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Hippeastrum elegans is a Brazilian Amaryllidaceae plant producing galantamine (GAL), an anticholinesterase drug for Alzheimer's disease, besides other alkaloids such as pseudolycorine (PSE), narciclasine (NAR) and sanguinine (SAN). Therefore, we used a metabolomic approach to investigate the influence of the harvest time on its chemical composition and acetylcholinesterase activity (AChE). Alkaloid extracts were analyzed by UPLC-ESI-MS and 1H NMR, then assessed for AChE inhibitory activity. These data were combined and analyzed by Partial Least Square (PLS) regression. H. elegans was found to be rich in PSE and NAR, achieving higher contents in 270 and 390 days of cultivation, respectively. However, the highest anti-AChE activities were observed for 450 days-bulbs extracts. PLS indicated pseudolycorine as the discriminant compound for this extract, hence responsible for its higher anti-AChE activity jointly with the known AChE inhibitors GAL and SAN. Thus, the cultivation of H. elegans appears to be a promising way for providing bioactive alkaloids.

Sorption has been proposed as a promising approach towards a sustainable water decontamination and recently to the recycling of rare earth elements (REE). Although living seaweed have been shown to be capable of removing REE from contaminated solutions, no studies have yet compared the effects of REE competition on sorption onto different groups of seaweed. These effects were analysed in the present study by exposing six living seaweeds (Ulva lactuca, Ulva intestinalis, Fucus spiralis, Fucus vesiculosus, Gracilaria sp. and Osmundea pinnatifida) (3 g/L, fresh weight) to mono-element and multi-element solutions of Y, La, Ce, Pr, Nd, Eu, Gd, Tb and Dy (1 μmol/L). Results show a preference towards light REE in mono-element solutions, which is reduced when in competition with other REE. The competitive effect is less pronounced in heavy REE indicating that these are still able to bind to the macroalgae despite the presence of competing ions. Contrary to water content (%), seaweed specific surface area (cm2/g) shows to be an important factor in the sorption of REE, since larger surface area is associated with higher removal and larger competitive effect.

The phytochemical reinvestigation from the heartwood of the extracts of Cordia glazioviana led to the isolation of four still undescribed hydroquinones derivatives designated as cordiaquinol D (1), cordiaquinol E (2), (10R)-10,11-dihydrofuran-1,4-dihydroxy-globiferin (3) and 2-[(1’E,6’E)-3’,8’‑dihydroxy-3’,7’-dimethylocta-1’,6’-dienyl]-benzene-1,4-diol (4), along with the naphthoquinone 6-[(2’R)-2’-hydroxy-3’,6’-dihydro-2H-pyran-5’-yl]-2‑methoxy- 7‑methylnaphthalene-1,4-dione (5). Additionally, six previously known compounds were also isolated: rel-1,4-dihydroxy-8α,11α;9α,11α-diepoxy-2-methoxy-8aβ-methyl- 5,6,7,8,8a,9,10,10a‑octahydro-10-antracenone (6), didehydroconicol (7), 1β,6β-dihydroxy-7-epieudesm-3-ene (8), 1β,6β-dihydroxy-7-epi-eudesm-4(15)-ene (9), 10,11-dihydroxybisabolol (10), and hamanasal-A (11). The structures of the new compounds were assigned by high-resolution mass spectrometry (HRMS) and nuclear magnetic resonance (NMR) analyses. The relative stereochemistry of 3, 4, and 5 was improved by quantum mechanical calculations. Eight, out of the eleven isolated compounds (2-9), were tested through cellular viability and lipopolysaccharide (LPS)-induced inflammation assays against RAW 264.7 macrophage-like cells. Compounds 3-5 exhibited a stronger effect on LPS-induced NO production (half-maximal inhibitory concentration (IC50) 50.34, 105.83, and 66.73 μM, respectively).

no. 760801\NEMOSINE UID/QUI/50006/2020 Preserving culture heritage cellulose acetate-based historical films is a challenge due to the long-term instability of these complex materials and a lack of prediction models that can guide conservation strategies for each particular film. In this work, a cellulose acetate degradation model is proposed as the basis for the selection of appropriate strategies for storage and conservation for each specimen, considering its specific information. Due to the formulation complexity and diversity of cellulose acetate-based films produced over the decades, we hereby propose a hybrid modeling approach to describe the films degradation process. The problem is addressed by a hybrid model that uses as a backbone a first-principles based model to describe the degradation kinetics of the pure cellulose diacetate polymer. The mechanistic model was successfully adapted to fit experimental data from accelerated aging of plasticized films. The hybrid model considers then the specificity of each historical film via the development of two chemometric models. These models resource on gas release data, namely acetic acid, and descriptors of the films (manufacturing date, AD-strip value and film type) to assess the current polymer degradation state and estimate the increase in the degradation rate. These estimations are then conjugated with storage conditions (e.g., temperature and relative humidity, presence of adsorbent in the film’s box) and used to feed the mechanistic model to provide the required time degradation simulations. The developed chemometric models provided predictions with accuracy more than 87%. We have found that the storage archive as well as the manufacturing company are not determining factors for conservation but rather the manufacturing date, off gas data as well as the film type. In summary, this hybrid modeling was able to develop a practical tool for conservators to assess films conservation state and to design storage and conservation policies that are best suited for each cultural heritage film. publishersversion published

Nitric oxide (NO) and hydrogen sulfide (H2 S) have been recognized as important signalling molecules involved in multiple physiological functions, including wound healing. Their exogenous delivery has been established as a new route for therapies, being the topical application the nearest to commercialization. Nevertheless, the gaseous nature of these therapeutic agents and their toxicity at high levels imply additional challenges in the design of effective delivery systems, including the tailoring of their morphology and surface chemistry to get controllable release kinetics and suitable lifetimes. This review highlights the increasing interest in the use of these gases in wound healing applications by presenting the various potential strategies in which NO and/or H2 S are the main therapeutic agents, with focus on their conceptual design, release behaviour and therapeutic performance. These strategies comprise the application of several types of nanoparticles, polymers, porous materials, and composites as new releasing carriers of NO and H2 S, with characteristics that will facilitate the application of these molecules in the clinical practice.

