The EN-TEx resource of multi-tissue personal epigenomes & variant-impact models.

Understanding how genetic variants impact molecular phenotypes is a key goal of functional genomics, currently hindered by reliance on a single haploid reference genome. Here, we present the EN-TEx resource of 1,635 open-access datasets from four donors (∼30 tissues × âˆ¼15 assays). The datasets are mapped to matched, diploid genomes with long-read phasing and structural variants, instantiating a catalog of >1 million allele-specific loci. These loci exhibit coordinated activity along haplotypes and are less conserved than corresponding, non-allele-specific ones. Surprisingly, a deep-learning transformer model can predict the allele-specific activity based only on local nucleotide-sequence context, highlighting the importance of transcription-factor-binding motifs particularly sensitive to variants. Furthermore, combining EN-TEx with existing genome annotations reveals strong associations between allele-specific and GWAS loci. It also enables models for transferring known eQTLs to difficult-to-profile tissues (e.g., from skin to heart). Overall, EN-TEx provides rich data and generalizable models for more accurate personal functional genomics.

Sympathetic neuro-adipose connections mediate leptin-driven lipolysis.

Leptin is a hormone produced by the adipose tissue that acts in the brain, stimulating white fat breakdown. We find that the lipolytic effect of leptin is mediated through the action of sympathetic nerve fibers that innervate the adipose tissue. Using intravital two-photon microscopy, we observe that sympathetic nerve fibers establish neuro-adipose junctions, directly "enveloping" adipocytes. Local optogenetic stimulation of sympathetic inputs induces a local lipolytic response and depletion of white adipose mass. Conversely, genetic ablation of sympathetic inputs onto fat pads blocks leptin-stimulated phosphorylation of hormone-sensitive lipase and consequent lipolysis, as do knockouts of dopamine ß-hydroxylase, an enzyme required for catecholamine synthesis. Thus, neuro-adipose junctions are necessary and sufficient for the induction of lipolysis in white adipose tissue and are an efferent effector of leptin action. Direct activation of sympathetic inputs to adipose tissues may represent an alternative approach to induce fat loss, circumventing central leptin resistance. PAPERCLIP.

Community-developed checklists for publishing images and image analyses.

Images document scientific discoveries and are prevalent in modern biomedical research. Microscopy imaging in particular is currently undergoing rapid technological advancements. However, for scientists wishing to publish obtained images and image-analysis results, there are currently no unified guidelines for best practices. Consequently, microscopy images and image data in publications may be unclear or difficult to interpret. Here, we present community-developed checklists for preparing light microscopy images and describing image analyses for publications. These checklists offer authors, readers and publishers key recommendations for image formatting and annotation, color selection, data availability and reporting image-analysis workflows. The goal of our guidelines is to increase the clarity and reproducibility of image figures and thereby to heighten the quality and explanatory power of microscopy data.

ATG9A regulates the dissociation of recycling endosomes from microtubules to form liquid influenza A virus inclusions.

It is now established that many viruses that threaten public health establish condensates via phase transitions to complete their lifecycles, and knowledge on such processes may offer new strategies for antiviral therapy. In the case of influenza A virus (IAV), liquid condensates known as viral inclusions, concentrate the 8 distinct viral ribonucleoproteins (vRNPs) that form IAV genome and are viewed as sites dedicated to the assembly of the 8-partite genomic complex. Despite not being delimited by host membranes, IAV liquid inclusions accumulate host membranes inside as a result of vRNP binding to the recycling endocytic marker Rab11a, a driver of the biogenesis of these structures. We lack molecular understanding on how Rab11a-recycling endosomes condensate specifically near the endoplasmic reticulum (ER) exit sites upon IAV infection. We show here that liquid viral inclusions interact with the ER to fuse, divide, and slide. We uncover that, contrary to previous indications, the reported reduction in recycling endocytic activity is a regulated process rather than a competition for cellular resources involving a novel role for the host factor ATG9A. In infection, ATG9A mediates the removal of Rab11a-recycling endosomes carrying vRNPs from microtubules. We observe that the recycling endocytic usage of microtubules is rescued when ATG9A is depleted, which prevents condensation of Rab11a endosomes near the ER. The failure to produce viral inclusions accumulates vRNPs in the cytosol and reduces genome assembly and the release of infectious virions. We propose that the ER supports the dynamics of liquid IAV inclusions, with ATG9A facilitating their formation. This work advances our understanding on how epidemic and pandemic influenza genomes are formed. It also reveals the plasticity of recycling endosomes to undergo condensation in response to infection, disclosing new roles for ATG9A beyond its classical involvement in autophagy.

