CO2 separation from natural gas is considered to be a crucial strategy to mitigate global warming problems, meet product specification, pipeline specs and other application specific requirements. Silica xerogels (SX) are considered to be potential materials for CO2 capture due to their high specific surface area. Thus, a series of silica xerogels functionalized with imidazolium, phosphonium, ammonium and pyridinium-based room-temperature ionic liquids (RTILs) were synthesized. The synthesized silica xerogels were characterized by NMR, helium pycnometry, DTA-TG, BET, SEM and TEM. CO2 sorption, reusability and CO2/CH4 selectivity were assessed by the pressure-decay technique. Silica xerogels containing IL demonstrated advantages compared to RTILs used as separation solvents in CO2 capture processes including higher CO2 sorption capacity and faster sorption/desorption. Using fluorinated anion for functionalization of silica xerogels leads to a higher affinity for CO2 over CH4. The best performance was obtained by SX- [bmim] [TF2N] (223.4 mg CO2/g mg/g at 298.15 K and 20 bar). Moreover, SX- [bmim] [TF2N] showed higher CO2 sorption capacity as compared to other reported sorbents. CO2 sorption and CO2/CH4 selectivity results were submitted to an analysis of variance and the means compared using Tukey's test (5%).

Imidazolium-based ionic liquids (ILs) with different cation alkyl chain ([i-C5mim] or [C4mim]) and inorganic anions ([Cl−], [Tf2N−], [PF6−] and [DCA−]) were synthesized and immobilized in commercial mesoporous silica. The synthesized supported ILs (SILs) were characterized using NMR, FTIR, TGA, BET, SEM and TEM. CO2 sorption capacity, reusability and CO2/N2 selectivity were assessed by the pressure-decay technique. The effects of IL concentration, cation and anion chemical structure in CO2 sorption capacity and CO2/N2 separation performance were evaluated. Tests evidenced that the presence of branching on the cation alkyl side chain increases CO2/N2 selectivity. The immobilization of the IL [i-C5TPIm][Cl] on mesoporous silica in different concentrations (50, 20, 10 and 5 %) revealed that lower IL concentration results in higher CO2 sorption capacity. Immobilization of ILs containing fluorinated anions at low concentrations in the mesoporous silica support may promote the improvement of the CO2/N2 selectivity without interfering on CO2 sorption capacity of the original support. CO2 sorption capacity value shown by sample SIL-5 % - [i-C5TPIm][Tf2N] (79.50 ± 0.70 mg CO2  g-1) was close to the value obtained for the pristine mesoporous silica (81.70 ± 2.20 mg CO2 g-1) and the selectivity (4.30 ± 0.70) was more than twice of the one obtained for the support alone (2.32 ± 0.4). Recycle tests demonstrated that the ILs immobilized in mesoporous silica samples are stable, providing a new option to be used in CO2 capture processes.

Microfluidic (MF) advancements have been leveraged toward the development of state-of-the-art platforms for molecular diagnostics, where isothermal amplification schemes allow for further simplification of DNA detection and quantification protocols. The MF integration with loop-mediated isothermal amplification (LAMP) is today the focus of a new generation of chip-based devices for molecular detection, aiming at fast and automated nucleic acid analysis. Here, we combined MF with droplet digital LAMP (ddLAMP) on an all-in-one device that allows for droplet generation, target amplification, and absolute quantification. This multilayer 3D chip was developed in less than 30 minutes by using a low-cost and extremely adaptable production process that exploits direct laser writing technology in “Shrinky-dinks” polystyrene sheets. ddLAMP and target quantification were performed directly on-chip, showing a high correlation between target concentration and positive droplet score. We validated this integrated chip via the amplification of targets ranging from five to 500,000 copies/reaction. Furthermore, on-chip amplification was performed in a 10 µL volume, attaining a limit of detection of five copies/µL under 60 min. This technology was applied to quantify a cancer biomarker, c-MYC, but it can be further extended to any other disease biomarker.

The relationship between linear chain (ethylene oxide units) length of polymerisable monomers with morphology, electro-optical properties and 13C nuclear magnetic resonance (NMR) spectroscopy of the corresponding polymer-dispersed liquid crystal (PDLC) films was investigated. The preferred liquid crystal molecule alignment and permanent memory effect of PDLC were greatly influenced by the length of the molecular chain of prepolymers to be incorporated as a polymer matrix. By increasing the number of ethylene oxide in prepolymer chain and maintaining the number of functionalities (polymerisable groups in each monomer molecule), the permanent memory effect of PDLC increased, as proved by solid-state 13C NMR spectroscopy.

