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Metalloenzymes are the most proficient nature catalysts that are responsible for diverse biochemical transformations introducing excellent selectivity and performing at high rates, using intricate mutual relationships between metal ions and proteins. Inspired by nature, chemists started using naturally occurring proteins as templates to harbor non-native metal catalysts for the sustainable synthesis of molecules for pharmaceutical, biotechnological and industrial purposes. Therefore, metalloenzymes are the relevant targets for the design of artificial biocatalysts. The search and development of new scaffolds capable of hosting metals with high levels of selectivity could significantly expand the scope of bio-catalysis. To meet this challenge, herein, three native scaffolds: [1Fe-4Cys] (rubredoxin), [3Fe-4S] (ferredoxin), and [S2MoS2CuS2MoS2]-ORP (orange protein) protein scaffolds are case studies describing templates for the synthesis of non-native monomeric to mixed metal–sulfur clusters, which mimic native Ni containing metalloenzymes including [Ni-Fe] Hydrogenase and [Ni-Fe] CO Dehydrogenase. The non-native metal-substituted metalloproteins are not only useful for catalysis but also as spectroscopic probes.

Detection of stress biomarkers molecules, non-invasively, through (non-induced) sweat sampling is an important research field since sweat is a potential diagnostic fluid for early and continuous human health monitoring, not only for stress-related conditions directly but also for other pathologies (e.g., associated with chronic diseases). The simultaneous detection of multiple potential biomarkers in sweat samples, using simple and low-cost electrochemical methods (detecting patterns or “electrochemical fingerprints”) requiring no sample preparation and its correlation with physiological conditions, is an attractive methodology but not readily achievable. Several of these potential biomarkers’ electrochemical response presents very close oxidation potentials, among other factors that hamper the detection, such as pH dependence of the electrochemical response or partial adsorption on electrode surfaces. Disposable screen-printed electrode materials, with relatively low-cost, could be useful to overcome the difficulties. A set of selected potential stress-related (non-protein) biomarkers (tyrosine, phenylalanine, dopamine, serotonin, and hydrocortisone) was used in the current study for qualitative electrochemical detection on different screen-printed carbon-based electrodes. The detection was attained in simulated sweat solutions and real sweat samples. The goal was to evaluate the electrochemical response on the different surfaces and determine the most suitable carbon-based screen-printed electrodes that may be used in future sensing devices., This work was supported by the Associate Laboratory for Green Chemistry–LAQV which is fnanced by national funds from FCT/MCTES (UIDB/50006/2020 and UIDP/50006/2020). Fundação para a Ciência e Tecnologia provided fnancial support through Project PTDC/SAU-SOC/28390/2017 (STRESSSENSE).

Citrate, a major component of processed foods, reduces weight gain without resolving insulin resistance.

The effect of silica molar content on the performance of Ni/CeO2-SiO2 during the steam reforming of propane was investigated. Nickel precursors supported over ceria-silica with different molar contents of ceria:silica (65:35, 75:25, 85:15 and 100:0) were synthetized and named Ni65CS, Ni75CS, Ni85CS and NiCe, respectively. BET surface area and in situ XRD results showed that a higher silica molar content in the support contributes to an increase in the surface area and to smaller Ni average crystallite size. Temperature Programmed Reduction and in situ X-ray absorption near edge spectroscopy indicate a direct relationship between the silica molar content on the metal-support interaction and ceria dispersion and reducibility. Ni65CS and Ni75CS had lower carbon accumulation rate than the other catalysts, as demonstrated by thermogravimetric analysis. Ni75CS presented the highest conversion (around 75%) during catalytic tests at 600 °C and did not suffer from deactivation after 25 h. Based on the results, the optimum ceria:silica content in the support was 75:25, since this produced a more stable catalyst and smaller carbon deposition.

The water retention curve is widely used in studies involving soil. The management systems directly influence soil structure by altering water retention dynamics. Several equations are used to adjust the retention of water in the soil, but most of the time, the choice of these models occurs in an arbitrary way. From this problem, it was proposed with the present study to relate the best mathematical model to water retention, taking into account the different management systems adopted, based on previously established adjustment criteria. For the accomplishment the study, a soil of caulinitic mineralogy and average texture was utilized. The treatments were area under native Cerrado (Savanna), eucalyptus plantation with six and twelve years of cultivation, pasture with two and six years of cultivation, conventional plantation with two and eight years of cultivation, no-till with three and six years of cultivation. From the adjustment criteria for non-linear models, it was found that the management influences the choice of the water retention model. It is possible to observe that the greatest divergences between the models occurred close to the soil saturation zone, and that the Fredlung-Xing model is more efficient in adjusting the water retention curve under conservationist management systems.

