791
Pyruvate Oxidase Biosensors Based on Glassy Carbon Electrodes Modified with Carbon Nanotubes and Poly(Neutral Red) Synthesized in Ethaline Deep Eutectic Solvent
Leote, RJB; Ghica, ME; Brett, CMA
APR 2022, ELECTROANALYSIS, 34
DOI: 10.1002/elan.202100164
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A novel nanostructured platform for pyruvate oxidase biosensors comprises poly(neutral red) (PNR) prepared by electropolymerization of NR in ethaline deep eutectic solvent (DES) with acid dopant, on a multiwalled carbon nanotubes (MWCNT) modified glassy carbon electrode (GCE). Characterization was by cyclic voltammetry and electrochemical impedance spectroscopy and morphology was examined by scanning electron microscopy. Ascorbate and H2O2 gave a better response at PNRDES/GCE than at PNRaq/GCE. Biosensors for pyruvate and phosphate, immobilizing pyruvate oxidase onto PNRDES/MWCNT/GCE enabled selective determination of pyruvate and phosphate, with micromolar limits of detection. Pyruvate was determined in onion samples and phosphate in water samples.
792 Open Access
Photodegradation of Azathioprine in the Presence of Sodium Thiosulfate
Toulbe, N; Smaranda, I; Negrila, C; Bartha, C; Manta, CM; Baibarac, M
APR 2022, INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES, 23, 3975
DOI: 10.3390/ijms23073975
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The effect of sodium thiosulfate (ST) on the photodegradation of azathioprine (AZA) was analyzed by UV-VIS spectroscopy, photoluminescence (PL), FTIR spectroscopy, Raman scattering, X-ray photoelectron (XPS) spectroscopy, thermogravimetry (TG) and mass spectrometry (MS). The PL studies highlighted that as the ST concentration increased from 25 wt.% to 75 wt.% in the AZA:ST mixture, the emission band of AZA gradual downshifted to 553, 542 and 530 nm. The photodegradation process of AZA:ST induced: (i) the emergence of a new band in the 320-400 nm range in the UV-VIS spectra of AZA and (ii) a change in the intensity ratio of the photoluminescence excitation (PLE) bands in the 280-335 and 335-430 nm spectral ranges. These changes suggest the emergence of new compounds during the photo-oxidation reaction of AZA with ST. The invoked photodegradation compounds were confirmed by studies of the Raman scattering, the FTIR spectroscopy and XPS spectroscopy through: (i) the downshift of the IR band of AZA from 1336 cm(-1) to 1331 cm(-1), attributed to N-C-N deformation in the purine ring; (ii) the change in the intensity ratio of the Raman lines peaking at 1305 cm(-1) and 1330 cm(-1) from 3.45 to 4.57, as the weight of ST in the AZA:ST mixture mass increased; and (iii) the emergence of a new band in the XPS O1s spectrum peaking at 531 eV, which was associated with the C=O bond. Through correlated studies of TG-MS, the main key fragments of ST-reacted AZA are reported.
793
Water denitration over titania-supported Pt and Cu by combined photocatalytic and catalytic processes: Implications for hydrogen generation properties in a photocatalytic system
Vasile, A; Papa, F; Bratan, V; Munteanu, C; Teodorescu, M; Atkinson, I; Anastasescu, M; Kawamoto, D; Negrila, C; Ene, CDD; Spataru, T; Balint, I
APR 2022, JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING, 10, 107129
DOI: 10.1016/j.jece.2022.107129
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The present work provides a new approach to the water denitration process and a facile strategy of catalyst preparation for the efficient hydrogen generation. The main focus of the research reported here was nitrate removal from aqueous solutions and simultaneous hydrogen generation under UV-Vis-light irradiation. This is a very important aspect in case of practical applications, eliminating the external source of hydrogen. Aiming to get a deeper understanding on the role of surface structures (size and shape of nanoparticles) towards the reduction mechanism and to establish basic principles for an efficient process, Pt-Cu/TiO2 and Pt-Cu/TiO2 modified with well-defined Pt nanoparticles were employed. The synthesized materials were characterized using various physicochemical techniques and tested comparatively for: (i) nitrate catalytic reduction by hydrogen (dark reaction) and (ii) nitrate photocatalytic reduction by in-situ generated solar hydrogen. In order to enhance overall denitration reaction by combined photocatalytic and catalytic processes, photo-generated charges and in-situ generated H-2 as reducing agent were used. Improvement of catalytic performances of nitrate hydrogenation reaction (~100% NO3 over line conversion) related to intimate contact between Pt and Cu was obtained. The in-situ generated H-2 by water splitting over the studied catalysts reduces efficiently NO3 over line ions. Enhanced photo-catalytic activity toward solar H-2 production by deposited well-defined Pt nanoparticles (~10 nm) was achieved. In order to make possible decontamination of polluted waters using in-situ generated H-2 under light exposure, the future optimization of such photo-catalytic systems looks promising.
