purity and accessible surface area in h-BN thermo-oxidative stability. These findings highlight the importance of focusing on purity and surface area control in developing BN-based nanomaterials, offering a path to enhance their performance in extreme thermal and oxidative conditions.

Energy Landscape of Relaxation and Interaction of an Amino Acid, Glutamine (L), on Pristine and Au/Ag/Cu-Doped TiO2 Surfaces.

Studying the interaction of inorganic systems with organic ones is a highly important avenue for finding new drugs and treatment methods. Tumor cells show an increased demand for amino acids due to their rapid proliferation; thus, targeting their metabolism is becoming a potential oncological therapeutic strategy. One of the inorganic materials that show antitumor properties is titanium dioxide, while its doping was found to enhance interactions with biological systems. Thus, in this study, we investigated the energy landscape of glutamine (L), an amino acid, on pristine and doped TiO2 surfaces. We first locally optimized 2D-slab structures of pristine and Au/Ag/Cu-doped anatase (001 and 101 surfaces) and similarly optimized a single molecule of glutamine in vacuum. Next, we placed the pre-optimized glutamine molecule in various orientations and on a variety of locations onto the relaxed substrate surfaces (in vacuum) and performed ab initio relaxations of the molecule on the substrate slabs. We employed the DFT method with a GGA-PBE functional implemented in the Quantum Espresso code. Comparisons of the optimized conformations and electronic structures of the amino acid in vacuum and on the surfaces yield useful insights into various biological processes.

Band Gap Engineering of Newly Discovered ZnO/ZnS Polytypic Nanomaterials.

We report on a new class of ZnO/ZnS nanomaterials based on the wurtzite/sphalerite architecture with improved electronic properties. Semiconducting properties of pristine ZnO and ZnS compounds and mixed ZnO1-xSx nanomaterials have been investigated using ab initio methods. In particular, we present the results of our theoretical investigation on the electronic structure of the ZnO1-xSx (x = 0.20, 0.25, 0.33, 0.50, 0.60, 0.66, and 0.75) nanocrystalline polytypes (2H, 3C, 4H, 5H, 6H, 8H, 9R, 12R, and 15R) calculated using hybrid PBE0 and HSE06 functionals. The main observations are the possibility of alternative polytypic nanomaterials, the effects of structural features of such polytypic nanostructures on semiconducting properties of ZnO/ZnS nanomaterials, the ability to tune the band gap as a function of sulfur content, as well as the influence of the location of sulfur layers in the structure that can dramatically affect electronic properties. Our study opens new fields of ZnO/ZnS band gap engineering on a multi-scale level with possible applications in photovoltaics, light-emitting diodes, laser diodes, heterojunction solar cells, infrared detectors, thermoelectrics, or/and nanostructured ceramics.

Synthesis, Characterization, and Electronic Properties of ZnO/ZnS Core/Shell Nanostructures Investigated Using a Multidisciplinary Approach.

ZnO/ZnS core/shell nanostructures, which are studied for diverse possible applications, ranging from semiconductors, photovoltaics, and light-emitting diodes (LED), to solar cells, infrared detectors, and thermoelectrics, were synthesized and characterized by XRD, HR-(S)TEM, and analytical TEM (EDX and EELS). Moreover, band-gap measurements of the ZnO/ZnS core/shell nanostructures have been performed using UV/Vis DRS. The experimental results were combined with theoretical modeling of ZnO/ZnS (hetero)structures and band structure calculations for ZnO/ZnS systems, yielding more insights into the properties of the nanoparticles. The ab initio calculations were performed using hybrid PBE0 and HSE06 functionals. The synthesized and characterized ZnO/ZnS core/shell materials show a unique three-phase composition, where the ZnO phase is dominant in the core region and, interestingly, the auxiliary ZnS compound occurs in two phases as wurtzite and sphalerite in the shell region. Moreover, theoretical ab initio calculations show advanced semiconducting properties and possible band-gap tuning in such ZnO/ZnS structures.

Structure Prediction and Mechanical Properties of Silicon Hexaboride on Ab Initio Level.

Silicon borides represent very appealing industrial materials for research owing to their remarkable features, and, together with other boride and carbide-based materials, have very wide applications. Various Si-B phases have been investigated in the past, however a limited number of studies have been done on the pristine SiB6 compound. Structure prediction using a data mining ab initio approach has been performed in pure silicon hexaboride. Several novel structures, for which there are no previous experimental or theoretical data, have been discovered. Each of the structure candidates were locally optimized on the DFT level, employing the LDA-PZ and the GGA-PBE functional. Mechanical and elastic properties for each of the predicted and experimentally observed modifications have been investigated in great detail. In particular, the ductility/brittleness relationship, the character of the bonding, Young's modulus E, bulk modulus B, and shear modulus K, including anisotropy, have been calculated and analyzed.

Cell wall response to UV radiation in needles of Picea omorika.

