First-principles calculations of hematite (α-Fe2O3) by self-consistent DFT+U+V

Owing to the confined Fe-3d orbitals and self-interaction error of exchange-correlation functionals, approximate DFT fails to describe iron oxides electronic structure and magnetic properties accurately. Hybrid DFT or DFT + U can solve these problems, but the former is expensive, and the latter only considers on-site interactions. Here, we used DFT + U + V, a DFT + U extension including inter-site interactions, to simulate the structural, magnetic, and electronic properties, along with Fe and O K-edge XAS spectra of α-Fe2O3. Two types of atomic orbital projectors were studied, orthogonalized and non-orthogonalized. DFT + U + V improves the description of the structural, magnetic, and electronic properties of α-Fe2O3 compared to approximate DFT. The accuracy of the correction depends on the orbital projector used. DFT + U + V with orthogonalized projectors achieves the best experimental agreement at a fraction of hybrid DFT cost. This work emphasizes the importance of inter-site interactions and the type of atomic orbital projectors used in the theoretical research of α-Fe2O

First-principles calculations of magnetite (Fe3o4) above the Verwey temperature by using self-consistent DFT + U + V

In this report, we have used the DFT + U + V approach, an extension of the DFT + U approach that takes into account both on-site and intersite interactions, to simulate structural, magnetic, and electronic properties together with the Fe and O K-edge XAS spectra of Fe3O4 above the Verwey temperature (Tv). Moreover, we compared the simulated XAS spectra with experimental XAS data. We examined both orthogonalized and nonorthogonalized atomic orbital projectors and compared DFT + U + V to DFT, DFT + U, and HSE as a hybrid functional. It is noteworthy that, despite the widespread use of the same Hubbard U value for Feoct and Fetet at the DFT + U level in the literature, the HP code identified two distinct values for them using the Hubbard approaches (DFT + U and DFT + U + V). The resulting Hubbard U and V parameters are strongly dependent on the chosen orbital projectors. This study demonstrates how DFT + U + V can improve the structural, magnetic, and electronic properties of Fe3O4 compared to approximate DFT and DFT + U. In this context, DFT + U + V supports the half-metallic character of the bulk crystal Fe3O4 above Tv, since the Fermi level is found in the t2g band with a Feoct down-spin. Thus, the observations in the current study emphasize the significance of intersite interactions in the theoretical analysis of Fe3O4 above the TvPID-2020-112770-C2

Fabrication and characterization of nanostructured porous silicon-silver composite layers by cyclic deposition: Dip-coating vs spin-coating

“This is the Accepted Manuscript version of an article accepted for publication in Nanotechnology. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it. The Version of Record is available online at https://doi.org/10.1088/1361-6528/ab96e5”Composites of nanostructured porous silicon and silver (nPSi-Ag) have attracted great attention due to the wide spectrum of applications in fields such as microelectronics, photonics, photocatalysis and bioengineering, Among the different methods for the fabrication of nanostructured composite materials, dip and spin-coating are simple, versatile, and cost-effective bottom-up technologies to provide functional coatings. In that sense, we aimed at fabricating nPSi-Ag composite layers. Using nPSi layers with pore diameter of 30 nm, two types of thin-film techniques were systematically compared: cyclic dip-coating (CDC) and cyclic spin-coating (CSC). CDC technique formed a mix of granular and flake-like structures of metallic Ag, and CSC method favored the synthesis of flake-like structures with Ag and Ag2O phases. Flakes obtained by CDC and CSC presented a width of 110 nm and 70 nm, respectively. Particles also showed a nanostructure surface with features around 25 nm. According to the results of EDX and RBS, integration of Ag into nPSi was better achieved using the CDC technique. SERS peaks related to chitosan adsorbed on Ag nanostructures were enhanced, especially in the nPSi-Ag composite layers fabricated by CSC compared to CDC, which was confirmed by FTDT simulations. These results show that CDC and CSC produce different nPSi-Ag composite layers for potential applications in bioengineering and photonicsThis work was financially supported by Fondo Nacional de Desarrollo Científico y Tecnológico FONDECYT–Chile (grant number 11180395), FONDEQUIP–Chile (project 160152

Functionalization of breast implants by cyclodextrin in-situ polymerization: a local drug delivery system for augmentation mammaplasty

