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Dr. Teddy TITE

Scientific Researcher II

Dr. Teddy TITE, Scientific researcher rank II (since 2019), born in 1976, has a Master’s degree in Physics at University of Louis Pasteur Strasbourg – France (1999), a MSc degree in Physics (University of Lorraine, France) (2000), and a PhD degree in Materials science (University of Lorraine, France) (2004). Work experience: National Institute of Materials Physics (NIMP) (2018 – to date); University Politehnica of Bucharest – Romania; University Jean Monnet - Saint-Etienne, France; Research Center for Applied Sciences, Academia sinica Taïwan; National Taiwan University; National Chiayi University Taïwan; work stages at University of Warsaw – Poland; Main areas of interest/expertise: physical vapor deposition processes; characterization of materials (e.g. optical spectroscopy, atomic force microscopy, electrochemistry). Publications (last updated November 2022):  53 articles published in Web of Science® (WoS) journals with impact factor (e.g., Appl. Surf. Sci.; Biosensors and Bioelectronics; Journal of Nanobiotechnology; ACS Appl. Mater. Interfaces); Hirsch index (WoS): 15; Citations (without self-citations): 776. Awards: „Best Poster” Award at EMRS Fall Meeting Symposium B (2021) (project PED PN-III-P2-2.1-PED-2019-4519). Coordinated project: 1 national project (PN-III-P2-2.1-PED-2019-4519, 23/10/2020-22/10/2022) as principal coordinator. Professional profile web-links: Brainmap: https://www.brainmap.ro/teddy-tite; ORCID ID: 0000-0002-2839-9012; WoS ResearcherID: L-1612-2016.

1

DNA-RNA Nucleobase-Coated ZnO Nanostructures for Interface Engineering in Organic Optoelectronics

Breazu, C; Stanculescu, A; Socol, M; Rasoga, O; Preda, N; Costas, A; Stan, GE; Popescu, DG; Petre, G; Iftimie, S; Tite, T

AUG 22 2025, ACS APPLIED NANO MATERIALS, 8

DOI: 10.1021/acsanm.5c02516

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Due to the importance of buffer layers in interface engineering, the development of more variants and the rational design of materials have a significant influence on the performance of optoelectronic devices. This study provides a strategy to increase device performance by facilitating efficient charge transfer and defect passivation by combining the properties of eco-friendly materials (adenine, cytosine, guanine, thymine, and uracil) with the physicochemical properties of metal oxides. The aim of this paper was to investigate the interaction of zinc oxide (ZnO) nanostructures (seed, nanoparticles, and nanowires) with nucleobase layers and to discuss their potential applications as organic-inorganic interfacial bilayers. The impact is analyzed from structural, morphological, optical, and electrical points of view. Nucleobase-ZnO nanostructure layers present high optical transparency in the visible range. Electrical measurements confirmed that the high surface area of nanowires can enhance interactions with nucleobases, leading to better charge transfer. The results showed that these nucleobase-ZnO nanostructure layers are promising interface materials for enhancing optoelectronic device performance through interfacial charge transport and light management, while enabling the design of environmentally friendly devices.

2

Mixed network former effect on the ion-dynamics of Sodium Alumino-Phospho-Silicate glasses

Keshri, SR; Mandal, I; Gaddam, A; Ganisetti, S; Haque, S; Venkateswaran, C; Stan, GE; Tite, T; Ghosh, A; Gosvami, NN; Krishnan, NMA; Allu, AR

APR 15 2025, ACTA MATERIALIA, 288, 120837

DOI: 10.1016/j.actamat.2025.120837

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Developing new glass electrolytes with the necessary room-temperature ionic conductivity (similar to 10(-3) Scm(-1)) for solid-state batteries, especially sodium-ion (Na+) batteries, has been impeded by the lack of a clear relationship between composition, structure, and conductivity in glass materials. This study highlights the impact of the mixed glass formers on the structure, Na+-ion dynamics, and glass conductivity. To this end, we substituted SiO2 for P2O5 in sodium alumino-phosphate glass while maintaining a constant molar concentration of Al2O3 and Na2O. A detailed analysis combining molecular simulations and experiments revealed that the glass containing 15 mol% SiO2 exhibited the highest DC ionic conductivity of similar to 9 x 10(-6) Scm(-1) at 473 K, followed by a decrease for 20 mol% SiO2. To understand this behavior, microscopic characteristic length such as critical hopping distance and Na+ diffusion coefficients were correlated with structural changes using AC conductivity analysis. Altogether, we elucidate the composition-dependent Na+ ion dynamics in the alumino-phosphate glass system, with factors like mobile charge carrier concentration, ion mobility, and coulombic forces influenced by the structure of different glass compositions.

3

Bioengineered Y2O3 nanorods and their potential blue-emitting phosphors

Diallo, A; Ndiaye, S; Tite, T; Yahsi, U; Diculescu, VC; Seck, A; Dioum, A; Ngom, BD; Ahmad, I; Galca, AC; Azizi, S

MAR 22 2025, BULLETIN OF MATERIALS SCIENCE, 48, 50

DOI: 10.1007/s12034-025-03406-5

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This article describes a new synthesis of nanoscaled Y2O3 that is bioinspired. It has been confirmed that Callistemon viminalis flower extract works well as a chelator when used to bioengineer high-shape anisotropy nanorods of single-phase Y2O3 . X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, fourier transform infrared spectroscopy and photoluminescence spectroscopy were used to analyse the structural, morphological, surface and optical features. The photoluminescent spectra of the bio-engineered nanorods show blue emissions. As the annealing temperature was increased from 300 to 500 degrees C, the blue colour purity values of the synthesized Y2O3 nanorods were 58.1, 80.7 and 77.0% at 300, 400 and 500 degrees C respectively. The chromaticity coordinates (0.2020, 0.1931), (0.1660, 0.1082) and (0.1714, 0.1226) from the photoluminescence spectra of the biosynthesized Y2O3 nanorods were used to determine these values. The CIE y-component coordinate values of the bioengineered blue-emitting nanophosphors suggest their potential for applications in display technology and white light-emitting diodes.