The search for H2S donors has been increasing due to the multiple therapeutic effects of the gas. However, the use of nanoporous materials has not been investigated despite their potential. Zeolites and activated carbons are known as good gas adsorbents and their modification with chitosan may increase the material biocompatibility and simultaneously its release time in aqueous solution, thus making them good H2S donors. Herein, we modified with chitosan a series of A zeolites (3A, 4A and 5A) with different pore sizes and an activated carbon obtained from glycerin. The amount of H2S adsorbed was evaluated by a volumetric method and their release capacity in aqueous solution was measured. These studies aimed to verify which of the materials had appropriate H2S adsorption/release properties to be considered a potential H2S donor. Additionally, cytotoxicity assays using HeLa cells were performed. Considering the obtained results, the chitosan composite with the A zeolite with the larger pore opening was the most promising material to be used as a H2S donor so a further cytotoxicity assay using H2S loaded was conducted and no toxicity was observed.

[EN] In this work, we obtained chirped Bragg gratings by post-coating uniform poly (methylmethacrylate) (PMMA) microstructured polymer optical fiber Bragg gratings (POFBGs) with an UV cure adhesive. The main advantage of the proposed method consists on being a cost-effective and simple solution, since no special phase mask, addi tional etching or gradient thermal annealing are required. A comparison between the fabricated chirped Bragg grating¿s performance and previous reported methods in the literature is presented. As a compact sensor with two different active areas (adhesive coated and uncoated sections of the POFBG), the developed sensing device can be used for multiparameter sensing, namely for strain, humidity and temperature monitoring. Allying the proposed flexible and low-cost fabrication technique with the intrinsic characteristics of POFs, one may conclude that the developed sensor has high potential for multiparameter sensing in possible future engineering and biomedical applications., National Natural Science Foundation of China (62003046) ; The Spanish Ministerio de Ciencia, Innovacion y Universidades RTI2018-101658-B-I00 FOCAL Project; Guangdong Basic and Applied Basic Research Foundation (2021A1515011997) ; Guangdong Recruitment Program of Foreign Experts (2020A1414010393) ; C. Marques ac-knowledges Fundacao para a Ciencia e a Tecnologia (FCT) through the CEECIND/00034/2018 (iFish project) and this work was developed within the scope of the project i3N, UIDB/50025/2020 &UIDP/50025/2020, financed by national funds through the FCT/MEC. Luis Pereira and Tiago Paixao also acknowledge FCT for the grant with references SFRH/BD/146295/2019 and PD/BD/128265/2016, respectively.

Background Evidence shows potential reduction in oxidative stress after Roux-en-Y gastric bypass. However, this outcome can vary, with postsurgery time, type of markers significantly altered, and possible relation with cardiometabolic risk markers, thus indicating the need for more studies. Objective To evaluate changes in oxidative stress and its relation with cardiometabolic risk markers in Roux-en-Y gastric bypass patients after 3 and 12 months postsurgery. Setting Federal University of Vicosa, Brazil. Methods All data were collected before surgery and after 3 and 12 months postsurgery. Biochemical data were collected, and insulin resistance was determined by homeostasis model assessment of insulin resistance, triglyceride/glucose index, and triglycerides/high-density lipoprotein cholesterol. Additionally, catalase, superoxide dismutase, ferric-reducing antioxidant power, nitric oxide, carbonylated protein, and malondialdehyde were analyzed. Results After 3 months postsurgery, excess weight loss was 46%. It increased to 82% after 12 months. We observed a significant reduction in levels of serum insulin, triglycerides, homeostasis model assessment of insulin resistance, triglyceride/glucose index, and triglycerides/high-density lipoprotein cholesterol indices and nitric oxide, throughout the entire study period. Also, reduced levels of total cholesterol, low-density lipoprotein, serum glucose, malondialdehyde, and superoxide dismutase were observed at 3 and 12 months postsurgery compared with baseline. On the other hand, reduction in ferric-reducing antioxidant power occurred only at 3 months postsurgery. We also observed that nitric oxide was positively correlated with triglycerides, percent excess weight loss, total cholesterol/high-density lipoprotein cholesterol, and triglyceride/glucose index. Conclusion Roux-en-Y gastric bypass is able to reduce oxidative stress, insulin resistance, and improve lipid profile after 3 and 12 months postsurgery. Furthermore, changes in oxidative stress and cardiometabolic risk markers are correlated.

Chitosan is a biopolymer obtained by deacetylation of chitin extracted from sub-products of the food industry and it is rich in nitrogen content. Pyrolyzed chitosan– and chitosan-periodic mesoporous organosilica (PMO)– based porous materials with different pore structures and chemical features are prepared using different dry methods and ensuing pyrolysis at 800 °C, for application in the CO2/CH4 adsorption/separation. The highest CO2 adsorption capacity (1.37 mol·kg−1 at 100 kPa; 1.9 mol·kg−1 at 500 kPa) and the best selectivity for CO2/CH4 separation (95 at 500 kPa) is obtained using 1.5% (m/v) of chitosan solution dried under supercritical CO2. This material combines a good CO2 adsorption capacity with one of the highest selectivities for CO2/CH4 separation of the literature, arising as a promising alternative adsorbent for natural gas or biogas upgrading at reduced cost. The presence of high nitrogen content together with pores of diameter around 2 nm leads to an increase of the CO2 adsorption capacity. In the case of chitosan-PMO-based materials, the activation step using both acid and crushing methods is crucial to increase the CO2 adsorbed amount. Here, the highest CO2 adsorption capacity and the highest selectivity are obtained by the chitosan-PMO crushed adsorbent and the chitosan-PMO material activated with sulfuric acid, respectively. These observations indicate the importance of the controlled attack of the material surface to enhance the diffusion of the target gases within the adsorbent, avoiding the adsorption of other species.

