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Dr. Ioana Dorina KUNCSER

Scientific Researcher II

Laboratory of Atomic Structures and Defects in Advanced Materials (LASDAM)

ioana[DOT]vlaicu[AT]infim[DOT]ro

Projects

1. Innovative nano-materials and architectures for integrated piezoelectric energy harvesting applications

Project Type: M-EraNet, Start Date: 2016-06-01 End Date: 2019-05-31

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Publications

1. Low traces of acetone detection with WO3-based chemical sensors
Authors: Stanoiu, A; Vlaicu, ID; Iacoban, AC; Mihalcea, CG; Ghica, C; Florea, OG; Dinu, IV; Mercioniu, I; Simion, CE

Published: APR 1 2024, MATERIALS CHEMISTRY AND PHYSICS, 316, 129105, DOI: 10.1016/j.matchemphys.2024.129105

This work presents the ability of WO3-based sensors to detect low traces of acetone, specifically within the range of 0.25-5 ppm, specific to the in -field atmosphere. The WO3 powder was synthesised through the hydrothermal method. Morpho-structural investigations showed a monoclinic structure and a good crystallization of the WO3 powder, containing well -grown and faceted grains along low -index crystallographic planes. The paste obtained by mixing the powder with propanediol was screen -printed as a thick layer onto commercial alumina substrates, obtaining the chemical sensors. A dynamic computer -controlled Gas Mixing System was utilized to ensure controlled airflow with variable relative humidity and acetone concentrations. The sensor response was explained based on physico-chemical equations, taking into consideration pre -adsorbed species of oxygen and water, both of which are relevant constituents of atmospheric conditions. The results highlight the applicative potential of WO3, having a good signal-to-noise ratio in relative humidity conditions up to 90% and a pronounced sensitive selectivity to acetone.
2. Characterization of defect structures in nanoscaled W-doped TiO2 tested as supercapacitor electrode materials
Authors: Ammar, AU; Stefan. M; Macavei, SG; Tripon, S; Pana, O; Leostean, C; Vlaicu, ID; Rostas, AM; Erdem, E

Published: JAN 2023, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 34, 8, DOI: 10.1007/s10854-022-09540-8

In this work, Tungsten(W)-doped TiO2 nanoparticles were synthesized using the sol-gel method and were used as electrode materials in supercapacitor applications. The structural and morphological properties of the prepared samples were analyzed by means of XRD, STEM, TEM, and XPS. The analysis of the defect centers was carried out using EPR spectroscopy. The electrochemical analysis of the assembled supercapacitor was done using cyclic voltammetry, galvanostatic cycling with potential limitation technique, potentiostatic electrochemical impedance spectroscopy, and voltage-holding experiments. All the presented samples showed paramagnetic defects in the EPR analysis, while 0.5% W-doped TiO2 showed a maximum signal intensity. The supercapacitor performance from the synthesized electrode material showed highly encouraging results. The equivalent series resistance (R-s) value for all the designs showed values under "1 omega,' which reflects high conductivity. As the maximum EPR intensity comes from TiO2 doped with 0.5% W, the supercapacitor performance of this sample was tested with a newly designed five-electrode system. This design showed superior performance compared to any other used designs with a specific capacitance of 25.5 F g(-1), with an energy density of 14.16 Wh kg (-1 )at 302 kW kg (-1).
3. Atomic scale insight into the decomposition of nanocrystalline zinc hydroxynitrate toward ZnO using Mn2+ paramagnetic probes
Authors: Vlaicu, ID; Stefan, M; Radu, C; Culita, DC; Radu, D; Ghica, D

Published: APR 6 2023, FRONTIERS IN CHEMISTRY, 11, 1154219, DOI: 10.3389/fchem.2023.1154219

Layered zinc hydroxynitrate (ZHN), with the chemical formula Zn-5 (OH)(8) (NO3)(2)center dot 2H(2)O, exhibits a range of special properties such as anion-exchange and intercalation capacity, as well as biocompatibility, making it attractive for a large variety of applications in fields from nanotechnology to healthcare and agriculture. In this study nanocrystalline ZHN doped with 1,000 ppm Mn2+ was prepared by two synthesis methods (coprecipitation and solid state reaction) using similar environment-friendly precursors. The complex morpho-structural [X-ray diffraction, scanning and transmission electron microscopy, textural analysis] and spectroscopic [Fourier transform infrared and electron paramagnetic resonance (EPR)] characterization of the two ZHN nanopowders showed similar crystalline structures with Mn2+ ions localized in the nanocrystals volume, but with differences in their morphological and textural characteristics, as well as in the doping efficiency. ZHN obtained by coprecipitation consists of larger nanoplatelets with more than two times larger specific surface area and pore volume, as well as a dopant concentration than in the ZHN sample obtained by solid state reaction. The thermal stability and the on-set of the structural phase transformation have been investigated at atomic scale with high accuracy by EPR, using Mn2+ as paramagnetic probes. The on-set of the ZHN structural phase transformation toward ZnO was observed by EPR to take place at 110 degrees C and 130 degrees C for the samples prepared by coprecipitation and solid state reaction, respectively, evidencing a manganese induced local decrease of the transformation temperature. Our results contribute to the selection of the most appropriate ZHN synthesis method for specific applications and in the development of new green, cost-effective synthesis routes for Mn2+ doped nano-ZnO.
4. The influence of the synthesis method on Gd2O3 morpho-structural properties and sensitivity to CO2 under in-field conditions
Authors: Simion, CE; Vlaicu, ID; Iacoban, AC; Mihalcea, CG; Ghica, C; Stanoiu, A

Published: FEB 15 2023, MATERIALS CHEMISTRY AND PHYSICS, 296, 127354, DOI: 10.1016/j.matchemphys.2023.127354

