Correction: Popova et al. Ni-Cu and Ni-Co-Modified Fly Ash Zeolite Catalysts for Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone. Molecules 2024, 29, 99.

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Modification of micro-crystalline graphite and carbon black by acetone, toluene, and phenol.

The chemical interactions of two types of graphite and two types of carbon black (CB) with acetone, toluene, and phenol were studied in order to evaluate the influence of chemical treatment on the structure and morphology of the carbon phases. The experimental treatment of carbon phases was carried out at room temperature for 1 hour. The chemical and phase composition were studied by x-ray photoelectron (XP) and Raman spectroscopies, while the morphology and structure were determined by powder x-ray diffraction, as well as transmission electron microscopy techniques. To shed light on the most probable explanation of the observed results, we performed simulations and calculations of the binding energies of acetone, toluene, and phenol with model carbon phases: a perfect graphene sheet and a defective graphene sheet containing various structural defects (vacancies as well as zigzag and armchair edges). Simulations show that all non-covalent and most covalent coupling reactions are exothermic, with acetone coupling having the higher calorimetric effect. Based on the results of the simulations and the XP spectroscopy measurements, the probable reactions taking place during the respective treatments are outlined. The conducted studies (both theoretical and experimental) show that the treatment of graphite powders and CB with acetone, toluene, or phenol can be used as a preliminary stage of their modification and/or functionalization, including their conversion into graphene-like (defective graphene, reduced graphene oxide, and/or graphene oxide) phases. For example, the treatment of SPHERON 5000 with acetone significantly facilitates their subsequent modification with laser radiation to graphene-like phases.

Blending Approach Preparation of PVA-g-PMA Films with Embedded "Green" Synthesized Silver Nanoparticles for Acetone Optical Detection.

The blending approach (also known as the ex-situ approach) was used for the deposition of thin composite films comprising poly(vinyl alcohol-graft-methyl acrylate) (PVA-g-PMA) and silver nanoparticles (AgNPs). Firstly, the copolymer aqueous dispersion was synthesized through the redox polymerization of methyl acrylate (MA) on poly(vinyl alcohol) (PVA) using ammonium cerium (IV) nitrate as the initiator. Then, AgNPs were synthesized through a "green" method using the water extract of lavender based on by-products of the essential oil industry, and then they were blended with the polymer. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to determine nanoparticle size, along with their stability over time in suspension, during the 30-day period. Thin films of the PVA-g-PMA copolymer, with different AgNP volume fractions varying between 0.008 and 0.260%, were deposited via the spin-coating method on Si substrates, and their optical properties were explored. UV-VIS-NIR spectroscopy and non-linear curve fitting were used for the determination of the refractive index, extinction coefficient, and thickness of the films, while photoluminescence measurements at room temperature were conducted for studying the emission of the films. The concentration dependence of film thickness was observed and showed that thickness increased linearly from 31 nm to 75 nm when the nanoparticles' weight content increased from 0.3 wt% to 2.3 wt%. The sensing properties toward acetone vapors were tested in a controlled atmosphere by measuring reflectance spectra before and during exposure to the analyte molecules in the same film spot; the swelling degree of films was calculated and compared to the corresponding undoped samples. It was shown that the concentration of AgNPs of 1.2 wt% in the films is optimal for the enhancement of the sensing response toward acetone. The influence of AgNPs on the films' properties was revealed and discussed.

Ni-Cu and Ni-Co-Modified Fly Ash Zeolite Catalysts for Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone.

Monometallic (Ni, Co, Cu) and bimetallic (Ni-Co, Ni-Cu) 10-20 wt.% metal containing catalysts supported on fly ash zeolite were prepared by post-synthesis impregnation method. The catalysts were characterized by X-ray powder diffraction, N2 physisorption, XPS and H2-TPR methods. Finely dispersed metal oxides and mixed oxides were detected after the decomposition of the impregnating salt on the relevant zeolite support. Via reduction intermetallic, NiCo and NiCu phases were identified in the bimetallic catalysts. The catalysts were studied in hydrodeoxygenation of lignocellulosic biomass-derived levulinic acid to γ-valerolactone (GVL) in a batch system by water as a solvent. Bimetallic, 10 wt.% Ni, and 10 wt.% Cu or Co containing fly ash zeolite catalysts showed higher catalytic activity than monometallic ones. Their selectivity to GVL reached 70-85% at about 100% conversion. The hydrogenation activity of catalysts was found to be stronger compared to their hydration ability; therefore, the reaction proceeds through formation of 4-hydroxy pentanoic acid as the only intermediate compound.

