Experimental and Theoretical Study on Electron Ionization and Fragmentation of Propylene Oxide─the First Chiral Molecule Detected in the Interstellar Medium.

Propylene oxide, CH3CHOCH2, is the first chiral molecule detected in space and the third C3 oxide detected toward the Sagittarius B2 (Sgr B2 (N)) molecular cloud, the others being propanal, CH3CH2CHO, and acetone, (CH3)2CO. With homochirality being ubiquitous in the building blocks of living matter, the formation and decay paths of propylene oxide in space are of specific interest. Motivated by the significant role of photo- and secondary electrons in astrochemistry, we have studied electron ionization and fragmentation of propylene oxide. Ion appearance energies are determined and compared to threshold values for the respective processes calculated at the G4MP2 level of theory, and potential reaction pathways are computed at the DFT level of theory. Electron ionization is found to destabilize propylene oxide, leading to barrierless opening of the C1-C2 bond of the epoxy ring, hydrogen transfer, and fragmentation over the methyl vinyl ether or rupture of the C2-O bond of the epoxy ring and fragmentation of the allyl alcohol cation as an intermediate, rather than direct bond ruptures.

Flexed elbow, abducted shoulder, forearm supinated (FABS) reconstruction from three-dimensional elbow MRI: diagnostic performance assessment in biceps head anatomy and pathology.

AIM: To determine inter-reader analysis and diagnostic performance on digitally reconstructed virtual flexed, abducted, supinated (FABS) imaging from three-dimensional (3D) isotropic elbow magnetic resonance imaging (MRI). MATERIALS AND METHODS: Six musculoskeletal radiologists independently evaluated elbow MRI images with virtual FABS reconstructions, blinded to clinical findings and final diagnoses. Each radiologist recorded a binary result as to whether the tendon was intact and if both heads were visible, along with a categorical value to the type of tear and extent of retraction in centimetres where applicable. Kappa and interclass correlation (ICC) were reported with 95% confidence intervals. Areas under the receiver operating curve (AUC) were reported. RESULTS: FABS reconstructions were obtained successfully in all 48 cases. With respect to tendon intactness, visibility of both heads, and type of tear, the Kappa values were 0.66 (0.53-0.78), 0.24 (0.12-0.37), and 0.55 (0.43-0.66), respectively. For the extent of retraction, the ICC was 0.85 (0.79-0.91) when including the tendons with and without retraction and 0.78 (0.61-0.91) when only including tendons with retraction. For tear versus no tear, AUC values were 0.82 (0.74-0.89) to 0.96 (0.91-1.01). CONCLUSION: Digital reconstruction of FABS positioning is feasible and allows good assessment of individual tendon head tears and retraction with high diagnostic performance.

Evaluating total nitrogen and phosphorous concentrations in a watershed impacted by diverse anthropic activities in a developing country.

This research aims to identify critical contamination points by nutrients, their possible origin (point and nonpoint sources), their spatial distribution, and possible attenuation by natural and anthropogenic processes. The study area is the Velhas River Basin, located in the Southeast Region of Brazil (17.0°-20.5° S; 43.5°-45.0°W). A historical series of water quality monitoring, land cover map, demographic and agricultural censuses, sewage treatment diagnostics, and local hydrographic networks were used to achieve the objectives. In addition, the regions were divided into incremental areas, enabling individualized analyses of each sub-basin. Descriptive statistics, seasonality, categorized data tests, agglomerative hierarchical cluster analysis, and principal component analysis were used. There was a significant contribution of nutrients in the most important urban agglomeration of the basin, resulting in peak concentrations measured at that place. Although the values were reduced by the mouth (650 km), the percentage of legislation violations remained high. The effects of punctual contamination were intensified by the low percentage of treated sewage in the basin, the absence of adequate treatment technologies to remove nutrients, and the disorderly urbanization. Furthermore, it was estimated that the nutrient load from animal husbandry is approximately 75% of the load from domestic effluents due to the high number of cattle in the basin and the low percentage of forests.

Effects and mechanotransduction pathways of therapeutic ultrasound on healthy and osteoarthritic chondrocytes: a systematic review of in vitro studies.