In this study, we report the implications of the synthesis method on Gd2O3 sensitivity to CO2. The rare-earth oxide was prepared by wet chemical co-precipitation and by hydrothermal method. The obtained powders labelled Gd2O3-CoP and Gd2O3-HT were deposited as thick films over commercial Al2O3 substrates provided with Pt electrodes and a back-side heater. Both powders consist of the same crystallographic phase, with a significant difference appearing in selected area electron diffraction patterns, transmission electron microscopy images at higher magnification and X-ray diffraction spectra, with respect to the crystallization degree. The associated role in sensing properties is revealed via electrical resistance variations determined by CO2 concen-trations in the range between 400 and 3000 ppm and variable relative humidity between 0 and 50%RH, similar to the in-field atmosphere. The proposed CO2 interaction mechanism is based on phenomenological in-vestigations which highlight the electronic affinity variation as the effect of dipoles induced by the in-field conditions on the Gd2O3 surface.
5. Characterization of defect structures in nanoscaled W-doped TiO2 tested as supercapacitor electrode materials
Authors: Ammar, AU; Stefan, M; Macavei, SG; Tripon, S; Pana, O; Leostean, C; Vlaicu, ID; Rostas, AM; Erdem, E

Published: JAN 2023, JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS, 34, 8, DOI: 10.1007/s10854-022-09540-8

In this work, Tungsten(W)-doped TiO2 nanoparticles were synthesized using the sol-gel method and were used as electrode materials in supercapacitor applications. The structural and morphological properties of the prepared samples were analyzed by means of XRD, STEM, TEM, and XPS. The analysis of the defect centers was carried out using EPR spectroscopy. The electrochemical analysis of the assembled supercapacitor was done using cyclic voltammetry, galvanostatic cycling with potential limitation technique, potentiostatic electrochemical impedance spectroscopy, and voltage-holding experiments. All the presented samples showed paramagnetic defects in the EPR analysis, while 0.5% W-doped TiO2 showed a maximum signal intensity. The supercapacitor performance from the synthesized electrode material showed highly encouraging results. The equivalent series resistance (R-s) value for all the designs showed values under "1 omega,' which reflects high conductivity. As the maximum EPR intensity comes from TiO2 doped with 0.5% W, the supercapacitor performance of this sample was tested with a newly designed five-electrode system. This design showed superior performance compared to any other used designs with a specific capacitance of 25.5 F g(-1), with an energy density of 14.16 Wh kg (-1 )at 302 kW kg (-1).
6. Atomic scale insight into the decomposition of nanocrystalline zinc hydroxynitrate toward ZnO using Mn2+ paramagnetic probes
Authors: Vlaicu, ID; Stefan, M; Radu, C; Culita, DC; Radu, D; Ghica, D

Published: APR 6 2023, FRONTIERS IN CHEMISTRY, 11, 1154219, DOI: 10.3389/fchem.2023.1154219

Layered zinc hydroxynitrate (ZHN), with the chemical formula Zn-5 (OH)(8) (NO3)(2)center dot 2H(2)O, exhibits a range of special properties such as anion-exchange and intercalation capacity, as well as biocompatibility, making it attractive for a large variety of applications in fields from nanotechnology to healthcare and agriculture. In this study nanocrystalline ZHN doped with 1,000 ppm Mn2+ was prepared by two synthesis methods (coprecipitation and solid state reaction) using similar environment-friendly precursors. The complex morpho-structural [X-ray diffraction, scanning and transmission electron microscopy, textural analysis] and spectroscopic [Fourier transform infrared and electron paramagnetic resonance (EPR)] characterization of the two ZHN nanopowders showed similar crystalline structures with Mn2+ ions localized in the nanocrystals volume, but with differences in their morphological and textural characteristics, as well as in the doping efficiency. ZHN obtained by coprecipitation consists of larger nanoplatelets with more than two times larger specific surface area and pore volume, as well as a dopant concentration than in the ZHN sample obtained by solid state reaction. The thermal stability and the on-set of the structural phase transformation have been investigated at atomic scale with high accuracy by EPR, using Mn2+ as paramagnetic probes. The on-set of the ZHN structural phase transformation toward ZnO was observed by EPR to take place at 110 degrees C and 130 degrees C for the samples prepared by coprecipitation and solid state reaction, respectively, evidencing a manganese induced local decrease of the transformation temperature. Our results contribute to the selection of the most appropriate ZHN synthesis method for specific applications and in the development of new green, cost-effective synthesis routes for Mn2+ doped nano-ZnO.
7. Influence of relative humidity on CO2 interaction mechanism for Gd-doped SnO2 with respect to pure SnO2 and Gd2O3
Authors: Ghica, C; Mihalcea, CG; Simion, CE; Vlaicu, ID; Ghica, D; Dinu, IV; Florea, OG; Stanoiu, A

Published: OCT 1 2022, SENSORS AND ACTUATORS B-CHEMICAL, 368, 132130, DOI: 10.1016/j.snb.2022.132130

The paper aims to identify the CO2 interaction mechanism for chemical sensors based on Gd-doped SnO2, SnO2 and Gd2O3 powders deposited as thick sensitive layers. The low reactivity of CO2 conferred by the thermodynamic stability and chemical inertia can be offset by the presence of relative humidity. The sensitive powders were prepared by wet chemical co-precipitation method. The Gd concentration was varied from 1% to 20 at% in order to determine the limit for Gd integration as a doping ion prior to chemical segregation as a secondary phase. Analytical transmission electron microscopy points to a homogeneous Gd doping of the nanostructured SnO2 powders for low doping concentrations and the formation of a nanocomposite based on SnO2 as main phase and cubic Gd2O3 as secondary phase for the highly doped samples. The electrical resistance is either influenced by the density of oxygen vacancies, or is the result of compensation for two opposite behaviours into the SnO2- Gd2O3 nanocomposite structures. The CO2 exposure to humid atmosphere determines distinct behaviours cor-responding to SnO2 and Gd2O3 as constitutive elements. The associated CO2 interaction mechanism is based on simultaneous DC electrical resistance and Contact Potential Difference measurements, which allow decoupling the ionosorption from the dipolar processes, thus highlighting specific chemical interactions on the SnO2 and Gd2O3 surfaces.
8. A new method for obtaining the magnetic shape anisotropy directly from electron tomography images
Authors: Radu, C; Vlaicu, ID; Kuncser, AC

Published: JUL 5 2022, BEILSTEIN JOURNAL OF NANOTECHNOLOGY, 13, DOI: 10.3762/bjnano.13.51