4

Large-scale synthesis of monolayer WS2 by low-temperature sulfurization of oxidized magnetron sputtered monolayer W precursors in a microreactor

Velea, A; Simandan, ID; Mihai, C; Baibarac, M; Vaduva, M; Udrescu, A; Smaranda, I; Bocirnea, AE; Tite, T; Zaki, MY; Kuncser, A; Sava, F

JUN 30 2025, NANOTECHNOLOGY, 36, 265601

DOI: 10.1088/1361-6528/ade25f

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We report large-scale synthesis of monolayer WS2 films obtained by sulfurization of oxidized magnetron sputtered monolayer W precursors. Literature routes typically require similar to 800 degrees C, well above the 400 degrees C limit imposed by back-end-of-line (BEOL) integration. Here, using an enhanced chemical vapor deposition (CVD) approach, the magnetron sputtered ultrathin W precursor (a W monolayer film, 0.27 nm thick, which in ambient air becomes a WOx monolayer) is sulfurized at the lowest possible temperature (450 degrees C) within a microreactor, which consists of a sandwich-like structure formed by the precursor and a clean Si substrate. The obtained WS2 material has a good crystallinity and uniform morphology across the entire growth substrate, as confirmed by detailed characterization. These results highlight the versatility of the method combining magnetron sputtering and microreactor-CVD, facilitating its applications to wafer-scale synthesis of monolayer WS2, heterogeneously integrated into electronic circuits (a major objective for next-generation electronics and optoelectronics). Additionally, we investigate in detail the properties of WS2 films synthesized from a bilayer W precursor (0.43 nm thick), under the same conditions, and we calculated the frequencies of the second-order Raman scattering modes. For electrical measurements, we fabricated WS2/few-layer-graphene heterostructures, whose atomically clean interface yields reliable, low-resistance contacts. These devices exhibit resistive switching behavior, likely governed by vacancy migration, making it a promising candidate for memristive applications. Our results demonstrate that electronics-grade monolayer WS2 can be synthesized at 450 degrees C, approaching the BEOL requirement of 400 degrees C.

5

Fabrication of High-Quality MoS2/Graphene Lateral Heterostructure Memristors

Mihai, C; Simandan, ID; Sava, F; Tite, T; Bocirnea, A; Vaduva, M; Zaki, MY; Baibarac, M; Velea, A

AUG 13 2025, NANOMATERIALS, 15, 1239

DOI: 10.3390/nano15161239

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Integrating two-dimensional transition-metal dichalcogenides with graphene is attractive for low-power memory and neuromorphic hardware, yet sequential wet transfer leaves polymer residues and high contact resistance. We demonstrate a complementary metal-oxide-semiconductor (CMOS)-compatible, transfer-free route in which an atomically thin amorphous MoS2 precursor is RF-sputtered directly onto chemical vapor-deposited few-layer graphene and crystallized by confined-space sulfurization at 800 degrees C. Grazing-incidence X-ray reflectivity, Raman spectroscopy, and X-ray photoelectron spectroscopy confirm the formation of residue-free, three-to-four-layer 2H-MoS2 (roughness: 0.8-0.9 nm) over 1.5 cm x 2 cm coupons. Lateral MoS2/graphene devices exhibit reproducible non-volatile resistive switching with a set transition (SET) near +6 V and an analogue ON/OFF approximate to 2.1, attributable to vacancy-induced Schottky-barrier modulation. The single-furnace magnetron sputtering + sulfurization sequence avoids toxic H2S, polymer transfer steps, and high-resistance contacts, offering a cost-effective pathway toward wafer-scale 2D memristors compatible with back-end CMOS temperatures.

6

GRAPHENE FOR ELECTRONIC DEVICES - SYNTHESIS AND CHARACTERIZATION

Apostol, M; Enache, A; Diculescu, V; Tite, T; Onea, M; Enculescu, I; Matei, E; Andronescu, E

2024, UNIVERSITY POLITEHNICA OF BUCHAREST SCIENTIFIC BULLETIN SERIES B-CHEMISTRY AND MATERIALS SCIENCE, 86

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In this paper, graphene was obtained on a copper substrate using the CVD method, and then it was transferred to various substrates such as glass and SiO2/Si patterned with metallic interdigitated electrodes. The graphene thus obtained was characterized using Raman spectroscopy, scanning electron microscopy (SEM), current-voltage measurements, and electrochemical methods, in order to be used for sensing applications.

7 Open Access

Synthesis of WS2 Ultrathin Films by Magnetron Sputtering Followed by Sulfurization in a Confined Space

Sava, F; Simandan, ID; Buruiana, AT; Bocirnea, AE; El Khouja, O; Tite, T; Zaki, MY; Mihai, C; Velea, A

MAR 2024, SURFACES, 7

DOI: 10.3390/surfaces7010008

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In the quest for advanced materials suitable for next-generation electronic and optoelectronic applications, tungsten disulfide (WS2) ultrathin films have emerged as promising candidates due to their unique properties. However, obtaining WS2 directly on the desired substrate, eliminating the need for transfer, which produces additional defects, poses many challenges. This paper aims to explore the synthesis of WS2 ultrathin films via physical vapor deposition (PVD) followed by sulfurization in a confined space, addressing the challenge of film formation for practical applications. Precursor layers of tungsten and WS2 were deposited by RF magnetron sputtering. Subsequent sulfurization treatments were conducted in a small, closed, graphite box to produce WS2 films. The physical and chemical properties of these precursor and sulfurized layers were thoroughly characterized using techniques such as X-ray reflectometry (XRR), X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The findings reveal notable distinctions in film thickness, structural orientation, and chemical composition, attributable to the different precursor used. Particularly, the sulfurized layers from the tungsten precursor exhibited a preferred orientation of WS2 crystallites with their (00L) planes parallel to the substrate surface, along with a deviation from parallelism in a small angular range. This study highlights the necessity of precise control over deposition and sulfurization parameters to tailor the properties of WS2 films for specific technological applications.