Hydrodemethoxylation/Dealkylation on Bifunctional Nanosized Zeolite Beta.

Mono-, and bimetallic Ni-, Ru-, and Pt-modified nanosized Beta zeolite catalysts were prepared by the post synthesis method and characterized by powder X-ray diffraction (XRD), nitrogen physisorption, HRTEM microscopy, temperature-programmed reduction (TPR-TGA), ATR FT-IR spectroscopy, and by solid-state MAS-NMR spectroscopy. The presence of nanosized nickel-oxide, ruthenium-oxide, and platinum species was detected on the catalysts. The presence of Brønsted and Lewis acid sites, and incorporation of nickel ions into zeolite lattice was proven by FT-IR of adsorbed pyridine. The structural changes in the catalyst matrix were investigated by solid state NMR spectroscopy. The catalysts were used in a gas-phase hydrodemethoxylation and dealkylation of 2-methoxy-4-propylphenol as a lignin derivative molecule for phenol synthesis.

Preparation, characterization and catalytic activity of NiOx and NiOx/ZrO2 for oxidation of phenol in aqueous solution.

In the present study bulk NiO(x) and supported NiO(x)/ZrO(2) catalysts have been prepared. The bulk NiO(x) was synthesized using the precipitation-oxidation method with reverse order of precipitation while deposition-precipitation technique was used for the preparation of zirconia supported catalyst. The as-prepared samples were characterized by means of XRD, HRTEM, SAED, IR-spectroscopy, and chemical analyses. It was found that under the applied synthesis procedure nanosized and highly dispersed oxide materials with high active oxygen content were obtained. The catalytic activity and selectivity of these oxide catalysts have been studied in reaction of low-temperature oxidation of phenol in aqueous phase. The effects of several parameters such as catalyst amount, temperature and solution pH on the degradation efficiency of the process were also investigated. Experimental results demonstrated that phenol could be completely degraded under all reaction conditions, except at pH = 12.

Synthesis of 2D PtSe2 Nanolayers on Glass Substrates and Their Integration in Near-Infrared Light Shutters.

PtSe2 has asserted its key role among the emerging 2D transition metal dichalcogenides, however, its simplified growth process with controlled number of layers, high crystalline quality, and on inexpensive substrates is still challenging. Here, we report the synthesis details of PtSe2 layers on soda lime glass substrates by selenization of predeposited Pt layers using the thermally assisted conversion method at atmospheric pressure. PtSe2 syntheses are confirmed by X-ray photoelectron spectroscopy and Raman analysis. The layers were further investigated with transmission electron microscopy and optical ellipsometry, revealing the thickness and its dependence on the metal precursor sputtering time. Finally, the integration of PtSe2 as transparent conductive layers in polymer-dispersed liquid crystal structures operating as near-infrared light shutters is demonstrated and device performance is discussed. The proposed simple and inexpensive synthesis approach opens up new directions toward PtSe2 potential technological applications, including ITO-free optoelectronics.

Electrospun Fibers of Biocompatible and Biodegradable Polyesters, Poly(Ethylene Oxide) and Beeswax with Anti-Bacterial and Anti-Fungal Activities.

