Gaseous Hydrocarbon Separations Using Functionalized Ionic Liquids

International audienceThe functionalization of the side chains on the cation or the anion of an ionic liquid is a common approach to tailor its properties for different processes including the separation of gases. In this paper, we present the current state of the art concerning the usage of ionic liquids for hydrocarbon separations. We also show how the functionalization of ionic liquids or the appropriate anion/cation combinations can contribute to the increase of the performance of the ionic liquids for the separation of gaseous hydrocarbons – either by improving the capacity of the ionic liquid to absorb a given gas or by increasing the selectivity towards a particular hydrocarbon. Original results concerning the usage of olefin-complexing metal salts of lithium (I), nickel (II) and copper (II) dissolved in ionic liquids for selectively absorbing light olefins are presented. It is observed that the absorption capacity of an imidazolium-based ionic liquid is doubled by the addition of a copper (II) salt. This result is compared with the effect of the functionalization of the ionic liquid and the advantages and difficulties of the two approaches are analyzed.La fonctionnalisation des chaînes latérales sur le cation ou l’anion d’un liquide ionique est une approche commune pour adapter ses propriétés pour les différents processus, y compris la séparation de gaz. Dans cet article, nous présentons l’état actuel des recherches concernant l’utilisation de liquides ioniques pour les séparations d’hydrocarbures gazeux. Nous montrons comment la fonctionnalisation de liquides ioniques ou des combinaisons d’anions/cations appropriées peuvent contribuer à l’augmentation de leur performance pour la séparation des hydrocarbures gazeux – soit par l’amélioration de la capacité du liquide ionique pour absorber un gaz donné ou en augmentant la sélectivité pour un hydrocarbure particulier. Des résultats originaux concernant l’utilisation de sels métalliques de lithium (I), le nickel (II) et le cuivre (II) dissous dans des liquides ioniques pour absorber sélectivement des oléfines légères sont présentés. On constate que la capacité d’absorption d’un liquide ionique à base d’imidazolium est doublée par addition d’un sel de cuivre (II). Ce résultat est comparé avec l’effet de la fonctionnalisation du liquide ionique. Les avantages et les difficultés de ces deux approches sont analysés

Recycling of cellulases in lignocellulosic hydrolysates using alkaline elution

The recovery of cellulases from lignin, lignocellulosic hydrolysates and cellulose by alkaline washes at pH 9 and 10 was examined. The effect of the pH on the structural stability of purified Cel7A was analyzed by circular dichroism. Purified Cel7A showed conformational changes at pH 9 and 10 that were reversible at pH 4.8. Temperature influenced the enzymatic hydrolysis of wheat straw and may be critical for the efficiency of cellulase recycling from wheat straw hydrolysates. Operation at moderate temperatures (37 °C) resulted in a rate of saccharification 19% higher than that obtained at 50° C, improving cellulase recycling by 49%. Over 60% of the enzyme activity on the synthetic substrate 4-methylumbelliferyl-β-d-cellobioside (MUC) may be recovered by using a simple alkaline wash. This is thus a promising strategy for enzyme recycling that is simple to implement at industrial scale, economical and effective.The authors acknowledge funding through FP7 KACELLE (Kalundborg Cellulosic Ethanol) project for supporting his work. We also thank Dr. Mai Ostergaard Haven for critical reviewing of the manuscript and Dr. Jane Lindedam for supplying the lignin

COSMO-RS Selection and Solubility Experiments

Funding Information: This work was also supported by Associate Laboratory for Green Chemistry–LAQV, financed by national funds from FCT/MCTES (UID/QUI/50006/2020), the contracts of Individual Call to Scientific Employment Stimulus 2020.00835.CEECIND (J.M.M.A.)/2021.01432.CEECIND (A.B.P.) and by FCT/MCTES (Portugal) through the project PTDC/EQU-EQU/29737/2017. The authors thank Solvay for providing the ionic liquid tri(butyl) ethylphosphonium diethylphosphate. M.C.G. and J.A. thank IDEX-LYON for financial support (Programme Investissement d’Avenir ANR-16-IDEX-0005). Publisher Copyright: © 2022 American Chemical Society. All rights reserved.In recent years, the fight against climate change and the mitigation of the impact of fluorinated gases (F-gases) on the atmosphere is a global concern. Development of technologies that help to efficiently separate and recycle hydrofluorocarbons (HFCs) at the end of the refrigeration and air conditioning equipment life is a priority. The technological development is important to stimulate the F-gas capture, specifically difluoromethane (R-32) and 1,1,1,2-tetrafluoroethane (R-134a), due to their high global warming potential. In this work, the COSMO-RS method is used to analyze the solute-solvent interactions and to determine Henry's constants of R-32 and R-134a in more than 600 ionic liquids. The three most performant ionic liquids were selected on the basis of COSMO-RS calculations, and F-gas absorption equilibrium isotherms were measured using gravimetric and volumetric methods. Experimental results are in good agreement with COSMO-RS predictions, with the ionic liquid tributyl(ethyl)phosphonium diethyl phosphate, [P2444][C2C2PO4], being the salt presenting the highest absorption capacities in molar and mass units compared to salts previously tested. The other two ionic liquids selected, trihexyltetradecylphosphonium glycinate, [P66614][C2NO2], and trihexyl(tetradecyl)phosphonium 2-cyano-pyrrole, [P66614][CNPyr], may be competitive as far as their absorption capacities are concerned. Future works will be guided on evaluating the performance of these ionic liquids at an industrial scale by means of process simulations, in order to elucidate the role in process efficiency of other relevant absorbent properties such as viscosity, molar weight, or specific heat.publishersversionpublishe