Acridine derivatives have been found with anticancer and antinociceptive activities. Herein, we aimed to evaluate the toxicological, antitumor, and antinociceptive actions of N’-(6-chloro-2-methoxyacridin-9-yl)-2-cyanoacetohydrazide (ACS-AZ), a 9-aminoacridine derivative with antimalarial activity. The toxicity was assessed by acute toxicity and micronucleus tests in mice. The in vivo antitumor effect of ACS-AZ (12.5, 25, or 50 mg/kg, intraperitoneally, i.p.) was determined using the Ehrlich tumor model, and toxicity. The antinociceptive efficacy of the compound (50 mg/kg, i.p.) was investigated using formalin and hot plate assays in mice. The role of the opioid system was also investigated. In the acute toxicity test, the LD50 (lethal dose 50%) value was 500 mg/kg (i.p.), and no detectable genotoxic effect was observed. After a 7-day treatment, ACS-AZ significantly (p < 0.05) reduced tumor cell viability and peritumoral microvessels density, suggesting antiangiogenic action. In addition, ACS-AZ reduced (p < 0.05) IL-1β and CCL-2 levels, which may be related to the antiangiogenic effect, while increasing (p < 0.05) TNF-α and IL-4 levels, which are related to its direct cytotoxicity. ACS-AZ also decreased (p < 0.05) oxidative stress and nitric oxide (NO) levels, both of which are crucial mediators in cancer known for their angiogenic action. Moreover, weak toxicological effects were recorded after a 7-day treatment (biochemical, hematological, and histological parameters). Concerning antinociceptive activity, ACS-AZ was effective on hotplate and formalin (early and late phases) tests (p < 0.05), characteristic of analgesic agents with central action. Through pretreatment with the non-selective (naloxone) and μ1-selective (naloxonazine) opioid antagonists, we observed that the antinociceptive effect of ACS-AZ is mediated mainly by μ1-opioid receptors (p < 0.05). In conclusion, ACS-AZ has low toxicity and antitumoral activity related to cytotoxic and antiangiogenic actions that involve the modulation of reactive oxygen species, NO, and cytokine levels, in addition to antinociceptive properties involving the opioid system.

The rational design and functionalization of small, simple, and stable peptides scaffolds is an attractive avenue to mimic catalytic metal-centres of complex proteins, relevant for the design of metalloenzymes with environmental, biotechnological and health impacts. The de novo designed α

The use of Yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) in medicine has rapidly expanded over the past decade, driven by its advantageous properties, showing potential to overcome titanium alloy in implant fabrication. The release of metal ions and the aesthetic problems of titanium alloy implants are the main reasons for this trend. In addition to meeting expectations regarding its properties, an implant must possess intrinsic capacities such as auto-diagnostic and auto-treatment. Thus, based on the concept of smart implants, this work proposes a hybrid approach for printing a part of the communication system of a zirconia implant by resorting to laser technology, aiming to endow the implant with intrinsic capacities. Therefore, the antenna was designed and then printed on the zirconia surface. The laser was applied as a versatile tool, whether for preparing the surface of the material in a subtractive way, by creating the micro-cavity, or for printing the silver-based antenna in an additive way through laser technology. The silver powder was used as the conductor material of the antenna. The results revealed that the antenna is capable of communicating from inside the body with the outside world without needing to have an exterior antenna attached to the skin., This work has been supported by the FCT (Fundação para a Ciência e Tecnologia -Portugal) in the scope of the projects UID/EEA/04436/2019; Magsense_POCI-01-0247-FEDER-033783, Add.Additive_Manufacturing to Portuguese Industry_POCI-01-0247-FEDER-024533, grant SFRH/BD/ 116554/2016 and the CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) for the grant 205791/2014-0