Protein aggregation-inhibition: a therapeutic route from Parkinson's disease to sickle cell anemia.

Protein aggregation is implicated in multiple diseases, so-called proteinopathies, ranging from neurodegenerative disorders such as Alzheimer's disease and Parkinson's disease (PD) to type 2 diabetes mellitus and sickle cell disease (SCD). The structure of the protein aggregates and the kinetics and mechanisms of aggregation have been the object of intense research over the years toward the development of therapeutic routes, including the design of aggregation inhibitors. Nonetheless, the rational design of drugs targeting aggregation inhibition remains a challenging endeavor because of multiple, disease-specific factors, including an incomplete understanding of protein function, the multitude of toxic and non-toxic protein aggregates, the lack of specific drug binding targets, discrepant action mechanisms of aggregation inhibitors, or a low selectivity, specificity, and/or drug potency, reflected in the high concentrations required for some inhibitors to be effective. Herein, we provide a perspective of this therapeutic route with emphasis on small molecules and peptide-based drugs in two diverse diseases, PD and SCD, aiming at establishing links among proposed aggregation inhibitors. The small and large length-scale regimes of the hydrophobic effect are discussed in light of the importance of hydrophobic interactions in proteinopathies. Some simulation results are reported on model peptides, illustrating the impact of hydrophobic and hydrophilic groups in water's hydrogen-bond network with an impact on drug binding. The seeming importance of aromatic rings and hydroxyl groups in protein-aggregation-inhibitor-drugs is emphasized along with the challenges associated with some inhibitors, limiting their development into effective therapeutic options, and questioning the potential of this therapeutic route.

Antimicrobial and antibiofilm properties of procyanidins: potential for clinical and biotechnological applications.

Procyanidins (PCs) have emerged as agents with potential antimicrobial and antibiofilm activities, although their mechanisms of action and structure-activity relationships remain poorly understood. This review assessed the potential mechanisms of action and applications of these compounds to explore these aspects. Studies on the antimicrobial properties of PCs suggest that they are involved in osmotic imbalance, DNA interactions and metabolic disruption. Although less studied, their antibiofilm activities include antiadhesive effects and the modulation of mobility and quorum sensing. However, most research has used uncharacterized plant extracts for in vitro assays, limiting the understanding of the structure-activity relationships of PCs and their in vivo mechanisms. Clinical trials on the antimicrobial and antibiofilm properties of PCs have not clarified these issues due to nonstandardized methodologies, inadequate chemical characterization, and the limited number of studies, preventing a consensus and evaluation of the in vivo effects. Additionally, patent analysis revealed that technological developments in the antimicrobial and antibiofilm uses of PCs are concentrated in health care and dental care, but new biotechnological uses are emerging. Therefore, while PCs are promising antimicrobial and antibiofilm compounds, further research into their chemical structures and mechanisms of action is crucial for evidence-based applications in biotechnology and health care.

Wild-Type α-Synuclein Structure and Aggregation: A Comprehensive Coarse-Grained and All-Atom Molecular Dynamics Study.

