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 Tv.

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: ß-CD/citric acid and 2-hydroxypropyl-ß-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 applications.

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-Fe2O3.

Coatings of Cyclodextrin/Citric-Acid Biopolymer as Drug Delivery Systems: A Review.

In the early 2000s, a method for cross-linking cyclodextrins (CDs) with citric acid (CTR) was developed. This method was nontoxic, environmentally friendly, and inexpensive compared to the others previously proposed in the literature. Since then, the CD/CTR biopolymers have been widely used as a coating on implants and other materials for biomedical applications. The present review aims to cover the chemical properties of CDs, the synthesis routes of CD/CTR, and their applications as drug-delivery systems when coated on different substrates. Likewise, the molecules released and other pharmaceutical aspects involved are addressed. Moreover, the different methods of pretreatment applied on the substrates before the in situ polymerization of CD/CTR are also reviewed as a key element in the final functionality. This process is not trivial because it depends on the surface chemistry, geometry, and physical properties of the material to be coated. The biocompatibility of the polymer was also highlighted. Finally, the mechanisms of release generated in the CD/CTR coatings were analyzed, including the mathematical model of Korsmeyer-Peppas, which has been dominantly used to explain the release kinetics of drug-delivery systems based on these biopolymers. The flexibility of CD/CTR to host a wide variety of drugs, of the in situ polymerization to integrate with diverse implantable materials, and the controllable release kinetics provide a set of advantages, thereby ensuring a wide range of future uses.

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 material.

Hydrothermal control of the lithium-rich Li2MnO3 phase in lithium manganese oxide nanocomposites and their application as precursors for lithium adsorbents.

Lithium manganese oxides (LMOs) are key materials due to their role in Li-ion batteries and lithium recovery from aqueous lithium resources. In the present work, we investigated the effect of the crystallization temperature on the formation by hydrothermal synthesis of LMO nanocomposites with high Li/Mn ratios. It is demonstrated that LMOs with a high Li/Mn ratio can be formed by systematically favoring the lithium-rich layered monoclinic phase (Li2MnO3) in a mixture of monoclinic and spinel crystalline phases. LMO nanocomposites have been characterized in terms of morphology, size, crystallinity, chemical composition and surface properties. Moreover, lithium adsorption experiments were conducted using acid-treated LMOs (HMOs) to evaluate the functionality of the nanocomposites as lithium adsorbent materials in a LiCl buffer solution. This study spotlights the structural, compositional, and functional properties of different LMO nanocomposites obtained by the hydrothermal method using the same Li and Mn precursor compounds at slightly different crystallization temperatures. According to our knowledge, this is the first report of the successful application of the lithium-rich Li2MnO3 phase in lithium manganese oxide nanocomposites as lithium adsorbent materials. Therefore, specific LMO nanocomposites with controlled amounts of the layered phase can be engineered to optimize lithium recovery from aqueous lithium resources.

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

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 photonics.

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

Long-term chronic 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, n = 9) and long-term intermittent hypoxia (CIH2x2; 2 days of hypoxia/2 days of normoxia, n = 10) in a chamber (428 Torr, 4,600 m of altitude) for 46 days and compared to rats under normoxia (NX, n = 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 elicits milder effects on pulmonary artery medial layer muscularization and subsequent right ventricular hypertrophy than CH. However, CIH2x2 induces greater and characteristic alterations of the adventitial layer.

Plasma and liver lipid profiles in rats exposed to chronic hypobaric hypoxia: changes in metabolic pathways.

Lipid metabolism under chronic hypoxia (CH) has not received equal attention as intermittent hypoxia (IH). To determine the CH-induced changes in plasma and liver, as well as the mRNA and protein expression of two key enzymes in the triglyceride and cholesterol biosynthesis pathways, SREBP-1 (HMG-CoA reductase) and SREBP-2 (SCD-1), we exposed adult male Wistar rats to CH (4600 m; n=15) for 30 days compared to normoxic rats (n=15). The CH rats exhibited weight loss (p<0.001), higher hematocrit (%), and higher hemoglobin (g/dL) (p<0.01). In the plasma of CH rats, total cholesterol and LDL-cholesterol increased at day 15. VLDL-cholesterol and triglycerides (p<0.01) greatly increased (35%), while HDL-cholesterol decreased (p<0.01). Triglycerides and VLDL-cholesterol remained elevated by 28% at day 30 (p<0.01). Hepatic triglycerides increased two-fold, while total cholesterol increased by 51% (p<0.001; p<0.05). Upregulation of SCD-1 mRNA and protein was observed in the CH rats (p<0.01); however, no differences were observed in HMG-CoA reductase mRNA or protein expression in both groups. In conclusion, CH, like IH, alters lipid profiles by increasing triglycerides in the plasma and liver and upregulating triglyceride biosynthesis without affecting the cholesterol biosynthetic pathway. Additional involved mechanisms require further study because of the importance of lipids in cardiovascular risk.

Fabrication and characterization of a chemically oxidized-nanostructured porous silicon based biosensor implementing orienting protein A.

Nanostructured porous silicon (PSi) elicits as a very attractive material for future biosensing systems due to its high surface area, biocompatibility and well-established fabrication methods. In order to engineer its performance as a biosensor transducer platform, the density of immunoglobulins properly immobilized and oriented onto the surface needs to be optimized. In this work we fabricated and characterized a novel biosensing system focusing on the improvement of the biofunctionalization cascade. The system consists on a chemically oxidized PSi platform derivatized with 3-aminopropyltriethoxysilane (APTS) that is coupled to Staphylococcus protein A (SpA). The chemical oxidation has previously demonstrated to enhance the biofunctionalization process and here "by implementing SpA" a molecularly oriented immunosensor is achieved. The biosensor system is characterized in terms of its chemical composition, wettability and optical reflectance. Finally, this system is successfully exploited to develop a biosensor for detecting asymmetric dimethylarginine (ADMA), an endogenous molecule involved in cardiovascular diseases. Therefore, this work is relevant from the point of view of design and optimization of the biomolecular immobilization cascade on PSi surfaces with the added value of contribution to the development of new assays for detecting ADMA with a view on prevention of cardiovascular diseases.