Influence of Ionic Liquids on the Morphology of Corn Flour/Polyester Mixtures

Polymer mixtures based on native corn flour and synthetic biodegradable polyester are prepared in one processing step. Melt mixing is performed in a laboratory micro-compounder. Starch contained in native corn flour is plasticized either by commonly used glycerol/water mixture or by two types of ionic liquids, 1-allyl-3-methylimidazolium chloride, and 1-butyl-3-methylimidazolium chloride. Efficiency of plasticizers on the compatibility of native corn flour with polyester and starch plasticizing ability is evaluated and compared. The structure of mixtures is examined using scanning electron microscopy and wide-angle X-ray scattering. It is found that the plasticizer applied has a crucial effect on the resulting morphology. Both ionic liquids show a better plasticizing effect on starch compared to the traditional glycerol/water plasticizer. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimMinistry of Education, Youth and Sports of the Czech Republic-Program NPU I [LO1504

The Neuroprotective Action of Amidated-Kyotorphin on Amyloid β Peptide-Induced Alzheimer’s Disease Pathophysiology

Kyotorphin (KTP, l-tyrosyl-l-arginine) is an endogenous dipeptide initially described to have analgesic properties. Recently, KTP was suggested to be an endogenous neuroprotective agent, namely for Alzheimer’s disease (AD). In fact, KTP levels were shown to be decreased in the cerebrospinal fluid of patients with AD, and recent data showed that intracerebroventricular (i.c.v.) injection of KTP ameliorates memory impairments in a sporadic rat model of AD. However, this administration route is far from being a suitable therapeutic strategy. Here, we evaluated if the blood-brain permeant KTP-derivative, KTP-NH2, when systemically administered, would be effective in preventing memory deficits in a sporadic AD animal model and if so, which would be the synaptic correlates of that action. The sporadic AD model was induced in male Wistar rats through i.c.v. injection of amyloid β peptide (Aβ). Animals were treated for 20 days with KTP-NH2 (32.3 mg/kg, intraperitoneally (i.p.), starting at day 3 after Aβ administration) before memory testing (Novel object recognition (NOR) and Y-maze (YM) tests). Animals were then sacrificed, and markers for gliosis were assessed by immunohistochemistry and Western blot analysis. Synaptic correlates were assessed by evaluating theta-burst induced long term potentiation (LTP) of field excitatory synaptic potentials (fEPSPs) recorded from hippocampal slices and cortical spine density analysis. In the absence of KTP-NH2 treatment, Aβ-injected rats had clear memory deficits, as assessed through NOR or YM tests. Importantly, these memory deficits were absent in Aβ-injected rats that had been treated with KTP-NH2, which scored in memory tests as control (sham i.c.v. injected) rats. No signs of gliosis could be detected at the end of the treatment in any group of animals. LTP magnitude was significantly impaired in hippocampal slices that had been incubated with Aβ oligomers (200 nM) in the absence of KTP-NH2. Co-incubation with KTP-NH2 (50 nM) rescued LTP toward control values. Similarly, Aβ caused a significant decrease in spine density in cortical neuronal cultures, and this was prevented by co-incubation with KTP-NH2 (50 nM). In conclusion, the present data demonstrate that i.p. KTP-NH2 treatment counteracts Aβ-induced memory impairments in an AD sporadic model, possibly through the rescuing of synaptic plasticity mechanisms.publishersversionpublishe