8 Open Access

Abundant Catalytic Edge Sites in Few-Layer Horizontally Aligned MoS2 Nanosheets Grown by Space-Confined Chemical Vapor Deposition

Velea, A; Buruiana, AT; Mihai, C; Matei, E; Tite, T; Sava, F

JUN 2024, CRYSTALS, 14, 551

DOI: 10.3390/cryst14060551

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Recently, a smart strategy for two-dimensional (2D) materials synthesis has emerged, namely space-confined chemical vapor deposition (CVD). Its extreme case is the microreactor method, in which the growth substrate is face-to-face stacked on the source substrate. In order to grow 2D transition metal dichalcogenides by this method, transition metal oxides, dispersed in very small amounts on the source substrate, are used as source materials in most of the published reports. In this paper, a colloidal dispersion of MoS2 in saline solution is used and MoS2 nanosheets with various shapes, sizes (between 5 and 60 mu m) and thicknesses (2-4 layers) have been synthesized. Small MoS2 flakes (regular or defective) are present on the surface of the nanosheets. Catalytic sites, undercoordinated atoms located at the edges of MoS2 flakes and nanosheets, are produced in a high number by a layer-plus-island (Stranski-Krastanov) growth mechanism. Several double-resonance Raman bands (at 147, 177, 187, 225, 247, 375 cm(-1)) are assignable to single phonon processes in which the excited electron is elastically scattered on a defect. The narrow 247 cm(-1) peak is identified as a topological defect-activated peak. These findings highlight the potential of defect engineering in material property optimization, particularly for solar water splitting applications.

9 Open Access

Two-step process for the fabrication of direct FLG\MoS2 heterostructures

Buruiana, AT; Bocirnea, AE; Sava, F; Matei, E; Tite, T; Mariana, A; Simandan, ID; Galca, AC; Velea, A

AUG 1 2024, MATERIALS CHEMISTRY AND PHYSICS, 322, 129530

DOI: 10.1016/j.matchemphys.2024.129530

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MoS2 has proven its efficacy in flexible electronics, transistor devices, and various biological and chemical applications. However, it is still challenging to achieve large-area MoS2 monolayers with desired material quality and electrical properties to fulfill the requirement for practical applications. Moreover, the main strategy for the preparation of a 2D heterostructure it is based on the sequential stacking of the layered materials using wet or dry transfer methods which introduces many defects. This paper presents an economically viable and straightforward two-step methodology to obtain MoS2 thin films, encompassing magnetron sputtering deposition of Mo and subsequent annealing in a sulfur-rich environment. This approach successfully yielded MoS2 thin films on Si\SiO2 substrates. Additionally, heterostructures consisting of few layer graphene (FLG) and MoS2 were directly obtained using the same method. The utilization of grazing incidence X-ray diffraction verified the formation of the hexagonal MoS2 phase, a finding further confirmed by Raman spectroscopy. X-ray photoelectron spectroscopy (XPS) investigations revealed the successful sulfurization process, with surface-bound oxides forming only subsequent to air exposure. Comprehensive assessment involving X-ray reflectivity, atomic force microscopy and XPS collectively inferred the fabrication of thin films comprised of a small number of MoS2 layers covering the entire substrate. Electrical assessments exhibited an electrical hysteresis, demonstrating its potential for memristor applications. Overall, this study outlines a cost-effective fabrication method for producing nanoscale MoS2 thin films with excellent properties, avoiding the use of toxic gases such as H2S. These findings contribute to the potential development of cutting-edge applications.

10 Open Access

Synthesis of Wrinkled MoS2 Thin Films Using a Two-Step Method Consisting of Magnetron Sputtering and Sulfurization in a Confined Space

Mihai, C; Simandan, ID; Sava, F; Buruiana, AT; Bocirnea, AE; Tite, T; Zaki, MY; Velea, A

MAY 2024, SUSTAINABILITY, 16, 3819

DOI: 10.3390/su16093819

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Considering the increasing need for sustainable and economical energy storage solutions, the integration of layered materials such as MoS2 into these systems represents an important step toward enhancing energy sustainability and efficiency. Exploring environmentally responsible fabrication techniques, this study assesses wrinkled MoS2 thin films synthesized from distinct Mo and MoS2 targets, followed by sulfurization conducted in a graphite box. We utilized magnetron sputtering to deposit precursor Mo and MoS2 films on Si substrates, achieving thicknesses below 20 nm. This novel approach decreases sulfur by up to tenfold during sulfurization due to the confined space technique, contributing also to avoiding the formation of toxic gases such as SO2 or the necessity of using H2S, aligning with sustainable materials development. Thinner MoS2 layers were obtained post-sulfurization from the MoS2 precursors, as shown by X-ray reflectometry. Raman spectroscopy and grazing X-ray diffraction analyses confirmed the amorphous nature of the as-deposited films. Post-sulfurization, both types of films exhibited crystalline hexagonal MoS2 phases, with the sulfurized Mo showing a polycrystalline nature with a (100) orientation and sulfurized MoS2 displaying a (00L) preferred orientation. The X-ray photoelectron spectroscopy results supported a Mo:S ratio of 1:2 on the surface of the films obtained using the MoS2 precursor films, confirming the stoichiometry obtained by means of energy dispersive X-ray spectroscopy. Scanning electron microscopy and atomic force microscopy images revealed micrometer-sized clusters potentially formed during rapid cooling post-sulfurization, with an increased average roughness. These results open the way for the further exploration of wrinkled MoS2 thin films in advanced energy storage technologies.