Marine natural products have emerged as an important source for drug development, notably in the field of anticancer therapy. Still, the limited effectiveness of current therapies for central nervous system tumors indicates the need to identify new therapeutic targets and also novel pharmacological agents. In this context, proteasome inhibitors are appearing as a promising new treatment for these diseases. Herein, cytotoxic extracts produced by four marine bacteria recovered from the Brazilian endemic ascidian Euherdmania sp. were screened to evaluate their potential as proteasome inhibitors. The extract from marine Streptomyces sp. BRA-346 was selected for further investigation due to the potent proteasome inhibitory activity it displayed. Bioassay-guided fractionation led to an enriched fraction (proteasome inhibition IC50 = 45 ng/mL), in which the presence of dihydroeponemycin (DHE), known for its proteasome inhibitory effect, and related compounds were annotated by mass spectrometry and further confirmed by comparison with DHE standard. Both DHE and the epoxyketone-containing fraction were evaluated in glioma cell lines, displaying high cytotoxicity in HOG and T98G cells (GI50 of 1.6 and 1.7 ng/mL for DHE, and 17.6 and 28.2 ng/mL for the BRA-346 fraction, respectively). Additional studies showed that the epoxyketone-containing fraction (at GI50 levels) led to an accumulation of ubiquitinated proteins and up-regulation of genes related to ER-stress response, suggesting treated cells are under proteasome inhibition. DHE induced similar effects in treated cells but at concentrations 25 times its GI50, suggesting that the other epoxyketone compounds in the bacteria extract derived fraction may contribute to enhance proteasome inhibition and further cellular effects in glioma cells. These findings revealed the molecular pathways modulated by this class of compounds in glioma cells and, moreover, reinforced the potential of this marine bacteria in producing a cocktail of structurally-related compounds that affect the viability of glioma cells.

Ethylene is a core building block in the chemical industry and its separation from ethane is very challenging due to high energy requirements. Adsorption-based processes can be an alternative to current processes based on cryogenic distillation. In this work, we explore for the first time the application of periodic mesoporous organosilica (PMO) materials, whose surface properties can be tuned with different functional groups. With the aim of correlating the PMO structure with ethane and ethylene adsorption, eight different PMO materials have been prepared, viz. the phenylene-bridged PMO, PMO aminated at the organic bridges, and PMO functionalized by silylation of free silanol (inorganic) moieties. High pressure adsorption isotherms were measured, and the separation selectivity and phase diagrams of a binary mixture of ethane and ethylene were estimated. Results have shown that, overall, the PMO studied tend to be more selective towards ethylene than ethane probably due to the interactions between the quadrupole moment of ethylene and the free silanols in the samples. After silylation, the novel materials presented surfaces with higher affinity towards ethane than those of the pristine material. For the aminated samples, functionalization with primary amines originated materials displaying better selectivity towards ethylene than those functionalized with secondary or tertiary amines.

International audience

The release of potentially toxic elements into the environment, and their effects on aquatic ecosystems still present a real threat. To avoid such contamination, the use of biological sorbents as an alternative to conventional and expensive water remediation techniques has been proposed. The present study evaluated the potential of 0.5 g L−1 of peanut, hazelnut, pistachio, walnut, and almond shells to remove the requisite concentrations of cadmium (Cd), lead (Pb), and mercury (Hg) from contaminated water. Hazelnut shells were identified as the sorbent with the highest potential and were evaluated in mono- and multi-contaminated mineral water. The influence of sorbent-intrinsic and solution-intrinsic characteristics were assessed. Differences among sorbents were attributed to varying percentages of their main components: cellulose, hemicellulose, and lignin. Matrix complexity increase caused a decrease in Cd removal, presumably due to the diminution in electrostatic interaction, and complexation with anions such as Cl-. When simultaneously present in the solution, contaminants competed, with Pb showing higher affinity to the sorbent than Hg. High efficiencies (&gt, 90%) obtained for hazelnut shells for all elements in ultrapure water and for Pb and Hg in mineral water) reveals the high potential of this low-cost and abundant waste for use in the remediation of contaminated waters (circular economy).

UIDB/04028/2020 UIDP/04028/2020 UID/QUI/50006/2019 A deep understanding of the degradation of cellulose diacetate (CDA) polymer is crucial in finding the appropriate long-term stability solution. This work presents an investigation of the reaction mechanism of hydrolysis using electronic density functional theory calculations with the B3LYP/6-31++G*∗ level of theory to determine the energetics of the degradation reactions. This information was coupled with the transition-state theory to establish the kinetics of degradation for both the acid-catalyzed and noncatalyzed degradation pathways. In this model, the dependence on water concentration of the polymer as a function of pH and the evaporation of acetic acid from the polymer is explicitly accounted for. For the latter, the dependence of the concentration of acetic acid inside the films with the partial pressure on the surrounding environment was measured by sorption isotherms, where Henry's law constant was measured as a function of temperature. The accuracy of this approach was validated through comparison with experimental results of CDA-accelerated aging experiments. This model provides a step forward for the estimation of CDA degradation dependence on environmental conditions. From a broader perspective, this method can be translated to establish degradation models to predict the aging of other types of polymeric materials from first-principles calculations. publishersversion published