OBJECTIVE: To investigate the effects and mechanotransduction pathways of therapeutic ultrasound on chondrocytes. METHOD: PubMed, EMBASE and Web of Science databases were searched up to 19th September 2021 to identify in vitro studies exploring ultrasound to stimulate chondrocytes for osteoarthritis (OA) treatment. Study characteristics, ultrasound parameters, in vitro setup, and mechanotransduction pathways were collected. Risk of bias was judged using the Risk of Bias Assessment for Non-randomized Studies (RoBANS) tool. RESULTS: Thirty-one studies were included comprising healthy and OA chondrocytes and explants. Most studies had high risk of performance, detection and pseudoreplication bias due to lack of temperature control, setup calibration, inadequate semi-quantitatively analyzes and independent experiments. Ultrasound was applied to the culture plate via acoustic gel, water bath or culture media. Regardless of the setup used, ultrasound stimulated the cartilage production and suppressed its degradation, although the effect size was nonsignificant. Ultrasound inhibited p38, c-Jun N-terminal kinases (JNK) and factor nuclear kappa B (NFκB) pathways in OA chondrocytes to reduce apoptosis, inflammation and matrix degradation, while triggered phosphoinositide-3-kinase/akt (PI3K/Akt), extracellular signal-regulated kinase (ERK), p38 and JNK pathways in healthy chondrocytes to promote matrix synthesis. CONCLUSION: The included studies suggest that ultrasound application induces therapeutic effects on chondrocytes. However, these results should be interpreted with caution because high risk of performance, detection and pseudoreplication bias were identified. Future studies should explore the application of ultrasound on human OA chondrocytes cultures to potentiate the applicability of ultrasound towards cartilage regeneration of knee with OA.

The influence of simultaneous pancreas-kidney transplantation on the evolution of diabetic foot lesions and peripheral arterial disease.

PURPOSE: Simultaneous pancreas-kidney transplantation (SPKT) remains the best treatment option in patients with type 1 diabetes and chronic kidney failure. There are only a few studies addressing the potential ischemic deterioration of peripheral arterial disease (PAD) due to blood diverting from the iliac artery to the kidney graft. We aimed to evaluate diabetic foot lesions and PAD evolution in SPKT recipients and investigate if they are more frequent in ipsilateral lower limb of kidney graft. METHODS: We developed a retrospective cohort, including patients submitted to SPKT in our tertiary center, between 2000 and 2017. Diabetic foot lesions and PAD frequencies were compared in the period before and after transplantation. RESULTS: Two hundred and eleven patients were included, 50.2% (n = 106) female, with a median age at transplantation of 35 years (IQR 9). After a median follow-up period of 10 years (IQR 7), patient, kidney, and pancreatic graft survival were 90.5% (n = 191), 83.4% (n = 176), and 74.9% (n = 158), respectively. Before transplant, 2.8% (n = 6) had PAD and 5.3% (n = 11) had history of foot lesions. In post-transplant period, 17.1% (n = 36) patients presented PAD and 25.6% (n = 54) developed diabetic foot ulcers, 47.6% (n = 35) of which in the ipsilateral and 53.3% (n = 40) in the contralateral lower limb of the kidney graft (p = 0.48). Nine patients (4.3%) underwent major lower limb amputation, 3 (30%) ipsilateral and 7 (70%) contralateral to the kidney graft (p = 0.29). CONCLUSIONS: Diabetic foot lesions were not more frequent in the ipsilateral lower limb of the kidney graft, therefore downgrading the 'steal syndrome' role in these patients.

Efficacy of resveratrol in male urogenital tract dysfunctions: an evaluation of pre-clinical data.

