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1.
Molecules ; 29(10)2024 May 10.
Article in English | MEDLINE | ID: mdl-38792100

ABSTRACT

Carbonization of biomass residues followed by activation has great potential to become a safe process for the production of various carbon materials for various applications. Demand for commercial use of biomass-based carbon materials is growing rapidly in advanced technologies, including in the energy sector, as catalysts, batteries and capacitor electrodes. In this study, carbon materials were synthesized from hardwood using two carbonization methods, followed by activation with H3PO4, KOH and NaOH and doping with nitrogen. Their chemical composition, porous structure, thermal stability and structural order of samples were studied. It was shown that, despite the differences, the synthesized carbon materials are active catalysts for oxygen reduction reactions. Among the investigated carbon materials, NaOH-activated samples exhibited the lowest Tafel slope values, of -90.6 and -88.0 mV dec-1, which are very close to the values of commercial Pt/C at -86.6 mV dec-1.

2.
Langmuir ; 40(11): 5945-5958, 2024 Mar 19.
Article in English | MEDLINE | ID: mdl-38456424

ABSTRACT

Amphiphilic diblock copolymers containing a block of 2-methacryloyloxyethyl phosphorylcholine (MPC) with unique properties to prevent nonspecific protein adsorption and enhance lubrication in aqueous media and a block of dopamine methacrylamide (DOPMA) distinguished by excellent adhesion performance were synthesized by reversible addition fragmentation chain transfer (RAFT) polymerization for the first time. The DOPMA monomer with an acetonide-protected catechol group (acetonide-protected dopamine methacrylamide (ADOPMA)) was used, allowing the prevention of undesirable side reactions during polymerization and oxidation during storage. The adsorption behavior of the diblock copolymers with protected and unprotected catechol groups on gold surfaces was probed using attenuated total reflection (ATR)-Fourier transform infrared (FTIR) spectroscopy, surface-enhanced infrared absorption spectroscopy (SEIRAS), and reflection-absorption infrared spectroscopy (RAIRS). The copolymers pMPC-b-pADOPMA demonstrated physisorption with rapid adsorption and ultrasound-assisted desorption, while the copolymers pMPC-b-DOPMA exhibited chemical adsorption with slower dynamics but a stronger interaction with the gold surface. SEIRAS and RAIRS allowed proving the reorientation of the diblock copolymers during adsorption, demonstrating the exposure of the pMPC block toward the aqueous phase.

3.
Materials (Basel) ; 16(17)2023 Aug 30.
Article in English | MEDLINE | ID: mdl-37687616

ABSTRACT

This study focuses on fabricating cobalt particles deposited on graphitic carbon nitride (Co/gCN) using annealing, microwave-assisted and hydrothermal syntheses, and their employment in hydrogen and oxygen evolution (HER and OER) reactions. Composition, surface morphology, and structure were examined using inductively coupled plasma optical emission spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The performance of Co-modified gCN composites for the HER and OER were investigated in an alkaline media (1 M KOH). Compared to the metal-free gCN, the modification of gCN with Co enhances the electrocatalytic activity towards the HER and OER. Additionally, thermal annealing of both Co(NO3)2 and melamine at 520 °C for 4 h results in the preparation of an effective bifunctional Co3O4/gCN catalyst for the HER with the lower Eonset of -0.24 V, a small overpotential of -294.1 mV at 10 mA cm-2, and a low Tafel slope of -29.6 mV dec-1 in a 1.0 M KOH solution and for the OER with the onset overpotential of 286.2 mV and overpotential of 422.3 mV to achieve a current density of 10 mA cm-2 with the Tafel slope of 72.8 mV dec-1.

