Extrinsic Point Defects in TiO2-Acetylacetone Charge-Transfer Complex and Their Effects on Optical and Photochemical Properties.

TiO2-based visible-light-sensitive nanomaterials are widely studied for photocatalytic applications under UV-Vis radiation. Among the mechanisms of visible-light sensitization, extrinsic oxygen vacancies have been introduced into TiO2 and charge-transfer complexes (CTCs) have been formed between chelating ligands, such as acetylacetone, and nanocrystalline TiO2 (TiO2-ACAC). However, the influence of extrinsic oxygen vacancies on the photocatalytic performance of TiO2-based CTCs is unknown. In this work, surface/bulk extrinsic oxygen vacancies were introduced into TiO2-ACAC through calcination at 270 °C under static air, argon, and hydrogen atmospheres. TiO2-ACAC CTCs were characterized by X-ray powder diffraction, thermogravimetric analysis, diffuse-reflectance spectroscopy, photoluminescence, electron paramagnetic resonance (EPR), and X-ray photoelectron spectroscopy techniques. The correlation between EPR-spin trapping and tetracycline (TC) photodegradation, using scavengers, highlighted the key role of the superoxide radical in TC degradation by TiO2-ACAC CTCs under low-power visible-light radiation. The increased extrinsic oxygen vacancies concentration was not beneficial for the photocatalytic performance of TiO2 CTCs, since bulk extrinsic oxygen vacancies additionally act as recombination centers. In fact, the TiO2-ACAC CTC with the lowest extrinsic oxygen vacancies concentration exhibited the highest photocatalytic performance for TC degradation due to an adequate distribution of extrinsic bulk oxygen vacancies, which led to the trapped electrons undergoing repeated hopping, reducing the recombination rates and improving the efficiency in superoxide radicals production. Our findings indicated that TiO2-ACAC CTCs are able to degrade pollutants via interactions with electronic holes and principally superoxide radicals and also, provided fundamental information about the influence of surface/bulk extrinsic oxygen vacancies on the photocatalytic performance, lattice parameters, and optical and photochemical properties of TiO2-based CTCs.

Review on infrared nanospectroscopy of natural 2D phyllosilicates.

Phyllosilicates have emerged as a promising class of large bandgap lamellar insulators. Their applications have been explored from the fabrication of graphene-based devices to 2D heterostructures based on transition metal dichalcogenides with enhanced optical and polaritonics properties. In this review, we provide an overview of the use of infrared (IR) scattering-type scanning near-field optical microscopy (s-SNOM) for studying nano-optics and local chemistry of a variety of 2D natural phyllosilicates. Finally, we bring a brief update on applications that combine natural lamellar minerals into multifunctional nanophotonic devices driven by electrical control.

Metabolomic insights in advanced cardiomyopathy of chronic chagasic and idiopathic patients that underwent heart transplant.

Heart failure (HF) studies typically focus on ischemic and idiopathic heart diseases. Chronic chagasic cardiomyopathy (CCC) is a progressive degenerative inflammatory condition highly prevalent in Latin America that leads to a disturbance of cardiac conduction system. Despite its clinical and epidemiological importance, CCC molecular pathogenesis is poorly understood. Here we characterize and discriminate the plasma metabolomic profile of 15 patients with advanced HF referred for heart transplantation - 8 patients with CCC and 7 with idiopathic dilated cardiomyopathy (IDC) - using gas chromatography/quadrupole time-of-flight mass spectrometry. Compared to the 12 heart donor individuals, also included to represent the control (CTRL) scenario, patients with advanced HF exhibited a metabolic imbalance with 21 discriminating metabolites, mostly indicative of accumulation of fatty acids, amino acids and important components of the tricarboxylic acid (TCA) cycle. CCC vs. IDC analyses revealed a metabolic disparity between conditions, with 12 CCC distinctive metabolites vs. 11 IDC representative metabolites. Disturbances were mainly related to amino acid metabolism profile. Although mitochondrial dysfunction and loss of metabolic flexibility may be a central mechanistic event in advanced HF, metabolic imbalance differs between CCC and IDC populations, possibly explaining the dissimilar clinical course of Chagas' patients.

Novel Possible Protein Targets in Neovascular Age-Related Macular Degeneration: A Pilot Study Experiment.