α-Synuclein (α-syn) is a 140 amino acid intrinsically disordered protein (IDP) and the primary component of cytotoxic oligomers implicated in the etiology of Parkinson's disease (PD). While IDPs lack a stable three-dimensional structure, they sample a heterogeneous ensemble of conformations that can, in principle, be assessed through molecular dynamics simulations. However, describing the structure and aggregation of large IDPs is challenging due to force field (FF) accuracy and sampling limitations. To cope with the latter, coarse-grained (CG) FFs emerge as a potential alternative at the expense of atomic detail loss. Whereas CG models can accurately describe the structure of the monomer, less is known about aggregation. The latter is key for assessing aggregation pathways and designing aggregation inhibitor drugs. Herein, we investigate the structure and dynamics of α-syn using different resolution CG (Martini3 and Sirah2) and all-atom (Amber99sb and Charmm36m) FFs to gain insight into the differences and resemblances between these models. The dependence of the magnitude of protein-water interactions and the putative need for enhanced sampling (replica exchange) methods in CG simulations are analyzed to distinguish between force field accuracy and sampling limitations. The stability of the CG models of an α-syn fibril was also investigated. Additionally, α-syn aggregation was studied through umbrella sampling for the CG models and CG/all-atom models for an 11-mer peptide (NACore) from an amyloidogenic domain of α-syn. Our results show that despite the α-syn structures of Martini3 and Sirah2 with enhanced protein-water interactions being similar, major differences exist concerning aggregation. The Martini3 fibril is not stable, and the binding free energy of α-syn and NACore is positive, opposite to Sirah2. Sirah2 peptides in a zwitterionic form, in turn, display termini interactions that are too strong, resulting in end-to-end orientation. Sirah2, with enhanced protein-water interactions and neutral termini, provides, however, a peptide aggregation free energy profile similar to that found with all-atom models. Overall, we find that Sirah2 with enhanced protein-water interactions is suitable for studying protein-protein and protein-drug aggregation.

Essential dynamics of ubiquitin in water and in a natural deep eutectic solvent.

Natural deep eutectic solvents (NADESs) comprised of osmolytes are of interest as potential biomolecular (cryo)protectants. However, the way these solvents influence the structure and dynamics of biomolecules as well as the role of water remains poorly understood. We carried out principal component analysis of various secondary structure elements of ubiquitin in water and a betaine : glycerol : water (1 : 2 : ζ; ζ = 0, 1, 2, 5, 10, 20, 45) NADES, from molecular dynamics trajectories, to gain insight into the protein dynamics as it undergoes a transition from a highly viscous anhydrous to an aqueous environment. A crossover of the protein's essential dynamics at ζ ∼ 5, induced by solvent-shell coupled fluctuations, is observed, indicating that ubiquitin might (re)fold in the NADES upon water addition at ζ > ∼5. Further, in contrast to water, the anhydrous NADES preserves ubiquitin's essential modes at high temperatures explaining the protein's seemingly enhanced thermal stability.

Properties and environmental quality of the overburden and tailings of manganese mining in the Eastern Amazon.

Knowledge about the characteristics of overburden and tailings from manganese (Mn) mining is essential for defining their levels of potentially toxic elements (PTEs) and appropriate environmental management. This study aimed to assess the total and bioavailable contents of PTEs in Mn mining areas in the Eastern Amazon, as well as the associated environmental risks. The samples were collected in areas of overburden and tailings deposition, in addition to forest soils in the Azul mine, Carajás Mineral Province, Brazil. These samples were characterized in terms of fertility, granulometry, and total and bioavailable PTE contents. The pH values of the forest soil were more acidic than those of the overburden and tailings, and the organic matter contents were considerably higher in the forest soil. All PTEs, especially Mn, Ba, Cu, Zn, and Pb, presented higher contents in the overburden and tailings. However, chemical fractionation revealed that PTEs were predominantly in the residual fraction, with percentage contents above 60% of the total content. These results suggest a low risk of environmental contamination. The findings of this study may support more efficient environmental rehabilitation in Mn mining areas in the Amazon.

Proteomic changes associated with the development of açaí (Euterpe oleracea Mart.) seeds.