4.
Materials (Basel) ; 16(17)2023 Aug 31.
Article in English | MEDLINE | ID: mdl-37687695

ABSTRACT

Nitrogen-doped activated carbons with controlled micro- and mesoporosity were obtained from wood and wastes via chemical processing using pre-treatment (pyrolysis at 500 °C and hydrothermally carbonization at 250 °C) and evaluated as oxygen reduction catalysts for further application in fuel cells. The elemental and chemical composition, structure and porosity, and types of nitrogen bonds of obtained catalyst materials were studied. The catalytic activity was evaluated in an alkaline medium using the rotating disk electrode method. It was shown that an increase in the volume of mesopores in the porous structure of a carbon catalyst promotes the diffusion of reagents and the reactions proceed more efficiently. The competitiveness of the obtained carbon materials compared to Pt/C for the reaction of catalytic oxygen reduction is shown.

5.
Front Bioeng Biotechnol ; 11: 1167753, 2023.
Article in English | MEDLINE | ID: mdl-37122855

ABSTRACT

Providing a 3D environment that mimics the native extracellular matrix is becoming increasingly important for various applications such as cell function studies, regenerative medicine, and drug discovery. Among the most critical parameters to consider are the scaffold's complicated micro-scale geometry and material properties. Therefore, stereolithography based on photopolymerization is an emerging technique because of its ability to selectively form volumetric structures from liquid resin through localized polymerization reactions. However, one of the most important parameters of the scaffold is biocompatibility, which depends not only on the material but also on the exposure conditions and post-processing, which is currently underestimated. To investigate this systematically, microporous scaffolds with pore sizes of 0.05 mm3 corresponding to a porosity of 16,4% were fabricated using the stereolithography printer Asiga PICO2 39 UV from the widely used resins FormLabs Clear and Flexible. The use of various polymers is usually limited for cells because, after wet chemical development, the non-negligible amount of remaining monomers intertwined in the photopolymerized structures is significantly toxic to cells. Therefore, the aim of this research was to find the best method to remove monomers from the 3D scaffold by additional UV exposure. For this purpose, a Soxhlet extractor was used for the first time, and the monomers were immersed in different alcohols. A Raman microspectroscopy was also used to investigate whether different post-processing methods affect DC (cross-linking) to find out if this specifically affects the biocompatibility of the scaffolds. Finally, mesenchymal stem cells from rat dental pulp were examined to confirm the increased biocompatibility of the scaffolds and their ability to support cell differentiation into bone tissue cells.

6.
Materials (Basel) ; 16(7)2023 Mar 23.
Article in English | MEDLINE | ID: mdl-37048845

ABSTRACT

Herein, we present a synthesis route for high-efficiency nitrogen-doped carbon materials using kraft pulping residue, black liquor, and wood charcoal as carbon sources. The synthesized nitrogen-doped carbon materials, based on black liquor and its mixture with wood charcoal, exhibited high specific surface areas (SSAs) of 2481 and 2690 m2 g-1, respectively, as well as a high volume of mesopores with an average size of 2.9-4.6 nm. The nitrogen content was approximately 3-4 at% in the synthesized nitrogen-doped carbon materials. A specific capacitance of approximately 81-142 F g-1 was achieved in a 1 M Na2SO4 aqueous solution at a current density of 0.2 A g-1. In addition, the specific capacitance retention was 99% after 1000 cycles, indicating good electrochemical stability.

