Electrolyte-gated organic transistors (EGOTs) can be operated as sensors with high selectivity and an outstandingly low limit of detection. Their response to interfacial interactions occurs either by capacitive coupling between gate and channel or by faradaic reactions. In this work, we endow a high-affinity sensing response to EGOTs based on the PEDOT:PSS channel by functionalization of the gate electrode with Ti3C2TX MXenes. MXene were synthesized in different conditions to tailor surface chemistry, while retaining a similar skeleton structure. The integration of MXene-based functionalization layers is shown to preserve the high transconductance in EGOT devices, while simultaneously tuning the switch-on voltage toward 0 V. This modulation enables a safe operational window in aqueous electrolytes, preventing unwanted electrochemical side reactions. We then demonstrated that EGOT with the surface-tailored MXene layers are sensitive to concentrations of the neurotransmitter dopamine down to sub-picomolar levels of detection. These unprecedented LODs indicate that modification of EGOTs gate with tailored or functionalized MXenes is a viable and versatile strategy to enhance sensitivity to relevant biomarkers.

Al1–xScxN (ASN) thin films, deposited by magnetron sputtering onto Pt(111)/Si substrates, were investigated to correlate microstructure, surface chemistry, and electrical behaviour. Structural characterisation confirmed the formation of the wurtzite ASN phase, while X-ray photoelectron spectroscopy revealed that the surface stoichiometry deviates from the bulk composition due to pronounced oxidation dominated by Sc–O bonding, accompanied by minor Al–O formation and traces of molecular N2. Surface oxidation, together with polarisation-bound leakage currents and electrode-interface asymmetry, contributes to the asymmetric leakage currents observed during ferroelectric hysteresis measurements.Dielectric spectroscopy shows that extrinsic surface species strongly influence the dielectric response. In the 380K–400 K range, the material recovers a stable insulating state under low-field excitation, indicating that the elevated dielectric losses observed at intermediate temperatures are extrinsic and do not originate from intrinsic lattice degradation. However, electrical recovery remains incomplete, as the bulk resistance remains significantly lower than its room-temperature value, pointing to persistent volume conduction. The residual conductivity is associated with intrinsic structural defects that enable charge transport via localised states, consistent with a correlated barrier-hopping conduction mechanism. The coexistence of reversible surface-related effects and intrinsic bulk disorder ultimately defines the electrical limitations of the ASN heterostructure and provides a consistent explanation for the premature dielectric breakdown observed under high electric fields.

The glass/FTO/TiO2/Sb2S3-x/P3HT/Au solar cells were investigated, with a focus on identifying the origin of performance degradation after exposure to high relative humidity and to mild heat stress. Analyzing the photovoltaic output and Deep-Level Transient Spectroscopy (DLTS) results, we probed the evolution of defect states after thermal exposure and after long-term storage of Sb2S3-x-based devices. The DLTS analysis revealed that shallow hole traps govern the stability of the Sb2S3-x cells. Significantly, it was shown that this shallow defect is not related to chlorine in the absorber, indicating an intrinsic origin. In the broader context of Sb2S3-x photovoltaics, this study underlines the paramount importance of defect engineering towards achieving more stable and efficient Sb2S3-x solar cells.

Magnesium and zinc are important additives or substituents in melt-quenched Na2O-CaO-SiO2-P2O5 bioactive glasses, due to their beneficial influence on glass stability and processability. They modify the dissolution kinetics of these glasses and impart favorable biological properties and functions to them. For rational bioactive glass design, it is essential to understand the local environments and distributions of these ions. While diffraction studies suggest MgO and ZnO to be close-to-four-coordinate in silicate glasses, their structural roles in the network are still under debate. Traditionally these oxides have been viewed as network modifiers, converting Si-O-Si linkages to anionic non-bridging oxygen atoms, whose charges are compensated by the divalent cations. It has been suggested that MgO4/2|(2-) or ZnO4/2|(2-) network-forming units (NFUs) may be present, forming Mg-O-Si or Zn-O-Si linkages. If such units are formed, they would attract modifier cations for charge compensation, which would in turn result in an increased degree of polymerization of the silicate species, the main network-forming component. This study explores the roles of MgO and ZnO in bioactive glasses with approximate composition 50SiO(2)-(50-x)[MO,M'O-2]-xP(2)O(5) in mol% (2 <= x <= 6), where M = Ca, Sr, Mg, Zn; M' = Na, K. Quantitative estimates of the various silicate and phosphate NFUs were obtained from Si-29 and P-31 solid-state nuclear magnetic resonance (NMR) spectroscopic techniques and molecular dynamics (MD) simulations, allowing the determination of the degree of network polymerization in terms of the average Si and P connectivities (-values). Both NMR spectroscopy and MD studies consistently revealed that the extent of Si polymerization increases, as expected, with P2O5 addition, reflecting the well-documented preferential cation attraction by the phosphate species. On the other hand, data obtained from a set of comparative samples containing either Mg, Zn, or a mixture of both showed no significant changes in the degree of silicate network polymerization. This result strongly supports a network-modifying role of both magnesium and zinc oxide, as suggested by previous works.