Açaí palm (Euterpe oleracea Mart.) seeds are a rich source of mannans, which can be used to generate bioethanol or be converted to high-value D-mannose, in addition to being a source of polyphenols with beneficial health properties. Here, we present a quantitative proteome dataset of açaí seeds at four stages of development (S1, S2, S3, and S4 stages), in which 2465 high confidence proteins were identified and 524 of them show statistically different abundance profiles during development. Several enzymes involved in the biosynthesis of nucleotide-sugars were quantified, especially those dedicated to the formation of GDP-mannose, which showed an increase in abundance between stages S1 and S3. Our data suggest that linear mannans found abundantly in endosperm cell walls are initially deposited as galactomannans, and during development lose the galactosyl groups. Two isoforms of alpha-galactosidase enzymes showed significantly increased abundances in the S3 and S4 stages. Additionally, we quantified the enzymes participating in the central pathway of flavonoid biosynthesis responsible for the formation of catechin and epicatechin, which are subunits of procyanidins, the main class of polyphenols in the açaí seeds. These proteins showed the same pattern of deposition, in which higher abundances were seen in the S1 and S2 stages.

The acquisition of thin sections of açaí (Euterpe oleracea Mart.) seed with elevated potassium content for molecular mapping by mass spectrometry imaging.

RATIONALE: Matrix-assisted laser desorption/ionization imaging mass spectrometry (MALDI-IMS) of tissues became popular in the last decade. Consequently, adapting sample preparation methods for different materials turned out to be a pivotal step for successful analysis due to the requirement of sample slices of 12-20 µm thickness. However, acquiring thin sections compatible with MALDI-IMS for unusual samples is challenging, as existing histological protocols may not be suitable, thus requiring new methods. Açaí (Euterpe oleracea Mart.) seed is an example of a challenging material due to its toughness and resistance to crack, therefore our goal was to develop a methodology to obtain thin (12-20 µm) and entire sections of açaí seeds for MALDI-IMS analysis. METHODS: Different strategies were evaluated for obtaining thin sections of seeds, and the combination of the following steps was found to be the most suitable option: (i) softening of seeds by water immersion for 24 h; (ii) transversal cut of seeds to obtain half-seeds using a razor blade and a hammer; (iii) half-seeds imbibition in gelatin; (iv) samples sectioning using a cryostat at -20°C to obtain samples with 12-20 µm thickness; (v) collection of samples in an indium tin oxide-coated glass slide covered by double-sided copper tape to avoid sample wrapping and ensure adhesion after unfreezing; and (vi) storage of samples in a -80°C freezer, if necessary. RESULTS: This adapted sample preparation method enabled the analysis of açaí seeds by MALDI-IMS, providing spatial distribution of carbohydrates in the endosperm. CONCLUSIONS: The adaptations developed for sample preparation will help investigate the metabolic and physiological properties of açaí seeds in future studies.

Comparative analysis of the biocompatibility of endothelial cells on surfaces treated by thermal plasma and cold atmospheric plasma.

In recent years, cold atmospheric plasma (CAP) is used for surface disinfection. However, little is known about its ability to improve biocompatibility of metallic surfaces when compared to thermal plasma methods. In this context, the study aimed to evaluate the response of human endothelial cells (Ea.hy926) on titanium surfaces treated by non-thermal plasma method and thermal plasma method under nitriding atmosphere. The wettability was characterized by the sessile drop method, the topography and roughness were evaluated by atomic force microscopy (AFM), and the microstructure by grazing angle X-ray diffraction (GIXRD). Endothelial cells were cultured and evaluated for morphology by scanning electron microscopy and viability by an MTT (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide) assay. CAP treatment reduced the contact angle of the Ti surface (13.43° ± 1.48; p<0.05), increasing hydrophilicity. Rz roughness was higher on the nitrided surface (220.44±20.30; p< 0.001) compared to the CAP treated surfaces (83.29 ± 11.61; p< 0.001) and polished (75.98 ±34.21a); p<0.001). The different applied plasma treatments created different titanium surfaces improving the biocompatibility of endothelial cells, however CAP results demonstrate its potential for biomedical applications, considering the low cost and ease of use of the technique, allowing surface treatments before clinical procedures.

