431 Open Access
Calcium Borohydride Ca(BH4)2: Fundamentals, Prediction and Probing for High-Capacity Energy Storage Applications, Organic Synthesis and Catalysis
Comanescu, C
JUN 5 2023, ENERGIES, 16, 4536
DOI: 10.3390/en16114536
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Calcium borohydride (Ca(BH4)(2)) is a complex hydride that has been less investigated compared to its lighter counterpart, magnesium borohydride. While offering slightly lower hydrogen storage capacity (11.5 wt% theoretical maximum, 9.6 wt% under actual dehydrogenation conditions), there are many improvement avenues for maximizing the reversible hydrogen storage that have been explored recently, from DFT calculations and polymorph investigations to reactive hydride composites (RHCs) and catalytic and nanosizing effects. The stability of Ca(BH4)(2), the possibility of regeneration from spent products, and the relatively mild dehydrogenation conditions make calcium borohydride an attractive compound for hydrogen storage purposes. The ionic conductivity enhancements brought about by the rich speciation of borohydride anions can extend the use of Ca(BH4)(2) to battery applications, considering the abundance of Ca relative to alkali metal borohydrides typically used for this purpose. The current work aims to review the synthetic strategies, structural considerations of various polymorphs and adducts, and hydrogen storage capacity of composites based on calcium borohydrides and related complex hydrides (mixed anions, mixed cations, additives, catalysts, etc.). Additional applications related to batteries, organic and organometallic chemistry, and catalysis have been briefly described.
432 Open Access
Photocatalytic Activity of the Blends Based on TiO2 Nanoparticles and Reduced Graphene Oxide for Degradation of Acetaminophen
Daescu, M; Chivu, M; Matei, E; Negrila, C; Cramariuc, O; Baibarac, M
JUN 4 2023, MOLECULES, 28, 4546
DOI: 10.3390/molecules28114546
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The aim of this work is to highlight the influence of blends based on TiO2 nanoparticles and reduced graphene oxide (RGO) on the photodegradation of acetaminophen (AC). To this end, the catalysts of TiO2/RGO blends with RGO sheet concentrations equal 5, 10, and 20 wt. % were prepared by the solid-state interaction of the two constituents. The preferential adsorption of TiO2 particles onto the RGO sheets' surfaces via the water molecules on the TiO2 particle surface was demonstrated by FTIR spectroscopy. This adsorption process induced an increase in the disordered state of the RGO sheets in the presence of the TiO2 particles, as highlighted by Raman scattering and scanning electron microscopy (SEM). The novelty of this work lies in the demonstration that TiO2/RGO mixtures, obtained by the solid-phase interaction of the two constituents, allow an acetaminophen removal of up to 95.18% after 100 min of UV irradiation. This TiO2/RGO catalyst induced a higher photodegradation efficiency of AC than TiO2 due to the presence of RGO sheets, which acted as a capture agent for the photogenerated electrons of TiO2, hindering the electron-hole recombination. The reaction kinetics of AC aqueous solutions containing TiO2/RGO blends followed a complex first-order kinetic model. Another novelty of this work is the demonstration of the ability of PVC membranes modified with Au nanoparticles to act both as filters for the removal of TiO2/RGO blends after AC photodegradation and as potential SERS supports, which illustrate the vibrational properties of the reused catalyst. The reuse of the TiO2/RGO blends after the first cycle of AC photodegradation indicated their suitable stability during the five cycles of pharmaceutical compound photodegradation.
