Densities, viscosities and derived thermophysical properties of water-saturated imidazolium-based ionic liquids

In order to evaluate the impact of the alkyl side chain length and symmetry of the cation on the thermophysical properties of water-saturated ionic liquids (ILs), densities and viscosities as a function of temperature were measured at atmospheric pressure and in the (298.15 to 363.15) K temperature range, for systems containing two series of bis(trifluoromethylsulfonyl)imide-based compounds: the symmetric [C n C n im][NTf2] (with n = 1-8 and 10) and asymmetric [C n C1im][NTf2] (with n = 2-5, 7, 9 and 11) ILs. For water-saturated ILs, the density decreases with the increase of the alkyl side chain length while the viscosity increases with the size of the aliphatic tails. The saturation water solubility in each IL was further estimated with a reasonable agreement based on the densities of water-saturated ILs, further confirming that for the ILs investigated the volumetric mixing properties of ILs and water follow a near ideal behaviour. The water-saturated symmetric ILs generally present lower densities and viscosities than their asymmetric counterparts. From the experimental data, the isobaric thermal expansion coefficient and energy barrier were also estimated. A close correlation between the difference in the energy barrier values between the water-saturated and pure ILs and the water content in each IL was found, supporting that the decrease in the viscosity of ILs in presence of water is directly related with the decrease of the energy barrier.

Selection of ionic liquids to be used as separation agents for terpenes and terpenoids

In this work, ionic liquids are evaluated for the first time as solvents for extraction and entrainers in separation processes involving terpenes and terpenoids. For that purpose, activity coefficients at infinite dilution, γ13 ∞, of terpenes and terpenoids, in the ionic liquids [C4mim]Cl, [C4mim][CH3SO3], [C4mim][(CH3)2PO4] and [C4mim][CF3SO3] were determined by gas−liquid chromatography at six temperatures in the range 398.15 to 448.15 K. On the basis of the experimental values, a correlation of γ13 ∞ with an increase of the solubility parameters is proposed. The infinite dilution thermodynamic functions were calculated showing the entropic effect is dominant over the enthalpic. Gas−liquid partition coefficients give indications about the recovery and purification of terpenes and terpenoids from ionic liquid solutions. Presenting a strong innovative character, COSMO-RS was evaluated for the description of the selectivities and capacities, showing to be a useful tool for the screening of ionic liquids in order to find suitable candidates for terpenes and terpenoids extraction, and separation. COSMO-RS predictions show that in order to achieve the maximum separation efficiency, polar anions should be used such as bis(2,4,4-trimethylpentyl)phosphinate or acetate, whereas high capacities require nonpolar cations such as phosphonium.

Interactions of pyridinium, pyrrolidinium or piperidinium based ionic liquids with water: measurements and COSMO-RS modelling

Looking for a better knowledge concerning water and ionic liquids (ILs) interactions, a systematic study of the activity coefficients of water in pyridinium, pyrrolidinium and piperidinium-based ILs at 298.2 K is here presented based on water activity measurements. Additionally, the study of the structural effects of the pyridinium-based cation is also pursued. The results show that non-aromatic ILs are interacting more with water than aromatic ones, and among the ortho, meta and para isomers of 1-butyl-methylpyridinium chloride, the ortho position confers a more hydrophilic character to that specific IL. The physicalchemistry of the solutions was interpreted based on dissociation constants, natural bond orbitals and excess enthalpies providing a sound basis for the interpretation of the experimental observations. These results show that hydrogen bonding controls the behavior of these systems, being the anion-water one of the most relevant interactions, but modulated by the anionecation interactions.

Why are some cyano-based ionic liquids better glucose solvents than water?

Among different classes of ionic liquids (ILs), those with cyano-based anions have been of special interest due to their low viscosity and enhanced solvation ability for a large variety of compounds. Experimental results from this work reveal that the solubility of glucose in some of these ionic liquids may be higher than in water – a well-known solvent with enhanced capacity to dissolve mono- and disaccharides. This raises questions on the ability of cyano groups to establish strong hydrogen bonds with carbohydrates and on the optimal number of cyano groups at the IL anion that maximizes the solubility of glucose. In addition to experimental solubility data, these questions are addressed in this study using a combination of density functional theory (DFT) and molecular dynamics (MD) simulations. Through the calculation of the number of hydrogen bonds, coordination numbers, energies of interaction and radial and spatial distribution functions, it was possible to explain the experimental results and to show that the ability to favorably interact with glucose is driven by the polarity of each IL anion, with the optimal anion being dicyanamide.

Carbon-supported ionic liquids as innovative adsorbents for CO2 separation from synthetic flue-gas

Fixed-bed thermodynamic CO2 adsorption tests were performed in model flue-gas onto Filtrasorb 400 and Nuchar RGC30 activated carbons (AC) functionalized with [Hmim][BF4] and [Emim][Gly] ionic liquids (IL). A comparative analysis of the CO2 capture results and N2 porosity characterization data evidenced that the use of [Hmim][BF4], a physical solvent for carbon dioxide, ended up into a worsening of the parent AC capture performance, due to a dominating pore blocking effect at all the operating temperatures. Conversely, the less sterically-hindered and amino acid-based [Emim][Gly] IL was effective in increasing the AC capture capacity at 353 K under milder impregnation conditions, the beneficial effect being attributed to both its chemical affinity towards CO2 and low pore volume reduction. The findings derived in this work outline interesting perspectives for the application of amino acid-based IL supported onto activated carbons for CO2 separation under post-combustion conditions, and future research efforts should be focused on the search for AC characterized by optimal pore size distribution and surface properties for IL functionalization.