7.
Colloids Surf B Biointerfaces ; 225: 113275, 2023 May.
Article in English | MEDLINE | ID: mdl-36965333

ABSTRACT

In this research, Cu2ZnSnS4 (CZTS) particles were successfully fabricated via the molten salt approach from the copper, zinc and tin sulphides as raw precursors. SEM analysis revealed that CZTS particles are tetragonal-shaped with sharp edges, smooth flat plane morphology, and crystal size varying from 10.8 to 28.7 µm. The phase and crystalline structure of synthesized powders were investigated using XRD analysis, which confirms the presence of a tetragonal crystal structure kesterite phase. The chemical composition of CZTS particles was evaluated by EDX spectroscopy, which identified the nearly stoichiometric composition with an averaged formula of Cu1.88Zn1.04SnS3.97. The TG/DTA-MS and ICP-OES analysis showed the possible decomposition pathways and predicted their degradation rate in aqueous solutions. The CZTS particles possessed highly effective concentration and time-dependent antimicrobial properties against medically relevant bacteria and yeast strains. The CZTS particles (1 g L-1) exhibited over 95.7 ± 1.9% killing efficiency towards M. luteus. In contrast, higher dosages (3.5 and 5 g L-1) led to its complete inactivation and reduced the P. aeruginosa cell viability to 43.2 ± 3.2% and 4.1 ± 1.1%, respectively. Moreover, the CZTS particles (0.5 g L-1) are responsible for causing 54.8 ± 1.8% of C. krusei and 89.7 ± 2.1% of C. parapsilosis yeasts death within the 24 h of exposure, which expanded to almost 100% when yeasts were treated with two times higher CZTS concentration (1.0 g L-1). The mechanism of action has been proposed and evidenced by monitoring the 2',7'-dichlorofluorescein (DCF) fluorescence, which revealed that the overproduction of reactive oxygen species (ROS) is responsible for microorganism death.


Subject(s)
Anti-Infective Agents , Anti-Infective Agents/pharmacology , Candida parapsilosis , Cell Survival , Copper/pharmacology , Pseudomonas aeruginosa , Saccharomyces cerevisiae
8.
ACS Omega ; 8(51): 49396-49405, 2023 Dec 26.
Article in English | MEDLINE | ID: mdl-38162725

ABSTRACT

The present study introduces a novel method for the synthesis of magneto-plasmonic nanoparticles (MPNPs) with enhanced functionality for surface-enhanced Raman scattering (SERS) applications. By employing pulsed laser ablation in liquid (PLAL) to synthesize plasmonic nanoparticles and wet chemistry to synthesize magnetic nanoparticles, we successfully fabricated chemically pure hybrid Fe3O4@Au and Fe3O4@Ag nanoparticles. We demonstrated a straightforward approach of an electrostatic attachment of the plasmonic and magnetic parts using positively charged polyethylenimine. The MPNPs displayed high SERS sensitivity and reproducibility, and the magnetic part allowed for the controlled separation of the nanoparticles from the reaction mixture, their subsequent concentration, and their precise deposition onto a specified surface area. Additionally, we fabricated alloy based MPNPs from AgxAu100-x (x = 50 and 80 wt %) targets with distinct localized surface plasmon resonance (LSPR) wavelengths. The compositions, morphologies, and optical properties of the nanoparticles were characterized by using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-vis spectroscopy, and multiwavelength Raman spectroscopy. A standard SERS marker, 4-mercaptobenzoic acid (4-MBA), validated the enhancement properties of the MPNPs and found an enhancement factor of 2 × 108 for the Fe3O4@Ag nanoparticles at 633 nm excitation. Lastly, we applied MPNP-enhanced Raman spectroscopy for the analysis of the biologically relevant molecule adenine and found a limit of detection of 10-7 M at 785 nm excitation. The integration of PLAL and wet chemical methods enabled the relatively fast and cost-effective production of MPNPs characterized by high SERS sensitivity and signal reproducibility that are required in various fields, including biomedicine, food safety, materials science, security, and defense.

