Dielectric Analysis of Blended Polysulfone/Polyethylenimine Membrane Contactors for CO2 Capture.

Polysulfone membranes, used as contactors for CO2 capture, are blended with two different hyperbranched polyethyleneimines modified with benzoyl chloride (Additive 1) and phenyl isocyanate (Additive 2) in different percentages. Fourier-transformed infrared spectra evidence the presence of urea and amide groups, whereas the field emission scanning electron microscopy images show differences in the microstructure of the blended membranes. Dielectric spectra determine the motions of the side and backbone chains, which can facilitate the diffusion of CO2 . The spectra consist of six dielectric processes; three of them are due to the polysulfone (γPSf , ßPSf , and αPSf ), whereas the rest are characteristic of the additive (γHPEI , ßHPEI , and αHPEI ). The benzoyl chloride and phenyl isocyanate functional groups introduce variations in molecular mobility and modify the relaxations associated with the hyperbranched polyethyleneimine (HPEI). The additives also increase the conductivity of the blended membranes, which can compromise the performance of the membranes, specifically in the case of Additive 1. Ion hopping is found to be the prevailing charge transport mechanism while both relaxations, αHPEI and αPSf , are actives. These results, together with the final morphology of the membranes, may explain the greater absorption capacity of the membranes prepared with the hyperbranched polyethyleneimine modified with Additive 2.

Readily regenerable amine-free CO2 sorbent based on a solid-supported carboxylate ionic liquid.

Accumulation of anthropogenic CO2 is undoubtedly the major cause of global warming. In addition to reducing emissions, minimising the threatening effects of climate change in the near future might also require the capture of enormous amounts of CO2 from point sources or from the atmosphere. In this regard, the development of novel affordable and energetically attainable capture technologies is greatly needed. In this work, we report rapid and greatly facilitated CO2 desorption for amine-free carboxylate ionic liquid hydrates as compared to a benchmark amine-based sorbent. Complete regeneration was achieved at moderate temperature (60 °C) over short capture-release cycles using model flue gas on a silica-supported tetrabutylphosphonium acetate ionic liquid hydrate (IL/SiO2), whereas the polyethyleneimine counterpart (PEI/SiO2) only recovered half its capacity after the first cycle in a rather sluggish release process under the same conditions. The IL/SiO2 sorbent achieved a slightly superior working CO2 capacity than PEI/SiO2. The easier regeneration of carboxylate ionic liquid hydrates, which behave as chemical CO2 sorbents leading to bicarbonate in a 1:1 stoichiometry, is due to their relatively low sorption enthalpies (≈40 kJ mol-1). The faster and more efficient desorption from IL/SiO2 fits a first-order kinetic model (k = 0.73 min-1), whereas a more complex process was observed for PEI/SiO2 (pseudo-first order initially, k = 0.11 min-1, pseudo-zero order at later stages). The remarkably low regeneration temperature, the absence of amines and the non-volatility of the IL sorbent are favourable assets to minimise gaseous stream contamination. Importantly, regeneration heats -a crucial parameter for practical application- are advantageous for IL/SiO2 (4.3 kJ g (CO2)-1) vs. PEI/SiO2, and fall within the range of typical amine sorbents indicating a remarkable performance at this proof-of-concept stage. Further structural design will enhance the viability of amine-free ionic liquid hydrates for carbon capture technologies.

Correction: Functionalized fluorescent terephthalate monomers and their attempted polyester formation.

Correction for 'Functionalized fluorescent terephthalate monomers and their attempted polyester formation' by Yvonne S. L. Choo et al., Org. Biomol. Chem., 2020, 18, 8735-8745, DOI: 10.1039/D0OB01533D.

An Up-to-Date Overview of Liquid Crystals and Liquid Crystal Polymers for Different Applications: A Review.

Liquid crystals have been extensively used in various applications, such as optoelectronic devices, biomedical applications, sensors and biosensors, and packaging, among others. Liquid crystal polymers are one type of liquid crystal material, combining their intrinsic properties with polymeric flexibility for advanced applications in displays and smart materials. For instance, liquid crystal polymers can serve as drug nanocarriers, forming cubic or hexagonal mesophases, which can be tailored for controlled drug release. Further applications of liquid crystals and liquid crystal polymers include the preparation of membranes for separation processes, such as wastewater treatment. Furthermore, these materials can be used as ion-conducting membranes for fuel cells or lithium batteries due to their broad types of mesophases. This review aims to provide an overall explanation and classification of liquid crystals and liquid crystal polymers. Furthermore, the great potential of these materials relies on their broad range of applications, which are determined by their unique properties. Moreover, this study provides the latest advances in liquid crystal polymer-based membranes and their applications, focusing especially on fuel cells. Moreover, future directions in the applications of various liquid crystals are highlighted.