Optimizing the interfaces in perovskite solar cells (PSCs) is essential for enhancing their performance, improving their stability, and making them commercially viable for large-scale deployment in solar energy harvesting applications. Point defects, like vacancies, have a dual role, as they can inherently provide a proper doping, but they can also reduce the collected current by trap-assisted recombination. Moreover, they can play an active role in ion migration and degradation. Using ab initio density functional theory calculations we investigate the changes in the band alignment induced by interfacial vacancy defects in a TiO 2/MAPI/Cu 2O based PSC. Depending on the type of the vacancy (Ti, Cu, O, Pb, I) in the oxide and perovskite materials, additional doping is superimposed on the already existing background. Their effect on the performance of the PSCs becomes visible, as shown by SCAPS simulations. The most significant impact is observed for p type doping of TiO 2 and n type doping of Cu 2O, while the effective doping of the perovskite layer affects one of the two interfaces. We discuss these results based on modifications of the band structure near the active interfaces and provide further insights concerning the optimization of electron and hole collection.

ABSTRACT Owing to the possibility of attaining variable oxidation states and coordination numbers, the specific structural roles of V 2 O 5 or Nb 2 O 5 in determining the local configurations of framework species in alkaline earth aluminoborosilicate glasses still need to be disclosed. This manuscript describes the structural changes induced by adding 5 mol% of V 2 O 5 or Nb 2 O 5 to a complex aluminoborosilicate glass (mol%) 10MgO–15CaO–25SrO–5Al 2 O 3 –5B 2 O 3 –40SiO 2 , aiming at elucidating the connectivity of these transition metal cations in the glass network. The resulting structural changes have been assessed by magic angle spinning‐nuclear magnetic resonance (MAS‐NMR) (for 29 Si, 27 Al, 11 B, 51 V, and 93 Nb nuclei), UV‐visible spectroscopy, scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared and Raman spectroscopy, differential thermal analysis (DTA), molecular dynamics (MD) simulations, and density functional theory (DFT) calculations. XPS analysis indicated the presence of V and Nb with a 5+ oxidation state. The NMR spectroscopy, MD simulations, and DFT calculations suggest that V exists in 4‐, 5‐, and 6‐coordination, whereas Nb exists mostly in 6‐coordination. Both V and Nb are well incorporated into the silicate network. The results do not suggest any clustering of either of the V‐ or Nb‐based units.

Background: Hepatocellular carcinoma is associated with high mortality and increasing incidence. Sorafenib, a cornerstone of therapy for advanced hepatocellular carcinoma, presents certain disadvantages, including low bioavailability and poor water solubility. This work describes a new strategy for sorafenib-targeted delivery aimed at improving treatment efficiency and reducing side effects. Methods: Magnetic nanoparticles coated with azelaic acid were modified with aptamer molecules that specifically recognize human liver cancer cell line HepG2, ensuring specificity for the tumor tissue. The nanoparticles were further loaded with sorafenib. The obtained drug delivery system was extensively characterized using UV-Vis spectrophotometry, transmission electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy. Results: The drug delivery system demonstrated a higher release of sorafenib at acidic pH compared to pH 7.4. The cell internalization of the bare and aptamer-modified magnetic nanoparticles was assessed in HepG2 and human normal foreskin fibroblasts BJ cell lines, demonstrating that the aptamer significantly enhances internalization in tumor cells, while having no impact on healthy cells. Conclusions: The sorafenib-modified nanoparticles exhibited excellent cytocompatibility with BJ cells across all tested concentrations, while showing cytotoxicity towards HepG2 cells at higher concentrations, confirming the selectivity of the system.