This work entails a comprehensive solid-state NMR and computational study of the influence of water and CO2 partial pressures on the CO2-adducts formed in amine-grafted silica sorbents. Our approach provides atomic level insights on hypothesised mechanisms for CO2 capture under dry and wet conditions in a tightly controlled atmosphere. The method used for sample preparation avoids the use of liquid water slurries, as performed in previous studies, enabling a molecular level understanding, by NMR, of the influence of controlled amounts of water vapor (down to ca. 0.7 kPa) in CO2 chemisorption processes. Details on the formation mechanism of moisture-induced CO2 species are provided aiming to study CO2 : H2O binary mixtures in amine-grafted silica sorbents. The interconversion between distinct chemisorbed CO2 species was quantitatively monitored by NMR under wet and dry conditions in silica sorbents grafted with amines possessing distinct bulkiness (primary and tertiary). Particular attention was given to two distinct carbonyl environments resonating at δC ∼161 and 155 ppm, as their presence and relative intensities are greatly affected by moisture depending on the experimental conditions. 1D and 2D NMR spectral assignments of both these 13C resonances were assisted by density functional theory calculations of 1H and 13C chemical shifts on model structures of alkylamines grafted onto the silica surface that validated various hydrogen-bonded CO2 species that may occur upon formation of bicarbonate, carbamic acid and alkylammonium carbamate ion pairs. Water is a key component in flue gas streams, playing a major role in CO2 speciation, and this work extends the current knowledge on chemisorbed CO2 structures and their stabilities under dry/wet conditions, on amine-modified solid surfaces., Solid-state NMR and molecular modeling provide structural insights on the influence of water upon CO2 chemisorption on primary and tertiary amine-grafted mesoporous silica sorbent materials.

Mercury is a very toxic metal that persists and accumulates in the living organisms present in the aquatic systems and its elimination is an urgent need. Two green (Ulva intestinalis and Ulva lactuca), brown (Fucus spiralis and Fucus vesiculosus), and red (Gracilaria sp. and Osmundea pinnatifida) marine macroalgae were tested for mercury removal from saline waters. The ability of each species was evaluated to the initial mercury concentrations of 50, 200, and 500 μg dm-3 along 72 h. In general, all species exhibited good performances, removing 80.9–99.9% from solutions with 50 μg dm-3, 79.3–98.6% from solutions with 200 μg dm-3, and 69.8–97.7% from solutions containing 500 μg dm-3 of mercury. Among the macroalgae, Ulva intestinalis showed the highest affinity to mercury and it presented an uptake ability up to 1888 μg g-1 of Hg(II) and bioconcentration factors up to 3823, which proved its promising potential on Hg removal.

Nitric oxide (NO) is one of the smallest endogenous molecules with particularly interesting aspects roles in biological systems, despite its toxicological potential. Solid carriers have potential biomedical interest in the delivery of exogenous NO for anti-bacterial, anti-thrombic and wound healing applications. In this work, we prepared nanoporous materials from clay based solids, of montmorillonite type, with the main goal of studying its potential in the field of storage and release of nitric oxide for therapeutic applications. Materials were characterized by X-ray diffraction, nitrogen adsorption at −196 °C, TG-DSC and chemical analysis. The kinetic data for the nitric oxide storage and release, in selected materials, was obtained in gas and liquid phases. The released amounts of NO in the liquid phase were within the biological range and, for some materials, a slow release kinetics was obtained with, inclusively, an almost direct relation between the released fraction and time. Toxicological assays with HeLa cells indicated that the materials have low cytotoxicity.

International audience; Materials for the controlled release of nitric oxide (NO) are of interest for therapeutic applications. However, to date, many suffer from toxicity and stability issues, as well as poor performance. Herein, we propose a new NO adsorption/release mechanism through the formation of nitrites on the skeleton of a titanium‐based metal–organic framework (MOF) that we named MIP‐177, featuring a suitable set of properties for such an application: (i) high NO storage capacity (3 μmol mg−1solid), (ii) excellent biocompatibility at therapeutic relevant concentrations (no cytotoxicity at 90 μg mL−1 for wound healing) due to its high stability in biological media (

The separation of ethane from a mixture of ethane/ethylene is a large scale process. Therefore, if adsorption is to be considered for this separation, besides the amounts adsorbed and selectivity type and values, the adsorbent also needs to have a relatively low cost. Considering the large volume of glycerol coming from biodiesel production it is also important to find new applications for this substance. With this goal, we synthesized a series of glycerin-activated carbons via a two-step procedure involving carbonization followed by chemical activation. The prepared adsorbents presented high surface areas, ranging from 1166 to 2150 m2 g−1 and have pore volumes between 0.63 and 1.03 cm3g−1. The glycerin-activated carbons were evaluated as adsorbents for adsorption-separation of ethane and ethylene. All the adsorbents showed to be ethane selective, that is to say, the materials exhibited higher adsorption capacity of ethane than ethylene. This is a key factor, related with the nature of the materials surface, for their application in the separation of ethylene from a mixture of ethane/ethylene. Ethane adsorption capacity was in the range 8.92–14.81 mmol g−1. Therefore, a low-cost by-product of biodiesel production – glycerin – can be transformed in a material that has promising properties for adsorption-separation of C2H6/C2H4.

In this work, the thermo-optic coefficient (TOC) of ethanol-water mixtures, through refractive index and temperature measurements are determined using an etched optical fiber tip based on a multimode interferometer. The proposed probe is fabricated by fusion-splicing a 5.2 mm long coreless fiber section to a single mode fiber. To reduce the sensor dimensions and improve its sensitivity towards external medium variations, the fiber tip is subjected to wet chemical etching using a solution of 40% hydrofluoric acid, presenting a final diameter of 24.4 μm. The TOC of each solution is estimated and, in the case of deionized water and pure ethanol, its value is of −1.128 × 10−4 °C−1 and −3.117 × 10−4 °C−1, respectively.