9.
Nanomaterials (Basel) ; 12(22)2022 Nov 15.
Article in English | MEDLINE | ID: mdl-36432303

ABSTRACT

To fabricate graphene-based high-frequency electronic and optoelectronic devices, there is a high demand for scalable low-contaminated graphene with high mobility. Graphene synthesized via chemical vapor deposition (CVD) on copper foil appears promising for this purpose, but residues from the polymethyl methacrylate (PMMA) layer, used for the wet transfer of CVD graphene, drastically affect the electrical properties of graphene. Here, we demonstrate a scalable and green PMMA removal technique that yields high-mobility graphene on the most common technologically relevant silicon (Si) substrate. As the first step, the polarity of the PMMA was modified under deep-UV irradiation at λ = 254 nm, due to the formation of ketones and aldehydes of higher polarity, which simplifies hydrogen bonding in the step of its dissolution. Modification of PMMA polarity was confirmed by UV and FTIR spectrometry and contact angle measurements. Consecutive dissolution of DUV-exposed PMMA in an environmentally friendly, binary, high-polarity mixture of isopropyl alcohol/water (more commonly alcohol/water) resulted in the rapid and complete removal of DUV-exposed polymers without the degradation of graphene properties, as low-energy exposure does not form free radicals, and thus the released graphene remained intact. The high quality of graphene after PMMA removal was confirmed by SEM, AFM, Raman spectrometry, and by contact and non-contact electrical conductivity measurements. The removal of PMMA from graphene was also performed via other common methods for comparison. The charge carrier mobility in graphene films was found to be up to 6900 cm2/(V·s), demonstrating a high potential of the proposed PMMA removal method in the scalable fabrication of high-performance electronic devices based on CVD graphene.

10.
Molecules ; 27(19)2022 Oct 03.
Article in English | MEDLINE | ID: mdl-36235068

ABSTRACT

The imidazole ring (Im) of histidine side chains plays a unique role in the function of proteins through covalent bonding with metal ions and hydrogen bonding interactions with adjusted biomolecules and water. At biological interfaces, these interactions are modified because of the presence of an electric field. Self-assembled monolayers (SAMs) with the functional Im group mimic the histidine side chain at electrified interfaces. In this study, we applied in-situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) to probe the structure and hydrogen bonding of Im-functionalized SAM on smooth Au at the electrochemical interface. The self-assembly of molecules on the Au induced the proton shift from N1 atom (Tautomer-I), which is the dominant form of Im in the bulk sample, to N3 atom (Tautomer-II). The impact of electrode potential on the hydrogen bonding interaction strength of the Im ring was identified by SHINERS. Temperature-Raman measurements and density functional theory (DFT) analysis revealed the spectral marker for Im ring packing (mode near 1496-1480 cm-1) that allowed us to associate the confined and strongly hydrogen bonded interfacial Im groups with electrode polarization at -0.8 V. Reflection adsorption IR (RAIR) spectra of SAMs with and without Im revealed that the bulky ring prevented the formation of a strongly hydrogen bonded amide group network.


Subject(s)
Gold , Nanoparticles , Amides , Electrodes , Gold/chemistry , Histidine/chemistry , Hydrogen , Imidazoles , Protons , Spectrum Analysis, Raman/methods , Water
11.
Materials (Basel) ; 15(20)2022 Oct 17.
Article in English | MEDLINE | ID: mdl-36295289

ABSTRACT

An essential amino acid, histidine, has a vital role in the secondary structure and catalytic activity of proteins because of the diverse interactions its side chain imidazole (Im) ring can take part in. Among these interactions, hydrogen donating and accepting bonding are often found to operate at the charged interfaces. However, despite the great biological significance, hydrogen-bond interactions are difficult to investigate at electrochemical interfaces due to the lack of appropriate experimental methods. Here, we present a surface-enhanced infrared absorption spectroscopy (SEIRAS) and density functional theory (DFT) study addressing this issue. To probe the hydrogen-bond interactions of the Im at the electrified organic layer/water interface, we constructed Au-adsorbed self-assembled monolayers (SAMs) that are functionalized with the Im group. As the prerequisite for spectroelectrochemical investigations, we first analyzed the formation of the monolayer and the relationship between the chemical composition of SAM and its structure. Infrared absorption markers that are sensitive to hydrogen-bonding interactions were identified. We found that negative electrode polarization effectively reduced hydrogen-bonding strength at the Im ring at the organic layer-water interface. The possible mechanism governing such a decrease in hydrogen-bonding interaction strength is discussed.