Nonexistence of regular stationary solution in a metric nonsymmetric theory of gravitation

It is proven that the field equations of a previously studied metric nonsymmetric theory of gravitation do not admit any non-singular stationary solution which represents a field of non-vanishing total mass and non-vanishing total fermionic charge.

Phase transitions and spatially ordered counterion association in ionic-lipid membranes: A statistical model

We propose a statistical model to account for the gel-fluid anomalous phase transitions in charged bilayer- or lamellae-forming ionic lipids. The model Hamiltonian comprises effective attractive interactions to describe neutral-lipid membranes as well as the effect of electrostatic repulsions of the discrete ionic charges on the lipid headgroups. The latter can be counterion dissociated (charged) or counterion associated (neutral), while the lipid acyl chains may be in gel (low-temperature or high-lateral-pressure) or fluid (high-temperature or low-lateral-pressure) states. The system is modeled as a lattice gas with two distinct particle types-each one associated, respectively, with the polar-headgroup and the acyl-chain states-which can be mapped onto an Ashkin-Teller model with the inclusion of cubic terms. The model displays a rich thermodynamic behavior in terms of the chemical potential of counterions (related to added salt concentration) and lateral pressure. In particular, we show the existence of semidissociated thermodynamic phases related to the onset of charge order in the system. This type of order stems from spatially ordered counterion association to the lipid headgroups, in which charged and neutral lipids alternate in a checkerboard-like order. Within the mean-field approximation, we predict that the acyl-chain order-disorder transition is discontinuous, with the first-order line ending at a critical point, as in the neutral case. Moreover, the charge order gives rise to continuous transitions, with the associated second-order lines joining the aforementioned first-order line at critical end points. We explore the thermodynamic behavior of some physical quantities, like the specific heat at constant lateral pressure and the degree of ionization, associated with the fraction of charged lipid headgroups.

Neural control of the heart: developmental changes in ionic conductances in mammalian intrinsic cardiac neurons

The expression and properties of ionic channels were investigated in dissociated neurons from neonatal and adult rat intracardiac ganglia. Changes in the hyperpolarization-activated and ATP-sensitive K+ conductances during postnatal development and their role in neuronal excitability were examined. The hyperpolarization-activated nonselective cation current, I-h, was observed in all neurons studied and displayed slow time-dependent rectification. An inwardly rectifying K+ current, I-K(I), was present in a population of neurons from adult but not neonatal rats and was sensitive to block by extracellular Ba2+. Using the perforated-patch recording configuration, an ATP-sensitive K+ (K-ATP) conductance was identified in greater than or equal to 50% of intracardiac neurons from adult rats. Levcromakalim evoked membrane hyperpolarization, which was inhibited by the sulphonylurea drugs. glibenclamide and tolbutamide. Exposure to hypoxic conditions also activated a membrane current similar to that induced by levcromakalim and was inhibited by glibenclamide. Changes in the complement of ion channels during postnatal development may underlie observed differences in the function of intracardiac ganglion neurons during maturation. Furthermore, activation of hyperpolarization-activated and KATP channels in mammalian intracardiac neurons may play a role in neural regulation of the mature heart and cardiac function during ischaemia-reperfusion. (C) 2002 Elsevier Science B.V All rights reserved.

Light shutters from nanocrystalline cellulose rods in a nematic liquid crystal

This work reports a recently developed electro-optical (EO) device that can potentially be used as a light shutter or a privacy window. By using nanocrystalline cellulose rods, we were able to improve some of the most relevant parameters characterising the EO behaviour. A brief description of the proposed working mechanism for these devices is presented, and numerical simulations based on this mechanism of both the optical transmission and the cells' electrical capacitance are compared with the obtained results, validating the underlying working model considered.

Antibacterial activity of Ionic Liquids based on ampicillin against resistant bacteria

Antibacterial activity of novel Active Pharmaceutical Ingredient Ionic Liquids (API-ILs) based on ampicillin anion [Amp] have been evaluated. They showed growth inhibition and bactericidal properties on some sensitive bacteria and especially some Gram-negative resistant bacteria when compared to the [Na][Amp] and the initial bromide and chloride salts. For these studies were analysed the minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBIC) against sensitive Gram-negative bacteria Escherichia coli ATCC 25922 and Klebsiella pneumonia (clinically isolated), as well as sensitive Gram positive S. Aureus ATCC 25923, Staphylococcus epidermidis and Enterococcus faecalis and completed using clinically isolated resistent strains: E. coli TEM CTX M9, E. coli CTX M2 and E. coli AmpC Mox. From the obtained MIC values of studied APIs-ILs and standard [Na][Amp] were derived RDIC values (relative decrease of inhibitory concentration). High RDIC values of [C16Pyr][Amp] especially against two resistant Gram-negative strains E. coli TEM CTX M9 (RDIC>1000) and E. coli CTX M2 (RDIC>100) point clearly to a potential promising role of APIs-ILs as antimicrobial drugs especially against resistant bacterial strains.