Results from the portuguese register

Objective Our aims were to evaluate the correlation between Juvenile Arthritis Disease Activity Score 27-joint reduced count (JADAS27) with erythrocyte sedimentation rate (ESR) and JADAS27 with C-reactive protein (CRP) scores and to test the agreement of both scores on classifying each disease activity state. We also aimed at verifying the correlation of the 2 scores across juvenile idiopathic arthritis (JIA) categories and to check the correlation between JADAS27-ESR and clinical JADAS27 (JADAS27 without ESR). Methods A nationwide cohort of patients with JIA registered in the Portuguese Register, Reuma.pt, was studied. JADAS27-CRP was adapted by replacing ESR with CRP level as the inflammatory marker. JADAS27-CRP was calculated similarly to JADAS27-ESR as the simple linear sum of its 4 components. Pearson's correlations and K statistics were used in the analyses. Results A total of 358 children had full data to calculate JADAS27; 65.4% were female and the mean ± SD disease duration was 11.8 ± 9.1 years. The correlation coefficient between JADAS27-ESR and JADAS27-CRP was 0.967 (P < 0.0001), although the correlation coefficient between ESR and CRP level was 0.335 (P < 0.0001). The strong correlation between JADAS27-ESR and JADAS27-CRP was maintained when compared within each JIA category. The agreement between JADAS27-ESR and JADAS27-CRP across the 4 activity states was very good, showing 91.1% of the observations in agreement; K = 0.867 (95% confidence interval 0.824-0.91). The correlation between JADAS27 with ESR and JADAS27 without ESR was high (r = 0.97, P < 0.0001). Conclusion JADAS27 based on CRP level correlated closely with JADAS27-ESR across all disease activity states and JIA categories, indicating that both measures can be used in clinical practice. Moreover, the correlation of JADAS27 with and without ESR was also high, suggesting that this tool might be useful even in the absence of laboratorial measures.publishersversionpublishe

Effectiveness and long-term retention of anti-tumour necrosis factor treatment in juvenile and adult patients with juvenile idiopathic arthritis: data from Reuma.pt

Methods. We prospectively collected patient and disease characteristics from patients with JIA who started biological therapy. Adverse events were collected during the follow-up period. Predictors of response at 1 year and drug retention rates were assessed at 4 years of treatment for the first biologic agent.Results. A total of 812 JIA patients [65% females, mean age at JIA onset 6.9 years (s.d. 4.7)], 227 received biologic therapy; 205 patients (90.3%) were treated with an anti-TNF as the first biologic. All the parameters used to evaluate disease activity, namely number of active joints, ESR and Childhood HAQ/HAQ, decreased significantly at 6 months and 1 year of treatment. The mean reduction in Juvenile Disease Activity Score 10 (JADAS10) after 1 year of treatment was 10.4 (s.d. 7.4). According to the definition of improvement using the JADAS10 score, 83.3% respond to biologic therapy after 1 year. Fourteen patients discontinued biologic therapies due to adverse events. Retention rates were 92.9% at 1 year, 85.5% at 2 years, 78.4% at 3 years and 68.1% at 4 years of treatment. Among all JIA subtypes, only concomitant therapy with corticosteroids was found to be univariately associated with withdrawal of biologic treatment (P = 0.016).Conclusion. Biologic therapies seem effective and safe in patients with JIA. In addition, the retention rates for the first biologic agent are high throughout 4 years

Predicting site index from climate and soil variables for cork oak (Quercus suber L.) stands in Portugal

Site productivity, assessed through site index, was modelled using partial least squares regression as a function of soil and climatic variables. Two alternative models were developed: a full model, considering all available explanatory variables, and a reduced model, considering only variables that can be obtained without digging a soil pit. The reduced model was used for mapping the site index distribution in Portugal, on the basis of existing digital cartography available for the whole country. The developed models indicate the importance of water availability and soil water holding capacity for site index value distribution. Site index was related to climate, namely evaporation and frost, and soil characteristics such as lithology, soil texture, soil depth, thickness of the A horizon and soil classification. The variability of the estimated values within the map (9.5–16.8 m with an average value of 13.4 m) reflects the impact of soil characteristics on the site productivity estimation. These variables should be taken into consideration during the establishment of new plantations of cork oak, and management of existing plantations. Results confirm the potential distribution of cork oak in coastal regions. They also suggest the existence of a considerable area, located both North and South of the Tagus river, where site indices values of medium (]13;15]) to high (]15;17]) productivity classes may be expected. The species is then expected to be able to have good productivity along the northern coastal areas of Portugal, where presently it is not a common species but where, according to historical records, it occurred until the middle of the sixteenth century. The present research focused on tree growth. Cork growth and cork quality distribution needs to be further researched through the establishment of long term experimental sites along the distribution area of cork oak, namely in the central and northern coastal areas of the countryinfo:eu-repo/semantics/publishedVersio