11 Open Access

Pulsed laser deposited V2O3 thin-films on graphene/aluminum foil for micro-battery applications

Tite, T; Ungureanu, C; Buga, M; Stavarache, I; Matei, E; Negrila, CC; Trupina, L; Spinu-Zaulet, A; Galca, AC

MAR 15 2023, JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 933, 117290

DOI: 10.1016/j.jelechem.2023.117290

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The development of new thin-film cathodes triggered a recent research interest in energy storage applications. Over the past years, vanadium oxides have been extensively explored as promising electrodes for batteries owing to their rich valence states and remarkable electrochemical properties. Herein, we report on the synthe-sis of undoped and Sn doped V2O3 thin-films on graphene (G)/Al foil by pulsed laser deposition followed by rapid thermal annealing in N2 at low temperature (similar to 430 degrees C). The obtaining V2O3 phase on graphene/Al foil (G/Al) has been confirmed by X-ray diffraction and Raman and X-ray photoelectron spectroscopy analyses. The synthesized vanadium oxide films were tested as cathodes in coin cells. The electrochemical properties have been systematically investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge discharge (GCD) measurements. A superior electrochemical performance was observed for the V2O3 on G/Al structures, with an initial capacity of around 300 mAh g-1, with respect to the bare G/Al electrode. The use of the Sn-doped (5 mol%) V2O3 thin-films improved slightly the initial capac-ity up to a value of ca. 311 mAh g-1. Both V2O3/G/Al and Sn-doped V2O3/G/Al exhibited excellent cycling performances after 40 cycles with a capacity maintenance at a C-rate C/20 of 317 mAh g-1. Long-term cycling test (up to 200 cycles) showed that the Sn doping could be an excellent strategy to improve the stability of the electrodes, which yielded a capacity loss of only 0.128% per cycle. Possible mechanisms are presented and dis-cussed. This work could serve as point of reference for future developments in the field of batteries employing vanadium oxide-based thin-films deposited by physical vapor deposition techniques.

12 Open Access

TiO2 Phase Ratio's Contribution to the Photocatalytic Activity

Stepanova, A; Tite, T; Ivanenko, I; Enculescu, M; Radu, C; Culita, DC; Rostas, AM; Galca, AC

OCT 25 2023, ACS OMEGA, 8

DOI: 10.1021/acsomega.3c05890

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Photocatalysis is one of the approaches for solving environmental issues derived from extremely harmful pollution caused by industrial dyes, medicine, and heavy metals. Titanium dioxide is among the most promising photocatalytic semiconductors; thus, in this work, TiO2 powders were prepared by a hydrothermal synthesis using titanium tetrachloride TiCl4 as a Ti source. The effect of the hydrochloric acid (HCl) concentration on TiO2 formation was analyzed, in which a thorough morpho-structural analysis was performed employing different analysis methods like XRD, Raman spectroscopy, SEM/TEM, and N-2 physisorption. EPR spectroscopy was employed to characterize the paramagnetic defect centers and the photogeneration of reactive oxygen species. Photocatalytic properties were tested by photocatalytic degradation of the rhodamine B (RhB) dye under UV light irradiation and using a solar simulator. The pH value directly influenced the formation of the TiO2 phases; for less acidic conditions, the anatase phase of TiO2 crystallized, with a crystallite size of approximate to 9 nm. Promising results were observed for TiO2, which contained 76% rutile, showing a 96% degradation of RhB under the solar simulator and 91% under UV light after 90 min irradiation, and the best result showed that the sample with 67% of the anatase phase after 60 min irradiation under the solar simulator had a 99% degradation efficiency.

13

Development of ceramic coatings on titanium alloy substrate by laser cladding with pre-placed natural derived-slurry: Influence of hydroxyapatite ratio and beam power

Mocanu, AC; Miculescu, F; Stan, GE; Tite, T; Miculescu, M; Tierean, MH; Pascu, A; Ciocoiu, RC; Butte, TM; Ciocan, LT

APR 1 2023, CERAMICS INTERNATIONAL, 49

DOI: 10.1016/j.ceramint.2022.11.227

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The attraction towards Ti and its alloys reside in their superior mechanical and tribological features, as compared to CaPs, which are renowned for their compositional and structural features similar to those of natural bones. However, Ti-based materials suffer from limited biocompatibility and inertness when implanted for extended periods. As such, surface modification with ceramic coatings is required in order to achieve proper biomedical features and enhance their overall behavior in the human body. Hence, this study outlined for the first time the prospect of coating several Ti6Al4V substrates (disks) with bovine-bone derived hydroxyapatite (HA) by laser cladding technique with pre-placed slurry. During laser processing the input materials merge depending on the heating rate/temperature and clad materials. The proposed sample preparation set-up, followed for the first time in this study, involved the concomitant modulation of two parameters: the natural HA ratio (100 wt%, and 50 wt % HA + 50 wt% Ti blends) and laser beam power (500-1000 W range). The laser beam was applied after the ceramic slurries (prepared HA/HA-based blends mixed with polyvinyl alcohol) were placed inside the priorly machined channels on the metallic Ti disks. Partially overlapped cladding tracks (similar to 30% overlapping ratio) resulted and the investigations were further performed in cross-section view. The structural analyses confirmed the formation of calcium titanate as main phase for all samples and the arrest of HA only for those prepared with 100% HA ratio at low to medium laser powers. In addition, the morpho-compositional evaluation revealed the formation of a fully ceramic coating only for the latter sample sets. Further, the surface wettability (contact angle and surface free energy) and Vickers micro-hardness results led to the selection of the optimal technological parameters for the development of ceramic cladded layers with prospect compatibility with regenerative med-icine applications.