Con el objeto de describir la relación entre las variables climáticas y las respuestas fisiológicas, 20 ovejas fueron asignadas a: Con Sombra (CS): sombra artificial (12:00 - 14:00 h) en corral con techo de malla sombra (70%); Sin Sombra (SS): sin ofrecimiento de sombra. Se determinó radiación solar (RS; W/m2), temperatura ambiental (°C), humedad relativa (%), temperatura de globo negro (TGN; °C) e índice de temperatura-humedad (ITH; unidades), temperatura superficial (TS; °C; termómetro infrarrojo), temperatura corporal (TC; °C; termómetro digital), frecuencia respiratoria (FR; mov/min; observación directa) y coeficiente de tolerancia al calor (CTC; unidades) (PROC MIXED; SAS).Adicionalmente, los datos fueron analizados por componentes principales (InfoStat/E, 2008).CS presenta una menor TS (35,9) en comparación con SS (38,9; P ≤ 0,01); igual ocurre en TC (P ≤ 0,01). La FR en CS (112,3) fue superior a SS (139,6; P ≤ 0,01). El CTC fue mayor en SS (7,8) vs. CS (5,8; P ≤ 0,01), indicando mejor bienestar térmico en CS. La TS en lomo, cadera y/o costado presenta alta relación con TC. TGN > 42,8 y de RS > 529,1 podrían indicar reducciones del bienestar térmico. Basado en la TC y FR, el punto de quiebre del ITH en ovinos es > 80.

The wealth of site-selective structural information on CO2 speciation, obtained by spectroscopic techniques, is often hampered by the lack of easy-to-control synthetic routes. Herein, an alternative experimental protocol that relies on the high sensitivity of 13 C chemical shift anisotropy (CSA) tensors to proton transfer, is presented to unambiguously distinguish between ionic/charged and neutral CO2 species, formed upon adsorption of 13 CO2 in amine-modified porous materials. Control of the surface amine spacing was achieved through the use of amine protecting groups during functionalisation prior to CO2 adsorption. This approach enabled the formation of either "isolated" or "paired" carbamate/carbamic acid species, providing a first experimental NMR proof towards the identification of both aggregation states. Computer modelling of surface CO2 -amine adducts assisted the solid-state NMR assignments and validated various hydrogen-bond arrangements occurring upon formation of isolated/aggregated carbamic acid and alkylammonium carbamate ion species. This work extends the understanding of chemisorbed CO2 structures formed at pore surfaces and reveals structural insight about the protonation source responsible for the proton-transfer mechanism in such aggregates.

For carbon dioxide sequestration purposes or for fuel production from biogas, CO2 needs to be separated from other gases in large scale processes and “green” and sustainable methodologies for this are not currently in use. Adsorption can be a viable alternative and one way of promoting the CO2 adsorption, and hence the selectivity of the adsorbent, is surface modification with amine groups. In the present work, we used a sustainable methodology to prepare amine modified clays by the insertion of amino acids in a raw clay. The adsorbed amounts of carbon dioxide in these low-cost materials reached 0.8 mmol/g (at a temperature of 25 °C and a pressure of 8 bar), and selectivity values of 170 for the CO2 /CH4 separation (at 9 bar) were achieved.

The separation of CO2/CH4 gas mixtures on mesoporous SBA-15 functionalized with primary, secondary and tertiary amines, and a diamine (primary and secondary), was studied by gas adsorption, solid state nuclear magnetic resonance (ssNMR) and electronic structure density functional theory (DFT) techniques to evaluate the possible application of amine functionalized mesoporous silicas in the purification of natural or biogas sources. High pressure adsorption, up to 10 bar, showed a strong selective interaction of CO2 with primary amine, secondary amine and diamine that give separation selectivities up to 25, 3300 and 15000, respectively, due to the chemisorption of CO2. Notably, not all amines are saturated at pressures below 40 kPa, as demonstrated by the 13C ssNMR spectra with variable 13CO2 pressure. Furthermore, ssNMR and DFT results indicated that physisorbed CO2 interacts with the formed chemisorbed species, providing a possible explanation for the high selectivity observed even beyond the saturation of amines. Reaction Gibbs energies of CO2 with the amines estimated by DFT computational methods are in excellent agreement with observed differences in the experimental Henry’s constants, selectivities and phase diagrams. Preliminary assessment of the materials for possible application on cyclic separation by pressure modulation indicated that although secondary amine and diamine originate very high selectivities, they are not very suitable for applications because of the lower working capacities (below 1.3 mmol g−1). The material functionalized with primary amine presents a better compromise between the high selectivity for separation and a good working capacity (about 2 mmol g−1).

A new polycyclic antibiotic, pradimicin-IRD, was isolated from actinobacteria Amycolatopsis sp. IRD-009 recovered from soil of Brazilian rainforest undergoing restoration area. This molecule is the major compound produced in solid culture media. The new compound was detected by a focused method of precursor ion (high-performance liquid chromatography coupled to tandem mass spectrometer) developed previously to identify unusual aminoglycosyl sugar moieties. The compound was isolated and its structure was, therefore, elucidated by high-resolution mass spectrometry, and 1D and 2D nuclear magnetic resonance experiments. Pradimicin-IRD displayed potential antimicrobial activity against Streptococcus agalactiae (MIC 3.1 μg/mL), Pseudomonas aeruginosa (MIC 3.1 μg/mL) and Staphylococcus aureus (MIC 3.1 μg/mL), and also cytotoxicity against tumour and non-tumour cell lines with IC50 values ranging from 0.8 μM in HCT-116 colon carcinoma cells to 2.7 μM in MM 200 melanoma cells. Particularly, these biological properties are described for the first time for this chemical class.

