Description of the thermodynamic properties and fluid-phase behavior of aqueous solutions of linear,branched, and cyclic amines

The SAFT-γ Mie group-contribution equation of state is used to represent the fluid-phase behavior of aqueous solutions of a variety of linear, branched, and cyclic amines. New group interactions are developed in order to model the mixtures of interest, including the like and unlike interactions between alkyl primary, secondary, and tertiary amine groups (NH₂, NH, N), cyclic secondary and tertiary amine groups (cNH, cN), and cyclic methine-amine groups (cCHNH, cCHN) with water (H₂O). The group-interaction parameters are estimated from appropriate experimental thermodynamic data for pure amines and selected mixtures. By taking advantage of the group-contribution nature of the method, one can describe the fluid-phase behavior of mixtures of molecules comprising those groups over broad ranges of temperature, pressure, and composition. A number of aqueous solutions of amines are studied including linear, branched aliphatic, and cyclic amines. Liquid–liquid equilibria (LLE) bounded by lower critical solution temperatures (LCSTs) have been reported experimentally and are reproduced here with the SAFT-γ Mie approach. The main feature of the approach is the ability not only to represent accurately the experimental data employed in the parameter estimation, but also to predict the vapor–liquid, liquid–liquid, and vapor–liquid–liquid equilibria, and LCSTs with the same set of parameters. Pure compound and binary phase diagrams of diverse types of amines and their aqueous solutions are assessed in order to demonstrate the main features of the thermodynamic and fluid-phase behavior.     

κ-Opioid Signaling in the Lateral Hypothalamic Area Modulates Nicotine-Induced Negative Energy Balance

Several studies have reported that nicotine, the main bioactive component of tobacco, exerts a marked negative energy balance. Apart from its anorectic action, nicotine also modulates energy expenditure, by regulating brown adipose tissue (BAT) thermogenesis and white adipose tissue (WAT) browning. These effects are mainly controlled at the central level by modulation of hypothalamic neuropeptide systems and energy sensors, such as AMP-activated protein kinase (AMPK). In this study, we aimed to investigate the kappa opioid receptor (κOR)/dynorphin signaling in the modulation of nicotine’s effects on energy balance. We found that body weight loss after nicotine treatment is associated with a down-regulation of the κOR endogenous ligand dynorphin precursor and with a marked reduction in κOR signaling and the p70 S6 kinase/ribosomal protein S6 (S6K/rpS6) pathway in the lateral hypothalamic area (LHA). The inhibition of these pathways by nicotine was completely blunted in κOR deficient mice, after central pharmacological blockade of κOR, and in rodents where κOR was genetically knocked down specifically in the LHA. Moreover, κOR-mediated nicotine effects on body weight do not depend on orexin. These data unravel a new central regulatory pathway modulating nicotine’s effects on energy balance.     

Structural,electronic paramagnetic resonance and magnetic properties of praseodymium-doped rare earth CeO2 semiconductors

In this work, praseodymium (Pr) doped cerium oxide (CeO₂) was prepared using the microwave-assisted hydrothermal method (MAH) and the properties were investigated by X-ray diffraction analysis (XRD), Raman spectroscopy, Field Emission Gun Scanning Electron Microscope (FEG-SEM), BET method, Photoluminescence spectroscopy (PL), Fourier-transform infrared spectroscopy (FTIR), Ultraviolet–visible spectroscopy (UV–Vis), Electron paramagnetic resonance spectroscopy (EPR) and Magnetometry. The results showed that increasing the Pr-doping promotes a structural disorder due to increased oxygen vacancies. XRD confirmed a cubic structure without deleterious phases with modifications in the structure caused by alteration in the cerium oxidation state as well as changes in the crystallite size and strain obtained by Wellinson-Hall method. Raman spectroscopy shows that changing the Pr content results in samples with different defect densities at short range. FEG-SEM showed that the nanocrystals are agglomerated with small particles tend to aggregate spontaneously to decrease the surface energy. BET method showed that the Pr doping results in a gain of specific surface area. PL indicated that Pr³⁺ leads to distinct emissions; red emission associated to oxygen vacancies located near the conduction band (shallow defects), green emission associated to electron-hole recombination and orange emission associated to shallow defects and electron-hole recombination. FTIR indicated the complete process of nucleation with no other phase. UV–Vis showed the transitions between oxygen 2p, cerium 4f and praseodymium 4f states. The EPR signal shows events occurring around 344 mT. These events can be related due the presence of paramagnetic elements containing unpaired electrons, such as Ce (III), which is indicative of cerium reduction caused by Pr ions, as evidenced by Rietveld data. Regardless of the Pr concentration used in this research, the magnetic measurements show a superparamagnetic system below the blocking temperature of ~20 K and a paramagnetic system above this temperature, which indicates no significant changes in the average size of the nanoparticles. Surface area, crystallite size and the temperature are important parameters, which control the magnetic properties of such N-type semiconductors.     