Fibrous materials composed of core-sheath fibers from poly(ethylene oxide) (PEO), beeswax (BW) and 5-nitro-8-hydroxyquinoline (NQ) were prepared via the self-organization of PEO and BW during the single-spinneret electrospinning of a homogeneous blend solution of the partners. Additionally, the application of the same approach enabled the preparation of fibrous materials composed of core-double sheath fibers from PEO, poly(L-lactide) (PLA) and NQ or 5-chloro-7-iodo-8-hydroxyquinoline (CQ), as well as from PEO, poly(ε-caprolactone) (PCL) and NQ. The consecutive selective extraction of BW and of the polyester with hexane and tetrahydrofuran, respectively, evidenced that core-double sheath fibers from PEO/polyester/BW/drug consisted of a PEO core, a polyester inner sheath and a BW outer sheath. In order to evaluate the possibility of the application of fibrous materials from PEO/BW/NQ, PEO/PLA/BW/NQ, PEO/PCL/BW/NQ and PEO/PLA/BW/CQ for plant protection, microbiological studies were performed using both phytopathogenic microorganisms (Pseudomonas corrugata, Fusarium graminearum and Fusarium avenaceum) and beneficial microorganisms (Pseudomonas chlororaphis, Bacillus amyloliquefaciens and Trichoderma asperellum). It was found that the fibrous materials had anti-bacterial and anti-fungal activity against both phytopathogenic and beneficial microorganisms. This is the first report on the activity of fibrous materials loaded with 8-hydroxyquinoline derivatives not only against phytopathogenic but also against beneficial microorganisms that are of importance in agriculture.

Impact of Ce/Zr Ratio in the Nanostructured Ceria and Zirconia Composites on the Selective CO2 Adsorption.

High surface-area, mesoporous CeO2, ZrO2, and Ce-Zr composite nanoparticles were developed using the hydrothermal template-assisted synthesis method. Samples were characterized using XRD, N2 physisorption, TEM, XPS, and FT-IR spectroscopic methods. The CO2 adsorption ability of the obtained materials was tested under dynamic and equilibrium conditions. A high CO2 adsorption capacity in CO2/N2 flow or CO2/N2/H2O was determined for all studied adsorbents depending on their composition flow. A higher CO2 adsorption was registered for Ce-Zr composite nanomaterials due to the presence of strong O2- base sites and enriched surface oxygen species. The role of the Ce/Zr ratio is the process of the formation of highly active and selective adsorption sites is discussed. The calculated heat of adsorption revealed the processes of chemisorption and physisorption. Experimental data could be appropriately described by the Yoon-Nelson kinetic model. The composites reused in five adsorption/desorption cycles showed a high stability with a slight decrease in CO2 adsorption capacities in dry flow and in the presence of water vapor.

Chlorhexidine-Silver Nanoparticle Conjugation Leading to Antimicrobial Synergism but Enhanced Cytotoxicity.

This study explored the potential synergism within chlorhexidine-silver nanoparticle conjugates against Influenza type A, Staphylococcus aureus, Escherichia coli, and Candida albicans. Silver nanoparticles (SN) were obtained by the reduction of silver ions with green tea total phenolic extract and conjugated with chlorhexidine (Cx). The particles were characterized by UV-Vis and FTIR spectroscopies, dynamic light scattering, X-ray diffraction, and transmission electron microscopy. A stable negatively charged nano-silver colloid (ζ = -50.01) was obtained with an average hydrodynamic diameter of 92.34 nm. In the presence of chlorhexidine, the spectral data and the shift of the zeta potential to positive values (ζ = +44.59) revealed the successful sorption of the drug onto the silver surface. The conjugates (SN-Cx) demonstrated potentiation in their effects against S. aureus and C. albicans and synergism against E. coli with minimal inhibitory concentrations of SN at 5.5 µg/mL + Cx 8.8 µg/mL. The SN showed excellent virucidal properties, increasing with time, and demonstrated low toxicity. However, the coupling of the cationic chlorhexidine with nano-silver did not reduce its intrinsic cytotoxicity on various cell lines (MDCK, BJ, and A549). The newly synthesized antimicrobial agent exhibited an extended and promising therapeutic spectrum and needs to be further evaluated regarding the designated route of administration in three-dimensional cell models (e.g., nasal, bronchial, dermal, ocular, etc.).

Environmentally Benign pSOFC for Emissions-Free Energy: Assessment of Nickel Network Resistance in Anodic Ni/BCY15 Nanocatalyst.