433 Open Access
Biological Response of Human Gingival Fibroblasts to Zinc-Doped Hydroxyapatite Designed for Dental Applications-An In Vitro Study
Badea, MA; Balas, M; Popa, M; Borcan, T; Bunea, AC; Predoi, D; Dinischiotu, A
JUN 2 2023, MATERIALS, 16, 4145
DOI: 10.3390/ma16114145
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This study aimed to investigate the biological response induced by hydroxyapatite (HAp) and zinc-doped HAp (ZnHAp) in human gingival fibroblasts and to explore their antimicrobial activity. The ZnHAp (with xZn = 0.00 and 0.07) powders, synthesized by the sol-gel method, retained the crystallographic structure of pure HA without any modification. Elemental mapping confirmed the uniform dispersion of zinc ions in the HAp lattice. The size of crystallites was 18.67 +/- 2 nm for ZnHAp and 21.54 +/- 1 nm for HAp. The average particle size was 19.38 +/- 1 nm for ZnHAp and 22.47 +/- 1 nm for HAp. Antimicrobial studies indicated an inhibition of bacterial adherence to the inert substrate. In vitro biocompatibility was tested on various doses of HAp and ZnHAp after 24 and 72 h of exposure and revealed that cell viability decreased after 72 h starting with a dose of 31.25 mu g/mL. However, cells retained membrane integrity and no inflammatory response was induced. High doses (such as 125 mu g/mL) affected cell adhesion and the architecture of F-actin filaments, while in the presence of lower doses (such as 15.625 mu g/mL), no modifications were observed. Cell proliferation was inhibited after treatment with HAp and ZnHAp, except the dose of 15.625 mu g/mL ZnHAp at 72 h of exposure, when a slight increase was observed, proving an improvement in ZnHAp activity due to Zn doping.
434 Open Access
Bistable Boron-Related Defect Associated with the Acceptor Removal Process in Irradiated p-Type Silicon-Electronic Properties of Configurational Transformations
Nitescu, A; Besleaga, C; Nemnes, GA; Pintilie, I
JUN 2023, SENSORS, 23, 5725
DOI: 10.3390/s23125725
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The acceptor removal process is the most detrimental effect encountered in irradiated boron-doped silicon. This process is caused by a radiation-induced boron-containing donor (BCD) defect with bistable properties that are reflected in the electrical measurements performed in usual ambient laboratory conditions. In this work, the electronic properties of the BCD defect in its two different configurations (A and B) and the kinetics behind transformations are determined from the variations in the capacitance-voltage characteristics in the 243-308 K temperature range. The changes in the depletion voltage are consistent with the variations in the BCD defect concentration in the A configuration, as measured with the thermally stimulated current technique. The A & RARR;B transformation takes place in non-equilibrium conditions when free carriers in excess are injected into the device. B & RARR;A reverse transformation occurs when the non-equilibrium free carriers are removed. Energy barriers of 0.36 eV and 0.94 eV are determined for the A & RARR;B and B & RARR;A configurational transformations, respectively. The determined transformation rates indicate that the defect conversions are accompanied by electron capture for the A & RARR;B conversion and by electron emission for the B & RARR;A transformation. A configuration coordinate diagram of the BCD defect transformations is proposed.
435 Open Access
Behavior of Cu-Y2O3 and CuCrZr-Y2O3 composites before and after irradiation
Martins, R; Antao, F; Correia, JB; Tejado, E; Pastor, J; Galatanu, A; Carvalho, PA; Alves, E; Dias, M
JUN 2023, NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH SECTION B-BEAM INTERACTIONS WITH MATERIALS AND ATOMS, 539
DOI: 10.1016/j.nimb.2023.03.011
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The Cu-Y2O3 and CuCrZr-Y2O3 materials have been devised as thermal barriers in nuclear fusion reactors. It is expected that in the nuclear environments, the materials should be working on extreme conditions of irradiation. In this work the Cu-Y2O3 and CuCrZr-Y2O3 were prepared and then irradiated in order to understand the surface irradiation resistance of the material. The composites were prepared in a glove box and consolidated with spark plasma sintering. The microstructures revealed regions of Y2O3 dispersion and Y2O3 agglomerates both in the Cu matrix and in the CuCrZr. The irradiated samples did not show any surface modification indicating that the materials seem to be irradiation resistant in the present situation. The thermal conductivity values for all the samples measured are lower than pure Cu and higher than pure W, however are higher than those expected, and therefore, the application of these materials as thermal barriers is compromised.