A new methodology to obtain magnetic information on magnetic nanoparticle (MNP) systems via electron tomography techniques is reported in this work. The new methodology is implemented in an under-development software package called Magn3t, written in Python and C++. A novel image-filtering technique that reduces the highly undesired diffraction effects in the tomography tiltseries has been also developed in order to increase the reliability of the correlations between morphology and magnetism. Using the Magn3t software, the magnetic shape anisotropy magnitude and direction of magnetite nanoparticles has been extracted for the first time directly from transmission electron tomography.
9. Synthesis and Characterization of Hematite-Based Nanocomposites as Promising Catalysts for Indigo Carmine Oxidation
Authors: Kuncser, AC; Rostas, AM; Zavoianu, R; Pavel, OD; Vlaicu, ID; Badea, M; Culita, DC; Tirsoaga, A; Olar, R

Published: JUL 2022, NANOMATERIALS, 12, 2511, DOI: 10.3390/nano12142511

The hematite-based nanomaterials are involved in several catalytic organic and inorganic processes, including water decontamination from organic pollutants. In order to develop such species, a series of bimetallic hematite-based nanocomposites were obtained by some goethite composites-controlled calcination. Their composition consists of various phases such as alpha-FeOOH, alpha-Fe2O3 or gamma-Fe2O3 combined with amorphous (Mn2O3, Co3O4, NiO, ZnO) or crystalline (CuO) oxides of the second transition ion from the structure. The component dimensions, either in the 10-30 or in the 100-200 nm range, together with the quasi-spherical or nanorod-like shapes, were provided by Mossbauer spectroscopy and powder X-ray diffraction as well as transmission electron microscopy data. The textural characterization showed a decrease in the specific area of the hematite-based nanocomposites compared with corresponding goethites, with the pore volume ranging between 0.219 and 0.278 cm(3)g(-1). The best catalytic activity concerning indigo carmine removal from water in hydrogen peroxide presence was exhibited by a copper-containing hematite-based nanocomposite sample that reached a dye removal extent of over 99%, which correlates with both the base/acid site ratio and pore size. Moreover, Cu-hbnc preserves its catalytic activity even after four recyclings, when it still reached a dye removal extent higher than 90%.
10. Facile synthesis of low toxicity iron oxide/TiO2 nanocomposites with hyperthermic and photo-oxidation properties
Authors: Popescu, T; Matei, CO; Culita, DC; Maraloiu, VA; Rostas, AM; Diamandescu, L; Iacob, N; Savopol, T; Ilas, MC; Feder, M; Lupu, AR; Iacoban, AC; Vlaicu, ID; Moisescu, MG

Published: APR 27 2022, SCIENTIFIC REPORTS, 12, 6887, DOI: 10.1038/s41598-022-11003-3

The present study aimed to assess the feasibility of developing low-cost multipurpose iron oxide/TiO2 nanocomposites (NCs) for use in combined antitumor therapies and water treatment applications. Larger size (approximate to 100 nm) iron oxide nanoparticles (IONPs) formed magnetic core-TiO2 shell structures at high Fe/Ti ratios and solid dispersions of IONPs embedded in TiO2 matrices when the Fe/Ti ratio was low. When the size of the iron phase was comparable to the size of the crystallized TiO2 nanoparticles (approximate to 10 nm), the obtained nanocomposites consisted of randomly mixed aggregates of TiO2 and IONPs. The best inductive heating and ROS photogeneration properties were shown by the NCs synthesized at 400 degrees C which contained the minimum amount of alpha-Fe2O3 and sufficiently crystallized anatase TiO2. Their cytocompatibility was assessed on cultured human and murine fibroblast cells and analyzed in relation to the adsorption of bovine serum albumin from the culture medium onto their surface. The tested nanocomposites showed excellent cytocompatibility to human fibroblast cells. The results also indicated that the environment (i.e. phosphate buffer or culture medium) used to disperse the nanomaterials prior to performing the viability tests can have a significant impact on their cytotoxicity.
11. Antiproliferative and antibacterial properties of biocompatible copper(II) complexes bearing chelating N,N-heterocycle ligands and potential mechanisms of action
Authors: Olar, R; Badea, M; Bacalum, M; Raileanu, M; Ruta, LL; Farcasanu, IC; Rostas, AM; Vlaicu, ID; Popa, M; Chifiriuc, MC

Published: OCT 2021, BIOMETALS, 34, 1172, DOI: 10.1007/s10534-021-00334-9

In an attempt to propose new applications for the biomedical field, complexes with mixed ligands {[Cu(bpy)(2)(mu 2OClO3)]ClO4}n (1) and [Cu(phen)(2)(OH2)](ClO4)(2) (2) (bpy: 2,2'-biyridine; phen and 1,10-phenantroline) were evaluated for their antibacterial and cytotoxicicity features and for the elucidation of some of the mechanisms involved. Complex (2) proved to be a very potent antibacterial agent, exhibing MIC and MBEC values 2 to 54 times lower than those obtained for complex (1) against both susceptible or resistant Gram-positive and Gram-negative strains, in planktonic or biofilm growth state. In exchange, complex (1) exhibited selective cytotoxicity against melanoma tumor cells (B16), proving a promising potential for developing novel anticancer drugs. The possible mechanisms of both antimicrobial and antitumor activity of the copper(II) complexes is their DNA intercalative ability coupled with ROS generation. The obtained results recommend the two complexes for further development as multipurpose copper-containing drugs.
12. Soft synthesis and characterization of goethite-based nanocomposites as promising cyclooctene oxidation catalysts
Authors: Kuncser, AC; Vlaicu, ID; Pavel, OD; Zavoianu, R; Badea, M; Radu, D; Culita, DC; Rostas, AM; Olar, R