Resveratrol is a polyphenol found naturally in fruits and plants. Recently, studies in humans and animal models have suggested beneficial properties of this polyphenol, such as improvements to metabolic and lipid profiles, along with antioxidant, anti-inflammatory and anti-proliferative effects. In the urogenital tract (UGT), resveratrol has also been tested clinically and experimentally as a therapeutic drug in several diseases; however, the translational efficacy of resveratrol, especially in UGT, is still a matter of debate. In the present review, we address the pre-clinical efficacy of resveratrol in UGT-related dysfunctions, focusing on lower urinary tract symptoms, non-cancerous prostatic disease (benign prostatic hyperplasia and prostatitis) and erectile dysfunction. In vitro studies indicate that resveratrol reduces inflammatory markers and oxidative stress, and improves endothelial function in UGT organs and cells isolated from humans and animals. Despite displaying low oral bioavailability, in vivo administration of resveratrol largely improves erectile dysfunction, benign prostatic hyperplasia, prostatitis and voiding impairments, as evidenced in different animal models. Resveratrol also acts as a microbiota modulator, which may explain some of its beneficial effects in vivo. In contrast to the large amount of pre-clinical data, there are insufficient clinical trials to establish resveratrol treatment efficacy in human UGT-related diseases. In summary, we provide an overview of the in vivo and in vitro efficacy of resveratrol in animal and human UGT dysfunctions, which may support future clinical trials.

The applicability of the "surprise question" as a prognostic tool in patients with severe chronic comorbidities in a university teaching outpatient setting.

BACKGROUND: Life expectancy in recent decades has increased the prevalence of chronic diseases in the population, requiring an approach to new health topics, such as discussions on quality of life and expectations about death and dying. The concept of advance directives (ADs) gives individuals the opportunity to make known their decisions about the treatments they would like to receive at the end of life. Despite the recognition of relevance in clinical practice, the applicability of the concept presents challenges, including establishing the appropriate prognosis for each patient and the ideal time to approach the patient. Some prognostic tools were developed, such as the surprise question (SQ): "Would you be surprised if your patient died in 12 months?", which is used in some clinical settings to predict patient deaths and to make decisions regarding ADs. The main objective of the present study was to evaluate the behavior of second-year resident physicians (PGY-2) when the SQ was applied. METHOD: In our observational study, from July 1, 2016, to February 28, 2017, (PGY-2) in the Internal Medicine Residency Program (IMRP) applied SQ to all patients with multiple and varied chronic no communicable comorbidities, who were followed up at the general medicine outpatient clinic (GMOC) of a tertiary university hospital in São Paulo- Brazil. The frequency of the outcome (death or non-death within 12 months) was analyzed by correlating it with the clinical data (impact of the studied variables). RESULTS: Eight hundred forty patients entered the study. Fitfty-two of them (6.2%) died within one year. PGY-2 predicted that two hundred and fourteen patients (25.5% of total) would die within a year (answer No to SQ), of which, 32 (14.9%) did so. The correct residents' prognosis for the subgroup of 626 patients (answer "Yes" to SQ) was NPV = 96.8% (CI = 95.4%-98.2%) and PPV = 14.9% (CI 10.1%-19, 6%). Answering "Yes" to SQ correlated negatively to addressing AD while the outcomes death and the answer No to SQ were positively correlated, according to the number of comorbidities. CONCLUSION: The SQ, in addition to care, contributed to health education, communication and care planning shared by the doctor and patient.

Leukocyte and platelet rich fibrin in the management of medication-related osteonecrosis of the jaw: A systematic review and meta-analysis.

BACKGROUND: Osteonecrosis of the jaw (ONJ) has a frequent adverse effect after the administration of nitrogenous bisphosphonates, as non-nitrogenous bisphosphonates are metabolized more rapidly and would produce this effect to a lesser extent. The objective of this study is to analyze the results obtained in the literature with the use of L-PRF in the treatment of ONJ through a systematic review and meta-analysis. MATERIAL AND METHODS: Medline (via PubMed), Cochrane, Web of Science and Grey Literature Database was screened from which 10 were selected. RESULTS: In the meta-analysis with full resolution, combining the use of L-PRF in the treatment of ONJ, a weighted proportion (PP) of 94.3% of complete resolution is obtained (95% CI: 91.2-97.4, p<0.001), with a low degree of heterogeneity, statistically significant (I2 = 29.02%; p<0.001). When analyzing the non-resolution data, a weighted proportion (PP) of 7.7% (95% CI: 3.6-11.9; p<0.001) was obtained with moderate heterogeneity (I2: 41.87%; p=0.112). In the meta-regression, no significant correlation was found between complete resolution and year of publication (intercept = 2.88, p=0.829). In consistency analysis no major changes in PP are identified when any of the studies are eliminated, demonstrating a high reliability in the combined results. CONCLUSION: L-PRF alone or in combination with other therapies in treatment of ONJ achieved high percentages of complete lesion resolution (94.3%). In studies where L-PRF is combined with other therapies, and where the effectiveness of the other therapy alone is analyzed, L-PRF has been shown higher percentages of resolution.