P. brasiliensis virulence is affected by SconC, the negative regulator of inorganic sulfur assimilation

Conidia/mycelium-to-yeast transition of Paracoccidioidesbrasiliensis is a critical step for the establishment of paracoccidioidomycosis, a systemic mycosis endemic in Latin America. Thus, knowledge of the factors that mediate this transition is of major importance for the design of intervention strategies. So far, the only known pre-requisites for the accomplishment of the morphological transition are the temperature shift to 37°C and the availability of organic sulfur compounds. In this study, we investigated the auxotrophic nature to organic sulfur of the yeast phase of Paracoccidioides, with special attention to P. brasiliensis species. For this, we addressed the role of SconCp, the negative regulator of the inorganic sulfur assimilation pathway, in the dimorphism and virulence of this pathogen. We show that down-regulation of SCONC allows initial steps of mycelium-to-yeast transition in the absence of organic sulfur compounds, contrarily to the wild-type fungus that cannot undergo mycelium-to-yeast transition under such conditions. However, SCONC down-regulated transformants were unable to sustain yeast growth using inorganic sulfur compounds only. Moreover, pulses with inorganic sulfur in SCONC down-regulated transformants triggered an increase of the inorganic sulfur metabolism, which culminated in a drastic reduction of the ATP and NADPH cellular levels and in higher oxidative stress. Importantly, the down-regulation of SCONC resulted in a decreased virulence of P. brasiliensis, as validated in an in vivo model of infection. Overall, our findings shed light on the inability of P. brasiliensis yeast to rely on inorganic sulfur compounds, correlating its metabolism with cellular energy and redox imbalances. Furthermore, the data herein presented reveal SconCp as a novel virulence determinant of P. brasiliensis.J.F.M. and J.G.R. were supported by a PhD grant from Fundacao para a Ciencia e Tecnologia (FCT). This work was supported by a grant from FCT (PTDC/BIA-MIC/108309/2008). M. Sturme. and M. Saraiva are Ciencia 2008 fellows. The authors would also like to thank FAPESP (Fundacao para Amparo a Pesquisa do Estado de Sao Paulo) and CNPq (Conselho Nacional de Desenvolvimento Cientifico e Tecnologico) for financial support. The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript

MAMMALS IN PORTUGAL : A data set of terrestrial, volant, and marine mammal occurrences in P ortugal

Mammals are threatened worldwide, with 26% of all species being includedin the IUCN threatened categories. This overall pattern is primarily associatedwith habitat loss or degradation, and human persecution for terrestrial mam-mals, and pollution, open net fishing, climate change, and prey depletion formarine mammals. Mammals play a key role in maintaining ecosystems func-tionality and resilience, and therefore information on their distribution is cru-cial to delineate and support conservation actions. MAMMALS INPORTUGAL is a publicly available data set compiling unpublishedgeoreferenced occurrence records of 92 terrestrial, volant, and marine mam-mals in mainland Portugal and archipelagos of the Azores and Madeira thatincludes 105,026 data entries between 1873 and 2021 (72% of the data occur-ring in 2000 and 2021). The methods used to collect the data were: live obser-vations/captures (43%), sign surveys (35%), camera trapping (16%),bioacoustics surveys (4%) and radiotracking, and inquiries that represent lessthan 1% of the records. The data set includes 13 types of records: (1) burrowsjsoil moundsjtunnel, (2) capture, (3) colony, (4) dead animaljhairjskullsjjaws, (5) genetic confirmation, (6) inquiries, (7) observation of live animal (8),observation in shelters, (9) photo trappingjvideo, (10) predators dietjpelletsjpine cones/nuts, (11) scatjtrackjditch, (12) telemetry and (13) vocalizationjecholocation. The spatial uncertainty of most records ranges between 0 and100 m (76%). Rodentia (n=31,573) has the highest number of records followedby Chiroptera (n=18,857), Carnivora (n=18,594), Lagomorpha (n=17,496),Cetartiodactyla (n=11,568) and Eulipotyphla (n=7008). The data setincludes records of species classified by the IUCN as threatened(e.g.,Oryctolagus cuniculus[n=12,159],Monachus monachus[n=1,512],andLynx pardinus[n=197]). We believe that this data set may stimulate thepublication of other European countries data sets that would certainly contrib-ute to ecology and conservation-related research, and therefore assisting onthe development of more accurate and tailored conservation managementstrategies for each species. There are no copyright restrictions; please cite thisdata paper when the data are used in publications.info:eu-repo/semantics/publishedVersio