Published: AUG 24 2021, RSC ADVANCES, 11, 27602, DOI: 10.1039/d1ra04211d

Goethite based nanocomposites with a different composition such as 6FeO(OH)center dot MnO(OH)center dot 0.5H(2)O (Mn-composite), xFeO(OH)center dot M(OH)(2)center dot yH(2)O (Co-composite (M: Co, x = 12, y = 3), Ni-composite (M: Ni, x = 7, y = 2)) and xFeO(OH)center dot MO center dot yH(2)O (Cu-composite (M: Cu, x = 5.5, y = 3), Zn-composite (M: Zn, x = 6, y = 1.5)) have been prepared by a soft chemical synthesis consisting in acetate hydrolysis. The data provided by Fourier transform infrared (FTIR), ultraviolet-visible-near infrared (UV-Vis-NIR), electron paramagnetic resonance (EPR) and Mossbauer spectra account for a slight modification of all composites' physicochemical properties compared to the starting material. Powder X-ray diffraction and transmission electron microscopy (TEM) investigations revealed the secondary phase nature and presence along with that of goethite. The TEM data are also consistent with a nano rod-like morphology with a 5-10 nm width and an average length of 40 nm. The catalytic oxidation of cyclooctene with O-2 using isobutyraldehyde as reductant and acetonitrile as a solvent was performed in batch conditions for 5 h at room temperature. The selectivity for the epoxide was higher than 99% for all tested solids. The conversion of cyclooctene decreased from 55% to 4% following the same order of variance as the base/acid sites ratio: Mn-composite > Fe-composite > Co-composite > Ni-composite > Zn-composite > Cu-composite. The 6FeO(OH)center dot MnO(OH)center dot 0.5H(2)O (Mn-composite) exhibited the most promising catalytic activity in cyclooctene oxidation, which can be correlated with the redox ability of Mn(iii) combined with the increased base character of this solid. The catalytic activity of this sample decreases by 10% after several successive reaction cycles.
13. Influence of surfactant-tailored Mn-doped ZnO nanoparticles on ROS production and DNA damage induced in murine fibroblast cells
Authors: Popescu, T; Matei, CO; Vlaicu, ID; Tivig, I; Kuncser, AC; Stefan, M; Ghica, D; Miclea, LC; Savopol, T; Culita, DC; Moisescu, MG

Published: OCT 22 2020, SCIENTIFIC REPORTS, 10, DOI: 10.1038/s41598-020-74816-0

The present study concerns the in vitro oxidative stress responses of non-malignant murine cells exposed to surfactant-tailored ZnO nanoparticles (NPs) with distinct morphologies and different levels of manganese doping. Two series of Mn-doped ZnO NPs were obtained by coprecipitation synthesis method, in the presence of either polyvinylpyrrolidone (PVP) or sodium hexametaphosphate (SHMTP). The samples were investigated by powder X-ray Diffraction, Transmission Electron Microscopy, Fourier-Transform Infrared and Electron Paramagnetic Resonance spectroscopic methods, and N-2 adsorption-desorption analysis. The observed surfactant-dependent effects concerned: i) particle size and morphology; ii) Mn-doping level; iii) specific surface area and porosity. The relationship between the surfactant dependent characteristics of the Mn-doped ZnO NPs and their in vitro toxicity was assessed by studying the cell viability, intracellular reactive oxygen species (ROS) generation, and DNA fragmentation in NIH3T3 fibroblast cells. The results indicated a positive correlation between the specific surface area and the magnitude of the induced toxicological effects and suggested that Mn-doping exerted a protective effect on cells by diminishing the pro-oxidative action associated with the increase in the specific BET area. The obtained results support the possibility to modulate the in vitro toxicity of ZnO nanomaterials by surfactant-controlled Mn-doping.
14. Electron paramagnetic resonance and microstructural insights into the thermal behavior of simonkolleite nanoplatelets
Authors: Rostas, AM; Kuncser, AC; Ghica, D; Palici, A; Maraloiu, VA; Vlaicu, ID

Published: MAY 7 2020, PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 22, 9512, DOI: 10.1039/d0cp00641f

The aim of this paper is the study of the thermal behavior of the simonkolleite Zn-5(OH)(8)Cl-2 center dot H2O (ZHC) by electron paramagnetic resonance (EPR) spectroscopy, in particular. It is well known that during heating ZHC undergoes a complex transformation which involves several overlapping stages. However, with reference to the data reported on this subject, it can be concluded that there is still an ongoing debate regarding the intermediate stages of this process. The data presented in this study support a simple decomposition process of the ZHC prepared using the precipitation method. The EPR data correlated to the data obtained by other experimental techniques, such as XRD, TEM, SEM and EDX, indicate that during the thermal treatment the ZHC suffers a partial decomposition to ZnO with no intermediate products. After annealing at 500 degrees C for 1 h, a recombination process of ZHC is observed. Moreover, the kinetics associated to these decomposition steps were determined and the evolution of the paramagnetic centers was also followed and studied. This study offers new information related to the thermal behavior of ZHC, especially regarding the EPR data which is reported for the first time on this subject and material.
15. Theoretical and Experimental Study of (Ba,Sr)TiO3 Perovskite Solid Solutions and BaTiO3/SrTiO3 Heterostructures
Authors: Rusevich, LL; Zvejnieks, G; Kotomin, EA; Krzmanc, MM; Meden, A; Kunej, S; Vlaicu, ID

Published: JAN 31 2019, JOURNAL OF PHYSICAL CHEMISTRY C, 123, 2036, DOI: 10.1021/acs.jpcc.8b09750

The results of experimental and theoretical ab initio study of structural and piezoelectric properties of (Ba,Sr)TiO3 perovskite solid solutions are discussed and compared. Experimentally, plate-like (Ba,Sr)TiO3 particles were synthesized by the topochemical conversion in the molten salt from Bi4Ti3O12 template plates. All dimensions (side length approximate to 1 mu m, thickness approximate to 200-400 nm) were well above the critical size necessary for observation of piezo- and ferroelectricity. The first-principles computations of the structural and electromechanical properties of solid solutions were performed with the CRYSTAL14 computer code within the linear combination of atomic orbitals approximation, using three advanced hybrid functionals of density functional theory. Different chemical compositions are considered for the ferroelectric and paraelectric phases. The calculated structural properties of solid solutions in tetragonal and cubic phases are in very good agreement with experimental data. Experimentally obtained and calculated band gaps are compared for cubic SrTiO3 and tetragonal BaTiO3. BaTiO3/SrTiO3 heterostructures were considered theoretically for different chemical compositions. The calculated piezoelectric properties of solid solutions and heterostructures in the ferroelectric phase are compared. It is predicted that both solid solutions and heterostructures improve the piezoelectric properties of bulk BaTiO3, but solid solutions are more preferable for equal Sr concentrations.
16. Evaluating the biological potential of some new cobalt (II) complexes with acrylate and benzimidazole derivatives
Authors: Vlaicu, ID; Olar, R; Maxim, C; Chifiriuc, MC; Bleotu, C; Stanica, N; Scaeteanu, GV; Dulea, C; Avram, S; Badea, M