Mammaplasty is a widely performed surgical procedure worldwide, utilized for breast reconstruction, in the context of breast cancer treatment, and aesthetic purposes. To enhance post-operative outcomes and reduce risks (hematoma with required evacuation, capsular contracture, implant-associated infection and others), the controlled release of medicaments can be achieved using drug delivery systems based on cyclodextrins (CDs). In this study, our objective was to functionalize commercially available silicone breast implants with smooth and textured surfaces through in-situ polymerization of two CDs: β-CD/citric acid and 2-hydroxypropyl-β-CD/citric acid. This functionalization serves as a local drug delivery system for the controlled release of therapeutic molecules that potentially can be a preventive treatment for post-operative complications in mammaplasty interventions. Initially, we evaluated the pre-treatment of sample surfaces with O2 plasma, followed by chitosan grafting. Subsequently, in-situ polymerization using both types of CDs was performed on implants. The results demonstrated that the proposed pre-treatment significantly increased the polymerization yield. The functionalized samples were characterized using microscopic and physicochemical techniques. To evaluate the efficacy of the proposed system for controlled drug delivery in augmentation mammaplasty, three different molecules were utilized: pirfenidone (PFD) for capsular contracture prevention, Rose Bengal (RB) as anticancer agent, and KR-12 peptide (KR-12) to prevent bacterial infection. The release kinetics of PFD, RB, and KR-12 were analyzed using the Korsmeyer-Peppas and monolithic solution mathematical models to identify the respective delivery mechanisms. The antibacterial effect of KR-12 was assessed against Staphylococcus epidermidis and Pseudomonas aeruginosa, revealing that the antibacterial rate of functionalized samples loaded with KR-12 was dependent on the diffusion coefficients. Finally, due to the immunomodulatory properties of KR-12 peptide on epithelial cells, this type of cells was employed to investigate the cytotoxicity of the functionalized samples. These assays confirmed the superior properties of functionalized samples compared to unprotected implants

Antibacterial films of silver nanoparticles embedded into carboxymethylcellulose/chitosan multilayers on nanoporous silicon: A layer-by-layer assembly approach comparing dip and spin coating

The design and engineering of antibacterial materials are key for preventing bacterial adherence and proliferation in biomedical and household instruments. Silver nanoparticles (AgNPs) and chitosan (CHI) are broad-spectrum antibacterial materials with different properties whose combined application is currently under optimization. This study proposes the formation of antibacterial films with AgNPs embedded in carboxymethylcellulose/chitosan multilayers by the layer-by-layer (LbL) method. The films were deposited onto nanoporous silicon (nPSi), an ideal platform for bioengineering applications due to its biocompatibility, biodegradability, and bioresorbability. We focused on two alternative multilayer deposition processes: cyclic dip coating (CDC) and cyclic spin coating (CSC). The physicochemical properties of the films were the subject of microscopic, microstructural, and surface–interface analyses. The antibacterial activity of each film was investigated against Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) bacteria strains as model microorganisms. According to the findings, the CDC technique produced multilayer films with higher antibacterial activity for both bacteria compared to the CSC method. Bacteria adhesion inhibition was observed from only three cycles. The developed AgNPs–multilayer composite film offers advantageous antibacterial properties for biomedical applicationsPID2020-112770RB-C2

Phonon structure, infra-red and raman spectra of Li2MnO3 by first-principles calculations

The layer-structured monoclinic Li2MnO3 is a key material, mainly due to its role in Li-ion batteries and as a precursor for adsorbent used in lithium recovery from aqueous solutions. In the present work, we used first-principles calculations based on density functional theory (DFT) to study the crystal structure, optical phonon frequencies, infra-red (IR), and Raman active modes and compared the results with experimental data. First, Li2MnO3 powder was synthesized by the hydrothermal method and successively characterized by XRD, TEM, FTIR, and Raman spectroscopy. Secondly, by using Local Density Approximation (LDA), we carried out a DFT study of the crystal structure and electronic properties of Li2MnO3. Finally, we calculated the vibrational properties using Density Functional Perturbation Theory (DFPT). Our results show that simulated IR and Raman spectra agree well with the observed phonon structure. Additionally, the IR and Raman theoretical spectra show similar features compared to the experimental ones. This research is useful in investigations involving the physicochemical characterization of Li2MnO3 materia

Adventitial alterations are the main features in pulmonary artery remodeling due to long-term chronic intermittent hypobaric hypoxia in rats

Long-termchronic intermittent exposure to altitude hypoxia is a labor phenomenon requiring further research. Using a rat model, we examined whether this type of exposure differed from chronic exposure in terms of pulmonary artery remodeling and other features. Rats were subjected to chronic hypoxia (CH, = 9) and long-term intermittent hypoxia (CIH2x2; 2 days of hypoxia/2 days of normoxia, = 10) in a chamber (428 Torr, 4,600m of altitude) for 46 days and compared to rats under normoxia (NX, = 10). Body weight, hematocrit, and right ventricle ratio were measured. Pulmonary artery remodeling was assessed using confocal microscopy of tissues stained with a nuclear dye (DAPI) and CD11b antibody. Both hypoxic conditions exhibited increased hematocrit and hypertrophy of the right ventricle, tunica adventitia, and tunica media, with no changes in lumen size. The medial hypertrophy area (larger in CH) depicted a significant increase in smooth muscle cell number. Additionally, CIH2x2 increased the adventitial hypertrophy area, with an increased cellularity and a larger prevalence of clustered inflammatory cells. In conclusion, CIH2x2 elicitsmilder effects on pulmonary artery medial layermuscularization and subsequent right ventricular hypertrophy than CH. However, CIH2x2 induces greater and characteristic alterations of the adventitial layerThis work was funded by GORE-FNDR-BIP: 30125349-0, AECID Nº A/030023/10, and CYTED-ALTMEDFIS grant

Upper lithospheric structure of the subduction zone offshore of southern Arauco peninsula, Chile, at ~38°S

