Synthesis and electrochemical properties of sulfur-nitrogen-doped multi-walled carbon nanotubes. - In: Fullerenes, nanotubes & carbon nanostructures, ISSN 1536-4046, Bd. 31 (2023), 11, S. 1082-1095
Multi-walled carbon nanotubes doped with sulfur and nitrogen (S-N-MWCNTs) were grown onto silicon/silicon oxide wafer by means of chemical vapor deposition upon decomposition of dimethyl sulfoxide (DMSO) and acetonitrile (ACN) in presence of catalyst. The S-N-MWCNTs were characterized by scanning electron microscopy combined with energy dispersive X-ray spectroscopy. The findings demonstrate that S-N-MWCNTs exhibit bamboo-shaped nanostructure, quite similar to pure nitrogen-doped carbon nanotubes. The S-N-MWCNTs were investigated with respect to their electrochemical response to ferrocyanide/ferricyanide, [Fe(CN)6]4-/3- in potassium chloride aqueous solutions by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. The recorded CVs demonstrate strong dependence of electrochemical response, electron transfer kinetics, and sensitivity of S-N-MWCNTs on concentration of decomposed DMSO precursor. Namely, upon increasing concentration of decayed DMSO up to 2% wt. the current density, the electron transfer kinetics, and the sensitivity of S-N-MWCNTs toward [Fe(CN)6]4-/3- tend to enhance. The extracted EIS results approve that when DMSO reaches the optimum concentration of 2% wt. the barrier for electron transfer decreases significantly leading, consequently, to faster electron transfer kinetics. The S-N-MWCNTs exhibit considerable stability and excellent reproducibility, and thus it can be considered suitable analytical tool for detection of redox systems at micromolar level.
https://doi.org/10.1080/1536383X.2023.2240916
Structural and optical properties of C70 fullerenes in aqueous solution. - In: Fullerenes, nanotubes & carbon nanostructures, ISSN 1536-4046, Bd. 31 (2023), 10, S. 983-988
The simple method of preparation of highly stable and purified C70 fullerene aqueous solution (C70FAS) is proposed. The features of structural stabilization of C70 fullerenes in an aqueous solution by studying their structural and optical properties using Raman, photoluminescence, infrared reflection-absorption, UV-VIS absorption, and dynamic light scattering spectroscopy methods were analyzed. The experimental results showed that the most likely mechanism for C70 fullerenes stabilization in water is surface hydroxylation with covalent attachment of water hydroxyls to C70 fullerene carbons. Raman and infrared absorption spectra of C70FAS showed characteristic vibrational bands of C70 fullerenes with a slight broadening and low-frequency shift of ∼1 cm^−1, indicating the attachment of water hydroxyls to the C70 fullerene carbons. The photoluminescence spectra showed excitonic emission bands of C70 molecules with intensity depending on their content. UV-VIS absorption spectra demonstrate the absorption bands typical for monomeric C70 fullerene. Finally, the dynamic light scattering data confirmed that C70FAS is a typical colloidal fluid containing both individual C70 molecules and their nano aggregates up to 100 nm. These findings provide insights into the stabilization mechanism of C70 fullerenes in water and may have implications for their potential application in nanobiotechnology.