Published: JUL 2019, APPLIED ORGANOMETALLIC CHEMISTRY, 33, DOI: 10.1002/aoc.4976

This paper presents the synthesis, physico-chemical and biological properties of four new coordination compounds with mixed ligands: acrylate ion (acr) and benzimidazole/benzimidazole derivatives with the general formula [Co(L)(2)(acr)(2)]center dot nH(2)O [(1) L: benzimidazole (HBzIm), n: 0.5; (2) L: 2-methylbenzimidazole (2-MeBzIm), n: 0.5; (3) L: 5-methylbenzimidazole (5-MeBzIm), n: 0; (4) L: 5,6-dimethylbenzimidazole (5,6-Me(2)BzIm), n: 0]. Their chemical formulae were achieved correlating the chemical analysis with mass spectrometry data, the ligands coordination modes were assigned by Fourier transform-infrared measurements, and the trigonal bipyramidal geometry of cobalt ion in complexes was assigned by data correlation of UV-Vis-NIR spectra and magnetic moments measurements. Single-crystal X-ray diffraction reveals a mononuclear structure with a pentacoordinated cobalt (II) ion, connected to two acrylato coordinated in different modes and two unidentate 5,6-dimethylbenzimidazole ligands for compound (4). The biological tests were performed against several microbial strains, the cytotoxicity was evaluated on HCT8 cellular lines and the cell cycle analysis was performed on HT29 cellular lines. Microbiological assays indicated that Co (II) complexes present a very good to good activity against Candida albicans 1760, Enterococcus faecium E5, Bacillus subtilis ATCC 6683 and Escherichia coli ATCC 25922. Predictive pharmacokinetic (ADME), toxicity and drug-likeness profiles were evaluated for Co (II) complexes. Our results highlight that Co (II) complexes depicted in the present study are suitable to be used as efficient pharmacological agents.
17. Tailoring the Dopant Distribution in ZnO:Mn Nanocrystals
Authors: Ghica, D; Vlaicu, ID; Stefan, M; Maraloiu, VA; Joita, AC; Ghica, C

Published: MAY 3 2019, SCIENTIFIC REPORTS, 9, DOI: 10.1038/s41598-019-43388-z

The synthesis of semiconductor nanocrystals with controlled doping is highly challenging, as often a significant part of the doping ions are found segregated at nanocrystals surface, even forming secondary phases, rather than incorporated in the core. We have investigated the dopant distribution dynamics under slight changes in the preparation procedure of nanocrystalline ZnO doped with manganese in low concentration by electron paramagnetic resonance spectroscopy, paying attention to the formation of transient secondary phases and their transformation into doped ZnO. The acidification of the starting solution in the co-precipitation synthesis from nitrate precursors lead to the decrease of the Mn2+ ions concentration in the core of the ZnO nanocrystals and their accumulation in minority phases, until similar to 79% of the Mn2+ ions were localized in a thin disordered shell of zinc hydroxynitrate (ZHN). A lower synthesis temperature resulted in polycrystalline Mn-doped ZHN. Under isochronal annealing up to 250 degrees C the bulk ZHN and the minority phases from the ZnO samples decomposed into ZnO. The Mn2+ ions distribution in the annealed nanocrystals was significantly altered, varying from a uniform volume distribution to a preferential localization in the outer layers of the nanocrystals. Our results provide a synthesis strategy for tailoring the dopant distribution in ZnO nanocrystals for applications ranging from surface based to ones involving core properties.
18. X-ray Crystal Structure, Geometric Isomerism, and Antimicrobial Activity of New Copper(II) Carboxylate Complexes with Imidazole Derivatives
Authors: Vlaicu, ID; Borodi, G; Scaeteanu, GV; Chifiriuc, MC; Marutescu, L; Popa, M; Stefan, M; Mercioniu, IF; Maurer, M; Daniliuc, CG; Olar, R; Badea, M

Published: DEC 2018, MOLECULES, 23, DOI: 10.3390/molecules23123253

Five new copper(II) acrylate complexes (acr is the acrylate anion: C3H3O2) with imidazole derivatives (2-methylimidazole/2-MeIm, 5-methylimidazole/5-MeIm, 2-ethylimidazole/2-EtIm) of type: cis-[Cu(2-RIm)(2)(acr)(2)]xH(2)O ((1): R = -CH3, x = 2; (4): R = -CH2-CH3, x = 0), trans-[Cu(2-RIm)(2)(acr)(2)] ((2): R = -CH3; (5): R = -CH2-CH3) and trans-[Cu(5-RIm)(2)(acr)(2)] ((3): R = -CH3) have been prepared and characterized by elemental analysis, Fourier Transform Infrared spectrometry (FTIR), Electron Paramagnetic Resonance (EPR), electronic reflectance spectroscopy, scanning electron microscopy, and mass spectrometry. The single crystal X-ray diffraction study of complexes (2) and (5) reveals that the copper(II) ion is located on an inversion center and show elongated octahedral geometry completed by two coplanar bidentate acrylates and two unidentate imidazole derivatives displayed in trans positions. For complex (4) the single crystal X-ray diffraction shows that the copper(II) ion is in a distorted octahedral environment which can be easily confused with a trigonal prism completed by two bidentate acrylates and two unidentate imidazole derivatives displayed in cis positions. These results indicate the fact that complexes (4) and (5) are the geometric isomers of the same compound bis(acrylate)-bis(2-ethylimidazole)-copper(II). Complexes (1) and (2), as well as (4) and (5), were produced simultaneously in the reaction of the corresponding copper(II) acrylate with imidazole derivatives in methanol solution. Furthermore, in order to be able to formulate potential applications of the obtained compounds, our next goal was to investigate the in vitro antimicrobial activity of the synthesized complexes against Gram-positive and Gram-negative bacteria, as well as fungal strains, of both clinical and ecological importance (biodeterioration of historical buildings). The trans isomers (2) and (5), followed by (4) have shown the broadest range of antimicrobial activity. In case of (1) and (2) isomers, the trans isomer (2) was significantly more active than cis (1), while the cis isomer (4) proved to be more active than trans (5). Taken together, the biological evaluation results indicate that the trans (2) was the most active complex, demonstrating its potential for the development of novel antimicrobial agents, with potential applications in the biomedical and restoration of architectural monuments fields.
19. Thermal, spectral and biological investigation of new nickel complexes with imidazole derivatives
Authors: Vlaicu, ID; Olar, R; Scaeteanu, GV; Silvestro, L; Maurer, M; Stanica, N; Badea, M

