771 Open Access
Fabrication of Novel Chitosan-Hydroxyapatite Nanostructured Thin Films for Biomedical Applications
Ciobanu, CS; Iconaru, SL; Predoi, D; Trusca, RD; Prodan, AM; Groza, A; Chifiriuc, MC; Beuran, M
DEC 2021, COATINGS, 11, 1561
DOI: 10.3390/coatings11121561
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In this study, we develop chitosan-hydroxyapatite (CS-HAp) composite layers that were deposited on Si substrates in radio frequency (RF) magnetron sputtering discharge in argon gas. The composition and structure of CS-HAp composite layers were investigated by analytical techniques, such as Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), metallographic microscopy (MM), and atomic force microscopy (AFM). On the other hand, in the present study the second order derivative of FT-IR-ATR spectra, for compositional analyses of CS-HAp, were used. The SEM, MM, and AFM data have shown the formation of CS-HAp composite layers. The surface of CS-HAp composite layers showed uniform growth (at an Ar gas working pressure of p = 2 x 10(-3) mbar). The surface of the CS-HAp composites coatings became more nanostructured, becoming granular as the gas pressure increased from 5 x 10(-3) to 1.2 x 10(-2) mbar. However, our studies revealed that the surface morphology of the CS-HAp composite layers varies with the Ar gas working pressure. At the same time, optical properties are slightly influenced by Ar pressure. Their unique physicochemical properties make them suitable for various applications in the biomedical field, if we consider the already proven antimicrobial properties of chitosan. The antifungal properties and the capacity of the CS-HAp composite layers to inhibit the development of fungal biofilms were also demonstrated using the Candida albicans ATCC 10231 (C. albicans) fungal strain.
772 Open Access
Nitrogen and Bromide Co-Doped Hydroxyapatite Thin Films with Antimicrobial Properties
Iconaru, SL; Ciobanu, CS; Predoi, D; Motelica-Heino, M; Negrila, CC; Badea, ML; Predoi, MV; Chifiriuc, CM; Popa, M
DEC 2021, COATINGS, 11, 1505
DOI: 10.3390/coatings11121505
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Hydroxyapatite (Ca-10(PO4)(6)(OH)(2), HAp), due to its high biocompatibility, is widely used as biomaterial. Doping with various ions of hydroxyapatite is performed to acquire properties as close as possible to the biological apatite present in bones and teeth. In this research the results of a study performed on thin films of hydroxyapatite co-doped with nitrogen and bromine (NBrHAp) are presented for the first time. The NBrHAp suspension was obtained by performing the adapted co-precipitation method using cetyltrimethylammonium bromide (CTAB). The thin layers of NBrHAp were obtained by spin-coating. The stability of the NBrHAp suspension was examined by ultrasound measurements. The thin layers obtained by the spin-coating method were examined by scanning electron microscopy (SEM), optical microscopy (OM), and metallographic microscopy (MM). The presence of nitrogen and bromine were highlighted by energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) studies. Fourier transform infrared spectroscopy (FTIR) was used to highlight the chemical status of nitrogen and bromine. In addition, the powder obtained from the NBrHAp suspension was analyzed by XRD. Moreover, the in vitro antimicrobial activity of the NBrHAp suspensions and coatings was investigated using the reference microbial strains Staphylococcus aureus ATCC 25923, Escherichia coli ATCC 25922, and Candida albicans ATCC 10231. The results highlighted the successful obtainment of N and Br co-doped hydroxyapatite suspension for the first time by an adapted co-precipitation method. The obtained suspension was used to produce pure NBrHAp composite thin films with superior morphological properties. The NBrHAp suspensions and coatings exhibited in vitro antimicrobial activity against bacterial and fungal strains and revealed their good antimicrobial activity.