Separation of azeotropic mixtures using high ionicity ionic liquids

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Facilitated CO2 separation membranes: mixing cyano and amino acid-based ionic liquids

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Cellulose nanorods in liquid crystalline elastomers for improved actuators

Nanotechnology plays a central role in ‘tailoring’ materials’ properties and thus improving its performances for a wide range of applications. Coupling nature nano-objects with nanotechnology results in materials with enhanced functionalities. The main objective of this master thesis was the synthesis of nanocrystalline cellulose (NCCs) and its further incorporation in a cellulosic matrix, in order to produce a stimuli-responsive material to moisture. The induced behaviour (bending/unbending) of the samples was deeply investigated, in order to determine relationships between structure/properties. Using microcrystalline cellulose as a starting material, acid hydrolysis was performed and the NCC was obtained. Anisotropic aqueous solutions of HPC and NCC were prepared and films with thicknesses ranging from 22μm to 61μm were achieved, by using a shear casting technique. Microscopic and spectroscopic techniques as well as mechanical and rheological essays were used to characterize the transparent and flexible films produced. Upon the application of a stimulus (moisture), the bending/unbending response times were measured. The use of NCC allowed obtaining films with response times in the order of 6 seconds for the bending and 5 seconds for the unbending, improving the results previously reported. These promising results open new horizons for building up improved soft steam engines.

Hypertonic/hyperoncotic solution in hypovolemic patients: experience in the emergency room

Hypertonic solutions have been studied extensively in the treatment of hypovolemic shock, both in experimental and clinical models. Safety, efficacy, and long-term effects on animals and patients have been evaluated. The present article reviews indications, safety, mortality rates, and outcome in patients with hemorrhagic hypovolemic shock who were treated after admission with a hypertonic/hyperoncotic solution under strict observation in the emergency room.

The relation of the concentration of macronutrients in the substrate and in the foliage to cell wall thickness and cellulose concentration in the xylem of slash pine (Pinus elliotti)

Sand culture experiments, using a sub-irrigation technique, were installed in order to find out the effects of the macronutrients N, P, K, Ca, Mg and S on growth, aspect, mineral composition, length of fibers, thickness of cell wall and cellulose concentration in slash pine. The aim was to obtain, under controlled conditions, basic information which could eventually lead to practical means designed to increase the rate of growth and to make of slash pine a richer source of cellulose. Nitrogen, Phosphorus, Potassium Experiment A 3 x 3 x 3 factorial design with two replicates was used. Nitrogen was supplied initially at the levels of 25, 50 and 100 ppm; phosphorus was given at the rates of 5, 10 and 20 ppm; potassium was supplied at the rates of 25, 50 and 100 ppm; six months after the experiment was started the first level for each element was dropped to zero. Others macro and all micronutrients were supplied at uniform rates. Fifteen hours of illumination per day were provided. The experimental technique for growing the slash pine seedlings proved quite satisfactory. Symptoms of deficiency of nitrogen, phosphorus and potassium were observed, described and recorded in photographs and water colors. These informations will help to identify abnormalities which may appear under field conditions. Chemical analysis of the several plant parts, on the other hand, give a valuable means to assess the nutritional status of slash pine, thus confirming when needed, the visual diagnosis. The correctness of manurial pratices, on the other hand, can be judged with the help of the analytical data tabulated. Under the experimental conditions nitrogen caused the highest increases on growth, as measured by increments in height and dry weights, whereas the effects of phosphorus and potassium were less marked. Cellulose concentration was not significantly affected by the treatments used. Higher levels of N seemed to decrease both length of fiber elements and the thickness of cell wall. The effects of P and K were not well defined. Calcium, Magnesium, Sulfur Experiment A 3 x 3 x 3 factorial design with two replicates was used. Calcium was supplied initially at the levels of 12.5, 25 and 50 ppm; magnesium and sulfur were given at the rates of 6, 12.5 and 25 ppm. Other macro and micronutrients were supplied at uniform rates, common to all treatments. Three months after starting the experiment the first level for each element was dropped to zero. Symptoms of deficiency of calcium, magnesium and sulfur were observed, described and recorded as in the case of the previous experiment. Chemical analysis were made, both for mineral content and cellulose concentration. Length of fibers and thickness of cell wall were measured. Both calcium and magnesium increase height, sulfur failing to give significant response. Dry weight was beneficially affected by calcium and sulfur. The levels of calcium, magnesium and sulfur in the needles associated with deficiency and maximum growth are comparable with those found in the literature. Cellulose concentration increased when the level of sulfur in the substrate was raised. The thickness of cell wall was negatively affected by the treatments; no effect was observed with regards to length of fibers.