Estimation of avian biodiversity is a cornerstone measure of ecosystem condition. Surveys conducted using autonomous recorders are often more efficient at estimating diversity than traditional point‐count surveys. However, there is limited research into the optimal temporal resolution for sampling—the trade‐off between the number of samples and sample duration when sampling a survey window with a fixed survey effort—despite autonomous recorders allowing easy repeat sampling compared to traditional survey methods. We assess whether the additional temporal coverage from high temporal resolution (HTR) sampling, consisting of 240 15‐s samples spread randomly across a survey window detects higher alpha and gamma diversity than low temporal resolution (LTR) sampling of four 15‐min samples at the same locations. We do so using an acoustic dataset collected from 29 locations in a region of very high avian biodiversity—the eastern Brazilian Amazon. We find HTR sampling outperforms LTR sampling in every metric considered, with HTR sampling predicted to detect approximately 50% higher alpha diversity, and 10% higher gamma diversity. This effect is primarily driven by increased coverage of variation in detectability across the morning, with the earliest period containing a distinct community that is often under sampled using LTR sampling. LTR sampling produced almost four times as many false absences for species presence. Additionally, LTR sampling incorrectly found 70 species (34%) at only a single forest type when they were in fact present in multiple forest types, while the use of HTR sampling reduced this to just two species (0.9%). When considering multiple independent detections of species, HTR sampling detected three times more uncommon species than LTR sampling. We conclude that high temporal resolution sampling of passive‐acoustic monitoring‐based surveys should be considered the primary method for estimating the species richness of bird communities in tropical forests.

Made available in DSpace on 2022-04-29T08:34:58Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-10-01 Consejo Nacional de Investigaciones Científicas y Técnicas Vocal sacs are among the most conspicuous features of anurans and are particularly striking in casque-headed treefrogs (Hylidae: Hylinae: Lophyohylini) with their wide array of morphologies. In this paper, we assessed the anatomy of vocal sacs in representatives of the Lophyohylini, described eight discrete characters and studied their evolution. We inferred that dorsolateral projections of the vocal sacs were already present during the early evolution of the tribe. Subsequently, they reached surprising volumes in some species, whereas in others they were notably reduced. We inferred between nine and 11 independent events of reduction of the size and lateral projections of the vocal sac, showing unprecedented levels of plasticity for the structure. Moreover, these events were strongly correlated with the colonization of phytotelmata as breeding sites, probably due to their confined space which hampers the inflation of large vocal sacs. Finally, we discuss the evolution of paired lateral vocal sacs in different groups of anurans, and the extent to which the paired and dorsally-projecting lobes of most Trachycephalus differ from those of distantly related taxa. Our findings highlight how variation in internal structure affects the shape of the inflated vocal sac and provides a framework applicable across the Anura. Laboratório de Herpetologia 11.330-900 Instituto de Biociências Campus Do Litoral Paulista Universidade Estadual Paulista, São Paulo División Herpetologiá Museo Argentino de Ciencias Naturales bernardino Rivadavia- CONICET, Avenida Ángel Gallardo 470 Departamento de Biodiversidad y Biologiá Experimental Facultad de Ciencias Exactas y Naturales Universidad de Buenos Aires Laboratório de Herpetologia 11.330-900 Instituto de Biociências Campus Do Litoral Paulista Universidade Estadual Paulista, São Paulo

BackgroundSARS-CoV-2 serologic surveys estimate the proportion of the population with antibodies against historical variants which nears 100% in many settings. New analytic approaches are required to exploit the full information in serosurvey data.MethodUsing a SARS-CoV-2 anti-Spike (S) protein chemiluminescent microparticle assay, we attained a semi-quantitative measurement of population IgG titres in serial cross-sectional monthly samples of routine blood donations across seven Brazilian state capitals (March 2021-November 2021). In an ecological analysis (unit of analysis: age-city-calendar month) we assessed the relative contributions of prior attack rate and vaccination to antibody titre in blood donors. We compared blood donor anti-S titre across the seven cities during the growth phase of the Delta variant of concern (VOC) and use this to predict the resulting age-standardized incidence of severe COVID-19 cases.ResultsOn average we tested 780 samples per month in each location. Seroprevalence rose to >95% across all seven capitals by November 2021. Driven proximally by vaccination, mean antibody titre increased 16-fold over the study. The extent of prior natural infection shaped this process, with the greatest increases in antibody titres occurring in cities with the highest prior attack rates. Mean anti-S IgG was a strong predictor (adjusted R2 =0.89) of the number of severe cases caused by the Delta VOC in the seven cities.ConclusionsSemi-quantitative anti-S antibody titres are informative about prior exposure and vaccination coverage and can inform on the potential impact of future SARS-CoV-2 variants.SummaryIn the face of near 100% SARS-CoV-2 seroprevalence, we show that average semi-quantitative anti-S titre predicted the extent of the Delta variant’s spread in Brazil. This is a valuable metric for future seroprevalence studies.