Salivary biomarkers present in patients with periodontitis without clinical distinction: findings from a meta-analysis.

BACKGROUND: A new classification for periodontitis has been adopted in clinical practice. However, there are still discussions regarding this new classification and difficulties in its adoption, both by professionals and researchers. Thus, this study aimed to evaluate which salivary biomarkers are present in periodontitis, following the new classification of periodontal diseases through meta-analysis. MATERIAL AND METHODS: A literature search was carried out in the scientific databases: PubMed, Scielo and Google scholar to select studies. The selection of studies was followed by two authors upon reading of the title, abstract and full text. The necessary data were collected and statistical analyses were performed using the Review Manager statistical software version 5.4, with calculation of Mean Difference, heterogeneity (I²) and funnel plot with P < 0.05. RESULTS: After following the selection criteria, 9 articles were selected for comparison. The studies address the presence of biomarkers in the saliva of patients with periodontitis and their possible use in the monitoring and diagnosis of the disease. For the meta-analytic comparison, a sample size of 1,983 individuals was used. Statistical analyses showed that nitric oxide, IL-6, IL-1B and osteoprotegerin are substances that are significantly present in patients with periodontitis (P < 0.05). CONCLUSIONS: IL-6, nitric oxide, IL-1B, TNF-α and osteoprotegerin are among the most present biomarkers in patients with periodontitis, and may be used in the future as a monitoring of periodontal disease. The present study also revealed that there was no statistically significant difference in the concentration of these biomarkers for clinical distinction from periodontitis.

Impacts of Covid-19 interventions on air quality: evidence from Brazilian metropolitan regions.

The Covid-19 pandemic has negatively disrupted the way our economy and society functions. Nonetheless, there have also been some positive externalities of the pandemic on the environment. This paper aims to evaluate the concentration of nitrogen dioxide in Brazilian metropolitan regions after the policies adopted to confront Covid-19. In terms of methodological approach, the study employs cross-sectional quantitative analyses to compare the period of 36 days, i.e., 12 March to 16 April-before (in 2019) and after (in 2020) the pandemic declaration. The data were obtained from the Sentinel 5-P low-Earth polar satellite concerning Brazilian metropolitan regions (n = 24). Thorough spatial and statistical analyses were undertaken to identify the pre- and during pandemic nitrogen dioxide concentrations. Complementarily, Spearman's correlation test was performed with variables that impact air quality. The study results a fall in nitrogen dioxide concentration levels in 21 of the 24 metropolitan regions which was observed. The Spearman's correlation coefficient between the nitrogen dioxide variation and the vehicle density was 0.485, at a significance level of 0.05. With these findings in mind, the paper advocates that while the pandemic has a significant negative consequence on the health of population globally, a series of measures that result in a new social organization directly interfere in the reduction of air pollution that contributes to the quality of the air we breathe.

Hyperglycemia alters N-glycans on colon cancer cells through increased production of activated monosaccharides.

Diabetes Mellitus (DM) is both, correlated and a known risk factor for colorectal cancer (CRC). Besides favoring the incidence of CRC, DM also accelerates its progression, worsening its prognosis. Previously, hyperglycemia, the DM hallmark, has been shown to lead to aberrant glycosylation of CRC cells, heightening their malignancy both in vivo and in vitro. Here we use mass spectrometry to elucidate the composition and putative structures of N-glycans expressed by MC38 cultured in normoglycemic (LG) and hyperglycemic-like conditions (HG). N-glycans, 67, were identified in MC38 cells cultured in LG and HG. The cells grown in HG showed a greater abundance of N-glycans when compared to LNG cells, without changes in the proportion of sialylated, fucosylated and mannosylated N-glycans. Among the identified N-glycans, 16 were differentially expressed, mostly mannosylated and fucosylated, with a minority of them being sialylated. Metabolomics analysis indicates that the alterations observed in the N-glycosylation may be mostly due to increase of the activated monosaccharides pool, through an increased glucose entrance into the cells. The alterations found here corroborate data from the literature regarding the progression of CRC, advocating for development or repositioning of effective treatments against CRC in diabetic patients.