Yttrium-doped barium cerate (BCY15) was used as ceramic matrix to obtain Ni/BCY15 anode cermet for application in proton-conducting solid oxide fuel cells (pSOFC). Ni/BCY15 cermets were prepared in two different types of medium, namely deionized water (W) and anhydrous ethylene glycol (EG) using wet chemical synthesis by hydrazine. An in-depth analysis of anodic nickel catalyst was made aiming to elucidate the effect of anode tablets' preparation by high temperature treatment on the resistance of metallic Ni in Ni/BCY15-W and Ni/BCY15-EG anode catalysts. On purpose reoxidation upon high-temperature treatment (1100 °C for 1 h) in air ambience was accomplished. Detailed characterization of reoxidized Ni/BCY15-W-1100 and Ni/BCY15-EG-1100 anode catalysts by means of surface and bulk analysis was performed. XPS, HRTEM, TPR, and impedance spectroscopy measurements experimentally confirmed the presence of residual metallic Ni in the anode catalyst prepared in ethylene glycol medium. These findings were evidence of strong metal Ni network resistance to oxidation in anodic Ni/BCY15-EG. Enhanced resistance of the metal Ni phase contributed to a new microstructure of the Ni/BCY15-EG-1100 anode cermet getting more stable to changes that cause degradation during operation.

Increase of photoinduced birefringence in a new type of anisotropic nanocomposite: azopolymer doped with ZnO nanoparticles.

We report a significant increase of about 50% of the photoinduced birefringence in nanocomposite films of azopolymers doped with ZnO nanoparticles compared with samples made from nondoped azopolymers. This increase is most pronounced at small concentrations of the nanoparticles of 0.5% and for the amorphous polymers used in our study. We observe also an improvement of the response time of more than 25% in some of the polymers, which allows for faster and more effective polarization optical recording.

Core-Sheath-Like Poly(Ethylene Oxide)/Beeswax Composite Fibers Prepared by Single-Spinneret Electrospinning. Antibacterial, Antifungal, and Antitumor Activities.

Composite fibrous materials are prepared from poly(ethylene oxide) (PEO) and beeswax (BW) by single-spinneret electrospinning using chloroform as a common solvent. The obtained fibers have core-sheath-like structure, as evidenced by the water contact angle values and corroborated by the results on the elemental composition of the fiber's surface determined by X-ray photoelectron spectroscopy (XPS) and by analyses with scanning electron microscopy of fibers before and after selective extraction of PEO or BW. Furthermore, the core-sheath-like structure is proven by transmission electron microscopy. This is attributed to self-assembly of BW molecules on the surface of the formed fibers driven by the incompatibility between PEO and BW. 5-Nitro-8-hydroxyquinoline (NQ) is embedded as a model drug with antibacterial, antifungal, and anticancer properties in the PEO/BW fibrous materials. XPS analyses reveal that NQ is present on the surface of the PEO/BW/NQ materials. Using a purposely designed cell for fixation of the fibrous materials the NQ release in phosphate buffer solution with рН 7.4 is followed. The new PEO/BW/NQ fibrous materials exhibit antibacterial activity against S. aureus and E. coli, antifungal effect against C. albicans, and selective anticancer activity against HeLa (human cervical adenocarcinoma cells) and SH-4 (human melanoma cells) cell lines.

Core/Double-Sheath Composite Fibers from Poly(ethylene oxide), Poly(L-lactide) and Beeswax by Single-Spinneret Electrospinning.

The conventional approach for preparation of core-sheath fibers is coaxial electrospinning. Single-spinneret electrospinning of emulsions is a much less common method to obtain core-sheath fibers. Core-sheath structure may be generated by electrospinning of homogeneous blend solutions; however, reports on such cases are still scarce. Herein, the preparation of nanofibrous composites from poly(ethylene oxide) (PEO), poly(L-lactide) (PLA) and beeswax (BW) by single-spinneret electrospinning of their homogeneous blend solutions in chloroform is reported. The produced fibers had core/double-sheath structure with a PEO core, PLA inner sheath and BW outer sheath. This original fiber structure was evidenced by transmission electron microscopy, selective extraction of BW or PEO, and X-ray photoelectron spectroscopy. The PLA/BW double sheath led to hydrophobicity of the PEO/PLA/BW mats. The tensile tests revealed that PEO/PLA/BW mats had substantially improved mechanical behavior as compared to PEO, PLA and PEO/BW mats. PEO/PLA/BW mats can be used as drug carriers as evidenced by the one-pot incorporation of the model drug 5-nitro-8-hydroxyquinoline (NQ) into the fibrous materials. Microbiological tests showed that PEO/PLA/BW/NQ had antimicrobial activity. Therefore, the new materials are promising for wound healing applications.