https://doi.org/10.1080/1536383X.2023.2229461
Current to biomass: media optimization and strain selection from cathode-associated microbial communities in a two-chamber electro-cultivation reactor. - In: Environments, ISSN 2076-3298, Bd. 10 (2023), 6, 97, S. 1-19
Cathode-associated microbial communities (caMCs) are the functional key elements in the conversion of excess electrical energy into biomass. In this study, we investigated the development of electrochemical caMCs based on two-chamber microbial electrolytic cells (MECs) after optimization of media composition. Microbial communities obtained from a historical soil sample were inoculated into the cathode chamber of MECs. The inorganic medium with (A) carbon dioxide in air or (B) 100 mM sodium bicarbonate as carbon source was used in the absence of any organic carbon source. After 12 days of operation, the experimental results showed that (1) the bacterial community in group B exhibited lush growth and (2) a single strain TX168 Epilithonimonas bovis isolated from group A indicated electrochemical activity and synthesized large volumes of biomass using sodium bicarbonate. We also analyzed the caMCs of the MECs and reference samples without electro-cultivation using 16S rRNA gene sequencing. The results showed that the caMCs of MECs in groups A and B were dominated by the genera Acinetobacter and Pseudomonas. The caMCs were further inoculated and cultured on different agars to isolate specific electroactive bacterial strains. Overall, our study highlights the possibility of converting excess energy into biomass by electro-cultivation and the importance of selecting appropriate media to enrich specific microbial communities and single strains in MECs.
https://doi.org/10.3390/environments10060097
Deformability and collision-induced reorientation enhance cell topotaxis in dense microenvironments. - In: Biophysical journal, ISSN 1542-0086, Bd. 122 (2023), 13, S. 2791-2807
In vivo, cells navigate through complex environments filled with obstacles such as other cells and the extracellular matrix. Recently, the term “topotaxis” has been introduced for navigation along topographic cues such as obstacle density gradients. Experimental and mathematical efforts have analyzed topotaxis of single cells in pillared grids with pillar density gradients. A previous model based on active Brownian particles (ABPs) has shown that ABPs perform topotaxis, i.e., drift toward lower pillar densities, due to decreased effective persistence lengths at high pillar densities. The ABP model predicted topotactic drifts of up to 1% of the instantaneous speed, whereas drifts of up to 5% have been observed experimentally. We hypothesized that the discrepancy between the ABP and the experimental observations could be in 1) cell deformability and 2) more complex cell-pillar interactions. Here, we introduce a more detailed model of topotaxis based on the cellular Potts model (CPM). To model persistent cells we use the Act model, which mimics actin-polymerization-driven motility, and a hybrid CPM-ABP model. Model parameters were fitted to simulate the experimentally found motion of Dictyostelium discoideum on a flat surface. For starved D. discoideum, the topotactic drifts predicted by both CPM variants are closer to the experimental results than the previous ABP model due to a larger decrease in persistence length. Furthermore, the Act model outperformed the hybrid model in terms of topotactic efficiency, as it shows a larger reduction in effective persistence time in dense pillar grids. Also pillar adhesion can slow down cells and decrease topotaxis. For slow and less-persistent vegetative D. discoideum cells, both CPMs predicted a similar small topotactic drift. We conclude that deformable cell volume results in higher topotactic drift compared with ABPs, and that feedback of cell-pillar collisions on cell persistence increases drift only in highly persistent cells.
https://doi.org/10.1016/j.bpj.2023.06.001
Five-level structural hierarchy: microfluidically supported synthesis of core-shell microparticles containing nested set of dispersed metal and polymer micro and nanoparticles. - In: Particle & particle systems characterization, ISSN 1521-4117, Bd. 14 (2023), 10, 2300030, S. 1-13
This study presents the development of a hierarchical design concept for the synthesis of multi-scale polymer particles with up to five levels of organization. The synthesis of core-shell microparticles containing nested sets of dispersed metal and polymer micro- and nanoparticles is achieved through in situ photopolymerization using a double co-axial capillaries microfluidic device. The flow rates of the carrier, shell, and core phases are optimized to control particle size and result in stable core-shell particles with well-dispersed three-level composites in the shell matrix. The robustness and reversibility of these core-shell particles are demonstrated through five cycles of drying and re-swelling, showing that the size and structure of core-shell particles remain unchanged. Additionally, the permeability and mobility of dye molecules within the shell matrix are tested and showed that different molecular weight dyes have different penetration times. This study highlights the potential of microfluidics as a powerful tool for the controlled and precise synthesis of complex structured materials and demonstrates the versatility and potential of these core-shell particles for sensing applications as particle-based surface-enhanced Raman scattering (SERS).