Triphenylboroxine stability under low-energy-electron interactions.

Triphenylboroxine (TPB) has chemical properties of great interest in organic synthesis, enabling the development of promising molecular architectures. Based on the possibility of the geometric arrangement of N-coordinated boron atoms, the dynamic interconversion ability of boroxine cages enables the optimization of relevant pharmacological properties in drug delivery, such as guest recognition and porosity. In addition, the synthesis of a novel 2D boroxine framework showed distinctive electronic and morphological properties that can be used in the design of new electronic devices. In the present study, the electron-driven fragmentation pathways from electron interactions with TPB using a gas-phase crossed-beam experiment have been investigated. The abundance of the molecular parent cation in the mass spectrum at 70 eV reflects the stability of TPB. The appearance energies of three fragment cations were reported, and the experimental first ionization potential was found at 9.12 ± 0.10 eV. Only the parent cation is formed in the energy range (∼9-16 eV) between the first ionization potential and the remaining thresholds. Regarding negative ion formation, four low-abundant anions in the electron energy range of 0-15 eV are discussed. These results indicate an interesting energy selectivity and stability of TPB upon electron interaction, which may justify the development of recent molecular architectures containing TPB used in a wide range of applications. These results are supported by quantum chemical calculations based on bound state techniques, electron ionization models and thermodynamic thresholds.

A fibre and phenolic-rich flour from Isabel grape by-products with stimulatory effects on distinct probiotics and beneficial impacts on human colonic microbiota in vitro.

This study evaluated the effects of a fibre and phenolic-rich flour (IGF) prepared from Isabel grape by-products on the growth and metabolism of different probiotics and distinct bacterial populations part of the human intestinal microbiota during an in vitro colonic fermentation. IGF was submitted to simulated gastrointestinal digestion before use in the experiments. IGF favoured the growth of the probiotics Lactobacillus acidophilus La-05, L. casei L-26 and Bifidobacterium lactis Bb-12, with viable counts of >7 log CFU per ml, as well as caused decreases in pH values and increases in organic acid production in the growth medium during 48 h of cultivation. IGF increased the population of beneficial micro-organisms forming the human intestinal microbiota, particularly Lactobacillus spp., decreased the pH values, and increased the lactic acid and short-chain fatty acid (acetic, butyric and propionic acids) production during 24 h of in vitro colonic fermentation. These results indicate the potential prebiotic effects of IGF, which should represent a novel sustainable added-value ingredient with functional properties and gut-health benefits.

RHCE variant alleles and risk of alloimmunization in Brazilians.

Variant RHCE alleles are found mainly in Afro-descendant individuals, as well as in patients with sickle cell disease (SCD). The most common variants are related to the RHCE*ce allele, which can generate partial e and c antigens. Although RHCE variant alleles have been extensively studied, defining their clinical significance is a difficult task. We evaluated the risk of RhCE alloimmunization as a consequence of partial antigens in patients with a positive phenotype transfused with red blood cell (RBC) units with the corresponding antigen. A retrospective study was performed with Brazilian patients, evaluating the number of antigen-positive transfused RBC units (incompatible due to partial antigen) in 27 patients with SCD carrying RHCE variant alleles who did not develop antibodies as well as evaluating the variants present in 12 patients with partial phenotype and correlated antibody (one patient with SCD and 11 patients with other pathologies). Two patients showed variant alleles with molecular changes that had not yet been described. Variant RHCE alleles were identified in a previous study using molecular methods. RHCE*ceVS.01 was the most frequent allele found among the patients without antibodies. Six patients with partial c antigen had a mean of 3.8 c+ RBC units transfused, and 10 patients with partial e antigen were exposed for a mean of 7.2 e+ RBC units. Among the variant alleles found in alloimmunized patients, the most frequent was RHCE*ceAR, which was found in five patients; the antibodies developed were anti-hrS and/or anti-c. Our results showed that RHCE*ceVS.01 is indeed the most frequent variant allele in our cohort of patients with SCD, but the partial antigens that were identified have low risk of alloimmunization. RHCE*ceAR is the most impactful variant in the Brazilian population with high risk of alloimmunization and clinically significant anti-hrS formation.