14 Open Access

Independent and complementary bio-functional effects of CuO and Ga2O3 incorporated as therapeutic agents in silica- and phosphate- based bioactive glasses

Tite, T; Popa, AC; Stuart, BW; Fernandes, HR; Chirica, IM; Lungu, GA; Macovei, D; Bartha, C; Albulescu, L; Tanase, C; Nita, S; Rusu, N; Grant, DM; Ferreira, JMF; Stan, GE

JUL 2022, JOURNAL OF MATERIOMICS, 8

DOI: 10.1016/j.jmat.2021.12.009

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The incorporation of therapeutic-capable ions into bioactive glasses (BGs), either based on silica (SBGs) or phosphate (PBGs), is currently envisaged as a proficient path for facilitating bone regeneration. In conjunction with this view, the single and complementary structural and bio-functional roles of CuO and Ga2O3 (in the 2-5 mol% range) were assessed, by deriving a series of SBG and PBG formulations starting from the parent glass systems, FastOs (R) BG -38.5SiO2-36.1CaO-5.6P2O5-19.2MgO-0.6CaF2, and 50.0P2O5-35.0CaO-10.0Na2O-5.0 Fe2O3 (mol%), respectively, using the process of melt-quenching. The inter-linked physico-chemistry -biological response of BGs was assessed in search of bio-functional triggers. Further light was shed on the structural role -as network former or modifier -of Cu and Ga, immersed in SBG and PBG matrices. The preliminary biological performance was surveyed in vitro by quantification of Cu and Ga ion release under homeostatic conditions, cytocompatibility assays (in fibroblast cell cultures) and antibacterial tests (against Staphylococcus aureus). The similar (Cu) and dissimilar (Ga) structural roles in the SBG and PBG vitreous networks governed their release. Namely, Cu ions were leached in similar concentrations (ranging from 10-35 ppm and 50-110 ppm at BG doses of 5 and 50 mg/mL, respectively) for both type of BGs, while the release of Ga ions was 1-2 orders of magnitude lower in the case of SBGs (i.e., 0.2-6 ppm) compared to PBGs (i.e., 9-135 ppm). This was attributed to the network modifier role of Cu in both types of BGs, and conversely, to the network former (SBGs) and network modifier (PBGs) roles of Ga. All glasses were cytocompatible at a dose of 5 mg/mL, while at the same concentration the antimicrobial efficiency was found to be accentuated by the coupled release of Cu and Ga ions from SBG. By collective assessment, the most prominent candidate material for the further development of implant coatings and bone graft substitutes was delineated as the 38.5SiO2-34.1CaO-5.6P2O5-16.2MgO-0.6CaF2-2.0CuO-3.0Ga2O3 (mol%) SBG system, which yiel-ded moderate Cu and Ga ion release, excellent cytocompatibility and marked antibacterial efficacy. (c) 2021 The Chinese Ceramic Society. Production and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

15

Layered SnSe nanoflakes with anharmonic phonon properties and memristive characteristics

Buruiana, AT; Bocirnea, AE; Kuncser, AC; Tite, T; Matei, E; Mihai, C; Zawadzka, N; Olkowska-Pucko, K; Kipczak, L; Babinski, A; Molas, MR; Velea, A; Galca, AC

OCT 15 2022, APPLIED SURFACE SCIENCE, 599, 153983

DOI: 10.1016/j.apsusc.2022.153983

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Understanding the phonon anharmonicity and temperature-dependent behavior of phonons that affect the thermal transport properties in 2D materials is crucial for developing efficient thermoelectric and memristor devices. SnSe has attracted significant interest because of its potential applications for developing such novel devices. Here, orthorhombic SnSe nanoflakes with a thickness of less than 100 nm and oriented along the [100] crystal axis were obtained using physical vapor transport at atmospheric pressure. Polarization-resolved Raman spectroscopy of SnSe nanoflakes was performed at a temperature of 5 K. Temperature-dependent frequencies and linewidths of Raman modes in tin selenide were fitted according to the anharmonic phonon coupling theory. The results indicate that both two and three order processes are responsible for the phonon decay in tin selenide. The memristive property was confirmed by electrical measurements of SnSe devices. SnSe memristors have an operating current of 10-4 A, similar to other transition-metal dichalcogenide memristors, but are more energy efficient than memristors based on defect migration, with a threshold voltage of 3 V.