436 Open Access
Graphene Supports for Metal Hydride and Energy Storage Applications
Comanescu, C
JUN 2023, CRYSTALS, 13, 878
DOI: 10.3390/cryst13060878
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Energy production, distribution, and storage remain paramount to a variety of applications that reflect on our daily lives, from renewable energy systems, to electric vehicles and consumer electronics. Hydrogen is the sole element promising high energy, emission-free, and sustainable energy, and metal hydrides in particular have been investigated as promising materials for this purpose. While offering the highest gravimetric and volumetric hydrogen storage capacity of all known materials, metal hydrides are plagued by some serious deficiencies, such as poor kinetics, high activation energies that lead to high operating temperatures, poor recyclability, and/or stability, while environmental considerations related to the treatment of end-of-life fuel disposal are also of concern. A strategy to overcome these limitations is offered by nanotechnology, namely embedding reactive hydride compounds in nanosized supports such as graphene. Graphene is a 2D carbon material featuring unique mechanical, thermal, and electronic properties, which all recommend its use as the support for metal hydrides. With its high surface area, excellent mechanical strength, and thermal conductivity parameters, graphene can serve as the support for simple and complex hydrides as well as RHC (reactive hydride composites), producing nanocomposites with very attractive hydrogen storage properties.
437 Open Access
Biocomposite Coatings Doped with Magnesium and Zinc Ions in Chitosan Matrix for Antimicrobial Applications
Predoi, D; Ciobanu, CS; Iconaru, SL; Raaen, S; Rokosz, K
JUN 2023, MATERIALS, 16, 4412
DOI: 10.3390/ma16124412
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Hydroxyapatite doped with magnesium and zinc in chitosan matrix biocomposites have great potential for applications in space technology, aerospace, as well as in the biomedical field, as a result of coatings with multifunctional properties that meet the increased requirements for wide applications. In this study, coatings on titanium substrates were developed using hydroxyapatite doped with magnesium and zinc ions in a chitosan matrix (MgZnHAp_Ch). Valuable information concerning the surface morphology and chemical composition of MgZnHAp_Ch composite layers were obtained from studies that performed scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), metallographic microscopy, and atomic force microscopy (AFM). The wettability of the novel coatings, based on magnesium and zinc-doped biocomposites in a chitosan matrix on a titanium substrate, was evaluated by performing water contact angle studies. Furthermore, the swelling properties, together with the coating's adherence to the titanium substrate, were also analyzed. The AFM results emphasized that the composite layers exhibited the surface topography of a uniform layer, and that there were no evident cracks and fissures present on the investigated surface. Moreover, antifungal studies concerning the MgZnHAp_Ch coatings were also carried out. The data obtained from quantitative antifungal assays highlight the strong inhibitory effects of MgZnHAp_Ch against C. albicans. Additionally, our results underline that after 72 h of exposure, the MgZnHAp_Ch coatings display fungicidal features. Thus, the obtained results suggest that the MgZnHAp_Ch coatings possess the requisite properties that make them suitable for use in the development of new coatings with enhanced antifungal features.
438 Open Access
A New Hybrid Stepper Motor, Compliant Piezoelectric Micro-Tweezer for Extended Stroke
Ivan, IA; Noveanu, DC; Gurgu, VI; Despa, V; Noveanu, S
JUN 2023, MICROMACHINES, 14, 1112
DOI: 10.3390/mi14061112
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The revolutionary economic potential of micro and nanotechnology is already recognized. Micro and nano-scale technologies that use electrical, magnetic, optical, mechanical, and thermal phenomena separately or in combination are either already in the industrial phase or approaching it. The products of micro and nanotechnology are made of small quantities of material but have high functionality and added value. This paper presents such a product: a system with micro-tweezers for biomedical applications-a micromanipulator with optimized constructive characteristics, including optimal centering, consumption, and minimum size, for handling micro-particles and constructive micro components. The advantage of the proposed structure consists mainly in obtaining a large working area combined with a good working resolution due to the double actuation principle: electromagnetic and piezoelectric.