773 Open Access
Micrometer Sized Hexagonal Chromium Selenide Flakes for Cryogenic Temperature Sensors
Buruiana, AT; Sava, F; Iacob, N; Matei, E; Bocirnea, AE; Onea, M; Galca, AC; Mihai, C; Velea, A; Kuncser, V
DEC 2021, SENSORS, 21, 8084
DOI: 10.3390/s21238084
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Nanoscale thermometers with high sensitivity are needed in domains which study quantum and classical effects at cryogenic temperatures. Here, we present a micrometer sized and nanometer thick chromium selenide cryogenic temperature sensor capable of measuring a large domain of cryogenic temperatures down to tenths of K. Hexagonal Cr-Se flakes were obtained by a simple physical vapor transport method and investigated using scanning electron microscopy, energy dispersive X-ray spectrometry and X-ray photoelectron spectroscopy measurements. The flakes were transferred onto Au contacts using a dry transfer method and resistivity measurements were performed in a temperature range from 7 K to 300 K. The collected data have been fitted by exponential functions. The excellent fit quality allowed for the further extrapolation of resistivity values down to tenths of K. It has been shown that the logarithmic sensitivity of the sensor computed over a large domain of cryogenic temperature is higher than the sensitivity of thermometers commonly used in industry and research. This study opens the way to produce Cr-Se sensors for classical and quantum cryogenic measurements.
774 Open Access
Low Blue Dose Photodynamic Therapy with Porphyrin-Iron Oxide Nanoparticles Complexes: In Vitro Study on Human Melanoma Cells
Nistorescu, S; Udrea, AM; Badea, MA; Lungu, I; Boni, M; Tozar, T; Dumitrache, F; Maraloiu, VA; Popescu, RG; Fleaca, C; Andronescu, E; Dinischiotu, A; Staicu, A; Balas, M
DEC 2021, PHARMACEUTICS, 13, 2130
DOI: 10.3390/pharmaceutics13122130
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The purpose of this study was to investigate the effectiveness in photodynamic therapy of iron oxide nanoparticles (gamma-Fe2O3 NPs), synthesized by laser pyrolysis technique, functionalized with 5,10,15,20-(Tetra-4-sulfonatophenyl) porphyrin tetraammonium (TPPS) on human cutaneous melanoma cells, after only 1 min blue light exposure. The efficiency of porphyrin loading on the iron oxide nanocarriers was estimated by using absorption and FTIR spectroscopy. The singlet oxygen yield was determined via transient characteristics of singlet oxygen phosphorescence at 1270 nm both for porphyrin functionalized nanoparticles and rose bengal used as standard. The irradiation was performed with a LED (405 nm, 1 mW/cm(2)) for 1 min after melanoma cells were treated with TPPS functionalized iron oxide nanoparticles (gamma-Fe2O3 NPs_TPPS) and incubated for 24 h. Biological tests revealed a high anticancer effect of gamma-Fe2O3 NPs_TPPS complexes indi-cated by the inhibition of tumor cell proliferation, reduction of cell adhesion, and induction of cell death through ROS generated by TPPS under light exposure. The biological assays were combined with the pharmacokinetic prediction of the porphyrin.
775 Open Access
Influence of Thickness on the Magnetic and Magnetotransport Properties of Epitaxial La0.7Sr0.3MnO3 Films Deposited on STO (001)
Greculeasa, SG; Stanciu, AE; Leca, A; Kuncser, A; Hrib, L; Chirila, C; Pasuk, I; Kuncser, V
DEC 2021, NANOMATERIALS, 11, 3389
DOI: 10.3390/nano11123389
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Epitaxial La0.7Sr0.3MnO3 films with different thicknesses (9-90 nm) were deposited on SrTiO3 (0 0 1) substrates by pulsed laser deposition. The films have been investigated with respect to morpho-structural, magnetic, and magneto-transport properties, which have been proven to be thickness dependent. Magnetic contributions with different switching mechanisms were evidenced, depending on the perovskite film thickness. The Curie temperature increases with the film thickness. In addition, colossal magnetoresistance effects of up to 29% above room temperature were evidenced and discussed in respect to the magnetic behavior and film thickness.