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.

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.

Layers of HfO2 and (Hf,Zr)O2 crystalline nano-particles are synthesized via direct liquid injection atomic layer deposition, and a comprehensive set of structural, chemical, and electrical characterizations is employed to elucidate their phase composition and functional behavior. X-ray photoelectron spectroscopy revealed a compositional contrast between the films: (Hf,Zr)O2 layers contained up to 45% stoichiometric oxide, while pure HfO2 films are dominated by sub-oxides, especially under strongly reducing conditions, in which exclusively sub-oxide phases and p-type semiconducting behavior is revealed. Electrical measurements indicated room-temperature stabilization of polar phases and tetragonal-to-orthorhombic phase transition with a Curie temperature near 200 K. FTIR spectroscopy confirmed the presence of tetragonal and orthorhombic HfO2 phases, providing insight into minor features observed ≈30° (2θ) in X-ray diffraction patterns. Notably, devices incorporating an AlN interlayer demonstrated a significant enhancement in pyroelectric performance, suggesting this strategy to advance the pyroelectric performance of HfO2-based materials, supporting their development for lead-free sensor technologies.

Synthetic bone graft substitutes, including calcium phosphates (CaP), bioactive glasses (BG), and their composites with biopolymer matrices are attracting interest for bone tissue repair and regeneration. A key challenge is accurately replicating the biological structure and functionality of natural bone and optimizing the porous structure to match trabecular bone. This has been addressed by doping CaPs with therapeutic ions and using scaffolding methods like polymeric sponge replication and different additive manufacturing techniques. Biomimetic approaches employing naturally occurring porous biominerals with pore sizes comparable to those of trabecular bone, offer promising alternatives. This work reviews the hydrothermal transformation of cuttlefish bone (CB) into CaP scaffolds, while preserving its original porous structure, producing hydroxyapatite (HA, Ca 10 (PO 4 ) 6 (OH) 2 ), tricalcium phosphate (TCP, Ca 3 (PO 4 ) 2 ), and biphasic CaPs, both undoped and therapeutic ion‐doped, constructs. Coating such biomimetic scaffolds with sol–gel‐derived BG and biopolymers produces multifunctional bone graft substitutes with enhanced mechanical and biological properties. Moreover, polymeric coatings can act as drug reservoirs, enabling controlled release of therapeutic agents. The review highlights that integrating biomimetic strategies with advanced coating solutions holds great promise for creating multifunctional scaffolds that mimic nature and improve therapeutic outcomes in bone tissue engineering.

Biodegradable templates are sought for targeted antibiotic administration/delivery in bone infections to avoid detrimental reactions during bone regeneration. We investigated two key-aspects in this direction: 1) the optimal antibiotic delineation, with thermal stability equivalent to the temperature involved for templates preparation and 2) the antibacterial templates development by a two-step homogenization process. The selected antibiotic - ampicillin (AMP) was mechanically and then thermally mixed with the prime materials: poly(lactic acid) (PLA) - the polymeric matrix, biogenic bovine bone-derived hydroxyapatite (HA, particles <40 mu m), and graphene nanoplatelets (GnP, micrometric range). For the first time, all materials were used in simultaneous modulated ratios for the synthesis of PLA/AMP (1-5 wt.%)/HA (0-30 wt.%)/GnP (0-3 wt.%) composites. The influence of the concomitant materials modulation was surveyed through several assays. The FTIR-ATR spectroscopy depicted a three-level model of overlapping structures asserting the solid molecular cross-linking between all materials, without structural alterations induced to any material (XRD analysis). The addition of AMP to the PLA matrix caused a slight particle conglomeration, alleviated through GnP addition. The microporous HA particles supported the adhesion to the PLA matrix and promoted the AMP particles' entrapment/attachment. Linked to the enhanced wettability of the composite materials, the phosphate buffered saline solution (PBS) degradation profiles revealed a pronounced burst during the first 14-28 days of incubation and a long-term, low-level process hereafter. Thus, the formation of pores and cavities were signalled along with the HA particles' fragmentation. The released AMP (percentage) pictured an ascending trendline during the 24 h of analysis, at all targeted ratios. The preservation of AMP features at 200 degrees C was endorsed by the strong antibacterial activity of composite materials against Staphylococcus aureus (S. Aureus) growth and the medium response against Escherichia coli (E. Coli) - the higher the drug release, the higher the inhibitory effect on bacteria evolution.