Synthesis and characterization of dendritic compounds containing nitrogen: monomer precursors in the construction of biomimetic membranes.

In this article, we synthesized a novel dendritic 2-oxazoline, 2-(3,4,5-tris(4-dodecyloxybenzyloxy)phenyl)-4,5-dihydro-1,3-oxazole), and its amide precursor N-(2-hydroxyethyl)-3,4,5-tris(4-dodecyloxybenzyloxy)benzamide. Of the distinct synthetic routes explored, it was established that the direct amidation of esters with sodium methoxide followed by the dehydrative cyclisation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone as oxidizing agent and triphenylphosphine was the most efficient route to synthesize the dendritic 2-oxazoline. Besides, N-(2-hydroxyethyl)-3,4,5-tris(4-dodecyloxybenzyloxy)benzamide exhibited a monotropic columnar mesophase, whilst the dendritic 2-oxazoline does not exhibited a liquid crystalline mesophase. At the end, the first attempts to polymerize the 2-oxazoline monomer via cationic ring opening polymerization showed promising results. Therefore, the dendritic 2-oxazoline could be used as a mesogenic monomer in the synthesis of side-chain liquid-crystalline polyoxazolines that might self-assembly into columnar structures.

Dielectric Properties in Oriented and Unoriented Membranes Based on Poly(Epichlorohydrin-co-Ethylene Oxide) Copolymers: Part III.

The dielectric spectra and conductivity properties of neat poly(epichlorohydrin-co-ethylene oxide)(PECH-co-EO) copolymer and two modified copolymers with a 20% or 40% of dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate units were analysed. A process of thermal orientation was applied to the copolymers to fine-tune the molecular motion of the side chains and determine their validity for cation transport materials. The study was conducted using Dielectric Thermal Analysis (DETA). The spectra of the modified unoriented and oriented copolymers consisted of five dielectric relaxations (δ, γ, ß, αTg, and αmelting). The analysis of the relaxations processes shows that as the grafting with the dendron units increases, both the lateral and main chains have a greater difficulty moving. The thermal orientation induces in the main chain partial crystallization, including the polyether segments, and modifies the cooperative motion of the main chain associated with the glass transition (αTg). A deep analysis of the electrical loss modulus revealed that the degree of modification only modifies the temperature peak of each relaxation, and this effect is more perceived if the dendron unit content is higher (40%). The thermal orientation process seems equal to the spectra of CP20-O and CP40-O to the point that the degree of modification does not matter. Nevertheless, the fragility index denotes the differences in the molecular motion between both copolymers (40% and 20%) due to the thermal orientation. The study of the electric conductivity showed that the ideal long-range pathways were being altered by neither the thermal orientation process nor the addition of dendrimers. The analysis of the through-plane proton conductivity confirmed that the oriented copolymer with the highest concentration of dendrimers was the best performer and the most suitable copolymer for proton transport materials.

Membranes for Cation Transport Based on Dendronized Poly(Epichlorohydrin-Co-Ethylene Oxide). Part 2: Membrane Characterization and Transport Properties.

In this paper, we report on the preparation and characterization of membranes out of two side-chain liquid crystalline copolymers, dendronized at two different extents (20 and 40%, CP20 and CP40, respectively). The membranes were characterized by atomic force microscopy (AFM), field-emission scanning electron microscopy (FESEM), contact angle (CA) analysis, and water uptake. Moreover, transport properties were studied by methanol and proton conductivity experiment and by linear sweep voltammetry (LSV). For the sake of comparison, the behavior of the grafted copolymers was compared with the unmodified copolyether CP0 and with Nafion 117. Results demonstrated that in CP20 and CP40, cation transport depends on the presence of defined cationic channels, not affected by water presence; the comparison between LSV experiments performed with different alkaline cations suggests that CP40 possesses channels with larger diameters and better-defined inner structures.

Membranes for Cation Transport Based on Dendronized Poly(epichlorohydrin-co-ethylene oxide). Part 1: The Effect of Dendron Amount and Column Orientation on Copolymer Mobility.