Eco-sustainable and recyclable porous carbons are reported as metal-free catalysts for the synthesis of benzodiazepines for the first time. The porous carbons were able to efficiently catalyse the synthesis of benzodiazepine 1 from o-phenylendiamine 2 and acetone 3 under mild conditions. Both acidic functions and the porosity of the catalysts were determinant features. High conversion values were obtained when using HNO3 oxidized carbons. The highest selectivity to benzodiazepine 1 was obtained in the presence of the most microporous catalyst N-N, which is indicative of the great influence of porous properties. Stronger acid sites and high microporosity of the carbon treated with H2SO4 yield benzodiazepine 1 with total selectivity.

Chromium is one of the most important raw materials for the European Union. Adsorption has become an important process for the recovery of metals from wastewaters, which has led to a demand for low-cost and eco-friendly adsorbents. The objective of this work was to use new and renewable carbon-based adsorbents from rice wastes in the removal/recovery of Cr(III) from synthetic and real wastewaters. Rice wastes were submitted to co-pyrolysis and the resulting char was optimized through physical and/or chemical activations/treatments. A commercial activated carbon was used for comparison purposes. All adsorbents were characterized (including an ecotoxicity test for the char precursor) and submitted to Cr(III) removal assays from a synthetic solution, in which two solid/liquid ratios (S/L) were tested (5 and 10 g/L). The CO2 activated carbon at a S/L = 5 g/L was the biomass-derived adsorbent that performed better, obtaining a maximum Cr(III) uptake capacity of 9.23 mg/g comparable to the one obtained by the commercial adsorbent at the same S/L (9.80 mg/g). The good results on this biomass-derived carbon were due to the effective volatile matter removal during the activation (from 22.7 to 4.25% w/w), which increased both surface area (from <5.0 to 325 m2/g) and ash content (from 30.0 to 40.4% w/w), allowing an increase in Cr(III) removal due to ion exchange mechanism and porosity development. The best adsorbent, under optimized conditions, was also applied to a chromium rich industrial wastewater. The results obtained in this real case application demonstrated a competition effect due to the presence of other ions.

Background The awareness of environmental and socio-economic impacts caused by greenhouse gas emissions from the livestock sector leverages the adoption of strategies to counteract it. Feed supplements can play an important role in the reduction of the main greenhouse gas produced by ruminants—methane (CH\textsubscript{4}). In this context, this study aims to assess the effect of two biochar sources and inclusion levels on rumen fermentation parameters \textit{in vitro}. Methods Two sources of biochar (agro-forestry residues, AFB, and potato peel, PPB) were added at two levels (5 and 10%, dry matter (DM) basis) to two basal substrates (haylage and corn silage) and incubated 24-h with rumen inocula to assess the effects on CH\textsubscript{4} production and main rumen fermentation parameters \textit{in vitro}. Results AFB and PPB were obtained at different carbonization conditions resulting in different apparent surface areas, ash content, pH at the point of zero charge (pHpzc), and elemental analysis. Relative to control (0% biochar), biochar supplementation kept unaffected total gas production and yield (mL and mL/g DM, \textit{p} = 0.140 and \textit{p} = 0.240, respectively) and fermentation pH (\textit{p} = 0.666), increased CH\textsubscript{4}production and yield (mL and mL/g DM, respectively, \textit{p} = 0.001) and ammonia-N (NH\textsubscript{3}-N, \textit{p} = 0.040), and decreased total volatile fatty acids (VFA) production (\textit{p} < 0.001) and H\textsubscript{2} generated and consumed (\textit{p} ≤ 0.001). Biochar sources and inclusion levels had no negative effect on most of the fermentation parameters and efficiency. Acetic:propionic acid ratio (\textit{p} = 0.048) and H\textsubscript{2} consumed (\textit{p} = 0.019) were lower with AFB inclusion when compared to PPB. Biochar inclusion at 10% reduced H\textsubscript{2} consumed (\textit{p} < 0.001) and tended to reduce total gas production (\textit{p} = 0.055). Total VFA production (\textit{p} = 0.019), acetic acid proportion (\textit{p} = 0.011) and H\textsubscript{2} generated (\textit{p} = 0.048) were the lowest with AFB supplemented at 10%, no differences being observed among the other treatments. The basal substrate affected most fermentation parameters independently of biochar source and level used. Discussion Biochar supplementation increased NH\textsubscript{3}-N content, \textit{iso}-butyric, \textit{iso}-valeric and valeric acid proportions, and decreased VFA production suggesting a reduced energy supply for microbial growth, higher proteolysis and deamination of substrate N, and a decrease of NH\textsubscript{3}-N incorporation into microbial protein. No interaction was found between substrate and biochar source or level on any of the parameters measured. Although AFB and PPB had different textural and compositional characteristics, their effects on the rumen fermentation parameters were similar, the only observed effects being due to AFB included at 10%. Biochar supplementation promoted CH\textsubscript{4} production regardless of the source and inclusion level, suggesting that there may be other effects beyond biomass and temperature of production of biochar, highlighting the need to consider other characteristics to better identify the mechanism by which biochar may influence CH\textsubscript{4} production.