Combined effects of hydrothermally-altered feldspar and water regime on cadmium minimization in rice.

The accumulation of cadmium (Cd) in grains and edible parts of crops poses a risk to human health. Because rice is the staple food of more than half of the world population, reducing Cd uptake by rice is critical for food safety. HydroPotash (HYP), an innovative potassium fertilizer produced with a hydrothermal process, has the characteristics of immobilizing heavy metals and potential use for remediating Cd-contaminated soils. The objective of this study was to evaluate the HYP as a soil amendment to immobilize Cd in acidic soils and to reduce the accumulation of Cd in rice tissues. The experiment was performed in a greenhouse with a Cecil sandy loam soil (pH 5.3 and spiked with 3 mg Cd kg-1) under either flooding conditions (water level at 4 cm above the soil surface) or at field capacity. Two hydrothermal materials (HYP-1 and HYP-2) were compared with K-feldspar + Ca(OH)2 (the raw material used for producing HYP), Ca(OH)2, zeolite, and a control (without amendment). After 30 days of soil incubation, HydroPotashs, the raw material, and Ca(OH)2 increased both soil solution pH and electrical conductivity. These materials also decreased soluble Cd concentration (up to 99.7%) compared with the control (p < 0.05). After 145 days, regardless of the materials applied, plant growth was favored (up to 35.8%) under the flooded regime. HydroPotash-1 was more effective for increasing dry biomass compared with other amendments under both water regimes. HydroPotashs reduced extractable Cd in soil, Cd content in plant biomass at tillering and maturing stage, and were efficient in minimizing Cd accumulation in rice grains.

Copper mining in the eastern Amazon: an environmental perspective on potentially toxic elements.

Mining activity is of great economic and social importance; however, volumes of metallic ore tailings rich in potentially toxic elements (PTEs) may be produced. In this context, managing this environmental liability and assessing soil quality in areas close to mining activities are fundamental. This study aimed to compare the concentrations of PTEs-arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg), molybdenum (Mo), nickel (Ni), lead (Pb) and zinc (Zn)-as well as the fertility and texture of Cu tailings and soils of native, urban and pasture areas surrounding a Cu mining complex in the eastern Amazon. The levels of PTEs were compared with soil prevention values, soil quality reference values, global average soil concentrations and average upper continental crust concentrations. The contamination factor (CF), degree of contamination (Cdeg), potential ecological risk index (RI), geoaccumulation index (Igeo) and pollution load index (PLI) were calculated. The levels of Co, Cu and Ni in the tailings area exceeded the prevention values, soil quality reference values and average upper continental crust concentrations; however, the tailings area was considered unpolluted according to PLI and RI and presented a low potential ecological risk. The high concentrations of PTEs are associated with the geological properties of the area, and the presence of PTEs-rich minerals supports these results. For the urban and pasture areas, none of the 11 PTEs analyzed exceeded the prevention values established by the Brazilian National Environment Council.

Changes in soil properties during iron mining and in rehabilitating minelands in the Eastern Amazon.

Open-cast iron mining causes drastic disturbances in soil properties. Recovery of soil chemical and physical properties is essential for successful revegetation and landscape rehabilitation. To identify changes in soil properties during the mining and revegetation process, soil samples were collected from undisturbed sites represented by forest and ferriferous savannas stocking above iron outcrops, called "cangas," in open-pit benches, and in rehabilitation chronosequences of iron waste piles in the Carajás Mineral Province (CMP), Eastern Amazon, Brazil. The samples were analyzed for chemical and physical properties. Our results showed that iron mining operations resulted in significant alteration of the chemical soil properties when forest and canga vegetation are suppressed to form open-pit benches or waste piles in the CMP. Mining substrates showed lower contents of soil organic matter (SOM) and nutrients than undisturbed areas of forests and cangas. In order to achieve the success of revegetation, nutrients have been added prior to plant establishment. We have demonstrated how soil fertility changes along with mineland rehabilitation, and the variation among chronosequence was attributable mainly due to contents of SOM, K, and B in the soil. The slight improvement of SOM found in rehabilitated waste piles reinforces the notion that recovery of soil quality can be a slow process in iron minelands in the CMP.