16 Open Access

Modulated Laser Cladding of Implant-Type Coatings by Bovine-Bone-Derived Hydroxyapatite Powder Injection on Ti6Al4V Substrates-Part I: Fabrication and Physico-Chemical Characterization

Mocanu, AC; Miculescu, F; Stan, GE; Pasuk, I; Tite, T; Pascu, A; Butte, TM; Ciocan, LT

NOV 2022, MATERIALS, 15, 7971

DOI: 10.3390/ma15227971

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The surface physico-chemistry of metallic implants governs their successful long-term functionality for orthopedic and dentistry applications. Here, we investigated the feasibility of harmoniously combining two of the star materials currently employed in bone treatment/restoration, namely, calcium-phosphate-based bioceramics (in the form of coatings that have the capacity to enhance osseointegration) and titanium alloys (used as bulk implant materials due to their mechanical performance and lack of systemic toxicity). For the first time, bovine-bone-derived hydroxyapatite (BHA) was layered on top of Ti6Al4V substrates using powder injection laser cladding technology, and then subjected, in this first stage of the research, to an array of physical-chemical analyses. The laser processing set-up involved the conjoined modulation of the BHA-to-Ti ratio (100 wt.% and 50 wt.%) and beam power range (500-1000 W). As such, on each metallic substrate, several overlapped strips were produced and the external surface of the cladded coatings was further investigated. The morphological and compositional (SEM/EDS) evaluations exposed fully covered metallic surfaces with ceramic-based materials, without any fragmentation and with a strong metallurgical bond. The structural (XRD, micro-Raman) analyses showed the formation of calcium titanate as the main phase up to maximum 800 W, accompanied by partial BHA decomposition and the consequential advent of tetracalcium phosphate (markedly above 600 W), independent of the BHA ratio. In addition, the hydrophilic behavior of the coatings was outlined, being linked to the varied surface textures and phase dynamism that emerged due to laser power increment for both of the employed BHA ratios. Hence, this research delineates a series of optimal laser cladding technological parameters for the adequate deposition of bioceramic layers with customized functionality.

17

The effect of fullerene layer on the aggregates formation in amyloid beta Langmuir-Blodgett films

Breazu, C; Rasoga, O; Socol, M; Ganea, P; Tite, T; Matei, E; Stanculescu, F; Stanculescu, A

JAN 30 2021, APPLIED SURFACE SCIENCE, 537, 147800

DOI: 10.1016/j.apsusc.2020.147800

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The investigation of the effect of carbon nanomaterials and lipids on the aggregation particularities of the amyloid beta/A beta(1-42) layers is important for understanding the generation mechanism of neuronal disorder and how it can be inhibited. Additionally, amyloids are nanomaterials with a wide area of potential applications from nanotechnology to biotechnology. This paper presents a study about the preparation of A beta(1-42) layer by two different methods, Langmuir-Blodgett (L-B) and drop cast (DC), on Si and Si covered by a layer of Buckminster fullerene, C-60, and on the effect of fullerene layer or/and cholesterol (Ch) on the generation of A beta(1-42) secondary structure forms, relevant for specific applications. AFM, SEM FTIR and Raman analysis offered details about the layer surface topography, morphology and particularities of the secondary structure generated in the process of A beta(1-42) molecules aggregation. This study showed that the presence of Ch inhibited the formation of fibrils in A beta(1-42) film deposited by L-B on Si covered by C-60 The structures developed during aggregation were correlated with the topography and roughness of the films. The presence of Ch determined a decrease in roughness for L-B film and increase in roughness for DC film deposited on Si covered by C-60 layer.

18

Phosphate bioglass thin-films: Cross-area uniformity, structure and biological performance tailored by the simple modification of magnetron sputtering gas pressure

Tite, T; Popa, AC; Chirica, IM; Stuart, BW; Galca, AC; Balescu, LM; Popescu-Pelin, G; Grant, DM; Ferreira, JMF; Stan, GE

MAR 1 2021, APPLIED SURFACE SCIENCE, 541, 148640

DOI: 10.1016/j.apsusc.2020.148640

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Currently, there is a considerable time-lag in the industrialisation of innovative technological solutions for the functionalization of osseous implants, with ever-demanding healthcare requirements (e.g., controlled release of therapeutic ions, match of biomaterial degradation - bone growth rates, antimicrobial efficiency). As third-generation biomaterials, phosphate bio-glasses (PBGs) have demonstrated an ability to stimulate specific biological responses from tissue to molecular level, by successfully coupling bioactive and resorbable material properties. Here, radio-frequency magnetron sputtered (RF-MS) PBGs were explored as sacrificial resorbable layers for prospective biomedical implant designs. A PBG powder with a 50-P2O5, 35-CaO, 10-Na2O and 5-Fe2O3 composition (mol%) was used as source (target) material. The influence of the argon working pressure (0.2-1 Pa) - one of the most prominent RF-MS variables - on the morphology, structure, uniformity, composition, degradation rate and cytocompatibility of PBG films was investigated. The engineered modification of physical-chemical and biological features of the PBG sputtered films was multi-parametrically surveyed by AFM, EDXS, spectroscopic ellipsometry, GIXRD, FTIR spectroscopy measurements and in vitro assays. Results suggested that the film thickness, composition, density and structure were preserved over a uniformity region having a diameter of similar to 30 mm, irrespective of sputtering pressure. The network connectivity and the surface porosity of the films were found to have antagonistic roles with respect to the in vitro degradation performance. The possibility of fine tuning the composition, structure and thereby biological interaction of the PBG films by conveniently modifying the sputtering pressure was shown (i.e., permitting their complete controlled degradation, without cytotoxic effects). This work is the first to show in vitro cytocompatibility outcomes of sputtered PBG films and their cross-area uniformity, and thus, it could prove to be an important technological step in their future biomedical application and suggest implications for future industrial scale-up.