12.
Colloids Surf B Biointerfaces ; 220: 112866, 2022 Dec.
Article in English | MEDLINE | ID: mdl-36174490

ABSTRACT

We used vibrational sum-frequency generation (VSFG) spectroscopy to elucidate the possible effect of various levels of isotopic substitution (H/D) on the properties of the DPPC monolayer by probing DPPC/D2O interface. We found that deuteration of the choline group has a great impact on monolayer properties, while monolayers with deuterated alkyl chains do not exhibit any differences under our experimental conditions. In addition, deuteration of the choline group strongly affected the hydration of the phosphate group. We showed by probing symmetric stretching vibration of phosphate group that denser packing only slightly reduced the hydration of DPPC-d13 and DPPC-d75 monolayers. Moreover, addition of calcium ions, which generally cause a marked dehydration of the lipid monolayer, had no effect on lipid monolayers with deuterated choline group. We proposed that one way to explain this experimental finding could be deuteration induced changes in the structure of lipid's choline group, resulting in a well-hydrated but Ca2+ ion blocking structure. These results have important implications for various spectroscopic techniques, which commonly use deuteration of phospholipids to circumvent overlapping between vibrational bands.


Subject(s)
1,2-Dipalmitoylphosphatidylcholine , Vibration , 1,2-Dipalmitoylphosphatidylcholine/chemistry , Spectrum Analysis/methods , Lecithins , Choline , Phosphates , Water/chemistry , Surface Properties
13.
Nanomaterials (Basel) ; 12(16)2022 Aug 19.
Article in English | MEDLINE | ID: mdl-36014725

ABSTRACT

Bifunctional magneto-plasmonic nanoparticles that exhibit synergistically magnetic and plasmonic properties are advanced substrates for surface-enhanced Raman spectroscopy (SERS) because of their excellent controllability and improved detection potentiality. In this study, composite magneto-plasmonic nanoparticles (Fe3O4@AgNPs) were formed by mixing colloid solutions of 50 nm-sized magnetite nanoparticles with 13 nm-sized silver nanoparticles. After drying of the layer of composite Fe3O4@AgNPs under a strong magnetic field, they outperformed the conventional silver nanoparticles during SERS measurements in terms of signal intensity, spot-to-spot, and sample-to-sample reproducibility. The SERS enhancement factor of Fe3O4@AgNP-adsorbed 4-mercaptobenzoic acid (4-MBA) was estimated to be 3.1 × 107 for a 633 nm excitation. In addition, we show that simply by changing the initial volumes of the colloid solutions, it is possible to control the average density of the silver nanoparticles, which are attached to a single magnetite nanoparticle. UV-Vis and SERS data revealed a possibility to tune the plasmonic resonance frequency of Fe3O4@AgNPs. In this research, the plasmon resonance maximum varied from 470 to 800 nm, suggesting the possibility to choose the most suitable nanoparticle composition for the particular SERS experiment design. We emphasize the increased thermal stability of composite nanoparticles under 532 and 442 nm laser light irradiation compared to that of bare Fe3O4 nanoparticles. The Fe3O4@AgNPs were further characterized by XRD, TEM, and magnetization measurements.

14.
Materials (Basel) ; 15(14)2022 Jul 12.
Article in English | MEDLINE | ID: mdl-35888313

ABSTRACT

Bismuth films with thicknesses between 6 and ∼30 nm were grown on Si (111) substrate by molecular beam epitaxy (MBE). Two main phases of bismuth - α-Bi and ß-Bi - were identified from high-resolution X-ray diffraction (XRD) measurements. The crystal structure dependencies on the layer thicknesses of these films were analyzed. ß-Bi layers were epitaxial and homogenous in lateral regions that are greater than 200 nm despite the layer thickness. Further, an increase in in-plane 2θ values showed the biaxial compressive strain. For comparison, α-Bi layers are misoriented in six in-plane directions and have ß-Bi inserts in thicker layers. That leads to smaller (about 60 nm) lateral crystallites which are compressively strained in all three directions. Raman measurement confirmed the XRD results. The blue-sift of Raman signals compared with bulk Bi crystals occurs due to the phonon confinement effect, which is larger in the thinnest α-Bi layers due to higher compression.