Dendronized polyethers give rise to columnar LC structures which can successfully act as cation transport materials. Therefore, we prepared two different materials, based on Poly(epichlorohydrin-co-ethylene oxide) (PECH-co-EO) grafted with methyl 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate, containing 20% or 40% modified units, respectively. The obtained polymers were characterized by differential scanning calorimetry (DSC), X-ray diffraction and optical microscopy between crossed polars (POM) and compared to the unmodified PECH-co-EO. In order to reach efficient transport properties, homeotropically oriented membranes were prepared by a fine-tuned thermal annealing treatment and were subsequently investigated by dynamic mechanical thermal analysis (DMTA) and dielectric thermal analysis (DETA). We found that the presence of the dendrons induces a main chain partial crystallization of the polyether chain and coherently increases the polymer Tg. This effect is more evident in the oriented membranes. As for copolymer orientation upon annealing, the cooling rate and the annealing temperature were the most crucial factors. DMTA and DETA confirmed that grafting with the dendron strongly hinders copolymer motions, but did not show great differences between unoriented and oriented membranes, regardless of the amount of dendrons.

Thermal and Mechanical Characterization of EMA-TEGDMA Mixtures for Cosmetic Applications.

Mixtures of methacrylic polymers are the most common materials for making composites to be used as resins for dental and cosmetic applications. Some of these mixtures are composed by poly(ethyl methacrylate) (PEMA) and poly(methyl methacrylate) (PMMA), which constitute a solid component to be mixed with a liquid component made out of methacrylate monomers. The reaction between the thermal initiator benzoyl peroxyde (BPO) present in the solid component and the activator of the polymerization process, N,N-dimethyl-p-toluidine (DMT) present in the liquid component, gives rise to thermoset materials. In the present study, different liquid formulations composed by a mixture of two methacrylic monomers, ethyl methacrylate (EMA) and triethylene glycol dimethacrylate (TEGDMA) for cosmetic applications, were prepared and characterized, using a commercial powder (POW) composed by PEMA and PMMA. With the aim of improving workability during final application of the material, it was necessary to slow down the polymerization rate of liquid formulations. Their thermal behavior was investigated by differential scanning calorimetric (DSC) in order to check the polymerization rate. Thermal stability of final materials was determined by thermogravimetric analysis (TGA). Dynamic mechanical thermal analysis (DMTA), microindentation hardness and impact tests were performed on final materials, to assess their performance with respect to standard formulation. The combination of thermal and mechanical properties allows choosing which formulations could be suitable for use in cosmetics.

In Situ Raman Spectroscopy as a Tool for Structural Insight into Cation Non-Ionomeric Polymer Interactions during Ion Transport.

Low-modified liquid-crystalline polyether (CP36), as a model compound, was synthesised with the purpose of preparing a membrane with columnar ionic channels. A free-standing cation permselective biomimetic membrane was successfully prepared and found to have channels made of polymeric columns homeotropically oriented, which was confirmed in X-ray diffraction (XRD) analysis. A first insight into a real-time interaction between two selected cations: H⁺ and Na⁺, and polyether during transport through the polymeric membrane was demonstrated using joined chronoamperometry and Raman spectroscopy techniques. Raman studies unveiled the possibility for smaller protons to bypass the usual ionic pathway via polyetheric chain and use outer part of ionic channel for conduction thanks to ester bonds.

[EFFICIENCY OF HAEMOGLOBIN REGENERATION IN THE NUTRITIONAL FERROPENIC ANAEMIA RECOVERY WITH GOAT MILK-BASED DIETS]. / EFICACIA DE REGENERACIÓN DE LA HEMOGLOBINA EN LA RECUPERACIÓN DE LA ANEMIA FERROPÉNICA NUTRICIONAL CON DIETAS ELABORADAS A BASE DE LECHE DE CABRA.