776 Open Access
Rhodamine B Photodegradation in Aqueous Solutions Containing Nitrogen Doped TiO2 and Carbon Nanotubes Composites
Udrescu, A; Florica, S; Chivu, M; Mercioniu, I; Matei, E; Baibarac, M
DEC 2021, MOLECULES, 26, 7237
DOI: 10.3390/molecules26237237
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In this work, new results concerning the potential of mixtures based on nitrogen doped titanium dioxide (TiO2:N) and carbon nanotubes (CNTs) as possible catalyst candidates for the rhodamine B (RhB) UV photodegradation are reported. The RhB photodegradation was evaluated by UV-VIS absorption spectroscopy using samples of TiO2:N and CNTs of the type of single-walled carbon nanotubes (SWNTs), double-wall carbon nanotubes (DWNTs), multi-wall carbon nanotubes (MWNTs), and single-walled carbon nanotubes functionalized with carboxyl groups (SWNT-COOH) having various concentrations of CNTs. The best photocatalytic performance was obtained for sample containing TiO2:N and 2.5 wt.% SWNTs-COOH, when approx. 85% of dye removal was achieved after 300 min. of UV irradiation. The reaction kinetics of RhB aqueous solutions containing TiO2:N/CNT mixtures followed a complex first-order kinetic model. The TiO2:N/CNTs catalyst induced higher photodegradation efficiency of RhB than TiO2:N due to the presence of CNTs, which act as adsorbent and dispersing agent and capture the photogenerated electrons of TiO2:N hindering the electron-hole recombination.
777
Mossbauer spectroscopy investigation of Fe oxide nanoparticles synthesized by a novel hydrothermal process over a wide pH range (3-13)
Comanescu, C; Palade, P; Kuncser, V
DEC 2021, HYPERFINE INTERACTIONS, 242, 42
DOI: 10.1007/s10751-021-01775-x
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Fe oxide magnetic nanoparticles (MNPs) in general and cobalt ferrite nanoparticles in particular have immense potential for applications in catalysis, medicine, information and energy storage, etc. MNPs feature interesting physical and chemical properties, different to those of corresponding bulk materials. The magnetic anisotropy constant of almost spherical CoFe2O4 MNPs is much higher than that of magnetite (Fe3O4) MNPs of similar geometrical parameters due to the magnetocrystalline contribution. CoFe2O4 shows significant magnetization at saturation, high coercive field and Curie temperature, and good chemical and magnetic stability, being therefore preferable to the most usual Fe3O4 MNPs. A surfactant-assisted synthetic route was employed to synthesize Fe oxide and in particular cobalt ferrite MNPs over a wide pH range (3-13), endeavor which allowed analysis of transient and parasitic phase identified in acidic reaction conditions.
778
Structural, morphological and magnetic investigations on cobalt ferrite nanoparticles obtained through green synthesis routes
Gingasu, D; Mindru, I; Culita, DC; Calderon-Moreno, JM; Bartha, C; Greculeasa, S; Iacob, N; Preda, S; Oprea, O
DEC 2021, APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING, 127, 892
DOI: 10.1007/s00339-021-05044-0
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This paper describes for the first time two processing routes-the precursor method and the two-step wet chemical process-for the synthesis of magnetic cobalt ferrite using the Tamarindus indica fruit extract. These green approaches are eco-friendly, safe and efficient alternatives to classical chemical methods. The aqueous extract from tamarind fruit contains numerous metabolites (organic acids, aminoacids). All these bioactive components are able to chelate metal ions leading to the formation of the multimetallic complex (precursor of cobalt ferrite). The obtained precursor was characterized by Fourier transform infrared spectroscopy (FTIR), thermal analysis, X-ray diffraction analysis (XRD) and magnetic measurements. The structure, morphology and magnetic behavior of the cobalt ferrite samples prepared through both synthesis routes were investigated by various characterization techniques: FTIR, XRD, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS), Mossbauer spectroscopy and magnetic measurements. XRD data confirmed that a cubic spinel structure was obtained for both ferrite powders with average crystallite size of 13 and 5 nm, respectively. The microstructure study by SEM revealed the formation of nanocrystallites assemblies using the precursor method and carbon-rich particles forming granulated micron-sized agglomerates, embedding ferrite nanocrystallites obtained through the two-step wet chemical process. Mossbauer spectroscopy results evidenced relaxation processes in the CoFe2O4 samples at room temperature, and the main characteristics of the involved sublattices were derived. The magnetic investigation revealed a typical magnetic behavior for a spinel, with CoFe2O4 nanoparticles ferrimagnetic at low temperature and superparamagnetic at room temperature.