15.
Materials (Basel) ; 15(11)2022 Jun 05.
Article in English | MEDLINE | ID: mdl-35683306

ABSTRACT

The synthesis of magnetic particles triggers the interest of many scientists due to their relevant properties and wide range of applications in the catalysis, nanomedicine, biosensing and magnetic separation fields. A fast synthesis of iron oxide magnetic particles using an eco-friendly and facile microwave-assisted solvothermal method is presented in this study. Submicron Fe3O4 spheres were prepared using FeCl3 as an iron source, ethylene glycol as a solvent and reductor and sodium acetate as a precipitating and nucleating agent. The influence of the presence of polyethylene glycol as an additional reductor and heat absorbent was also evaluated. We reduce the synthesis time to 1 min by increasing the reaction temperature using the microwave-assisted solvothermal synthesis method under pressure or by adding PEG at lower temperatures. The obtained magnetite spheres are 200-300 nm in size and are composed of 10-30 nm sized crystallites. The synthesized particles were investigated using the XRD, TGA, pulsed-field magnetometry, Raman and FTIR methods. It was determined that adding PEG results in spheres with mixed magnetite and maghemite compositions, and the synthesis time increases the size of the crystallites. The presented results provide insights into the microwave-assisted solvothermal synthesis method and ensure a fast route to obtaining spherical magnetic particles composed of different sized nanocrystallites.

16.
ACS Omega ; 7(12): 10539-10549, 2022 Mar 29.
Article in English | MEDLINE | ID: mdl-35382275

ABSTRACT

Vibrational spectroscopy provides the possibility for sensitive and precise detection of chemical changes in biomolecules due to development of cancers. In this work, label-free near-infrared surface enhanced Raman spectroscopy (SERS) was applied for the differentiation between cancerous and normal human bladder tissues via analysis of the extracellular fluid of the tissue. Specific cancer-related SERS marker bands were identified by using a 1064 nm excitation wavelength. The prominent spectral marker band was found to be located near 1052 cm-1 and was assigned to the C-C, C-O, and C-N stretching vibrations of lactic acid and/or cysteine molecules. The correct identification of 80% of samples is achieved with even limited data set and could be further improved. The further development of such a detection method could be implemented in clinical practice for the aid of surgeons in determining of boundaries of malignant tumors during the surgery.

17.
Front Chem ; 10: 859023, 2022.
Article in English | MEDLINE | ID: mdl-35402375

ABSTRACT

Hafnium oxide (HfO2) films on silicon have the potential for application in photovoltaic devices. However, very little is known about the photoelectrochemical and protective properties of HfO2 films on Si. In this study, ultrathin films of HfO2 in the range of 15-70 nm were deposited on p-Si and Au substrates by atomic layer deposition (ALD). Grazing incidence X-ray diffraction (GI-XRD) identified the amorphous structure of the layers. Quartz crystal nanogravimetry (QCN) with Si and Au substrates indicated dynamics of electrolyte intake into the oxide film. No indications of oxide dissolution have been observed in acid (pH 3) and alkaline (pH 12) electrolytes. Mott-Schottky plots showed that the dark Si surface adjacent to the SiHfO2 interface is positively charged in an acid electrolyte and negatively charged in an alkaline electrolyte. The number of photoelectrons was determined to be much greater than the doping level of silicon. The cathodic photoactivity of the p-Si electrode protected by HfO2 films was studied with respect to the reaction of hydrogen reduction in acid and alkaline solutions. In acid solution, the film enhanced the reduction process when compared to that on the coating free electrode. The acceleration effect was explained in terms of prevention of silicon oxide formation, whose passivating capability is higher than that of hafnia films. In an alkaline electrolyte, an inhibition effect of the film was determined. Hafnia films protected Si from corrosion in this medium; however, at the same time, the film reduced electrode activity.