19 Open Access

The Physico-Chemical Properties and Exploratory Real-Time Cell Analysis of Hydroxyapatite Nanopowders Substituted with Ce, Mg, Sr, and Zn (0.5-5 at.%)

Chirica, IM; Enciu, AM; Tite, T; Dudau, M; Albulescu, L; Iconaru, SL; Predoi, D; Pasuk, I; Enculescu, M; Radu, C; Mihalcea, CG; Popa, AC; Rusu, N; Nita, S; Tanase, C; Stan, GE

JUL 2021, MATERIALS, 14, 3808

DOI: 10.3390/ma14143808

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Cation-substituted hydroxyapatite (HA), standalone or as a composite (blended with polymers or metals), is currently regarded as a noteworthy candidate material for bone repair/regeneration either in the form of powders, porous scaffolds or coatings for endo-osseous dental and orthopaedic implants. As a response to the numerous contradictions reported in literature, this work presents, in one study, the physico-chemical properties and the cytocompatibility response of single cation-doped (Ce, Mg, Sr or Zn) HA nanopowders in a wide concentration range (0.5-5 at.%). The modification of composition, morphology, and structure was multiparametrically monitored via energy dispersive X-ray, X-ray photoelectron, Fourier-transform infrared and micro-Raman spectroscopy methods, as well as by transmission electron microscopy and X-ray diffraction. From a compositional point of view, Ce and Sr were well-incorporated in HA, while slight and pronounced deviations were observed for Mg and Zn, respectively. The change of the lattice parameters, crystallite size, and substituting cation occupation factors either in the Ca(I) or Ca(II) sites were further determined. Sr produced the most important HA structural changes. The in vitro biological performance was evaluated by the (i) determination of leached therapeutic cations (by inductively coupled plasma mass spectrometry) and (ii) assessment of cell behaviour by both conventional assays (e.g., proliferation-3-(4,5-dimethyl thiazol-2-yl) 5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium assay; cytotoxicity-lactate dehydrogenase release assay) and, for the first time, real-time cell analysis (RTCA). Three cell lines were employed: fibroblast, osteoblast, and endothelial. When monophasic, the substituted HA supported the cells' viability and proliferation without signs of toxicity. The RTCA results indicate the excellent adherence of cells. The study strived to offer a perspective on the behaviour of Ce-, Mg-, Sr-, or Zn-substituted HAs and to deliver a well-encompassing viewpoint on their effects. This can be highly important for the future development of such bioceramics, paving the road toward the identification of candidates with highly promising therapeutic effects.

20

Antimicrobial and Cytocompatible Bovine Hydroxyapatite-Alumina-Zeolite Composite Coatings Synthesized by Pulsed Laser Deposition from Low-Cost Sustainable Natural Resources

Popescu-Pelin, G; Ristoscu, C; Duta, L; Stan, GE; Pasuk, I; Tite, T; Stan, MS; Bleotu, C; Popa, M; Chifiriuc, MC; Oktar, FN; Nicarel, A; Mihailescu, IN

MAR 16 2020, ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 8

DOI: 10.1021/acssuschemeng.9b05031

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Bovine hydroxyapatite (BHA) and BHA blended with clinoptilolite (CLIN) and alumina (Al2O3) coatings were synthesized using pulsed laser deposition (PLD) with a KrF* excimer laser source (lambda = 248 nm, tau(FWHM) <= 25 ns). Physical-chemical characteristics and the potential use of coatings for preventing bacteria adhesion and biofilm formation were investigated. Optimized PLD conditions were selected for coatings with rough morphologies, suitable for good cell adhesion and implant anchorage and good replication of the source target composition. The crystallinity of composite coatings was progressively decreasing with the augment of the Al2O3 and CLIN contents, which in turn can facilitate an efficacious release of active components. Al2O3- and CLIN-containing coatings exhibited high cytocompatibility and specific antibiofilm profiles, preventing the initiation and maturation of bacterial biofilms. Optimum biological activity profiles associated with the use of sustainable and/or inexpensive materials are, in our opinion, of key importance for the future development of performant implant coatings, which should he perfectly compatible with the surrounding tissue while preventing postsurgical endogenous or nosocomial infections.

21 Open Access

The Beneficial Mechanical and Biological Outcomes of Thin Copper-Gallium Doped Silica-Rich Bio-Active Glass Implant-Type Coatings

Stan, GE; Tite, T; Popa, AC; Chirica, IM; Negrila, CC; Besleaga, C; Zgura, I; Sergentu, AC; Popescu-Pelin, G; Cristea, D; Ionescu, LE; Necsulescu, M; Fernandes, HR; Ferreira, JMF

NOV 2020, COATINGS, 10, 1119

DOI: 10.3390/coatings10111119

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Silica-based bioactive glasses (SBG) hold great promise as bio-functional coatings of metallic endo-osseous implants, due to their osteoproductive potential, and, in the case of designed formulations, suitable mechanical properties and antibacterial efficacy. In the framework of this study, the FastOs(R)BG alkali-free SBG system (mol%: SiO2-38.49, CaO-36.07, P2O5-5.61, MgO-19.24, CaF2-0.59), with CuO (2 mol%) and Ga2O3 (3 mol%) antimicrobial agents, partially substituting in the parent system CaO and MgO, respectively, was used as source material for the fabrication of intentionally silica-enriched implant-type thin coatings (similar to 600 nm) onto titanium (Ti) substrates by radio-frequency magnetron sputtering. The physico-chemical and mechanical characteristics, as well as the in vitro preliminary cytocompatibility and antibacterial performance of an alkali-free silica-rich bio-active glass coating designs was further explored. The films were smooth (R-RMS < 1 nm) and hydrophilic (water contact angle of similar to 65 degrees). The SBG coatings deposited from alkali-free copper-gallium co-doped FastOs(R)BG-derived exhibited improved wear performance, with the coatings eliciting a bonding strength value of similar to 53 MPa, Lc3 critical load value of similar to 4.9 N, hardness of similar to 6.1 GPa and an elastic modulus of similar to 127 GPa. The Cu and Ga co-doped SBG layers had excellent cytocompatibility, while reducing after 24 h the Staphylococcus aureus bacterial development with 4 orders of magnitude with respect to the control situations (i.e., nutritive broth and Ti substrate). Thereby, such SBG constructs could pave the road towards high-performance bio-functional coatings with excellent mechanical properties and enhanced biological features (e.g., by coupling cytocompatibility with antimicrobial properties), which are in great demand nowadays.