A joint interpretation of swath bathymetric, seismic refraction, wide-angle reflection, and multichannel seismic data was used to derive a detailed tomographic image of the Nazca-South America subduction zone system offshore southern Arauco peninsula, Chile at similar to 38 degrees S. Here, the trench basin is filled with up to 2.2 km of sediments, and the Mocha Fracture Zone (FZ) is obliquely subducting underneath the South American plate. The velocity model derived from the tomographic inversion consists of a similar to 7-km-thick oceanic crust and shows P wave velocities typical for mature fast spreading crust in the seaward section of the profile, with uppermost mantle velocities >8.4 km s(-1). In the trench-outer rise area, the top of incoming oceanic plate is pervasively fractured and likely hydrated as shown by extensional faults, horst-and-graben structures, and a reduction of both crustal and mantle velocities. These slow velocities are interpreted in terms of extensional bending-related faulting leading to fracturing and hydration in the upper part of the oceanic lithosphere. The incoming Mocha FZ coincides with an area of even slower velocities and thinning of the oceanic crust (10-15% thinning), suggesting that the incoming fracture zone may enhance the flux of chemically bound water into the subduction zone. Slow mantle velocities occur down to a maximum depth of 6-8 km into the upper mantle, where mantle temperatures are estimated to be 400-430 degrees C. In the overriding plate, the tomographic model reveals two prominent velocity transition zones characterized by steep lateral velocity gradients, resulting in a seismic segmentation of the marine fore arc. The margin is composed of three main domains: (1) a similar to 20 km wide frontal prism below the continental slope with Vp <= 3.5 km s(-1), (2) a similar to 50 km area with Vp = 4.5-5.5 km s(-1), interpreted as a paleoaccretionary complex, and (3) the seaward edge of the Paleozoic continental framework with Vp >= 6.0 km s(-1). Frontal prism velocities are noticeably lower than those found in the northern erosional Chile margin, confirming recent accretionary processes in south central Chile

Experimental and density functional theory study of the Li+ desorption in spinel/layered lithium manganese oxide nanocomposites using HCl

The increasing demand for portable electronic devices and batteries has led to a growing interest in Li compounds. Lithium manganese oxides (LMO) are the most popular lithium-ion sieves (LIS) precursor materials due to their high lithium adsorption capacity and selectivity. The key step in forming LIS is the lithium desorption process from the crystalline lattice of the LMO. However, this process has been less researched than its counterpart, the lithium adsorption process. In this line, there are some studies describing the process of lithium desorption in acid media from spinel-type LMO. Nevertheless, there is no evidence of the lithium desorption process of layered-type lithium-rich LMO in acidic media. In the present work, we investigated the lithium desorption behavior of different LMO nanocomposites in HCl. LMOs with different Li/Mn ratios were synthesized by promoting the lithium-rich layered phase (Li2MnO3). The morphology, size, crystallinity, chemical composition, and surface properties of LMO nanocomposites and delithiated products were studied. In addition, density functional theory (DFT) calculations were carried out to understand the differential lithium desorption behavior, confirming its dependence on the Li/Mn ratio of the LMO nanocomposites. Herein, we demonstrate that the lithium diffusion energy barrier plays a major role during lithium desorption from LMO nanocomposites. Our results suggest that an exhaustive characterization of lithium precursor materials (LMO) is necessary to select a suitable desorption processThis work was financially supported by CONICYT PFCHA/ DOCTORADO/2015-21151648 (Ruth Pulido), PFCHA/DOCTORADO/ 2017-21172001 (Nelson Naveas) and partially funded by project USAMPSA, PID-2020-112770-C22, from the Government of Spain. The simulations used in this paper have been performed in the Centro de Computacion ´ Científica-Universidad Autonoma ´ de Madrid (CCC-UAM); thanks to CPU time and other resources granted by the institutio

Green synthesized silver nanoparticles decorated on nanostructured porous silicon as an efficient platform for the removal of organic dye methylene blue

In the present work, nanostructured porous silicon (nPSi) thin films were used as a substrate for the deposition of green synthesized silver nanoparticles (AgNPs). Different kinds of AgNPs were green synthesized by using Peumo extract and changing AgNO3 concentration. UV-vis spectroscopy confirmed the success of the synthesis, and TEM characterization showed AgNPs with a like-spherical shape and an average diameter, which ranges from 4 to 25 nm, depending on the AgNO3 concentration used. Then, AgNPs were introduced into the nPSi layer with a mean pore diameter of 46 nm and 75% of porosity by capillary suction. Hybrid layers nPSi/AgNPs were characterized by SEM, XRD, and RBS, confirming that AgNPs were introduced into nPSi layers. The catalytic activity of the hybrid layer in the reduction of organic dyes in water was studied using methylene blue (MB) as a model dye. Experimental results showed a high catalytic activity in comparison with other hybrid systems. The kinetic reduction could be fitted to the first-order equation obtaining the best degradation rate of 8.6 min(-1) with AgNPs synthetized with 2 mM of AgNO3. In addition, the reusability of these layers was demonstrated after five cycles, showing promising results for their use in wastewater management