In this work, a dynamic model of an industrial acetylene hydrogenation reactor with a front-end configuration was developed, based on plant operation data. This type of reactor operates in transient state, not only due to the natural fluctuations in operating conditions but also due to the effects caused by the deactivation of the catalyst. To develop the dynamic model of the acetylene hydrogenation reactor a thorough study of the effect of operating conditions was performed; the influence of variables such as the inlet temperature of the 1st reactor, the flowrate, carbon monoxide concentration, on the activity, selectivity and stability of the catalyst was examined by choosing adequate periods of the operation of the reactor. To understand the reaction mechanism of this system, several published kinetics were tested but only one was finally fitted to the industrial data, to interpret the operation of the acetylene hydrogenation reactor. A set of operation periods was used to develop the model which was then validated by applying the model to a different set of operation periods. As a conclusion, the dynamic model that was developed and validated, using actual plant operation data, was able to adequately describe the outlet temperatures of the three reactors in the system as well as the outlet acetylene concentration of the 3rd reactor.

Lyotropic colloidal aqueous suspensions of cellulose nanocrystals (CNCs) can, after solvent evaporation, retain their chiral nematic arrangement. As water is removed the pitch value of the suspension decreases and structural colour-generating films, which are mechanically brittle in nature, can be obtained. Increasing their flexibility while keeping the chiral nematic structure and biocompatible nature is a challenging task. However, if achievable, this will promote their use in new and interesting applications. In this study, we report on the addition of different amounts of hydroxypropyl cellulose (HPC) to CNCs suspension within the coexistence of the isotropic-anisotropic phases and infer the influence of this cellulosic derivative on the properties of the obtained solid films. It was possible to add 50 wt.% of HPC to a CNCs aqueous suspension (to obtain a 50/50 solids ratio) without disrupting the LC phase of CNCs and maintaining a left-handed helical structure in the obtained films. When 30 wt.% of HPC was added to the suspension of CNCs, a strong colouration in the film was still observed. This colour shifts to the near-infrared region as the HPC content in the colloidal suspension increases to 40 wt.% or 50 wt.% The all-cellulosic composite films present an increase in the maximum strain as the concentration of HPC increases, as shown by the bending experiments and an improvement in their thermal properties.

Dodecamolydbophosphoric acid (HPMo) immobilized on USY zeolite was used as a catalyst for the acetalization of glycerol with pentanal at 70 °C. Catalysts were prepared with different amounts of heteropolyacid, and the most active sample was the HPMo2@Y catalyst (1.1 wt.%). The products of glycerol acetalization with pentanal were (2-butyl-1,3-dioxolan-4-yl)methanol, a five-member ring compound, and 2-butyl-1,3-dioxan-5-ol, a six-member ring compound. Good values of selectivity for the five-member ring compound (80–85%) were obtained with all materials. The reaction conditions were optimized using HPMo2@Y as a catalyst. The optimal conditions were determined to be 70 °C reaction temperature with 0.3 g catalyst and a 1:2.5 M ratio of glycerol to pentanal. The catalytic stability of HPMo2@Y was studied. The acetalization of glycerol with pentanal was performed using the same sample. High catalytic activity for HPMo2@Y was observed.