Published: OCT 2018, JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY, 134, 512, DOI: 10.1007/s10973-018-7133-y

Four new Ni(II) complexes with acrylate and imidazole (Him) or imidazole derivatives [2-methylimidazole(2-MeIm)/5-methylimidazole(5-MeIm)/2-ethylimidazole(2-EtIm)] as ligands were prepared and characterized. All coordination compounds were characterized by elemental analysis, infrared (FTIR) and ultraviolet-visible-near-infrared (UV-Vis-NIR) spectroscopy, mass spectroscopy, magnetic moments measurements and thermal analysis (TG). The resulted complexes were formulated as follows: [Ni(HIm)(2)(acr)(2)] (1), [Ni(2-MeIm)(2)(acr)(2)(H2O)] center dot H2O (2), [Ni(5-MeIm)(2)(acr)(2)]center dot H2O. (3), [Ni(2-EtIm)(2)(acr)(2)(H2O)] center dot H2O (4). On the basis of magnetic moments measurements and on UV-Vis-NIR spectra, for all Ni(II) complexes was proposed an octahedral stereochemistry. Acrylate ions act as bidentate in complexes (1) and (3); meanwhile, in (2) and (4) they behave as bidentate and unidentate. Antimicrobial activity of complexes was investigated on ATCC reference and clinical microbial strains. The MIC (minimum inhibitory concentration) values revealed moderate antimicrobial activity of complex (1) against Enterococcus faecium and of complex (2) against Pseudomonas aeruginosa and Bacillus subtilis.
20. Limits and Particularities of the Synthesis of Ba1-xCaxTiO3 for Piezoelectric Applications, by Topochemical Conversion from Molten Salt Solutions
Authors: Vlaicu, ID; Maraloiu, AV; Ghica, D; Mercioniu, IF; Stefan, M; Vlaicu, AM; Negrea, RF; Kuncser, AC; Bulat, S; Krzmanc, MM; Ciobanu, R; Plopa, O

Published: 2018, 2018 INTERNATIONAL CONFERENCE AND EXPOSITION ON ELECTRICAL AND POWER ENGINEERING (EPE), 1050, DOI:

Because of the unique properties of the ferroelectric perovskite particles with a well-defined anisotropic form like shape-and size dependent at low dimensions they have all the attention of the scientific world. Extensive morphostructural techniques will be used to characterize the piezoelectric material.
21. Origin and chemical composition of the amorphous material from the intergrain pores of self-assembled cubic ZnS:Mn nanocrystals
Authors: Stefan, M; Vlaicu, ID; Nistor, LC; Ghica, D; Nistor, SV

Published: DEC 31 2017, APPLIED SURFACE SCIENCE, 426, 350, DOI: 10.1016/j.apsusc.2017.07.172

We have shown in previous investigations that the low temperature collective magnetism observed in mesoporous cubic ZnS:Mn nanocrystalline powders prepared by colloidal synthesis, with nominal doping concentrations above 0.2 at.%, is due to the formation of Mn2+ clusters with distributed antifer romagnetic coupling localized in an amorphous phase found between the cubic ZnS:Mn nanocrystals. Here we investigate the composition, origin and thermal annealing behavior of this amorphous phase in such a mesoporous ZnS:Mn sample doped with 5 at.% Mn nominal concentration. Correlated analytical transmission electron microscopy, multifrequency electron paramagnetic resonance and Fourier transform infrared spectroscopy data show that the amorphous nanomaterial consists of unreacted precursor hydrated zinc and manganese acetates trapped inside the pores and on the surface of the cubic ZnS nanocrystals. The decomposition of the acetates under isochronal annealing up to 270 degrees C, where the mesoporous structure is still preserved, lead to changes in the nature and strength of the magnetic inter actions between the aggregated Mn2+ ions. These results strongly suggest the possibility to modulate the magnetic properties of such transition metal ions doped II-VI mesoporous structures by varying the synthesis conditions and/or by post-synthesis thermochemical treatments. (C) 2017 Elsevier B.V. All rights reserved.
22. Thermal behavior of new nickel(II) complexes with unsaturated carboxylates and heterocyclic N-donor ligands
Authors: Olar, R; Vlaicu, ID; Chifiriuc, MC; Bleotu, C; Stanica, N; Scaeteanu, GV; Silvestro, L; Dulea, C; Badea, M

Published: JAN 2017, JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY, 127, 741, DOI: 10.1007/s10973-016-5445-3

Synthesis and characterization of four new Ni(II) complexes with mixed ligands have been reported in the present paper. As interest ligands, acrylate (acr) ion together with one N-donor heterocyclic ligand, namely benzimidazole (HBzIm), 2-methylbenzimidazole (2-MeBzIm), 5-methylbenzimidazole (5-MeBzIm) or 5,6-dimethylbenzimidazole (5,6-Me(2)BzIm), was chosen. The syntheses afforded the complexes formulated as [Ni(HBzIm)(2)(acr)(2)(H2O)]center dot 3H(2)O (1), [Ni(2-MeBzIm)(2)(acr)(2)(H2O)]center dot 1.5H(2)O (2), [Ni(5-MeBzIm)(2)(acr)(2)(H2O)] (3) and [Ni(5,6-Me(2)BzIm)(2)(acr)(2)] (4). Complexes (1) and (2) contain crystallization water molecules and coordinated water molecules, both their nature and presence being confirmed on the basis of IR spectra and thermal analysis. In contrast to above-mentioned complexes, (3) contains only coordinated water molecule, while (4) is an anhydrous compound. Based on electronic spectra and magnetic measurements, a distorted octahedral stereochemistry was proposed for all Ni(II) complexes. Acrylate ions act both as unidentate and chelate ligands in complexes (1)-(3), while in complex (4) act only as chelate ligands. All used N-donor ligands function as monodentate in all Ni(II) complexes. Biological properties of complexes (1)-(4) were evaluated against several Gram(+), Gram(-) bacterial strains and against fungus Candida albicans.
23. Aggregates of Mn2+ Ions in Mesoporous Self-Assembled Cubic ZnS:Mn Quantum Dots: Composition, Localization, Structure, and Magnetic Properties
Authors: Nistor, SV; Stefan, M; Nistor, LC; Kuncser, V; Ghica, D; Vlaicu, ID