In the present study, we integrated liquid chromatography high-resolution mass spectrometry (LC-HRMS) and high-throughput DNA sequencing for prospecting cytotoxic specialized metabolites from Pseudofusicoccum stromaticum, an endophytic fungus associated to the medicinal plant Myracrodruon urundeuva. LC-HRMS profiling allowed identifying putatively eleven compounds in the ethyl acetate extract from P. stromaticum broth. Additionally, a chemical fractionation guided by cytotoxicity combined with spectrometric analysis resulted in the isolation of three compounds: the cyclopeptide cyclo-L-Phe-D-Leu-L-Leu-L-Leu-L-lle along with the known rotenoids rotenolone and tephrosin. MTT assay showed that tephrosin (IC50 0.51 μg mL−1) has strong cytotoxic effect and may be pointed out as the compound responsible for the antiproliferative activity of P. stromaticum. Next Generation Sequencing (NGS) and genome mining of P. stromaticum draft genome revealed 56 contigs codifying specialized metabolites biosynthesis-related enzymes. Nearly half of such genes (44.6%) could be mapped to orphan Biosynthetic Gene Clusters (BGCs) of related plant pathogens belonging to family Botryosphaeriaceae. Also, screening for rotenoids biosynthetic enzymes led to characterization of a putative chalcone isomerase-like (CHI-like) protein. This is the first report of rotenoids biosynthesized by a fungus, unveiling a unique ability of P. stromaticum.

This study focused on the impact of 3 key variables (macroalgae mass, water salinity, and Nd(III) initial concentration) on the performance of two living macroalgae (Ulva sp. and Gracilaria sp.) in the removal and bioaccumulation of Nd(III), finding the optimal operating conditions through the Response Surface Methodology (RSM). Experiments were carried out in batch conditions stablished using a Box-Behnken design of 3 factors-3 levels (macroalgae mass of 0.5, 3.0 and 5.5 g dm-3; water salinity of 10, 20 and 30; and Nd(III) initial concentration of 10, 255 and 500 µg dm-3). The linear, quadratic and combined effects of the variables were described by RSM through a second order polynomial function. Optimized conditions were calculated by nonlinear regression using the Nelder-Mead simplex algorithm. Results evidenced the great capacity of both species to remove Nd(III), with removals around 80 % for the conditions: initial concentration of Nd(III) of 255 µg dm-3, water salinity 10, and macroalgae mass of 5.5 g dm-3. 3-D Response Surfaces showed that after 72 h of experiment, the most impactful variable on the removal process was the macroalgae mass. Regarding bioaccumulation, for the conditions studied, the higher the Nd(III) initial concentration the greater was its accumulation. The RSM tool made it possible to obtain the optimal conditions for both species, for contact times of 72 and 120 h. The proposed methodology can be applied in the recovery of Nd (which is a critical element) from contaminated waters, with the aim of its reintroduction in industrial production processes (recycling).

Presence of reactive oxides, such as sodium, potassium, and magnesium oxides, compromise the pozzolanic activities of mineral additions to cement-based materials. That is because these oxides react with water to form hydroxides. Subsequently, these hydroxides may react with the otherwise non-reactive oxides, such as silicon and aluminum oxides, to form various silicate and aluminate phases in the cement-based material, that finally compete with the desired CSH phase. Further, the strong pozzolanic activity of the silica fume is seemingly due to its large ability to form the calcium silicate hydrated systems when compared with both metakaolin and fly ashes. All these results have been established by X-ray fluorescence, microstructural, and chemometric analyses that were applied to investigate the pozzolanic activities, thermodynamic, structural, and mechanical properties of a set of mineral systems widely applied to cement-based materials (silica fume, metakaolin, and fly ashes). The chemometric analyses revealed that the materials prepared with silica fume exhibited the largest mechanical properties, whereas the reference the lowest. The cement-based materials with metakaolin and fly ashes present intermediary resistances and similar behaviors. In conclusion, strict control of the purity of the material always needs to be performed to obtain mineral systems with powerful pozzolanic activities.

This work shows a comparative study between the thermocouples and fiber sensors response for the monitoring of temperature variations occurring in three different locations of a lithium battery. The battery is submitted to constant current charge and different discharge rates, under normal and abusive operating conditions. For this specific application, the results show that the fiber Bragg grating sensors have better resolution and a rise time 28.2% lower than the K‐type thermocouples, making them a better choice for the real time monitoring of the battery surface temperature as well as a useful tool for failure detection and an optimized management in batteries.

Type-2 diabetes (T2D) patients with body mass index (BMI) below 35 kg/m2 carry lower remission rates than severely obese T2D individuals submitted to “standard limb lengths” Roux-en-Y gastric bypass (RYGB). Mild-obese patients appear to have more severe forms of T2D, where the mechanisms of glycemic control after a standard-RYGB may be insufficient. The elongation of the biliopancreatic limb may lead to greater stimulation of the distal intestine, alterations in bile acids and intestinal microbiota, among other mechanisms, leading to better metabolic outcomes. The aim of this study is to evaluate the safety and efficacy of the RYGB with a biliopancreatic limb of 200 cm in the control of T2D in patients with BMI 30–35 kg/m2. From January 2011 to May 2015, 102 T2D patients with BMI from 30 to 34.9 kg/m2 underwent laparoscopic RYGB with the biliopancreatic-limb of 200 cm and the alimentary-limb of 50 cm. There were no deaths or reoperations. The mean follow-up was 28.1 months. The mean BMI dropped from 32.5 to 25.1 kg/m2, while the mean fasting glucose decreased from 182.9 to 89.8 mg/dl and the mean glycated hemoglobin (HbA1c) went from 8.7 to 5.2%. During follow-up, 92.2% had their T2D under complete control (HbA1c