OBJECTIVE: in spite of the high incidence/prevalence of iron deficiency anemia (IDA) and the beneficial effects derived from the consumption of goat milk, scarce is known about the recovery of the anemia following a balanced diet accompanied by the intake of goat milk of goat. The aim of the current study is to assess, in rats with experimentally induced nutritional iron deficiency anemia, the effects of goat or cow milk-based diets, supplied during 30 days, on the recovery of the anemia and the efficiency of regeneration of the hemoglobin. MATERIAL AND METHODS: 40 male Wistar albino rats newly weaned were divided at random in two experimental groups and they were fed ad libitum for 40 days with AIN-93G diet, either with normal iron content (control group, 45 mg/kg diet), or low iron content (anaemic group, 5 mg/kg diet). Samples of blood form the caudal vein were collected for the hematologic control of the anemia. Later, both experimental groups (control and iron deficient) were fed for 30 days with goat or cow milk- based diets. After finishing the experimental period and previous anesthesia the animals were withdrawn by canulation of the abdominal aorta, and the obtained blood was gathered in tubes with EDTA as anticoagulant for the later determination of hematologic parameters and the efficiency of regeneration of the hemoglobin. RESULTS AND DISCUSSION: after the consumption of a diet with low iron content during 40 days, the rats were anaemic, with a concentration of hemoglobin, hematocrit, serum iron, mean corpuscular volume (MCV), serum ferritin and low transferrin (p < 0.001), whereas the levels of platelets and the total iron binding capacity (TIBC) were raised (p < 0.001), findings consistent with the anemia induced experimentally in the animals. The efficiency of regeneration of the hemoglobin was higher in control and anaemic rats fed goat milk-based diet in comparison with those fed cow milk-based diet (p < 0.001) due to, partly, to the major levels of serum iron and hemoglobin, and to the best nutritive utilization of iron in the animals that consumed the goat milk-based diet thanks to the excellent nutritional characteristics of this type of milk. CONCLUSION: the consumption during 30 days of goat or cow milk-based diets favors the recovery of the iron deficiency anemia, especially with the goat milk, due to the major efficiency of regeneration of the hemoglobin, index that shows the quantity of iron of the diet used for the synthesis of hemoglobin. Therefore, it would be recommendable the consumption of goat milk in the context of a balanced diet in healthy populations and, especially in those at risk of suffering iron deficiency.

Objetivo: a pesar de la alta incidencia de anemia ferropénica y de los efectos beneficiosos derivados del consumo de leche de cabra, poco se conoce, en realidad, acerca de la recuperación de la anemia mediante una dieta equilibrada acompañada de la ingesta de leche de cabra. El objetivo del presente estudio es determinar, en ratas con anemia ferropénica nutricional, los efectos de dietas elaboradas a base de leche de cabra, en comparación con la de vaca, suministradas durante 30 días, sobre la recuperación de la anemia y la eficacia de regeneración de la hemoglobina. Material y métodos: se han utilizado 40 ratas macho Wistar albina recién destetadas divididas al azar en dos grupos experimentales y alimentadas ad libitum durante 40 días con dieta AIN-93G con contenido normal de hierro (grupo control, 45 mg/kg dieta), o bajo (grupo anémico, 5 mg/kg dieta). Se toman muestras de sangre de la vena caudal para el control hematológico de la anemia. Posteriormente, cada uno de los dos grupos experimentales (control y ferrodeficiente) fueron alimentados durante 30 días con dietas elaboradas a base de leche de cabra o vaca. Al finalizar el período experimental y previa anestesia, las ratas se desangran por canulación de la aorta abdominal, y la sangre obtenida se recoge en un tubo con EDTA como anticoagulante para la posterior determinación de los parámetros hematológicos y la eficacia de regeneración de la hemoglobina. Resultados y discusión: tras el consumo de una dieta con bajo contenido en hierro durante 40 días, las ratas eran anémicas, con una concentración de hemoglobina, hematocrito, hierro sérico, volumen corpuscular medio (VCM), ferritina sérica y saturación de la transferrina bajos (p < 0,001), mientras que los niveles de plaquetas y la capacidad total de unión al hierro (TIBC) estaban elevados (p < 0,001), hallazgos consistentes con la anemia inducida experimentalmente en ratas. La eficacia de regeneración de la hemoglobina era mayor en ratas controles y anémicas alimentadas con la dieta basada en leche de cabra respecto a las alimentadas a base de leche de vaca (p < 0,001) debido, en parte, a los mayores niveles de hierro sérico y hemoglobina, así como a la mejor utilización nutritiva del hierro en los animales que consumen una dieta basada en leche de cabra gracias a las excelentes características nutricionales de este tipo de leche. Conclusión: el consumo durante 30 días de dietas elaboradas a base de leche de cabra o vaca favorece la recuperación de la anemia ferropénica, especialmente con la dieta basada en leche de cabra, debido a la mayor eficacia de regeneración de la hemoglobina, índice que muestra la cantidad de hierro de la dieta destinada a la formación de hemoglobina. Por tanto, sería recomendable introducir en una dieta equilibrada la leche de cabra o sus derivados lácteos tanto en la población sana como con anemia.