Novel Approach for Synthesis of Graphene-like Phases by Pulsed Laser Ablation in a Flow-Mode Suspension.

The present study investigates the possibility of obtaining graphene-like phases (defected graphene, graphene oxide, and reduced graphene oxide) as fine suspensions by applying a novel pulsed laser ablation (PLA) approach in flow mode. Two types of suspensions of microcrystalline graphite in aqueous suspensions and two types of microcrystalline graphite in suspensions of 6% hydrogen peroxide solution were irradiated in a quartz tube through which they flow. The third (λ = 355 nm) and fourth harmonics (λ = 266 nm) of an Nd:YAG laser system (15 ns pulse duration and 10 Hz pulse repetition rate) were used. The morphology of the obtained particles was studied by transmission electron microscopy (TEM). Their phase composition and structure were explored by X-ray photoelectron spectroscopy, X-ray diffractometry, and Raman spectroscopy.

Effect of pH-Regulation on the Capture of Lipopolysaccharides from E. coli EH100 by Four-Antennary Oligoglycines in Aqueous Medium.

Bacterial lipopolysaccharides (LPS) are designated as endotoxins, because they cause fever and a wide range of pathologies in humans. It is important to develop effective methodologies to detect trace quantities of LPS in aqueous systems. The present study develops a fine-tuning procedure for the entrapment of trace quantities of LPS from E. coli EH100. The capture agents are self-assemblies (tectomers) formed by synthetic four-antennary oligoglycine (C-(CH2-NH-Gly7)4, T4). Based on previously performed investigations of bulk and adsorption-layer properties of aqueous solutions containing T4 and LPS, the optimal conditions for the entrapment interactions are further fine-tuned by the pH regulation of aqueous systems. A combined investigation protocol is developed, including dynamic light scattering, profile analysis tensiometry, microscopic thin-liquid-film techniques, and transmission electron microscopy. The key results are: (1) two types of complexes between T4 and LPS are generated-amphiphilic species and "sandwich-like" hydrophilic entities; the complexes are smaller at lower pH, and larger at higher pH; (2) an optimum range of pH values is established within which the whole quantity of the LPS is entrapped by the tectomers, namely pH = 5.04-6.30. The obtained data substantiate the notion that T4 may be used for an effective capture and the removal of traces of endotoxins in aqueous systems.

Waste Rose Flower and Lavender Straw Biomass-An Innovative Lignocellulose Feedstock for Mycelium Bio-Materials Development Using Newly Isolated Ganoderma resinaceum GA1M.

In this study, for the first time, the potential of rose flowers and lavender straw waste biomass was studied as feeding lignocellulose substrates for the cultivation of newly isolated in Bulgaria Ganoderma resinaceum GA1M with the objective of obtaining mycelium-based bio-composites. The chemical characterization and Fourier Transform Infrared (FTIR) spectroscopy established that the proximate composition of steam distilled lavender straw (SDLS) and hexane extracted rose flowers (HERF) was a serious prerequisite supporting the self-growth of mycelium bio-materials with improved antibacterial and aromatic properties. The basic physico-mechanical properties of the developed bio-composites were determined. The apparent density of the mycelium HERF-based bio-composites (462 kg/m3) was higher than that of the SDLS-based bio-composite (347 kg/m3) and both were much denser than expanded polystyren (EPS), lighter than medium-density fiber board (MDF) and oriented strand board (OSB) and similar to hempcrete. The preliminary testing of their compressive behavior revealed that the compressive resistance of SDLS-based bio-composite was 718 kPa, while for HERF-based bio-composite it was 1029 kPa and both values are similar to the compressive strength of hempcrete with similar apparent density. Water absorbance analysis showed, that both mycelium HERF- and SDLS-based bio-composites were hydrophilic and further investigations are needed to limit the hydrophilicity of the lignocellulose fibers, to tune the density and to improve compressive resistance.