https://doi.org/10.1002/ppsc.202300030
Oxymethylene ether (OME) fuel catalyst screening using in situ NMR spectroscopy. - In: Chemistry - a European journal, ISSN 1521-3765, Bd. 29 (2023), 33, e202203776, S. 1-9
Online NMR measurements are introduced in the current study as a new analytical setup for investigation of the oxymethylene dimethyl ether (OME) synthesis. For the validation of the setup, the newly established method is compared with state-of-the-art gas chromatographic analysis. Afterwards, the influence of different parameters, such as temperature, catalyst concentration and catalyst type on the OME fuel formation based on trioxane and dimethoxymethane is investigated. As catalysts, AmberlystTM 15 (A15) and trifluoromethanesulfonic acid (TfOH) are utilized. A kinetic model is applied to describe the reaction in more detail. Based on these results, the activation energy (A15: 48.0 kJ mol^-1 and TfOH: 72.3 kJ mol^-1) and the order in catalyst (A15: 1.1 and TfOH: 1.3) are calculated and discussed.
https://doi.org/10.1002/chem.202203776
Synthesis, characterization, and electrochemical performance of reduced graphene oxide decorated with Ag, ZnO, and AgZnO nanoparticles. - In: Carbon, ISSN 1873-3891, Bd. 213 (2023), 118178
Graphene oxide (GO) derived from the oxidization of graphite exhibits high specific surface area with potential in electrochemical applications. Furthermore, silver and zinc oxide nanoparticles, further denoted as AgNPs and ZnONPs, respectively, display superior physicochemical and electronic properties, that would significantly improve the electrocatalytic properties by being applied in electrochemical sensing. Consequently, in the present work, three different hybrid nanomaterials consisting of reduced graphene oxide (rGO) modified with either AgNPs, ZnONPs, or combined AgZnONPs were synthesized and characterized. The synthesis of GO was performed by a modified Hummer's method, while the decoration of GO with the nanoparticles was carried out by self-assembly solvothermal processes. The Ag-rGO, ZnO-rGO, and AgZnO-rGO nanocomposite hybrid materials were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) combined with energy-dispersive X-ray spectroscopy (EDX). Furthermore, the electrochemical responses of the fabricated nanocomposites towards the standard ferrocyanide/ferricyanide [Fe(CN)6]3-/4- redox system were investigated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) techniques. The results have been explained in terms of structural differences between the nanoparticles formed on the surface of the fabricated nanocomposite materials. Namely, the improved electrochemical performance of ZnO-rGO can be attributed to the high surface to volume ratio of ZnO, which provides greater area of electrode/electrolyte junction and consequently, large number of sites at the electrolyte-ZnO interface. The aim of the present work is the fabrication of novel high-performance rGO-based nanomaterials for applications in electrochemical sensing.
https://doi.org/10.1016/j.carbon.2023.118178
NMR and GPC analysis of alkyd resins: influence of synthesis method, vegetable oil and polyol content. - In: Polymers, ISSN 2073-4360, Bd. 15 (2023), 9, 1993, S. 1-14
Alkyd resins are oil-based polymers that have been widely used for generations in the surface coating industry and beyond. Characterization of these resins is of high importance to understand the influence of its components on its behavior, compatibility with other resins, and final quality to ensure high durability. Here, NMR spectroscopy and GPC were used for characterizing differences in the chemical structure, molecular distribution, and dispersity between oil-based and fatty acid-based alkyd polymers made from sacha inchi and linseed oils. Sancha inchi (Plukentia volubilis L.) is a fruit-bearing plant native to South America and the Caribbean, and has a rich unsaturated fatty acid content. The effect of vegetable oil and polyol selection on the synthesis of alkyd resins for coating applications was analyzed. The influence of two different synthesis methods, monoglyceride and fatty acid processes, was also compared. Important structural differences were observed using NMR: one-dimensional spectra revealed the degree of unsaturated fatty acid chains along the polyester backbone, whereas, 2D NMR experiments facilitated chemical shift assignments of all signals. GPC analysis suggested that alkyd resins with homogeneous and high molecular weights can be obtained with the fatty acid process, and that resins containing pentaerythritol may have uniform chain lengths.