Over the past two decades, the CICECO-hub scientists have devoted substantial efforts to advancing bioactive inorganic materials based on calcium phosphates and alkali-free bioactive glasses. A key focus has been the deliberate incorporation of therapeutic ions like Mg, Sr, Zn, Mn, or Ga to enhance osteointegration and vascularization, confer antioxidant properties, and impart antimicrobial effects, marking significant contributions to the field of biomaterials and bone tissue engineering. Such an approach is expected to circumvent the uncertainties posed by methods relying on growth factors, such as bone morphogenetic proteins, parathyroid hormone, and platelet-rich plasma, along with their associated high costs and potential adverse side effects. This comprehensive overview of CICECO-hub's significant contributions to the forefront inorganic biomaterials across all research aspects and dimensionalities (powders, granules, thin films, bulk materials, and porous structures), follows a unified approach rooted in a cohesive conceptual framework, including synthesis, characterization, and testing protocols. Tangible outcomes [injectable cements, durable implant coatings, and bone graft substitutes (scaffolds) featuring customized porous architectures for implant fixation, osteointegration, accelerated bone regeneration in critical-sized bone defects] were achieved. The manuscript showcases specific biofunctional examples of successful biomedical applications and effective translations to the market of bone grafts for advanced therapies.

The synergistic piezoelectric and osteoconductive properties of barium titanate (BT) and hydroxyapatite (HA) could stir the development of a new generation of synthetic bone graft substitutes, with capability for rapid and safe osseointegration. The research focused on two concurrent approaches for coupling the BT and HA materials: (i) conventional sintering of BT-HA powder mixtures; and (ii) functionalization of pre-sintered BT with HA coatings using magnetron sputtering (MS). Irrespective of the BT/HA ratios ranging from 95/5 to 80/20 wt.%, nanocrystalline or highly-crystallized nature of the powders, sub-micron- or micron-sized particle dimensions, and sintering temperature, it was observed that the BT-HA reactivity cannot be prevented above 800 °C. At higher temperatures in the range of 1000 – 1300 °C, HA undergoes decomposition and extensively reacts with BT, leading to the formation of several secondary phases such as CaTiO3, Ba2Ca(PO4)2, BaCa6(PO4)4O, BaCa(PO3)4, and β-Ca2P2O7. As a consequence, the cytocompatibility assessed in fibroblast and osteoblast cell cultures, as well as the piezoelectric response, were significantly altered.Applying HA coatings by MS to the sintered BT ceramics successfully preserved their piezoelectric properties, while also providing an unaltered cytocompatible and osteogenic-prone surface. The HA coatings were fully crystallized at post-deposition annealing temperatures of 550 and 700 °C, achieving crystalline qualities comparable to HA powders sintered at 1100 and 1200 °C, respectively. No reactivity events between BT and HA were observed. Partial reactivity was only noticeable upon annealing at 1000 °C. Therefore, it is suggested that the HA coating of BT is effective in seamlessly coupling the piezoelectric and osteogenic properties of the two constituents without compromise.

Bioactive glasses (BGs) are known for their selective ability to (i) form a mechanically strong interfacial bond with hard (bone) or soft tissues (gingivae or cartilages) (i.e., silica-, silica-phosphate-, phosphate-, borate-phosphate-, or silica-phosphate-borate-based BGs); or (ii) serve as reservoirs for fast-release of therapeutic (osteogenic, angiogenic, anticarcinogenic, or antimicrobial) ions (i.e., phosphate-based BGs and mesoporous BGs). The strength of the bone bond yielded by the osteoproductive-capable BGs is generally equivalent to, or higher than the bone strength. The resorbability of phosphate-based BG is dependent on the content of network formers and cross-linkers. All BGs elicit excellent biochemical compatibility. However, their fracture toughness is typically less than and the elastic modulus is greater than those of bone, indicating that most BGs have suboptimal biomechanical compatibility when used in load-bearing applications. One promising approach to overcome this problem is the development of BGs in coating form, applied to the surface of load-bearing endosseous implants. This work critically assesses BG thin-layers fabricated by the radio-frequency magnetron sputtering method, an industry-ready large-scale physical vapour deposition technology. It is demonstrated that, despite the relative lack of attention paid to this technology, it enables the development of unique BG coatings with efficacious therapeutic capabilities. Here, we present an overview of the most relevant developments achieved thus far, along with the remarkable advantages, drawbacks to overcome, and future perspectives with the intention of highlighting the vast possibilities of this specific field of research.