In this article, quantum mechanical/molecular mechanical (QM/MM) methods were used to study the full catalytic mechanism of xanthine oxidase (XO). XO catalyzes the conversion of xanthine (XAN) to uric acid (URC), in the presence of a molybdenum cofactor (Moco). The mechanism occurs through four reaction steps. Initially, the proton from the hydroxyl group of Moco passes to Glu1261 and the activated hydroxyl group makes a nucleophilic attack on XAN. Then, a hydride is transferred from the tetrahedral intermediate to the sulfur atom of the Moco, reducing Mo(VI) to Mo(IV). In the third step, one molecule of URC is formed through its protonation by Arg880. Once this reaction is complete, FAD is reduced to FADH2, oxidizing Mo(IV) to its initial oxidation state of Mo(VI). The enzymatic turnover is achieved with the reaction of one water molecule with the Moco. The rate-limiting step of the full catalytic mechanism is the hydride transfer that requires a free activation barrier of 16.9 kcal mol−1, which closely agrees with the experimental kcat value (18.3 s−1), which corresponds to approximately 15.7 kcal mol−1. This work also elucidates the key role played by Arg880 in the catalytic mechanism and the importance of Glu802 in the binding of the substrate. Both residues were previously shown to be important by mutagenesis studies, but their role was still not clearly understood. Additionally, it was observed that the presence of a tunnel of water molecules located close to Moco and Glu1261 is important for the enzymatic turnover. The determined transition state structures can now be used to help the development of transition-state analog inhibitors targeting XO.

Hydrogen production from steam reforming of liquefied petroleum gas (SR-LPG) process was studied over nickel, platinum, rhodium, and ruthenium-based catalysts supported on CeO2–SiO2 (CS). BET surface area, X-ray diffraction (XRD), temperature programmed reduction (TPR) and X-ray absorption near edge spectroscopy (XANES) techniques were used to characterize the samples. The catalytic activity and stability of the samples during SR-LPG were measured at 400 °C and 600 °C, respectively. XRD data were used to estimate the average crystallite size of ceria, which was small in all samples. For Pt and Rh containing samples, no diffraction peaks related to the metals were identified, which suggests high dispersion of these metals on the support. TPR and XANES experimental results showed that the addition of metals promoted the reduction of ceria. The order of catalyst activity for during SR-LPG at 400 °C was: Rh/CS » Pt/CS > Ru/CS » Ni/CS. Pt/CS and Rh/CS samples exhibited lower deactivation than nickel and ruthenium catalysts for SR-LPG at 600 °C during 24 h. Catalysts deactivation was mainly due to carbon deposition. In situ XRD data collected during SR-LPG at 600 °C revealed small increases in the mean particle sizes of Ni(0) and Ru (0), which could be pointed out as an additional cause for faster deactivation of the Ru/CS and Ni/CS catalysts.

Perovskites supported on Al2O3 (LaNi/AL) and CeO2–SiO2 (LaNi/CS) were tested as catalyst precursors for steam reforming of liquefied petroleum gas (SRLPG). The role of different supports in perovskites-derived catalysts performances was evaluated. A non-supported LaNiO3 (LaNi) was also synthesized for comparison. According to the in-situ X-Ray Diffraction analyses, a reduction temperature of 700 °C was enough to generate Ni0 and La2O3, except for LaNi/AL. X-ray absorption Near Edge Spectroscopy (XANES) showed a direct influence of the supports on the reducibility of the samples. At 600 °C, the supported precursors LaNi/AL and LaNi/CS were more stable than LaNi during the SRLPG reaction. The alumina support provided a higher activity to LaNi/AL mainly due to the strong metal-support interaction. At 700 °C, the LPG conversion of LaNi/CS was near 100%. At both temperatures, the lowest carbon accumulation rate was obtained by LaNi/CS likely due to ceria oxygen mobility.

GATA2 encodes a pioneer transcription factor that harbors two zinc fingers. It is a master regulator of hematopoiesis and is pivotal for self-maintenance and differentiation [1]. Heterozygous germl...