Published: JUL 7 2016, JOURNAL OF PHYSICAL CHEMISTRY C, 120, 14466, DOI: 10.1021/acs.jpcc.6b04866

The source of collective magnetism in II-VI semiconductor quantum dots (QDs) doped with Mn2+ ions at high nominal impurity levels is still under debate. In the particular case of mesoporous, self-assembled cubic ZnS:Mn QDs, quantitative electron paramagnetic resonance (EPR) studies have shown that the Mn2+ ions incorporated in the core and on the surface of the QDs cannot be responsible for the observed collective magnetism because they remain in a diluted paramagnetic state up to the 50 000 ppm nominal concentration. Here we investigate the composition, localization, structure, and magnetic properties of the aggregates of Mn2+ ions incorporated in the mesoporous cZnS:Mn as a possible source of the observed collective magnetism. Samples of mesoporous cubic ZnS:Mn prepared by coprecipitation at several nominal impurity levels from 200 to 50 000 ppm are investigated by EPR, magnetometry, and analytical high resolution (scanning) transmission electron microscopy. The low temperature magnetic properties of the Mn2+ aggregates change from paramagnetic-like, for samples with nominal impurity levels up to 2000 ppm, to ones specific to larger clusters with distributed antiferromagnetic coupling at higher concentrations, behaving superparamagnetically above a certain temperature. There is also strong evidence that the Mn2+ aggregates responsible for the observed low temperature collective magnetism are incorporated as an amorphous phase of mainly Mn-Zn-O composition, localized in the interstices and pores of the mesoporous structure of the cubic ZnS:Mn QDs.
24. Ferritin surplus in mouse spleen 14 months after intravenous injection of iron oxide nanoparticles at clinical dose
Authors: Tamion, A; Hillenkamp, M; Hillion, A; Maraloiu, VA; Vlaicu, ID; Stefan, M; Ghica, D; Rositi, H; Chauveau, F; Blanchin, MG; Wiart, M; Dupuis, V

Published: AUG 2016, NANO RESEARCH, 9, 2410, DOI: 10.1007/s12274-016-1126-6

In this study, we followed the biodegradation of ultra-small superparamagnetic iron oxide nanoparticles injected intravenously at clinical doses in mice. An advanced fitting procedure for magnetic susceptibility curves and low-temperature hysteresis loops was used to fully characterize the magnetic size distribution as well as the magnetic anisotropy energy of the injected P904 nanoparticles (Guerbet Laboratory). Additional magnetometry measurements and transmission electronic microscopy observations were systematically performed to examine dehydrated samples from the spleen and liver of healthy C57B16 mice after nanoparticle injection, with sacrifice of the mice for up to 14 months. At 3 months after injection, the magnetic properties of the spleen and liver were dramatically different. While the liver showed no magnetic signals other than those also present in the reference species, the spleen showed an increased magnetic signal attributed to ferritin. This surplus of ferritin remained constant up to 14 months after injection.
25. On the agent role of Mn2+ in redirecting the synthesis of Zn(OH)(2) towards nano-ZnO with variable morphology
Authors: Ghica, D; Vlaicu, ID; Stefan, M; Nistor, LC; Nistor, SV

Published: 2016, RSC ADVANCES, 6, 106741, DOI: 10.1039/c6ra23065b

One of the simplest routes to prepare polycrystalline Zn(OH)(2) is by coprecipitation, with zinc nitrate as a cation source. However, the addition of even minute amounts of manganese nitrate to the precursors used to prepare pure Zn(OH)(2) results in Mn2+ doped nanostructured ZnO. The comparison with other Mn2+ doped metal hydroxides prepared by the same coprecipitation method, involving metal nitrates precursors, shows that this behavior is unique, pertaining only to Zn(OH)(2). A systematic study of the samples prepared without and with variable amounts of Mn2+ ions, in the 1 to 5000 ppm nominal concentrations range showed that the re-routing of the reaction takes place even for the lowest nominal dopant concentration of 1 ppm. According to X-ray diffraction, transmission electron microscopy and Fourier transform infrared spectroscopy investigations, both crystallite size and morphology of the resulting nanostructured ZnO samples varied with the Mn2+ nominal concentration. Moreover, quantitative electron paramagnetic resonance investigations showed that the incorporation rate of the Mn2+ ions at different sites in the nanostructured ZnO depended on the nominal Mn2+ concentration. The results are discussed in terms of the coordination properties of the Mn2+ and Zn2+ ions and the nature of the reaction precursors.
26. Distribution and interaction of Mn2+ ions incorporated in cubic ZnS quantum dots over a broad concentration range
Authors: Nistor, SV; Stefan, M; Nistor, LC; Ghica, D; Vlaicu, ID

Published: MAR 25 2016, JOURNAL OF ALLOYS AND COMPOUNDS, 662, 199, DOI: 10.1016/j.jallcom.2015.11.203

The distribution and interaction of isolated Mn2+ impurity ions incorporated in 2.9 nm average diameter cubic ZnS quantum dots (QDs), prepared by surfactant-assisted liquid-liquid synthesis with initial impurity concentrations in the 20-50,000 ppm range, has been investigated by electron paramagnetic resonance (EPR) spectroscopy. The well resolved spectra, observed in the whole investigated concentration range, reflect the localization of the Mn2+ ions in the core and on the surface of the cZnS: Mn QDs at isolated sites. According to the analysis of the dependences of the concentration of incorporated isolated Mn2+ ions vs. initial impurity concentration and of the core localized Mn2+ ions spectra line-width vs. actual concentration, the isolated Mn2+ ions remain in the whole concentrations range in a diluted paramagnetic state characterized by dipolar magnetic interactions. Pulse EPR measurements of the spinespin dipolar interaction for the incorporated Mn2+ ions confirm their diluted distribution, which excludes these ions as a possible source of collective magnetism properties. (C) 2015 Elsevier B.V. All rights reserved.
27. Doping Ultrasmall Cubic ZnS Nanocrystals with Mn2+ Ions over a Broad Nominal Concentration Range
Authors: Nistor, SV; Stefan, M; Nistor, LC; Ghica, D; Vlaicu, ID; Joita, AC