Abstract Anaerobic microorganisms of the Geobacter genus are effective electron sources for the synthesis of nanoparticles, for bioremediation of polluted water, and for the production of electricity in fuel cells. In multistep reactions, electrons are transferred via iron/heme cofactors of c-type cytochromes from the inner cell membrane to extracellular metal ions, which are bound to outer membrane cytochromes. We measured electron production and electron flux rates to 5×105 e s−1 per G. sulfurreducens. Remarkably, these rates are independent of the oxidants, and follow zero order kinetics. It turned out that the microorganisms regulate electron flux rates by increasing their Fe2+/Fe3+ ratios in the multiheme cytochromes whenever the activity of the extracellular metal oxidants is diminished. By this mechanism the respiration remains constant even when oxidizing conditions are changing. This homeostasis is a vital condition for living systems, and makes G. sulfurreducens a versatile electron source.

The monoheme outer membrane cytochrome F (OmcF) from Geobacter sulfurreducens plays an important role in Fe(III) reduction and electric current production. The electrochemical characterization of this cytochrome has shown that its redox potential is modulated by the solution pH (redox-Bohr effect) endowing the protein with the necessary properties to couple electron and proton transfer in the physiological range. The analysis of the OmcF structures in the reduced and oxidized states showed that with the exception of the side chain of histidine 47 (His⁴⁷), all other residues with protonatable side chains are distant from the heme iron and, therefore, are unlikely to affect the redox potential of the protein. The protonatable site at the imidazole ring of His⁴⁷ is in the close proximity to the heme and, therefore, this residue was suggested as the redox-Bohr center. In the present work, we tested this hypothesis by replacing the His⁴⁷ with non-protonatable residues (isoleucine – OmcFH47I and phenylalanine – OmcFH47F). The structure of the mutant OmcFH47I was determined by X-ray crystallography to 1.13 Å resolution and showed only minimal changes at the site of the mutation. Both mutants were ¹⁵N-labeled and their overall folding was confirmed to be the same as the wild-type by NMR spectroscopy. The pH dependence of the redox potential of the mutants was measured by cyclic voltammetry. Compared to the wild-type protein, the magnitude of the redox-Bohr effect in the mutants was smaller, but not fully abolished, confirming the role of His⁴⁷ on the pH modulation of OmcF’s redox potential. However, the pH effect on the heme substituents’ NMR chemical shifts suggested that the heme propionate P₁₃ also contributes to the overall redox-Bohr effect in OmcF. In physiological terms, the contribution of two independent acid–base centers to the observed redox-Bohr effect confers OmcF a higher versatility to environmental changes by coupling electron/proton transfer within a wider pH range.

Understanding the specific molecular interactions between proteins and β1,3-1,4-mixed-linked d-glucans is fundamental to harvest the full biological and biotechnological potential of these carbohydrates and of proteins that specifically recognize them. The family 11 carbohydrate-binding module from Clostridium thermocellum (CtCBM11) is known for its binding preference for β1,3-1,4-mixed-linked over β1,4-linked glucans. Despite the growing industrial interest of this protein for the biotransformation of lignocellulosic biomass, the molecular determinants of its ligand specificity are not well defined. In this report, a combined approach of methodologies was used to unravel, at a molecular level, the ligand recognition of CtCBM11. The analysis of the interaction by carbohydrate microarrays and NMR and the crystal structures of CtCBM11 bound to β1,3-1,4-linked glucose oligosaccharides showed that both the chain length and the position of the β1,3-linkage are important for recognition, and identified the tetrasaccharide Glcβ1,4Glcβ1,4Glcβ1,3Glc sequence as a minimum epitope required for binding. The structural data, along with site-directed mutagenesis and ITC studies, demonstrated the specificity of CtCBM11 for the twisted conformation of β1,3-1,4-mixed-linked glucans. This is mediated by a conformation–selection mechanism of the ligand in the binding cleft through CH-π stacking and a hydrogen bonding network, which is dependent not only on ligand chain length, but also on the presence of a β1,3-linkage at the reducing end and at specific positions along the β1,4-linked glucan chain. The understanding of the detailed mechanism by which CtCBM11 can distinguish between linear and mixed-linked β-glucans strengthens its exploitation for the design of new biomolecules with improved capabilities and applications in health and agriculture. Database Structural data are available in the Protein Data Bank under the accession codes 6R3M and 6R31.