Mycobacterium tuberculosis (Mtb) has an old history as a human pathogen and still kills over one million people every year. One key feature of this bacterium is its dormancy: a phenomenon responsible for major changes in its metabolism and replication that have been associated with the need for a lengthy therapy for Mtb. This process is regulated by key heme-based sensors, particularly DosT and DevS (DosS), among other co-regulators, and also linked to nitrogen utilization (nitrate/nitrite) and stringent responses. In face of the current threat of tuberculosis, there is an urgent need to develop new therapeutic agents capable of targeting the dormant state, associated with the need for a lengthy therapy. Interestingly, many of those key proteins are indeed metallo-containing or metallo-dependent biomolecules, opening exciting bioinorganic opportunities. Here, we critically reviewed a series of small molecules targeting key proteins involved in these processes, including DosT/DevS/DevR, RegX3, MprA, MtrA, NarL, PknB, Rel, PPK, nitrate and nitrite reductases, GlnA1, aiming for new opportunities and alternative therapies. In the battle against Mycobacterium tuberculosis, new drug targets must be searched, in particular those involved in dormancy. A series of exciting cases for drug development involving metallo-containing or metallo-dependent biomolecules are reviewed, opening great opportunities for the bioinorganic chemistry community.

Sweat is a potential biological fluid for the non-invasive analytical assessment of diverse molecules, including biomarkers. Notwithstanding, the sampling methodology is critical, and it must be assessed prior to using sweat for clinical diagnosis. In the current work, the analytical methodology was further developed taking into account the sampling step, in view of the identification and level variations of sweat components that have potential to be stress biomarkers using separation by liquid chromatography and detection by tandem mass spectrometry, in order to attain a screening profile of 26 molecules in just one stage. As such, the molecule identification was used as a test for the evaluation of the sampling procedures, including the location on the body, using patches for long-term sampling and vials for direct sampling, through a qualitative approach. From this evaluation it was possible to conclude that the sampling may be performed on the chest or back skin. Additionally, possible interference was evaluated. The long-term sampling with patches can be used under both rest and exercise conditions with variation of the detected molecule’s levels. The direct sampling, using vials, has the advantage of not having interferences but the disadvantage of only being effective after exercise in order to have enough sample for sweat analysis.

Overfeeding during lactation has a deleterious impact on the baby’s health throughout life. In humans, early overnutrition has been associated with higher susceptibility to obesity and metabolic disorders in childhood and adulthood. In rodents, using a rodent litter size reduction model (small litter) to mimic early overfeeding, the same metabolic profile has been described. Therefore, the rodent small litter model is an efficient tool to investigate the adaptive mechanisms involved in obesogenesis. Besides central and metabolic dysfunctions, studies have pointed to the contribution of the endocrine system to the small litter phenotype. Hormones, especially leptin, insulin, and adrenal hormones, have been associated with satiety, glucose homeostasis, and adipogenesis, while hypothyroidism impairs energy metabolism, favoring obesity. Behavioral modifications, hepatic metabolism changes, and reproductive dysfunctions have also been reported. In this review, we update these findings, highlighting the interaction of early nutrition and the adaptive features of the endocrine system. We also report the sex-related differences and epigenetic mechanisms. This model highlights the intense plasticity during lactation triggering many adaptive responses, which are the basis of the developmental origins of health and disease (DOHaD) concept. Our review demonstrates the complexity of the adaptive mechanisms involved in the obesity phenotype promoted by early overnutrition, reinforcing the necessity of adequate nutritional habits during lactation.

Previously, we demonstrated that acute transcranial direct current stimulation (tDCS) reduced blood pressure (BP) and improved autonomic modulation in hypertensives. We hypothesized that acute and short-term tDCS intervention can promote similar benefits in resistant hypertensive patients (RHT). We assessed the impact of one (acute intervention) and ten (short-term intervention) tDCS or SHAM (20 min, each) sessions on BP, pulse interval (PI) and systolic blood pressure variabilities, humoral mechanisms associated with BP regulation, and cytokines levels. True RHT subjects (n = 13) were randomly submitted to one and ten SHAM and tDCS crossing sessions (1 week of “washout”). Hemodynamic (Finometer®, Beatscope), office BP, and autonomic variables (accessed through spectral analysis of the pulse-to-pulse BP signal, in the time and frequency domain – Fast Fourrier Transform) were measured at baseline and after the short-term intervention. 24 h-ambulatory BP monitoring was measured after acute and short-term protocols. Acute intervention: tDCS reduced BP, cardiac output, and increase high-frequency band of PI (vagal modulation to the heart). Short-term protocol: tDCS did not change BP and cardiac output parameters. In contrast, central systolic BP (−12%), augmentation index (−31%), and pulse wave velocity (34%) were decreased by the short-term tDCS when compared to SHAM. These positive results were accompanied by a reduction in the low-frequency band (−37%) and an increase of the high-frequency band of PI (+62%) compared to SHAM. These findings collectively indicate that short-term tDCS concomitantly improves resting cardiac autonomic control and pulse wave behavior and reduces central BP in RHT patients, https://ensaiosclinicos.gov.br/rg/RBR-8n7c9p.