Fire ignition patterns to manage prescribed fire behavior: Application to Mediterranean pine forests.

Climate change and the accumulation of surface fuel are leading to global changes in the occurrence of increasingly severe fires. In light of current budgetary constraints, prescribed fire can be a very cost-efficient tool for both reducing wildfire hazards and managing fire-prone landscapes. However, despite its widespread use in some countries, social and administrative constraints arise when applied at the European or larger scales. Science-based knowledge concerning fire behavior, fuel load reduction, and tree impacts is required to support the use of prescribed fire. Spatial ignition patterns can increase or decrease the spread rate, flame length, and flame residence time according to the objectives of a prescribed fire. This work aims to analyze fire behavior using different fire ignition patterns (strip-heading fire, flanking fire, and spot-heading fire) and meteorological and fuel conditions. Seventy-seven observations or sampling units using twenty-three prescribed fires were established for fire monitoring. Non-linear models based on environmental variables were fitted for the spread rate and flame length. Our study proposes a novel way of sharing scientific knowledge in relation to the most common distances between ignition lines and ignition points used in the southern Iberian Peninsula. The spread rate and flame length can be increased in strip-heading fire, by more than 3.5-fold and more than 1.95-fold, respectively, by modifying only the distance between ignition lines. Flanking fire could lead to a decrease in the spread rate by approximately half. Although spot-heading fire can reduce the spread rate by more than 78% and flame length by more than 41%, the highest distances between points could increase the flame residence time by 39-132%. This research seeks to achieve a trade-off between fire intensity and the impacts of fire on trees, soil, and surface roots.

Proteomic profile of vitrified in vitro-produced bovine embryos (Bos taurus indicus).

BACKGROUND: The proteomic profile of cryopreserved in vitro produced bovine embryos is little known but can provide insights on the successful application of cryo procedures in support of animal breeding. OBJECTIVE: To identify embryonic proteins and biomarkers related to improved cryotolerance of vitrified in vitro produced bovine embryos. MATERIALS AND METHODS: Proteins were isolated from embryo pools (n = 25 embryos per replicate) and analyzed using the nanoLC - MS/MS system. Further, the UniProtKB database (Uniprot -http://www.uniprot.org/) was used for protein identification. Proteins were classified based on their molecular mass, isoelectric point, and enzymatic activity. Post-translational modification predictions and functional gene ontology analysis were performed as well. Finally, a protein-protein interaction network was created to shed light on the embryo interactome. RESULTS: Based on the MS/MS approach, 66 proteins were identified from vitrified Bos taurus embryos. The retrieved proteins were presumably annotated, which allowed a description of the qualitative and functional aspects of the embryo proteome after the vitrification process. CONCLUSION: These findings allowed us to conclude that in vitro-produced vitrified embryos expressed proteins that underlie biological processes related to reproduction, stress and lipid metabolic process, which are essential to maintain embryo viability. doi.org/10.54680/fr22410110512.

In cardiac fibroblasts, interferon-beta attenuates differentiation, collagen synthesis, and TGF-ß1-induced collagen gel contraction.

Cardiac fibroblasts (CF) play a key role in the homeostasis of the extracellular matrix in cardiac tissue and are newly recognized as inflammatory supporter cells. Besides, CF-to-Cardiac myofibroblast differentiation is commanded by TGF-b, through SMAD signaling pathways, and these last cells are strongly implicated in cardiac fibrosis. In the heart IFN-ß is produced by CF; however, the role of IFN-ß, STAT proteins, and STAT-homo or heterodimers in the regulation of CF function with or without a fibrotic environment is unknown. CF were isolated from hearts of adult rats, and by western blot analysis we studied STAT1, STAT2, and STAT3 phosphorylation and through specific siRNA against these proteins we analyzed their role in CF functions such as differentiation (α-SMA expression); and pro-collagen type-I synthesis and secretion expression levels; collagen gels contraction and CF migration. In cultured adult rats CF, IFN-ß increases phosphorylation of STAT1, STAT2, and STAT3. Both STAT1 and STAT2 were involved in decreasing α-SMA and CF migration induced by TGF-ß1. Also, IFN-ß through STAT1 regulated pro-collagen type-I protein expression levels, and collagen gels contraction induced by TGF-ß1. STAT3 was not involved in any effects of IFN-ß studied. In conclusion, IFN-ß through STAT1 and STAT2 shows antifibrotic effects on CF TGF-ß1-treated, whereas STAT3 did not participate in such effect.