Periodic mesoporous organosilicas (PMO), with phenylene or biphenylene organic linkers, were thermally treated in flowing nitrogen atmosphere upon different conditions aiming the enhancement of their CO2 adsorption/separation properties. As-synthesized and template-extracted phenylene- and biphenylene-PMO were pyrolysed at 800 and 1200 °C. The effects of: i) the type of organic bridge; ii) the presence of nitrogen atoms; iii) the use of an acid catalyst prior to carbonization; and iv) pore size were investigated. It was found that pyrolysis promotes modifications in the physical-chemical and the textural properties of the PMO materials, being the formation of micropores one of the most notable differences. Furthermore, with the exception of biphenylene-PMO, the molecular-scale periodicity of the materials was strongly affected by the pyrolysis treatment probably as a result of SiC bond cleavage. The CO2 adsorption capacity and the selectivity for CO2/CH4 separation of all pyrolysed materials were enhanced. In general, the increase of the microporosity in the pyrolysed PMO is accompanied by an improvement of the CO2 adsorption properties with concomitant reduction of the CH4 adsorption behavior. The most interesting material for CO2/CH4 separation is the biphenylene-PMO pyrolysed at 1200 °C, with a selectivity of 9.5 at 25 °C and 500 kPa.

Coelenterazine, a member of the imidazopyrazinone class of chemiluminescent substrates, presents significant potential as a dynamic probe of reactive oxygen species in a biological environment, such as a superoxide anion, in which these species are important in cellular biology and pathology. The objective of the current study was to understand in what way the efficiency of singlet and triplet chemiexcitation could be modulated, towards a more efficient use of imidazopyrazinone-based compounds as dynamic chemiluminescent probes. To this end the thermolysis of imidazopyrazinone dioxetanone, substituted at the C8-position with electron-donating or electron-withdrawing groups, was characterized with a theoretical approach based on density functional theory. Substituents with different electron-donating/withdrawing characters have only a limited effect on the singlet chemiexcitation of anionic dioxetanone. For neutral dioxetanone, both electron-withdrawing and weak electron-donating substituents increase singlet chemiexcitation, to the contrary of strong electron-donating groups. During their thermolysis reaction, all molecules presented regions of degeneracy with triplet states, thereby indicating the possibility of triplet chemiexcitation.

The synthesis and structural characterization of two isostructural metal (M=Ni, Co) 3D framework structure that integrate vitamin B3 building blocks with NO delivery capabilities and low toxicity is presented. The compounds with a formula [M2(μ2-H2O)(μ-vitamin B3)4]·2H2O contain two crystallographic distinct divalent metal centres connected by a bridging water and carboxylate group from vitamin B3. The porous compounds have the capability of storing and releasing nitric oxide (NO) in a slow and reversible manner, with released amounts of 2.6 and 2.0μmol NOmgsolid-1, on the Ni and Co compound, respectively. The NO release followed a convenient slow release kinetic profile in both gas and liquid phases. Haemoglobin tests demonstrated that NO is released to the medium in a biologically active form, thus suitable to trigger the desired response in biological systems. The toxicity of the samples with and without loaded NO was evaluated from cytotoxicity tests in HeLa and HEKn cells, showing low toxicity of the compounds at concentrations below 180μgcm-3. The overall results indicate that these bio based MOFs are of interest for therapeutic applications related with NO delivery. STATEMENT OF SIGNIFICANCE.

In this work, we investigate the influence of some growth parameters such as high microwave power ranging from 3.0 to 4.0 kW and N2 additive on the incorporation of bonded hydrogen defects in nanocrystalline diamond (NCD) films grown through a small amount of pure N2 addition into conventional 4% CH4/H2 plasma using a 5 kW microwave plasma CVD system. Incorporation form and content of hydrogen point defects in the NCD films produced with pure N2 addition was analyzed by employing Fourier-transform infrared (FTIR) spectroscopy for the first time. A large amount of hydrogen related defects was detected in all the produced NCD films with N2 additive ranging from 29 to 87 µm thick with grain size from 47 nm to 31 nm. Furthermore, a specific new H related sharp absorption peak appears in all the NCD films grown with pure N2/CH4/H2 plasma at high powers and becomes stronger at powers higher than 3.0 kW and is even stronger than the 2920 cm−1 peak, which is commonly found in CVD diamond films. Based on these experimental findings, the role of high power and pure nitrogen addition on the growth of NCD films including hydrogen defect formation is analyzed and discussed.

This chapter focuses on new compositions of thermoplastic matrices and reinforcements to process by fused deposition modelling (FDM). The available materials for this additive manufacturing (AM) technique are generally limited to PLA—polylactic acid, ABS—acrylonitrile butadiene styrene and PA—polyamide (NYLON®) with temperature gradients and mechanical behaviours that are not suited for high-performance applications, such as aeronautics and automotive sector. In this work, an intensive research was made in order to evaluate mechanical, thermal and rheological properties considered important for 3D printing of commercial filaments. Results aided in the selection of high-performance reinforced materials for AM. Advanced polymers, such as PEEK—polyether ether ketone and PA66—polyamide 66, were the matrices chosen to produce high service nanocomposite formulations, each with varying amounts of multi-wall carbon nanotubes (MWCNTs). The resulting feedstock materials were characterized using the same techniques as the commercial filaments. Preliminary tests with printed parts of these composites were made in pursuance of their optimal printing parameters to undergo an experimental hybrid system (EHS).

Two steroids (1 and 2), two oxepin derivatives (3 and 4) and seven flavonoids (5–11) were isolated from the stems of Bauhinia pentandra. Their structures were elucidated on the basis of NMR spectroscopic data, and by comparison with data previously reported in the literature. The ethanol extract from the stems of B. pentandra and the compounds, 4, 5, 6, 7, 8 and 11 have been evaluated as acetylcholinesterase inhibitors, and among these, the compound 5 exhibited the strongest activity. In addition, all the isolated compounds are reported for the first time as constituents of B. pentandra.