The gut microbiota affects the host's metabolic phenotype, impacting health and disease. The gut-brain axis unites the intestine with the centers of hunger and satiety, affecting the eating behavior. Deregulation of this axis can lead to obesity onset. Litter size reduction is a well-studied model for infant obesity because it causes overnutrition and programs for obesity. We hypothesize that animals raised in small litters (SL) have altered circuitry between the intestine and brain, causing hyperphagia. We investigated vagus nerve activity, the expression of c-Fos, brain-derived neurotrophic factor (BDNF), gastrointestinal (GI) hormone receptors, and content of bacterial phyla and short-chain fatty acids (SCFAs) in the feces of adult male and female Wistar rats overfed during lactation. On the 3rd day after birth, litter size was reduced to 3 pups/litter (SL males or SL females) until weaning. Controls had normal litter size (10 pups/litter: 5 males and 5 females). The rats were killed at 5 months of age. The male and female offspring were analyzed separately. The SL group of both sexes showed higher food consumption and body adiposity than the respective controls. SL animals presented dysbiosis (increased Firmicutes, decreased Bacteroidetes) and had increased vagus nerve activity. Only the SL males had decreased hypothalamic GLP-1 receptor expression, while only the SL females had lower acetate and propionate in the feces and higher CCK receptor expression in the hypothalamus. Thus, overfeeding during lactation differentially changes the gut-brain axis, contributing to hyperphagia of the offspring of both sexes.

Caveolin-2 is a protein suitable for the study of interactions of caveolins with other proteins and lipids present in caveolar lipid rafts. Caveolin-2 has a lower tendency to associate with high molecular weight oligomers than caveolin-1, facilitating the study of its structural modulation upon association with other proteins or lipids. In this paper, we have successfully expressed and purified recombinant human caveolin-2 using E. coli. The structural changes of caveolin-2 upon interaction with a lipid bilayer of liposomes were characterized using bioinformatic prediction models, circular dichroism, differential scanning calorimetry, and fluorescence techniques. Our data support that caveolin-2 binds and alters cholesterol-rich domains in the membranes through a CARC domain, a type of cholesterol-interacting domain in its sequence. The far UV-CD spectra support that the purified protein keeps its folding properties but undergoes a change in its secondary structure in the presence of lipids that correlates with the acquisition of a more stable conformation, as shown by differential scanning calorimetry experiments. Fluorescence experiments using egg yolk lecithin large unilamellar vesicles loaded with 1,6-diphenylhexatriene confirmed that caveolin-2 adsorbs to the membrane but only penetrates the core of the phospholipid bilayer if vesicles are supplemented with 30% of cholesterol. Our study sheds light on the caveolin-2 interaction with lipids. In addition, we propose that purified recombinant caveolin-2 can provide a new tool to study protein–lipid interactions within caveolae., This work was supported by the Associate Laboratory for Green Chemistry—LAQV which is financed by national funds from FCT/MCTES (UID/QUI/50006/2020) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145-FEDER—007265). Experimental work was also supported by funding from Ayuda a Grupos de la Junta de Extremadura (Group BBB008-GR21051), co-financed by the European Funds for Structural Development (FEDER). AKSA thanks FCT/MCTES for the post-doctoral fellowship grants (SFRH/BPD/100069/2014), financed by national funds and co-financed by FSE. The BioLab is supported by the Applied Molecular Biosciences Research Unit—UCIBIO and the Associated Laboratory for Green Chemistry Research Unit—LAQV, which are financed by national funds from FCT/MCTES (UIDB/04378/2020 and UIDB/50006/2020, respectively) and co-financed by the ERDF under the PT2020 Partnership Agreement (POCI-01-0145- FEDER-007728 and POCI-01-0145-FEDER—007265, respectively).