794 Open Access
New Aspects Concerning the Ampicillin Photodegradation
Cercel, R; Paraschiv, M; Florica, CS; Daescu, M; Udrescu, A; Ciobanu, RC; Schreiner, C; Baibarac, M
APR 2022, PHARMACEUTICALS, 15, 415
DOI: 10.3390/ph15040415
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New aspects concerning the photodegradation (PD) of ampicillin are reported by photoluminescence (PL), Raman scattering and FTIR spectroscopy. The exposure of ampicillin in the absence (AM) and in the presence of the excipient (AMP) to UV light leads to an intensity diminution of the photoluminescence excitation (PLE) and photoluminescence (PL) spectra and the emergence of a new IR band at 3450 cm(-1). The photoluminescence studies demonstrate that the AM PD is amplified in the presence of excipients and an alkaline medium. In this last case, the PD process of AM involves the emergence of new compounds, whose presence is highlighted by: (i) the emergence of the isosbestic point at 300 nm in the UV-VIS spectra; (ii) a change in the ratio between the absorbance of IR bands situated in the spectral ranges 1200-1660 and 3250-3450 cm(-1); and (iii) a change in the ratio between the intensities of the Raman lines localized in the spectral ranges 1050-1800 and 2750-3100 cm(-1). A chemical mechanism of the PD processes of AM in an alkaline medium is proposed.
795 Open Access
'Put variety in White': Multi-analytical investigation of the white pigments inlaid on Early Chalcolithic pottery from Southern Romania
Opris, V; Velea, A; Secu, M; Rostas, AM; Buruiana, AT; Simion, CA; Mirea, DA; Matei, E; Bartha, C; Dimache, M; Lazar, C
APR 2022, JOURNAL OF ARCHAEOLOGICAL SCIENCE-REPORTS, 42, 103402
DOI: 10.1016/j.jasrep.2022.103402
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The current study aims to present and discuss the results obtained by complementary archaeometric methods applied for the first time on white pigments inlaid on excised pottery of the Boian-Vidra tradition (Early Chalcolithic, c. 4900-4600 BCE). The samples came from three settlements located in Southern Romania (Sultana-Ghetarie, Vidra, and Vladiceasca). They were selected considering that the pottery was produced in approximately contemporary sites, located relatively close to each other in the same geographical region, namely the Romanian Plain. The experimental part included the analysis of local samples of carbonate concretions and prehistoric animal bone ash as reference materials. Archaeometric investigations consisted in applying "in-air" PIXE and EDX methods for the chemical composition, XRD and FTIR for mineralogical data, SEM for microstructure observation, and EPR for the characterisation of the paramagnetic centres. Calcite, bone ash, and silica rich sediments were identified as the primary decorating pigments. The mixtures of calcite and bone-ash observed in 13 samples were specific to the sites at Vidra and Vladiceasca. Silica-rich sediments from distant sources were the main whitening materials in two samples from Vladiceasca, while for the samples from Sultana-Ghetarie, calcite was the only whitening mineral. The results show with a high degree of confidence the use of both local (i.e., carbonate neo-formations and bone ash) and exotic (silica-rich sediments) raw materials to obtain the white pigment applied to Boian-Vidra pottery. Thus, the current data show the adaptability of the potters with respect to the surrounding resources and also provide new evidence for a vast trade network of raw materials and/or finished products in the Lower Danube area during the Early Chalcolithic. The deliberate mixing of two whitening materials from different sources could be a technological choice and may highlight complex symbolic behaviours.
796
Influence of the synthesis parameters on the transport properties of Mg2Si0.4Sn0.6 solid solutions produced by melting and spark plasma sintering
Assahsahi, I; Popescu, B; Enculescu, M; Galatanu, M; Galca, AC; El Bouayadi, R; Zejli, D; Galatanu, A
APR 2022, JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS, 163, 110561
DOI: 10.1016/j.jpcs.2021.110561
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In this work, the influence of the preparation route on the structural, morphological, and thermoelectric properties of the Mg2Si0.4Sn0.6 solid solutions is investigated. The synthesis based on melting the constituent elements in a closed graphite crucible followed by spark plasma sintering allows mixing elements with a large difference of their melting temperatures and a good control of sample stoichiometry. The optimized synthesis route is validated by the doped V and Sb samples, which yield good thermoelectric performance. The n-type doping leads to two orders of magnitude increase of the carrier concentration, and thus a subsequent increase of the electrical conductivity, which, in turn, augments greatly the power factor of the Mg1.98V0.02Si0.385Sn0.6Sb0.015 to 42.61 x10(-4) Wm(-1)K 2 at 650K. Although doping slightly enlarges the thermal conductivity, a peak value of the figure of merit ZT similar to 1.15 is obtained at 723K, which is 20 times higher than the ZT of un-doped material.