Published: OCT 15 2015, JOURNAL OF PHYSICAL CHEMISTRY C, 119, 23789, DOI: 10.1021/acs.jpcc.5b08113

Although impurity doping of nanocrystals is essential in controlling their physical properties for various applications, the doping mechanism of ultrasmall, colloidal II-VI semiconductor nanocrystals, corresponding to the initial stages of growth, is not yet understood. In this study the concentrations of Mn2+ ions in the core, on the surface, and as an agglomerated separate phase in 2.9 nm cubic ZnS nanocrystals, prepared by a surfactant-assisted liquid liquid synthesis within 20 to 20 000 ppm nominal impurity concentration range, have been determined by quantitative multifrequency electron paramagnetic resonance. The unexpected strong decrease in the core doping efficiency with the nominal concentration increase, in contrast to the small variation of the doping efficiency for the surface-bound Mn2+ ions, and the sizable core doping efficiency observed for 1.8 nm nanocrystals were explained with the extended lattice defect assisted mechanism of incorporation. According to this mechanism, which is not size or shape limited, being active from the initial growth stages, the incorporation of Mn2+ ions takes place at surface sites with high binding energy on dislocation steps formed by the emerging stacking defects. High resolution transmission electron microscopy confirms the presence of such stacking defects in a large proportion of the investigated cubic ZnS nanocrystals, ensuring the operation of the proposed doping mechanism.
28. Thermal behaviour and characterisation of new biologically active Cu(II) complexes with benzimidazole as main ligand
Authors: Badea, M; Vlaicu, ID; Olar, R; Constand, M; Bleotu, C; Chifiriuc, MC; Marutescu, L; Lazar, V; Grecu, MN; Marinescu, D

Published: NOV 2014, JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY, 118, 1133, DOI: 10.1007/s10973-014-3745-z

Four coordination compounds of copper(II) were synthesised and characterised in solid state by elemental analysis, infrared, electronic and EPR spectroscopy, as well as by thermal analysis (TG/DTA). The complexes were formulated on the basis of experimental data as: [Cu(BzIm)(2)(H2O)]center dot H2O (1), [Cu-2(Acr)(4)(HBzIm)(2)] (2), [Cu(Acr)(2)(HBzIm)(2)] (3) and [Cu(Acr)(2)(HBzIm)(2)(H2O)]center dot H2O (4). IR data are in accordance with the unidentate nature of benzimidazole, in complexes (2), (3) and (4), and bridge bidentate nature of benzimidazole, in complex (1), while acrylato acts as uni- or bridge/chelate ligand. The electronic spectra display the characteristic pattern of square planar, square pyramidal, or octahedral stereochemistry, also confirmed by EPR spectra. Thermal decomposition evidenced several well-defined steps as dehydration of complexes (1) and (4), benzimidazole molecule releases for all complexes and acrylate decomposition in carbonate for complexes (3) and (4). In all four cases, the final residue after thermal treatment in air flow is copper(II) oxide, formed during the decomposition steps for complexes (3) and (4), and, respectively, after the oxidation of the metallic copper for complexes (1) and (2). Antimicrobial activities of the complexes have been determined by in vitro assays, against various Gram-negative and Gram-positive bacterial and fungal strains. Copper(II) complexes were also evaluated for their cytotoxicity on eukaryotic cells.
29. Synthesis, physico-chemical characterization and thermal behavior of new complexes with N4O2 donor set
Authors: Olar, R; Scaeteanu, G; Vlaicu, ID; Marutescu, L; Badea, M

Published: NOV 2014, JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY, 118, 1202, DOI: 10.1007/s10973-014-3809-0

Three new coordinative compounds of the type [Co(en)(2)CO3]center dot 0.75H(2)O (1) and [M(en)(2)(H2O)(2)]CO3 ((2) M:Ni, (3) M:Cu; en: ethylenediamine) were synthesized and characterized. The IR and UV-Vis spectral data indicate that ethylenediamine acts as chelate, while carbonate ions act as bidentate chelate ligand for (1)/counter ion for (2) and (3) generating complexes with octahedral stereochemistry. The thermal behavior provided confirmation of the complexes composition, as well as the number and the nature of water molecules and the intervals of thermal stability. The biological assays revealed a good activity against Enterococcus faecium for copper complex.
30. Thermal stability of new biologic active copper(II) complexes with 5,6-dimethylbenzimidazole
Authors: Vlaicu, ID; Constand, M; Olar, R; Marinescu, D; Grecu, MN; Lazar, V; Chifiriuc, MC; Badea, M

Published: SEP 2013, JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY, 113, 1377, DOI: 10.1007/s10973-013-2948-z

Three new coordinative compounds that contain mixed ligands (5,6-dimethylbenzimidazole and acrylato anion) were synthesized and characterized. The features of complexes have been assigned from microanalytical, IR, UV-Vis and EPR spectra as well as thermal analysis. IR data are in accordance with unidentate nature of 5,6-dimethylbenzimidazole while the acrilato ion acts as uni- or bidentate ligand. The electronic spectra display the characteristic pattern of square pyramidal or octahedral stereochemistry, which were confirmed by the EPR spectra. Antibacterial and antifungal activities of the complexes have been determined in vitro, against various Gram-negative and Gram-positive bacteria and fungi. The tested complexes exhibited different spectra of antimicrobial activity and inhibited the microbial ability to colonize the inert surfaces, acting as potential anti-adherence and biofilm-controlling agents. Thermal decomposition evidenced several well-defined steps as dehydration (complex 2), 5,6-dimethylbenzimidazole molecule release (all complexes) and the acrylate decomposition in carbonate (complex 3). The final residue is in all cases copper (II) oxide.
31. Antiproliferative and antibacterial properties of biocompatible copper(II) complexes bearing chelating N,N-heterocycle ligands and potential mechanisms of action
Authors: Olar, R; Badea, M; Bacalum, M; Raileanu, M; Ruta, LL; Farcasanu, IC; Rostas, AM; Vlaicu, ID; Popa, M; Chifiriuc, MC

Published: , BIOMETALS, DOI: 10.1007/s10534-021-00334-9

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