The UV-B represents the minor fraction of the solar spectrum, while UV-C is not contained in natural solar radiation, but both radiation types can cause damaging effects in plants. Cell walls (CWs) are one of the targets for external stressors. Juvenile P. omorika trees were treated either with 21 day-high doses UV-B or with 7 day- UV-C in open-top chambers. Using spectroscopic and biochemical techniques, it was shown that the response to UV radiation includes numerous modifications in needle CW structure: relative content of xylan, xyloglucan, lignin and cellulose decreased; cellulose crystallinity changed; yield of lignin monomers with stronger connection of CC in side chain with the ring increased; re-distribution of inter- and intra-polymer H-bonds occurred. The recovery was mediated by an increase in the activities and changes in isoform profiles of CW bound covalent peroxidases (POD) and polyphenol oxidases (PO) (UV-B), and ionic POD and covalent PO (UV-C). A connection between activities of specific POD/PO isoforms and phenolic species (m- and p-coumaric acid, pinoresinol and cinnamic acid derivatives) was demonstrated, and supported by changes in the sRNA profile. In vivo fluorometry showed phenolics accumulation in needle epidermal CWs. These results imply transversal connections between polymers and changed mechanical properties of needle CW as a response to UV. The CW alterations enabled maintenance of physiological functions, as indicated by the preserved chlorophyll content and/or organization. The current study provides evidence that in conifers, needle CW response to both UV-B and UV-C includes biochemical modifications and structural remodeling.

Boron Nitride Nanotubes Versus Carbon Nanotubes: A Thermal Stability and Oxidation Behavior Study.

Nanotubes made of boron nitride (BN) and carbon have attracted considerable attention within the literature due to their unique mechanical, electrical and thermal properties. In this work, BN and carbon nanotubes, exhibiting high purity (>99%) and similar surface areas (~200 m2/g), were systematically investigated for their thermal stability and oxidation behavior by combining thermal gravimetric analysis and differential scanning calorimetry methods at temperatures of up to ~1300 °C under a synthetic air flow environment. The BN nanotubes showed a good resistance to oxidation up to ~900 °C and fully transformed to boron oxide up to ~1100 °C, while the carbon nanotubes were stable up to ~450 °C and almost completely combusted up to ~800 °C. The different oxidation mechanisms are attributed to the different chemical nature of the two types of nanotubes.

Multiwalled carbon nanotubes modified with MoO2 nanoparticles for voltammetric determination of the pesticide oxyfluorfen.

A glassy carbon electrode was functionalized by MoO2 nanoparticle-decorated multiwalled carbon nanotubes (MWCNTs) and examined as a working electrode in oxyfluorfen (OXY) detection by differential pulse stripping voltammetry (DPSV). Measurement parameters were as follows: initial potential - 0.1 V, end potential + 0.5 V, accumulation potential - 0.15 V, accumulation time 80 s, and scan rate 50 mV s-1. A stripping potential of + 0.315 V vs. Ag/AgCl was employed. The pPesticide oxyfluorfen was determined in model samples by DPSV with good reproducibility (RSD <2.4%) in the concentration range 2.5 to 34.5 ng mL-1, with r = 0.99 and a limit of detection of 1.5 ng mL-1. These results are in the same range as those of HPLC/DAD, which is used as the comparative method. Recovery for OXY determination in a real river water sample was 102%. Analyses in Briton-Robinson buffer has shown to be pH dependent with the best response at pH 6.0. Structural characterization of MoO2-MWCNT by Raman spectroscopy, field emission scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray crystallography revealed a preserved MWCNT structure decorated with firmly attached clusters of MoO2 nanoparticles. Graphical abstract Glassy carbon electrode functionalized by MoO2 nanoparticle-decorated multiwalled carbon nanotubes is used as a working electrode in the voltammetric determination of pesticide oxyfluorfen in water.

Bacterial cellulose-lignin composite hydrogel as a promising agent in chronic wound healing.

Lignins and lignin-derived compounds are known to have antibacterial properties. The wound healing agents in the form of dressings produce faster skin repair and decrease pain in patients. In order to create an efficient antimicrobial agent in the form of dressing in the treatment of chronic wounds, a composite hydrogel of bacterial cellulose (BC) and dehydrogenative polymer of coniferyl alcohol (DHP), BC-DHP, was designed. Novel composite showed inhibitory or bactericidal effects against selected pathogenic bacteria, including clinically isolated ones. The highest release rate of DHP was in the first hour, while after 24 h there was still slow release of small amounts of DHP from BC-DHP during 72 h monitoring. High-performance liquid chromatography coupled with mass-spectrometry showed that BC-DHP releases DHP oligomers, which are proposed to be antimicrobially active DHP fractions. Scanning electron microscopy and atomic force microscopy micrographs proved a dose-dependent interaction of DHP with BC, which resulted in a decrease of the pore number and size in the cellulose membrane. The Fourier-transform infrared absorption spectra of the BC-DHP showed that DHP was partly bound to the BC matrix. The swelling and crystallinity degree were dose-dependent. All obtained results confirmed BC-DHP composite as a promising hydrogel for wounds healing.