22 Open Access

Sol-Gel Processing of Bismuth Germanate Thin-Films

Secu, M; Secu, CE; Tite, T; Polosan, S

MAR 2020, COATINGS, 10, 255

DOI: 10.3390/coatings10030255

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This study aims to obtain uniform and homogeneous bismuth germanate oxides thin films by spin coating and using the sol-gel technique with different precursors, followed by low-temperature annealing at 560 degrees C. By using Bi(NO3)(3) precursors, we have obtained transparent, yellowish thin films with a 200 nm thickness. The structural analysis of the initial sol-gel powder has shown the presence of two crystalline structures, the cubic Bi4Ge3O12 (BGO) and monoclinic Bi2GeO5 crystallites, which evolves towards the BGO structure after annealing. The elemental analysis confirmed the composition of the desired compound Bi4Ge3O12 with 60 wt % GeO2 and 40 wt % Bi2O5. On the other hand, by changing the precursor to (Bi(CH3COO)(2), the film thickness increased to 500 nm thicker due to the high viscosity of the sol, and a dominant monoclinic Bi2GeO5 crystalline structure appeared. The elemental analysis revealed a nonstoichiometric composition with 38 wt % GeO2 and 62 wt % Bi2O3. Due to the low GeO2 phase content that reacted with metastable Bi2GeO5, we obtained cubic Bi4Ge3O12 as a secondary phase, with Bi2GeO5 as a dominant crystalline phase. The redshifts of both absorptions and emissions spectra peaks confirmed a different disorder structure as an interplay between the cubic Bi4Ge3O12 (BGO) and monoclinic Bi2GeO5 phases.

23

Preparations of Silver/Montmorillonite Biocomposite Multilayers and Their Antifungal Activity

Iconaru, SL; Groza, A; Stan, GE; Predoi, D; Gaiaschi, S; Trusca, R; Chifiriuc, CM; Marutescu, L; Tite, T; Stanciu, GA; Hristu, R; Ghegoiu, L; Badea, ML; Turculet, CS; Ganciu, M; Chapon, P

DEC 2019, COATINGS, 9

DOI: 10.3390/coatings9120817

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In this study, the results about the influence of the surface morphology of layers based on montmorillonite (MMT) and silver (Ag) on antimicrobial properties are reported. The coating depositions were performed in the plasma of a radio frequency (RF) magnetron sputtering discharge. The studied layers were single montmorillonite layers (MMT) and silver/montmorillonite multilayers (MMT-Ag) obtained by magnetron sputtering technique with a different surface thickness. The resultant MMT-Ag biocomposite multilayers exhibited a uniform distribution of constituent elements and enhanced antimicrobial properties against fungal biofilm development. Glow-discharge optical emission spectroscopy (GDOES) analysis revealed the formation of MMT-Ag biocomposite multilayers following the deposit of a silver layer for an MMT layer that was initially deposited on a Si substrate. The surface morphology and thickness evaluation of deposited biocomposite layers were performed by scanning electron microscopy (SEM). A qualitative analysis of the chemical composition of thin layers was performed and the elements O, Ag, Mg, Fe, Al, and Si were identified in the MMT-Ag biocomposite multilayers. The in vitro antifungal assay proved that the inhibitory effect against the growth of Candida albicans ATCC 101231 CFU was more emphasized in the case of MMT-Ag biocomposite multilayers that in the case of the MMT layer. Cytotoxicity studies performed on HeLa cells showed that the tested layers did not show significant toxicity at the time intervals during which the assay was performed. On the other hand, it was observed that the MMT layers exhibited slightly higher biocompatible properties than the MMT-Ag composite layers.

24

Cationic Substitutions in Hydroxyapatite: Current Status of the Derived Biofunctional Effects and Their In Vitro Interrogation Methods

Tite, T; Popa, AC; Balescu, LM; Bogdan, IM; Pasuk, I; Ferreira, JMF; Stan, GE

NOV 2018, MATERIALS, 11

DOI: 10.3390/ma11112081

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High-performance bioceramics are required for preventing failure and prolonging the life-time of bone grafting scaffolds and osseous implants. The proper identification and development of materials with extended functionalities addressing socio-economic needs and health problems constitute important and critical steps at the heart of clinical research. Recent findings in the realm of ion-substituted hydroxyapatite (HA) could pave the road towards significant developments in biomedicine, with an emphasis on a new generation of orthopaedic and dentistry applications, since such bioceramics are able to mimic the structural, compositional and mechanical properties of the bone mineral phase. In fact, the fascinating ability of the HA crystalline lattice to allow for the substitution of calcium ions with a plethora of cationic species has been widely explored in the recent period, with consequent modifications of its physical and chemical features, as well as its functional mechanical and in vitro and in vivo biological performance. A comprehensive inventory of the progresses achieved so far is both opportune and of paramount importance, in order to not only gather and summarize information, but to also allow fellow researchers to compare with ease and filter the best solutions for the cation substitution of HA-based materials and enable the development of multi-functional biomedical designs. The review surveys preparation and synthesis methods, pinpoints all the explored cation dopants, and discloses the full application range of substituted HA. Special attention is dedicated to the antimicrobial efficiency spectrum and cytotoxic trade-off concentration values for various cell lines, highlighting new prophylactic routes for the prevention of implant failure. Importantly, the current in vitro biological tests (widely employed to unveil the biological performance of HA-based materials), and their ability to mimic the in vivo biological interactions, are also critically assessed. Future perspectives are discussed, and a series of recommendations are underlined.