439 Open Access
Dextran-Coated Iron Oxide Nanoparticles Loaded with 5-Fluorouracil for Drug-Delivery Applications
Predoi, D; Balas, M; Badea, MA; Ciobanu, SC; Buton, N; Dinischiotu, A
JUN 2023, NANOMATERIALS, 13, 1811
DOI: 10.3390/nano13121811
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This study aims to design and test different formulations composed of dextran-coated iron oxide nanoparticles (IONPs) loaded with 5-Fluorouracil (5-FU) with varying nanoparticle:drug ratios on colorectal cancer cells. The stable suspension of IONPs s was synthesized by the adapted co-precipitation method. The stable suspension of IONPs was mixed with a solution of dextran and 5-FU solubilized in a saline solution. The final suspensions with optimized ratios of IONP:5-FU in the final suspension were 0.5:1, 1:1, and 1.5:1. The information on the morphology and size distribution of the IONPs suspension and IONP loads with 5-FU was obtained using scanning electron microscopy (SEM). The presence of 5-FU and dextran on the surface of the IONPs was highlighted by energy-dispersive X-ray spectroscopy (EDS) studies. The determination of the surface charge of the nanoparticles in the final suspensions of IONP:5-FU was achieved by measuring the zeta potential (& zeta;). The hydrodynamic diameter of the resulting suspensions of IONP:5-FU was determined by dynamic light scattering (DLS). A cytocompatibility analysis was performed using Caco-2 (human epithelial colorectal adenocarcinoma) cells. In this research, our goal was to find a relationship between the formulation ratio of nanoparticles and drug, and the cellular response after exposure, as a strategy to increase the efficacy of this drug-delivery system. The nanoparticle uptake and antitumor activity, including modulation of oxidative stress, apoptosis, and proliferation biomarkers, were analyzed. The present study showed that the nanoformulation with the ratio IONP:5-FU 1.5:1 had the highest anti-tumor efficiency. Moreover, decreased MCM-2 expression in Caco-2 cells exposed to dextran-coated iron oxide nanoparticles loaded with 5-FU was demonstrated for the first time.
440 Open Access
Microstructural and Morphological Characterization of the Cobalt-Nickel Thin Films Deposited by the Laser-Induced Thermionic Vacuum Arc Method
Dinca, V; Mandes, A; Vladoiu, R; Prodan, G; Ciupina, V; Polosan, S
JUN 2023, COATINGS, 13, 984
DOI: 10.3390/coatings13060984
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Laser Induced-Thermionic Vacuum Arc (LTVA) technology was used for depositing uniform intermetallic CoNi thin films of 100 nm thickness. LTVA is an original deposition method using a combination of the typical Thermionic Vacuum Arc (TVA) system and a laser beam provided by a QUANTEL Q-Smart 850 Nd:YAG compact Q-switched laser with a second harmonic module. The novelty is related to the simultaneous deposition of a bi-component metallic thin film using photonic processes of the laser over the plasma deposition, which improves the roughness but also triggers the composition of the deposited thin film. Structural analysis of the deposited thin films confirms the formation of face-centered cubic (fcc) as the main phase CoNi and hexagonal Co3Ni as the minority phase, observed mainly using high-resolution transmission electron microscopy. The magneto-optical measurements suggest an isotropic distribution of the CoNi alloy thin films for the in-plan angular rotation. From the low coercive field of H-c = 40 Oe and a saturation field at 900 Oe, the CoNi thin films obtained by LTVA are considered semi-hard magnetic materials. Magnetic force microscopy reveals spherical magnetic nanoparticles with mean size of about 40-50 nm. The resistivity was estimated at rho = 34.16 mu Omega cm, which is higher than the values for bulk Co and Ni.