779
Organic Heterostructures with Indium-Free Transparent Conductor Electrode for Optoelectronic Applications
Petre, G; Stanculescu, A; Girtan, M; Socol, M; Breazu, C; Vacareanu, L; Preda, N; Rasoga, O; Stanculescu, F; Doroshkevich, AS
DEC 2021, PHYSICA STATUS SOLIDI A-APPLICATIONS AND MATERIALS SCIENCE
DOI: 10.1002/pssa.202100521
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Herein, the properties of the organic heterostructures with triple-layer ZnO/Ag/ZnO as a replacement for ITO and mixed layer containing arylenevinylene oligomer (based on triphenylamine or carbazole) donor and nonfullerene (perylene diimide) acceptor mixed in the ratio 1:2 and the effect of a buffer layer of PEDOT-PSS intercalated between triple layer and mixed organic layer are discussed. The UV-vis transmission and photoluminescence (PL) properties are investigated in correlation with the surface topography and reveal a good match between the absorption and emission domain, which can favor the generation of the charge carriers. The heterostructure with the mixed layer based on triphenylamine oligomer shows the widest absorption domain, and the PL spectra of the heterostructures realized with either triphenylamine or carbazole oligomer show peaks corresponding to the radiative decay of the donor and acceptor. The I-V characteristics in the dark indicate a slightly nonlinear behavior and the current is affected by the charge carriers recombination on the defects present in the thick mixed layer deposited by matrix-assisted pulsed laser evaporation. The effect of the PEDOT-PSS buffer layer on the electrical properties of the organic heterostructure with ZnO/Ag/ZnO electrode is also investigated.
780 Open Access
Arylenevinylene Oligomer-Based Heterostructures on Flexible AZO Electrodes
Stanculescu, A; Socol, M; Rasoga, O; Breazu, C; Preda, N; Stanculescu, F; Socol, G; Vacareanu, L; Girtan, M; Doroshkevich, AS
DEC 2021, MATERIALS, 14, 7688
DOI: 10.3390/ma14247688
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We investigated the optical and electrical properties of flexible single and bi-layer organic heterostructures prepared by vacuum evaporation with a p-type layer of arylenevinylene oligomers, based on carbazole, 3,3 ' bis(N hexylcarbazole)vinylbenzene = L13, or triphenylamine, 1,4 bis [4 (N,N' diphenylamino)phenylvinyl] benzene = L78, and an n-type layer of 5,10,15,20-tetra(4-pyrydil)21H,23H-porphyne = TPyP. Transparent conductor films of Al-doped ZnO (AZO) with high transparency, >90% for wavelengths > 400 nm, and low resistivity, between 6.9 x 10(-4) ohm center dot cm and 23 x 10(-4) ohm center dot cm, were deposited by pulsed laser deposition on flexible substrates of polyethylene terephthalate (PET). The properties of the heterostructures based on oligomers and zinc phthalocyanine (ZnPc) were compared, emphasizing the effect of the surface morphology. The measurements revealed a good absorption in the visible range of the PET/AZO/arylenevinylene oligomer/TPyP heterostructures and a typical injection contact behavior with linear (ZnPc, L78) or non-linear (L13) J-V characteristics in the dark, at voltages < 0.4 V. The heterostructure PET/AZO/L78/TPyP/Al showed a current density of similar to 1 mA/cm(2) at a voltage of 0.3 V. The correlation between the roughness exponent, evaluated from the height-height correlation function, grain shape, and electrical behavior was analyzed. Consequently, the oligomer based on triphenylamine could be a promising replacement of donor ZnPc in flexible electronic applications.