797 Open Access
The Synergistic Effect of the Laser Beam on the Thermionic Vacuum Arc Method for Titanium-Doped Chromium Thin Film Deposition
Vladoiu, R; Mandes, A; Dinca, V; Ciupina, V; Matei, E; Polosan, S
APR 2022, COATINGS, 12, 470
DOI: 10.3390/coatings12040470
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Laser-Induced Thermionic Vacuum Arc (LTVA) provides a better way to produce uniform metallic thin films than the classical Thermionic Vacuum Arc (TVA) method. In Ti-doped chromium thin films produced using LTVA, the amorphous chromium is superimposed with small bcc chromium nanoparticles. These amorphous/crystalline structures with small crystallites induce lower roughness and electrical resistivity, reducing electron-phonon scattering and increasing charge transport across LTVA thin films. A significant shift in resistivity for the LTVA samples is observed due to electron scattering on the phonon-crystalline structures in the TVA samples which exhibit larger crystallites. Meanwhile, the wettability measurements reveal a higher contact angle, resulting in a lower surface free energy and consecutively lower dissociation energy for the LTVA-produced thin films than the TVA samples.
798 Open Access
Analysis of Functionalized Ferromagnetic Memory Alloys from the Perspective of Developing a Medical Vascular Implant
Nan, A; Turcu, R; Tudoran, C; Sofronie, M; Chiriac, A
APR 2022, POLYMERS, 14, 1397
DOI: 10.3390/polym14071397
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Durable biocompatible metal vascular implants are still one of the significant challenges of contemporary medicine. This work presents the preparation of ferromagnetic biomaterials with shape memory in metal strips based on FePd (30 at% Pd) that is either not doped or doped with Ga and Mn, coated with poly(benzofuran-co-arylacetic acid) or polyglutamic acid. The coating of the metal strips with polymers was achieved after the metal surface had been previously treated with open-air cold plasma. The final functionalization was performed to induce anti-thrombogenic/thrombolytic properties in the resulting materials. SEM-EDX microscopy and X-ray photoelectron microscopy (XPS) determined the morphology and composition of the metal strips covered with polymers. In vitro tests of standardized thromboplastin time (PTT) and prothrombin time (PT) were performed to evaluate the thrombogenicity of these biofunctionalized materials for future possible monitoring of the implant in patients.
799
Combustion products agglomeration of propellant containing boron with fluorinated coatings
Lebedeva, EA; Astaf'eva, SA; Istomina, TS; Badica, P
APR 2022, COMBUSTION AND FLAME, 238, 111749
DOI: 10.1016/j.combustflame.2021.111749
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Boron powders with Mg were coated with polytrifluorochloroethylene (PCTFE, fluorine content is 52.6 wt%) and perfluoropelargonic acid (PFPA, fluorine content is 69.6 wt%). They were used to fabricate propellants that were burnt in a reaction chamber designed and fabricated in our lab. Combustion products were studied by Raman spectroscopy, powder agglomeration analysis, electron microscopy, and thermal analysis. Results indicate that surface modification of the initial powder by fluorine-containing components decrease the agglomeration of the combustion products and the strongest effect is for PCTFE. Powders microstructural features and thermal stability of the coatings are discussed as being at the origin of different behavior during combustion of the propellants.(c) 2021 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
800 Open Access
Ferromagnetism and Superconductivity in CaRuO3/YBa2Cu3O7-δ Heterostructures
Ionescu, AM; Ivan, I; Locovei, C; Onea, M; Crisan, A; Soltan, S; Schütz, G; Albrecht, J
APR 2022, MATERIALS, 15, 2345
DOI: 10.3390/ma15072345
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The deposition of a ferromagnetic layer can affect the properties of high-temperature superconductors underneath. We investigated the influence of ferromagnetic CaRuO3 on the properties of YBa2Cu3O7-x (YBCO) superconducting thin films when the layers are either in direct contact or separated by a barrier layer of 5 nm SrTiO3. Detailed measurements of the magnetic moment of the superconductor and ferromagnet as a function of temperature and magnetic field have been performed using SQUID magnetometry. Magnetometry and relaxation measurements show that the modification of the superconducting properties of YBCO strongly depends on the interaction with the ferromagnetic layer on top. The barrier layer has a significant impact on both the supercon-ducting properties of the YBCO film and the ferromagnetic ordering of CaRuO3. The physical properties mentioned above were discussed in correlation with the materials' structure determined by XRD analysis.