Age-related macular degeneration (AMD) is among the world's leading causes of blindness. In its neovascular form (nAMD), around 25% of patients present further anatomical and visual deterioration due to persistence of neovascular activity, despite gold-standard treatment protocols using intravitreal anti-VEGF medications. Thus, to comprehend, the molecular pathways that drive choroidal neoangiogenesis, associated with the vascular endothelial growth factor (VEGF), are important steps to elucidate the mechanistic events underneath the disease development. This is a pilot study, a prospective, translational experiment, in a real-life context aiming to evaluate the protein profiles of the aqueous humor of 15 patients divided into three groups: group 1, composed of patients with nAMD, who demonstrated a good response to anti-VEGF intravitreal injections during follow-up (good responsive); group 2, composed of patients with anti-VEGF-resistant nAMD, who demonstrated choroidal neovascularization activity during follow-up (poor/non-responsive); and group 3, composed of control patients without systemic diseases or signs of retinopathy. For proteomic characterization of the groups, mass spectrometry (label-free LC-MS/MS) was used. A total of 2,336 proteins were identified, of which 185 were distinctly regulated and allowed the differentiation of the clinical conditions analyzed. Among those, 39 proteins, including some novel ones, were analyzed as potential disease effectors through their pathophysiological implications in lipid metabolism, oxidative stress, complement system, inflammatory pathways, and angiogenesis. So, this study suggests the participation of other promising biomarkers in neovascular AMD, in addition to the known VEGF.

Changes in Serum Thiol-Disulphide Homeostasis in Sheep with Gastrointestinal Nematodes.

This work aimed to evaluate the thiol-disulphide homeostasis in serum of lambs naturally infected by gastrointestinal nematodes presenting different levels of parasite load indirectly indicated by faecal worm egg counts (EPG). Furthermore, the possible changes in the thiol-disulphide dynamic after different procedures to reduce the parasitic charge, such as the integrated crop-livestock system or anthelmintic treatment, were assessed. The results were compared with a panel of various oxidative stress and inflammatory biomarkers. The lambs were divided into three groups: animals highly infected (EPG higher than 5000) and packed cell volume (PCV) lower than 24% (G1); animals highly infected (EPG higher than 5000) and normal PCV (>24%) (G2); and animals presenting EPG lower than 5000 and normal PCV (>24%) (G3). The highly infected lambs (G1 and G2) showed lower total thiol (TT) and native thiol (SH) (p ≤ 0.01) than those from G3. After treatment, TT and SH increased significantly in all groups (p ≤ 0.01), and the disulphide (SS)/TT and SS/SH ratios decreased significantly (p < 0.01) in G1 and G2. These results show that the thiol-disulphide balance was impaired in lambs infected by gastrointestinal nematodes and that it could be potentially used as a biomarker to monitor this disease.

Innovative Approaches to Assess Intermediate Cardiovascular Risk Subjects: A Review From Clinical to Metabolomics Strategies.

Current risk stratification strategies for coronary artery disease (CAD) have low predictive value in asymptomatic subjects classified as intermediate cardiovascular risk. This is relevant because not all coronary events occur in individuals with traditional multiple risk factors. Most importantly, the first manifestation of the disease may be either sudden cardiac death or acute coronary syndrome, after rupture and thrombosis of an unstable non-obstructive atherosclerotic plaque, which was previously silent. The inaccurate stratification using the current models may ultimately subject the individual to excessive or insufficient preventive therapies. A breakthrough in the comprehension of the molecular mechanisms governing the atherosclerosis pathology has driven many researches toward the necessity for a better risk stratification. In this Review, we discuss how metabolomics screening integrated with traditional risk assessments becomes a powerful approach to improve non-invasive CAD subclinical diagnostics. In addition, this Review highlights the findings of metabolomics studies performed by two relevant analytical platforms in current use-mass spectrometry (MS) hyphenated to separation techniques and nuclear magnetic resonance spectroscopy (NMR) -and evaluates critically the challenges for further clinical implementation of metabolomics data. We also discuss the modern understanding of the pathophysiology of atherosclerosis and the limitations of traditional analytical methods. Our aim is to show how discriminant metabolites originated from metabolomics approaches may become promising candidate molecules to aid intermediate risk patient stratification for cardiovascular events and how these tools could successfully meet the demands to translate cardiovascular metabolic biomarkers into clinical settings.

Use of Mass Spectrometry to Screen Glycan Early Markers in Hepatocellular Carcinoma.

Association between altered glycosylation patterns and poor prognosis in cancer points glycans as potential specific tumor markers. Most proteins are glycosylated and functionally arranged on cell surface and extracellular matrix, mediating interactions and cellular signaling. Thereby, aberrant glycans may be considered a pathological phenotype at least as important as changes in protein expression for cancer and other complex diseases. As most serum glycoproteins have hepatic origin, liver disease phenotypes, such as hepatocellular carcinoma (HCC), may present altered glycan profile and display important modifications. One of the prominent obstacles in HCC is the diagnostic in advanced stages when patients have several liver dysfunctions, limiting treatment options and life expectancy. The characterization of glycomic profiles in pathological conditions by means of mass spectrometry (MS) may lead to the discovery of early diagnostic markers using non-invasive approaches. MS is a powerful analytical technique capable of elucidating many glycobiological issues and overcome limitations of the serological markers currently applied in clinical practice. Therefore, MS-based glycomics of tumor biomarkers is a promising tool to increase early detection and monitoring of disease.