Sub‐stochiometric nickel oxide (NiOx) films were investigated as a hole selective contact option in silicon (Si) heterojunction solar cells. Numerical simulations were carried out to evaluate the impacts of the NiOx electronic properties variations and the NiOx/Si interface defect density (Dit) on device performance. Simulation data suggest that the best performance is achievable for wide bandgaps (Eg) and corresponding high valence band edge (EVB) positions in the NiOx films. Overall, in simulations, the performance remains practically unchanged for the nickel vacancy concentrations [VNi] = 1017–1021 cm−3, assuming high EVB and low Dit. The experimental data measured using NiOx films prepared by radio‐frequency magnetron sputtering reveal that the increase in [VNi] lifts the conductivity, concurrently decreasing Eg and EVB. As a result, we concluded that the performance of the fabricated sputtered NiOx/Si heterojunction solar cell is limited by high Dit as well as narrow Eg and low EVB.

This work was devoted to the first multi-parametric unitary comparative analysis of a selection of sintered piezoceramic materials synthesised by solid-state reactions, aiming to delineate the most promising biocompatible piezoelectric material, to be further implemented into macro-porous ceramic scaffolds fabricated by 3D printing technologies. The piezoceramics under scrutiny were: KNbO3, LiNbO3, LiTaO3, BaTiO3, Zr-doped BaTiO3, and the (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 solid solution (BCTZ). The XRD analysis revealed the high crystallinity of all sintered ceramics, while the best densification was achieved for the BaTiO3-based materials via conventional sintering. Conjunctively, BCTZ yielded the best combination of functional properties—piezoelectric response (in terms of longitudinal piezoelectric constant and planar electromechanical coupling factor) and mechanical and in vitro osteoblast cell compatibility. The selected piezoceramic was further used as a base material for the robocasting fabrication of 3D macro-porous scaffolds (porosity of ~50%), which yielded a promising compressive strength of ~20 MPa (higher than that of trabecular bone), excellent cell colonization capability, and noteworthy cytocompatibility in osteoblast cell cultures, analogous to the biological control. Thereby, good prospects for the possible development of a new generation of synthetic bone graft substitutes endowed with the piezoelectric effect as a stimulus for the enhancement of osteogenic capacity were settled.

Novel biomaterials with promising bone regeneration potential, derived from rich, renewable, and cheap sources, are reported. Thus, thin films were synthesized from marine-derived (i.e., from fish bones and seashells) hydroxyapatite (MdHA) by pulsed laser deposition (PLD) technique. Besides the physical–chemical and mechanical investigations, the deposited thin films were also evaluated in vitro using dedicated cytocompatibility and antimicrobial assays. The morphological examination of MdHA films revealed the fabrication of rough surfaces, which were shown to favor good cell adhesion, and furthermore could foster the in-situ anchorage of implants. The strong hydrophilic behavior of the thin films was evidenced by contact angle (CA) measurements, with values in the range of 15–18°. The inferred bonding strength adherence values were superior (i.e., ~49 MPa) to the threshold established by ISO regulation for high-load implant coatings. After immersion in biological fluids, the growth of an apatite-based layer was noted, which indicated the good mineralization capacity of the MdHA films. All PLD films exhibited low cytotoxicity on osteoblast, fibroblast, and epithelial cells. Moreover, a persistent protective effect against bacterial and fungal colonization (i.e., 1- to 3-log reduction of E. coli, E. faecalis, and C. albicans growth) was demonstrated after 48 h of incubation, with respect to the Ti control. The good cytocompatibility and effective antimicrobial activity, along with the reduced fabrication costs from sustainable sources (available in large quantities), should, therefore, recommend the MdHA materials proposed herein as innovative and viable solutions for the development of novel coatings for metallic dental implants.

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.

This work evaluates the effects of manganese (Mn) doping on the morpho-structural features, mechanical performance, and in vitro biological response of beta-tricalcium phosphate (β-TCP) derived bioceramics for bone tissue engineering applications. Five different Mn doping levels (i.e., 0.01