Bioinformatic characterization of the extracellular lipases from Kluyveromyces marxianus

Lipases are hydrolytic enzymes that break the ester bonds of triglycerides, generating free fatty acids and glycerol. Extracellular lipase activity has been reported for the nonconventional yeast Kluyveromyces marxianus, grown in olive oil as a substrate, and the presence of at least eight putative lipases has been detected in its genome. However, to date, there is no experimental evidence on the physiological role of the putative lipases nor their structural and catalytic properties. In this study, a bioinformatic analysis of the genes of the putative lipases from K. marxianus L-2029 was performed, particularly identifying and characterizing the extracellular expected enzymes, due to their biotechnological relevance. The amino acid sequence of 10 putative lipases, obtained by in silico translation, ranged between 389 and 773 amino acids. Two of the analysed putative proteins showed a signal peptide, 25 and 33 amino acids long for KmYJR107Wp and KmLIP3p, and a molecular weight of 44.53 and 58.23 kDa, respectively. The amino acid alignment of KmLIP3p and KmYJR107Wp with the crystallized lipases from a patatin and the YlLip2 lipase from Yarrowia lipolytica, respectively, revealed the presence of the hydrolase characteristic motifs. From the 3D models of putative extracellular K. marxianus L-2029 lipases, the conserved pentapeptide of each was determined, being GTSMG for KmLIP3p and GHSLG for KmYJR107Wp; besides, the genes of these two enzymes (LIP3 and YJR107W) are apparently regulated by oleate response elements. The phylogenetic analysis of all K. marxianus lipases revealed evolutionary affinities with lipases from abH15.03, abH23.01, and abH23.02 families.     

Performance Evaluation of Two High‐Shear Impellers in an Unbaffled Stirred Tank

High‐shear impellers (HSIs) are mixers used in industrial stirred tanks to incorporate powders into liquids and break down particle agglomerates. A detailed numerical study of two commercial ring‐style HSIs of laboratory scale was carried out and their performance was compared with the Rushton turbine (RT). It was found that power and pumping numbers or their ratio cannot be simply connected for properly selecting an impeller in applications where highly localized viscous dissipation is desirable. The ratio of the average viscous dissipation in the impeller swept volume to the mean in the entire volume at two constant values of power input turned out to be lower for HSIs compared to that evaluated for RT. However, at higher power input, the dimensionless average viscous dissipation in the blade swept volume was found to be similar for the HSI of two rings and the RT, corroborating the high local viscous dissipation of this HSI when operated at higher speeds.     

Environmental and individual exposure to secondhand aerosol of electronic cigarettes in confined spaces: Results from the TackSHS Project†

Secondhand electronic cigarette (e-cigarette) aerosol (SHA) might impair indoor air quality and expose bystanders. This study aims to investigate exposure to SHA in controlled conditions of enclosed settings simulating real-world scenario. An experiment was performed in a car and in a room, in which SHA was generated during a 30-minute ad libitum use of an e-cigarette. The experiment was replicated on five consecutive days in each setting. We measured PM_2.5, airborne nicotine concentrations, and biomarkers of exposure to SHA, such as nicotine metabolites, tobacco-specific nitrosamines, propylene glycol, and glycerol in bystanders’ saliva samples before, during, and after the exposure period. Self-reported health symptoms related to exposure to SHA were also recorded. The results showed that the highest median PM_2.5 concentration was recorded during the exposure period, being 21 µg/m³ in the room setting and 16 µg/m³ in the car setting—about twofold increase compared to the baseline. Most concentrations of the airborne nicotine and all biomarkers were below the limit of quantification in both settings. Bystanders in both settings experienced some short-term irritation symptoms, expressed as dry throat, nose, eyes, and phlegm. In conclusion, short-term use of an e-cigarette in confined spaces increased indoor PM_2.5 level and caused some irritation symptoms in bystanders.     

Total arsenic, lead, cadmium, copper, and zinc in some salt rivers in the northern Andes of Antofagasta, Chile

Lake Velenje is located in one of the most polluted regions in Slovenia, the Salek Valley. The major source of pollution in the valley is the coal-fired thermal power plant in Sostanj (STPP, capacity 775 MW). It has five separate units. All units have electrostatic precipitators for fly ash removal. Unit 4 also has installed a wet flue gas desulfurisation system (FGD system). Total mercury (THg) concentrations were measured in lignite, slag and ash samples from the STPP. In flue gas, different mercury species (THg, MeHg, Hg2+, Hg0) were determined separately for unit 4 and unit 5 which use different flue gas cleaning technology. Mercury and methyl mercury (MeHg) concentrations were also measured in lake water at different depths, in inflow water, outflow water, rain, snow and lake sediments in order to establish the influence of the power plant on the lake. Most mercury emitted from the power plant is in the elemental form. The ratio between oxidised and elemental Hg depends on the flue gas cleaning technology. Mass balance calculations have been performed for the STPP. The results show that the major sources of mercury in Lake Velenje are wet deposition and lake inflows. Total and MeHg concentrations in the water column are very low and can be compared to other non-contaminated freshwater lakes in the world.     

Palladium Nanoparticles in Water: A Reusable Catalytic System for the Cycloetherification or Benzannulation of α‐Allenols

A convenient ligand‐free catalytic system has been developed for the chemoselective cyclization reaction of various α‐allenol derivatives by palladium nanoparticles (PdNPs) in an aqueous reaction medium.