https://doi.org/10.3390/polym15091993
Fullerene C60 films on dental implants: durability study after in vitro short-term exposure. - In: Diamond and related materials, ISSN 0925-9635, Bd. 135 (2023), 109886
The carbon fullerene C60 is an anti-inflammatory substance that reduces cellular stress levels. In this study, C60 fullerenes were deposited on complex dental implants to improve cell attachment and vitality. For the first time, fullerene C60 films were deposited via high-vacuum sublimation on complex-shaped Ti-6Al-4V dental implants with a threaded-screw design. The “as-deposited” fullerene C60 films were compared with fullerene C60 films on dental Ti-6Al-4V implants using a threaded-screw design after three weeks of incubation in Hank's balanced salt solution (HBSS). It was proven by Raman spectroscopy that the incubation in potassium and alkali-ion rich HBSS at 37 ˚C resulted in a reduction of monomeric fullerene C60 fraction and an increase in dimer, linear chain and polymerized C60 molecules. Furthermore, the structure of the C60 films differed depending on the measurement position on dental implants with a threaded-screw design. The fraction of monomeric fullerene C60 was highest on top of the trapezoidal thread, which had a micropatterned topography. Nano-indentations were performed at this position with a maximum load of 1000 μN. The fullerene C60 films showed a nano-hardness of 0.3 ± 0.1 GPa and a Young's modulus of 7.6 ± 3.6 GPa at this position, which is typical for monomeric fullerene C60 with weak interatomic interaction in the face-centred-cubic crystal structure. The murine embryonal calvarial stem-cell line MC3T3-E1 (ECACC, UK), which is driven toward osteogenic differentiation, spread out extremely well on the fullerene C60 film, with improved cell morphology compared to uncoated Ti-6Al-4V. Cell nuclei density were determined to be 237.5 cell nuclei per mm2 for the Ti-6Al-4V dental implants with a threaded-screw design with fullerene C60 coating in “as-deposited” condition. This was approximately 40 % better than that of uncoated Ti-6Al-4V dental implants with a threaded-screw design.
https://doi.org/10.1016/j.diamond.2023.109886
Archaeal and extremophilic bacteria from different archaeological excavation sites. - In: International journal of molecular sciences, ISSN 1422-0067, Bd. 24 (2023), 6, 5519, S. 1-18
Beside natural factors, human activities are important for the development of microbiomes. Thus, local soil bacterial communities are affected by recent activities such as agriculture, mining and industry. In addition, ancient human impacts dating back centuries or millennia have changed soils and can emboss the recent bacterial communities up to now, representing a certain long-term "memory of soil". Soil samples from five different archaeological excavation places were investigated for the presence of Archaea with a Next Generation Sequencing (NGS) analysis of the DNA coding for 16S r-RNA sequences. It was found that the abundance of Archaea differs strongly between less than one and more than 40 percent of bacteria. A Principal Component Analysis (PCA) of all samples shows that the archaeological excavation places can be distinguished from each other by the archaeal component of soil bacterial communities, which presents a typical pattern for each place. Most samples are marked by the dominance of Crenarchaeota, which are presented mainly by ammonia-related types. High contents of Nanoarchaeaota have been observed in one ash deposit of a historical saline and all samples of a historical tannery area. These samples are also marked by a significant presence of Dadabacteria. The specific abundancies of special Archaea - among them ammonia-oxidizing and sulphur-related types - are due obviously to former human activities and support the concept of the "ecological memory of soil".
https://doi.org/10.3390/ijms24065519