New Approach toward Laser-Assisted Modification of Biocompatible Polymers Relevant to Neural Interfacing Technologies.

We report on a new approach toward a laser-assisted modification of biocompatible polydimethylsiloxane (PDMS) elastomers relevant to the fabrication of stretchable multielectrode arrays (MEAs) devices for neural interfacing technologies. These applications require high-density electrode packaging to provide a high-resolution integrating system for neural stimulation and/or recording. Medical grade PDMS elastomers are highly flexible with low Young's modulus < 1 MPa, which are similar to soft tissue (nerve, brain, muscles) among the other known biopolymers, and can easily adjust to the soft tissue curvatures. This property ensures tight contact between the electrodes and tissue and promotes intensive development of PDMS-based MEAs interfacing devices in the basic neuroscience, neural prosthetics, and hybrid bionic systems, connecting the human nervous system with electronic or robotic prostheses for restoring and treating neurological diseases. By using the UV harmonics 266 and 355 nm of Nd:YAG laser medical grade PDMS elastomer is modified by ns-laser ablation in water. A new approach of processing is proposed to (i) activate the surface and to obtain tracks with (ii) symmetric U-shaped profiles and (iii) homogeneous microstructure This technology provides miniaturization of the device and successful functionalization by electroless metallization of the tracks with platinum (Pt) without preliminary sensitization by tin (Sn) and chemical activation by palladium (Pd). As a result, platinum black layers with a cauliflower-like structure with low values of sheet resistance between 1 and 8 Ω/sq are obtained.

Self-Assembly of a Thermally Responsive Double-Hydrophilic Copolymer in Ethanol-Water Mixtures: The Effect of Preferential Adsorption and Co-Nonsolvency.

Lower alcohols can induce a combined collapse-swelling de-mixing transition (lower critical solution temperature (LCST)-type co-nonsolvency) in aqueous solutions of poly( N-isopropylacrylamide) (PNIPAM) by interacting with the polymer's amide groups. This interaction results in an increase of the total surface area of hydrophobic sites and destabilizes the chains. Here, we make use of this phenomenon to drive the counterintuitive self-assembly of a PNIPAM-containing double-hydrophilic graft copolymer in water-ethanol mixtures at T ≪ LCST. Rheological frequency sweeps are used to quantify the distinct solvation states of PNIPAM at various temperatures and ethanol concentrations. The energy stored through elastic deformation at the de-mixing transition is simply related to the solvent binding. We find that the storage modulus decreases progressively, but nonlinearly with ethanol concentration, which evidences a preferential solvation pattern. Analogously, through a combination of dynamic light scattering and transmission electron microscope analyses, we demonstrate that a low-temperature structure variation takes place by adding ethanol following a similar solvent-content morphology dependent model.

Photocatalytic self-cleaning poly(L-lactide) materials based on a hybrid between nanosized zinc oxide and expanded graphite or fullerene.

New self-cleaning materials of polymer fibers decorated with a hybrid between nanosized zinc oxide and expanded graphite (EG) or fullerene (C60) were obtained. The new materials were prepared by applying electrospinning in conjunction with electrospraying. Poly(l-lactide) (PLA) was selected as a biocompatible and (bio)degradable polymer carrier. PLA solution was electrospun in combination with electrospraying of a suspension that contained the ZnO/EG or ZnO/C60 hybrid. Mats with different content of EG or C60 were obtained. The new materials were characterized by scanning and transmission electron microscopy (SEM and TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and X-ray diffraction analysis (XRD). The photocatalytic activity of the materials was evaluated by using model dyes. The formation of a hybrid between ZnO and EG led to enhancement of the photocatalytic activity of the mats at ZnO/EG weight ratios of 90/10 and 85/15. Increase in the photocatalytic activity of the ZnO-containing mats was also achieved by the formation of a hybrid between ZnO and C60 at a fullerene content of 0.5 and 1.0 wt.% in respect to ZnO weight. The new materials exhibited antibacterial activity as evidenced by the performed studies against Staphylococcus aureus.