18.
Materials (Basel) ; 15(5)2022 Feb 22.
Article in English | MEDLINE | ID: mdl-35268866

ABSTRACT

Graphene research and technology development requires to reveal adsorption processes and understand how the defects change the physicochemical properties of the graphene-based systems. In this study, shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) and graphene-enhanced Raman spectroscopy (GERS) coupled with density functional theory (DFT) modeling were applied for probing the structure of riboflavin adsorbed on single-layer graphene substrate grown on copper. Intense and detailed vibrational signatures of the adsorbed riboflavin were revealed by SHINERS method. Based on DFT modeling and detected downshift of prominent riboflavin band at 1349 cm-1 comparing with the solution Raman spectrum, π-stacking interaction between the adsorbate and graphene was confirmed. Different spectral patterns from graphene-riboflavin surface were revealed by SHINERS and GERS techniques. Contrary to GERS method, SHINERS spectra revealed not only ring stretching bands but also vibrational features associated with ribityl group of riboflavin and D-band of graphene. Based on DFT modeling it was suggested that activation of D-band took place due to riboflavin induced tilt and distortion of graphene plane. The ability to explore local perturbations by the SHINERS method was highlighted. We demonstrated that SHINERS spectroscopy has a great potential to probe adsorbed molecules at graphene.

19.
Spectrochim Acta A Mol Biomol Spectrosc ; 274: 121109, 2022 Jun 05.
Article in English | MEDLINE | ID: mdl-35286889

ABSTRACT

A detailed study on Raman spectroelectrochemistry of poly(N-methylaniline) (PNMA) layer deposited at a gold electrode was performed. Raman spectra were excited by four different laser wavelengths: UV line at 325 nm, a blue line at 442 nm, a red line at 633 nm, and a NIR line at 785 nm in solutions of different pH ranging from 1 to 9, and at different electrode potentials ranging from -0.5 V to 0.8 V. UV excitation reveals features characteristic for the reduced form of PNMA, even within the electrochemical potential range where oxidized forms of this polymer prevail. At a blue laser excitation, again, features of the reduced form are revealed, along with indications on the appearance of some kind of intermediate redox state within a definite potential window. Both red and NIR laser line excitations result in rich Raman features, disclosing all major redox forms as well as their interconversions by changing of electrode potential. The presence of polaronic form of PNMA even in pH-neutral and alkaline solutions has been disclosed. A detailed analysis of Raman vibrational bands is presented for different excitation wavelengths, different electrode potentials, and different solution acidities.


Subject(s)
Aniline Compounds , Spectrum Analysis, Raman , Hydrogen-Ion Concentration , Lasers
20.
Materials (Basel) ; 15(3)2022 Jan 29.
Article in English | MEDLINE | ID: mdl-35160993

ABSTRACT

The structural state and crystal structure of Lu(1-x)ScxFeO3 (0 ≤ x ≤ 1) compounds prepared by a chemical route based on a modified sol-gel method were investigated using X-ray diffraction, Raman spectroscopy, as well as scanning electron microscopy. It was observed that chemical doping with Sc ions led to a structural phase transition from the orthorhombic structure to the hexagonal structure via a wide two-phase concentration region of 0.1 < x < 0.45. An increase in scandium content above 80 mole% led to the stabilization of the non-perovskite bixbyite phase specific for the compound ScFeO3. The concentration stability of the different structural phases, as well as grain morphology, were studied depending on the chemical composition and synthesis conditions. Based on the data obtained for the analyzed samples, a composition-dependent phase diagram was constructed.

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