Six previously undescribed tropane alkaloids, designated as erythrobezerrines A-F, were isolated from the EtOH extract from the stem bark of Erythroxylum bezerrae Plowman. Their structures were elucidated based on the interpretation of the NMR and MS data and in some instances, confirmed by X-ray diffraction analysis. The cytotoxicity of the isolated compounds was evaluated against the cancer cell lines L929, PC-3, HCT-116, SNB-19 and NCI-H460, but only erythrobezerrine C showed moderate activity with IC50 values of 3.38 and 5.43 μM for HCT-116 and NCI-H460, respectively.

[EN] FBG in polymer optical fibers (POFs) is a promising technology for a wide range of sensing applications due to a lower Young¿s modulus and a large range of applying strain. Furthermore, POFs have several properties which make them attractive for biosensing applications such as nonbrittle nature, flexibility in bending and biocompatibility. Chirped Fiber Bragg gratings (CFBGs), which are characterized by a nonuniform modulation of the refractive index show a broad reflection spectrum, enabling shortlength distributed sensing. The combining benefits of POF and CFBGs is attractive for biomedical applications. Here, we present a novel method to obtain CFBG in POF with a postprocess uniform POF FBG by using resin., The Spanish Ministerio de Ciencia, Innovación y Universidades RTI2018­101658­B­I00 FOCAL Project; National Natural Science Foundation of China (61435006, 61525502); The Science and Technology Planning Project of Guangdong Province (2017B010123005, 2018B010114002); Local Innovation and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01X121). This work was developed within the scope of the project i3N, UIDB/50025/2020 & UIDP/50025/2020, financed by national funds through the FCT/MEC. Luís Pereira and Tiago Paixão acknowledge FCT for the grants SFRH/BD/146295/2019 and PD/BD/128265/2016, respectively. This work is also funded by national funds (OE), through FCT¿I.P., in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of the article 23, of the Decree­Law 57/2016, of August 29, changed by Law 57/2017, of July 19.

We present the first Bragg gratings fabricated in two, three and five rings undoped PMMA microstructured polymer optical fibres (mPOFs) with relative low cost 266 nm Nd:YAG laser in the 850 nm region. The fibers were connectorised with commercial ferrules for easy coupling with silica patch cables. Temperature, humidity and strain sensitivities are measured and also the impact of ring structure and the diameter of POF on the characterization measurements are studied for potential applications. We also analyzed the effect of the number of hexagonal rings structure in gratings fabrication, noticing that larger number of rings lead to more difficulties to obtain strong gratings, where we consider this performance due to the scattering effects. We demonstrate Bragg gratings fabrication in 5-rings structure mPOF after 6 min by using 266 nm Nd:YAG laser whereas no Bragg gratings have been fabricated so far using 325 nm He-Cd laser system. Up to 30 dB relative reflected power gratings are obtained in two rings mPOF, showing good time stability and promising results for undoped mPOF applications.

Chitosan is an environmentally-friendly active molecule that has been explored for numerous agricultural uses. Its use in crop protection is well-known, however, other properties, such as bioactivity, deserve attention. Moreover, the modes of actions of chitosan remain to be elucidated. The present study assessed the levels of total phenolic compounds, the antioxidant potential, and the expression of reactive oxygen species (ROS) scavenging genes in the berries (skins and seeds), leaves, cluster stems, and shoots upon chitosan application on two red grapevine varieties (Touriga Franca and Tinto C&atilde, o). The application of chitosan on the whole vine before and after veraison led to the increased levels of polyphenols, anthocyanins, and tannins in Tinto C&atilde, o berries, and polyphenols and tannins in Touriga Franca berries, respectively. CUPric Reducing Antioxidant Capacity (CUPRAC) and Ferric Reducing Antioxidant Power (FRAP) assays indicated an increase in the antioxidant potential of berries. With the exception of ascorbate peroxidase (APX), all the ROS pathway genes tested, i.e., iron-superoxide dismutase (Fe-SOD), copper-zinc-superoxide dismutase (Cu/Zn-SOD), catalase (CAT), glutathione reductase (GR), glutaredoxin (Grx), respiratory burst oxidase (Rboh), amine oxidase (AO), peroxidase (POD) and polyphenol oxidase (PPO), were found up-regulated in chitosan-treated berries. Results from the analyses of leaves, stems, and shoots revealed that chitosan not only induced the synthesis of phenolic compounds but also acted as a facilitator for the transfer of polyphenols from the leaves to the berries.

Nitric oxide (NO) presents innumerable biological roles, and its exogenous supplementation for therapeutic purposes has become a necessity. Some nanoporous materials proved to be potential vehicles for NO with high storage capacity. However, there is still a lack of information about their efficiency to release controlled NO and if they are biocompatible and biologically stable. In this work, we address this knowledge gap starting by evaluating the NO release and stability under biological conditions and their toxicity with primary keratinocyte cells. Titanosilicates (ETS-4 and ETS-10 types) and clay-based materials were the materials under study, which have shown in previous studies suitable NO gas adsorption/release rates. ETS-4 proved to be the most promising material, combining good biocompatibility at 180 μg/mL, stability and slower NO release. ETS-10 and ETAS-10 showed the best biocompatibility at the same concentration and, in the case of clay-based materials, CoOS is the least toxic of those tested and the one that releases the highest NO amount. The potentiality of these new NO donors to regulate biological functions was assessed next by controlling the mitochondrial respiration and the cell migration. NO-loaded ETS-4 regulates O2 consumption and cell migration in a dose-dependent manner. For cell migration, a biphasic effect was observed in a narrow range of ETS-4 concentration, with a stimulatory effect becoming inhibitory just by doubling ETS-4 concentration. For the other materials, no effective regulation was achieved, which highlights the relevance of the new assessment presented in this work for nanoporous NO carriers that will pave the way for further developments.