Barium Sulfide under Pressure: Discovery of Metastable Polymorphs and Investigation of Electronic Properties on ab Initio Level.

Barium sulfide (BaS) is an important precursor to other barium compounds with applications from ceramics and flame retardants to luminous paints and additives, and recent research shows potential technological applications in electrical and optical devices. Under normal conditions, BaS crystallizes in the NaCl type of structure, and with the increase in pressure BaS undergoes a structural phase transition to a CsCl type modification. This study presents modeling of barium sulfide under pressure with special focus on structural aspects and electronic properties. We predict metastable BaS polymorphs which have not yet been observed in the experiment or in previous calculations, and we investigated their vibrational and thermodynamical properties. Furthermore, we investigate the electronic properties of experimentally known structures as well as novel predicted modifications of BaS on ab initio level using Hartree-Fock, GGA-PBE, and the hybrid B3LYP functional. In this way, we address new possibilities of synthesizing BaS and possible band gap tuning which can have great applications in optoelectrical technologies.

Anti-cancer effects of cerium oxide nanoparticles and its intracellular redox activity.

Data on medical applications of cerium oxide nanoparticles CeO2 (CONP) are promising, yet information regarding their action in cells is incomplete and there are conflicting reports about in vitro toxicity. Herein, we have studied cytotoxic effect of CONP in several cancer and normal cell lines and their potential to change intracellular redox status. The IC50 was achieved only in two of eight tested cell lines, melanoma 518A2 and colorectal adenocarcinoma HT-29. Self-propagating room temperature method was applied to produce CONP with an average crystalline size of 4 nm. The results confirmed presence of Ce(3+) and O(2-) vacancies. The induction of cell death by CONP and the production of reactive oxygen species (ROS) were analyzed by flow-cytometry. Free radicals related antioxidant capacity of the cells was studied by the reduction of stable free radical TEMPONE using electron spin resonance spectroscopy. CONP showed low or moderate cytotoxicity in cancer cell lines: adenocarcinoma DLD1 and multi-drug resistant DLD1-TxR, non-small cell lung carcinoma NCI-H460 and multi-drug resistant NCI-H460/R, while normal cell lines (keratinocytes HaCaT, lung fetal fibroblasts MRC-5) were insensitive. The most sensitive were 518A2 melanoma and HT-29 colorectal adenocarcinoma cell lines, with the IC50 values being between 100 and 200 µM. Decreased rate of TEMPONE reduction and increased production of certain ROS species (peroxynitrite and hydrogen peroxide anion) indicates that free radical metabolism, thus redox status was changed, and antioxidant capacity damaged in the CONP treated 518A2 and HT-29 cells. In conclusion, changes in intracellular redox status induced by CONP are partly attributed to the prooxidant activity of the nanoparticles. Further, ROS induced cell damages might eventually lead to the cell death. However, low inhibitory potential of CONP in the other human cell lines tested indicates that CONP may be safe for human usage in industry and medicine.

Prediction of possible CaMnO3 modifications using an ab initio minimization data-mining approach.

We have performed a crystal structure prediction study of CaMnO3 focusing on structures generated by octahedral tilting according to group-subgroup relations from the ideal perovskite type (Pm\overline 3 m), which is the aristotype of the experimentally known CaMnO3 compound in the Pnma space group. Furthermore, additional structure candidates have been obtained using data mining. For each of the structure candidates, a local optimization on the ab initio level using density-functional theory (LDA, hybrid B3LYP) and the Hartree--Fock (HF) method was performed, and we find that several of the modifications may be experimentally accessible. In the high-pressure regime, we identify a post-perovskite phase in the CaIrO3 type, not previously observed in CaMnO3. Similarly, calculations at effective negative pressure predict a phase transition from the orthorhombic perovskite to an ilmenite-type (FeTiO3) modification of CaMnO3.

Suppression of inherent ferromagnetism in Pr-doped CeO2 nanocrystals.

Ce(1-x)Pr(x)O(2-δ) (0 ≤ x ≤ 0.4) nanocrystals were synthesized by self-propagating method and thoroughly characterized using X-ray diffraction, Raman and X-ray photoelectron spectroscopy and magnetic measurements. Undoped CeO2 nanocrystals exhibited intrinsic ferromagnetism at room temperature. Despite the increased concentration of oxygen vacancies in doped samples, our results showed that ferromagnetic ordering rapidly degrades with Pr doping. The suppression of ferromagnetism can be explained in terms of the different dopant valence state, the different nature of the vacancies formed in Pr-doped samples and their ability/disability to establish the ferromagnetic ordering.