Phytotoxicity test in check: Proposition of methodology for comparison of different method adaptations usually used worldwide.

Seed germination tests have been widely used in recent years to indicate the toxicity levels of samples of organic compounds, biosolids, residues and effluents. Lactuca sativa L, commonly known as lettuce, has been one of the main indicative species for these tests due to its high sensitivity to low levels of toxicity, when compared to other seeds and also because it is cultivated worldwide. Although this type of analysis or essay is being widely used, it is necessary to reflect on the various adaptations of methods used by different researchers worldwide. This work presents an innovative methodology that makes it possible to compare the different phytotoxicity methods currently used in the world, through four stages that include the coefficient of variation (CV) as the main classification criterion, also counting on an eliminatory criterion. The existence of a significant difference (P value < 0.05) between the evaluated tests was proven. The phytotoxicity test that presented the lowest CV was T8 (test with lettuce seeds at 25 °C, 60 min agitation, resting overnight, 5 mL of sample on the plate, 90 mm size plate). It has concluded that not all adaptations of this type of test are reliable. It has also concluded that there is a lack of standardization for the phytotoxicity test on a global scale, which makes the various researchers in the field end up promoting variations, adaptations for the phytotoxicity test; therefore, there is an urgent need for ways to compare these variations, as the innovation proposed by this work. With a single standard methodology, we conclude that it will make it possible to compare phytotoxicity in samples directly between countries and continents, being able to generate a worldwide panorama of phytotoxicity, publicizing and comparing the standardized phytotoxicity levels in each region.

Açaí (Euterpe oleracea Mart.) Seed Extracts from Different Varieties: A Source of Proanthocyanidins and Eco-Friendly Corrosion Inhibition Activity.

Euterpe oleracea Mart. (Arecaceae) is an endogenous palm tree from the Amazon region. Its seeds correspond to 85% of the fruit's weight, a primary solid residue generated from pulp production, the accumulation of which represents a potential source of pollution and environmental problems. As such, this work aimed to quantify and determine the phytochemical composition of E. oleracea Mart. seeds from purple, white, and BRS-Pará açaí varieties using established analytical methods and also to evaluate it as an eco-friendly corrosion inhibitor. The proanthocyanidin quantification (n-butanol/hydrochloric acid assay) between varieties was 6.4-22.4 (w/w)/dry matter. Extract characterization showed that all varieties are composed of B-type procyanidin with a high mean degree of polymerization (mDP ≥ 10) by different analytical methodologies to ensure the results. The purple açaí extract, which presented 22.4% (w/w) proanthocyanidins/dry matter, was tested against corrosion of carbon steel AISI 1020 in neutral pH. The crude extract (1.0 g/L) was effective in controlling corrosion on the metal surface for 24 h. Our results demonstrated that the extracts rich in polymeric procyanidins obtained from industrial açaí waste could be used to inhibit carbon steel AISI 1020 in neutral pH as an abundant, inexpensive, and green source of corrosion inhibitor.

Bioavailability of copper and nickel in naturally metal-enriched soils of Carajás Mining Province, Eastern Amazon, Brazil.