Oxygen effects on the electronic transport in stanene.

In this work, we study theoretically the structural, electronic and transport properties of oxidized stanene using a combination of density functional theory (DFT), quantum molecular dynamics and the Landauer-Büttiker theory for the ballistic transport. Our results clearly show that oxygen adsorb onto stanene surface in both molecular or atomic forms, thus causing considerable modifications to its electronic structure and transport properties. Nevertheless, our quantum conductance calculations reveal that, in spite of oxidation, stanene still remains a good conductor that might be applied as field effect transistors, gas sensors and other devices.

Metabolomic fingerprinting of Brazilian marine sponges: a case study of Plakinidae species from Fernando de Noronha Archipelago.

Marine sponges from the Plakinidae family are well known for hosting cytotoxic secondary metabolites and the Brazilian Atlantic coast and its oceanic islands have been considered as a hotspot for the discovery of new Plakinidae species. Herein, we report the chemical profile among cytotoxic extracts obtained from four species of Plakinidae, collected in Fernando de Noronha Archipelago (PE, Northeastern Brazil). Crude organic extracts of Plakinastrella microspiculifera, Plakortis angulospiculatus, Plakortis insularis, and Plakortis petrupaulensis showed strong antiproliferative effects against two different cancer cell lines (HCT-116: 86.7-100%; MCF-7: 74.9-89.5%) at 50 µg/mL, by the MTT assay. However, at a lower concentration (5 µg/mL), high variability in inhibition of cell growth was observed (HCT-116: 17.3-68.7%; MCF-7: 0.00-55.5%), even within two samples of Plakortis insularis which were collected in the west and east sides of the Archipelago. To discriminate the chemical profile, the samples were investigated by UHPLC-HRMS under positive ionization mode. The produced data was uploaded to the Global Natural Products Social Molecular Networking and organized based on spectral similarities for purposes of comparison and annotation. Compounds such as dipeptides, nucleosides and derivatives, polyketides, and thiazine alkaloids were annotated and metabolomic differences were perceived among the species. To the best of our knowledge, this is the first assessment for cytotoxic activity and chemical profiling for Plakinastrella microspiculifera, Plakortis insularis and Plakortis petrupaulensis, revealing other biotechnologically relevant members of the Plakinidae family.

Perfluoro effect on the electronic excited states of para-benzoquinone revealed by experiment and theory.

We report a comprehensive study on the electronic excited states of tetrafluoro-1,4-benzoquinone, through high-resolution vacuum ultraviolet photoabsorption spectroscopy and time-dependent density functional theory calculations performed within the nuclear ensemble approach. Absolute cross section values were experimentally determined in the 3.8-10.8 eV energy range. The present experimental results represent the highest resolution data yet reported for this molecule and reveal previously unresolved spectral structures. The interpretation of the results was made in close comparison with the available data for para-benzoquinone [Jones et al., J. Chem. Phys., 2017, 146, 184303]. While the dominant absorption features for both molecules arise from analogous π* ← π transitions, some remarkable differences have been identified. The perfluoro effect manifests in different ways: shifts in band positions and cross sections, appearance of features associated with excitations to σCF* orbitals, and spectrum broadening by quenching of either vibrational or Rydberg progressions. The level of agreement between experiment and theory is very satisfactory, yet that required the inclusion of nuclear quantum effects in the calculations. We have also discussed the role of temperature on the absorption spectrum, as well as the involvement of core-excited resonances in promoting dissociative electron attachment reactions in the 3-5 eV range.