Naturally elevated contents of copper (Cu) and nickel (Ni) are found in soils worldwide, and their potential toxicity is better understood when geochemical reactive fractions are identified and monitored. Thus, this study aimed to assess the bioavailability of Cu and Ni and estimate environmental risks in naturally metal-enriched soils of Carajás Mining Province, Eastern Amazon, Brazil. For that, 58 surficial soil samples were analyzed for their extractable contents of Cu and Ni by Mehlich 1. Next, 13 soil samples were selected for additional single and sequential extractions, for the determination of metal content in the shoots of grasses naturally growing in these soils and for calculating the risk assessment code. Despite the naturally high total concentrations, the contents of easily available Cu and Ni are a minor fraction of total concentrations (up to 10.15%), and the reducible oxide and residual pools hold the major proportion of total content of metals. This contributed to low bioavailability, low environmental risk, and also to low concentrations of these metals on grasses collected in the field. Soil organic matter, Fe2O3, Al2O3 and clay content have a dominant role in metals retention on studied soils. Our findings on the bioavailability of Cu and Ni in a region of great economic relevance for Brazil are important not only for predicting the elements' behavior in the soil-plant system but also for refining risk assessments and to provide useful data for environmental quality monitoring.

A validated Folin-Ciocalteu method for total phenolics quantification of condensed tannin-rich açaí (Euterpe oleracea Mart.) seeds extract.

ABSTRACT: The widely used methodology to quantify polyphenols-the Folin-Ciocalteu (FC) method-cannot be applied indiscriminately since different matrices may impair the assay's accuracy. Thus, this study aimed to adapt the FC method for the açaí seed extract, a tannin-rich extract with potential applications for various therapies. Firstly, a pre-method standardization was established to determine parameters such as reading wavelength (765 nm), reaction time (30 min), and the reference substance (pyrogallol). In the validation step, the adapted method responded linearly to the analyte (R2 = 0.9910), ensuring its selectivity (linearity and selectivity curves statistically parallel) and accuracy (99.18-101.43%). Furthermore, the method proved to be precise (RSD ≤ 2.63%) at the two levels assessed (repeatability and intermediate precision) and robust (RSD ≤ 4.45%) concerning variation on the Na2CO3 concentration and the reaction time. The limits of detection and quantification were also calculated (9.9 µg/mL and 33.1 µg/mL, respectively). An additional step for tannins quantification based on its reported selective precipitation by complexing agents was also evaluated; however, unspecific precipitation was observed, reducing the results' accuracy. Our work successfully adapted and validated a method for total phenolics quantification of açaí seed extract, resulting in 38 g of pyrogallol equivalent/100 g of extract.

Exploring a near-Hartree-Fock-Kohn-Sham approach to study electronic properties of azobenzene in interaction with gold: From clusters to the Au(111) surface.

The electronic properties of azobenzene (AB) in interaction with gold clusters and adsorbed on the Au(111) surface are investigated by adopting a near-Hartree-Fock-Kohn-Sham (HFKS) scheme. This scheme relies on a hybrid Perdew-Burke-Ernzerhof functional, in which the exact non-local HF exchange contribution to the energy is taken as 3/4. Ionization energies and electron affinities for gas phase AB are in very good agreement with experimental data and outer valence Green's function) calculations. The presence of C-H⋯Au interactions in AB-Aun complexes illustrates the role played by weak interactions between molecular systems and Au nanoparticles, which is in line with recent works on Au-H bonding. In AB-Aun complexes, the frontier orbitals are mainly localized on the gold platform when n ≥ 10, which indicates the transition from a molecular to a semiconducting regime. In the latter regime, the electronic density reorganization in AB-Aun clusters is characterized by significant polarization effects on the Au platform. The accuracy of the near-HFKS scheme for predicting adsorption energies of AB on Au(111) and the interest of combining exact non-local HF exchange with a non-local representation of the dispersion energy are discussed. Taking into account the significant computational cost of the exact non-local HF exchange contribution, calculations for the adsorption energies and density of states for AB adsorbed on Au(111) were carried out by using a quantum mechanics/molecular mechanics approach. The results strongly support near-HFKS as a promising methodology for predicting the electronic properties of hybrid organic-metal systems.