Role of Unimers to Polymersomes Transition in Pluronic Blends for Controlled and Designated Drug Conveyance.

This study investigates the nanoscale self-assembly from mixtures of two symmetrical poly(ethylene oxide)-poly(propylene oxide)-pol(ethylene oxide) (PEO-PPO-PEO) block copolymers (BCPs) with different lengths of PEO blocks and similar PPO blocks. The blended BCPs (commercially known as Pluronic F88 and L81, with 80 and 10% PEO, respectively) exhibited rich phase behavior in an aqueous solution. The relative viscosity (ηrel) indicated significant variations in the flow behavior, ranging from fluidic to viscous, thereby suggesting a possible micellar growth or morphological transition. The tensiometric experiments provided insight into the intermolecular hydrophobic interactions at the liquid-air interface favoring the surface activity of mixed-system micellization. Dynamic light scattering (DLS) and small-angle neutron scattering (SANS) revealed the varied structural morphologies of these core-shell mixed micelles and polymersomes formed under different conditions. At a concentration of ≤5% w/v, Pluronic F88 exists as molecularly dissolved unimers or Gaussian chains. However, the addition of the very hydrophobic Pluronic L81, even at a much lower (<0.2%) concentration, induced micellization and promoted micellar growth/transition. These results were further substantiated through molecular dynamics (MD) simulations, employing a readily transferable coarse-grained (CG) molecular model grounded in the MARTINI force field with density and solvent-accessible surface area (SASA) profiles. These findings proved that F88 underwent micellar growth/transition in the presence of L81. Furthermore, the potential use of these Pluronic mixed micelles as nanocarriers for the anticancer drug quercetin (QCT) was explored. The spectral analysis provided insight into the enhanced solubility of QCT through the assessment of the standard free energy of solubilization (ΔG°), drug-loading efficiency (DL%), encapsulation efficiency (EE%), and partition coefficient (P). A detailed optimization of the drug release kinetics was presented by employing various kinetic models. The [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] MTT assay, a frequently used technique for assessing cytotoxicity in anticancer research, was used to gauge the effectiveness of these QCT-loaded mixed nanoaggregates.

Modeling oceanic sedimentary methane hydrate growth through molecular dynamics simulation.

The crystallization process of methane hydrates in a confined geometry resembling seabed porous silica sedimentary conditions has been studied using molecular dynamics simulations. With this objective in mind, a fully atomistic quartz silica slit pore has been designed, and the temperature stability of a methane hydrate crystalline seed in the presence of water and guest molecule methane has been analyzed. NaCl ion pairs have been added in different concentrations, simulating salinity conditions up to values higher than average oceanic conditions. The structure obtained when the hydrate crystallizes inside the pore is discussed, paying special attention to the presence of ionic doping inside the hydrate and the subsequent induced structural distortion. The shift in the hydrate stability conditions due to the increasing water salinity is discussed and compared with the case of unconfined hydrate, concluding that the influence of the confinement geometry and pore hydrophilicity produces a larger deviation in the confined hydrate phase equilibria.

Effect of Antioxidant Supplementation on NET Formation Induced by LPS In Vitro; the Roles of Vitamins E and C, Glutathione, and N-acetyl Cysteine.

Neutrophil extracellular traps (NETs) require reactive oxygen species (ROS) to eliminate pathogens by inducing oxidative stress. However, this process can also cause tissue damage to the host. Neutrophils contain high concentrations of vitamin C (1.5 mM) compared to the bloodstream (0.1 mM), and this antioxidant can interact with vitamin E and glutathione (GSH) inside the cell to maintain the redox balance. Previous studies have investigated the effect of vitamins E or C and N-acetyl cysteine (NAC) on NET formation, but the interactions of these molecules in neutrophils remain unknown. In this study, we investigated the effect of antioxidants alone and two combinations on NET formation and oxidative stress. Neutrophils were pre-loaded with GSH + NAC or vitamin E + vitamin C + GSH + NAC (termed ALL), and LPS-induced NET formation was assessed using fluorometry and immunofluorescence. Antioxidant effects were evaluated by measuring the total antioxidant capacity (TAC), GSH/GSSG ratio, ROS production, nitrite + nitrate levels, and lipid peroxidation. Our results showed that even low doses of antioxidants are capable of decreasing NETs. Furthermore, the combinations augmented TAC and GSH/GSSG ratio and decreased ROS, nitrites + nitrates, and malondialdehyde (MDA) levels in supplemented neutrophils in vitro.

Exploring the impact of sodium salts on hydrotropic solubilization.

Some ionic liquids (ILs) were shown to display a strong ability to enhance the solubility of phenolic compounds through hydrotropy. However, evidence shows that salt ions in hydrotropic aqueous solutions may change the behavior of molecules by promoting possible interactions between the components of the system, thus causing changes in solubility. Herein, we study the impact of sodium salt anions on the hydrotropic dissolution of syringic acid using 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) as a hydrotrope, with a focus on dicyanamide Na[N(CN)2] and thiocyanate Na[SCN] salts. Dynamic light scattering, Raman spectroscopy, and nuclear magnetic resonance spectroscopy were used to investigate how the mixture of IL-salts affects the solvation. The results obtained show that [C4mim]Cl is able to increase the solubility of syringic acid 80-fold. Despite their structural similarities, the presence of Na[N(CN)2] or Na[SCN] in an aqueous solution of [C4mim]Cl induced opposite solubility trends. The addition of Na[N(CN)2] promotes a higher ability to solubilize syringic acid than in the corresponding IL system due to a pH buffering effect, resulting in the deprotonation of the solute. The addition of Na[SCN], on the other hand, induces a relative decrease in syringic acid solubilization at higher concentrations of ILs due to the negative contribution of the NaCl formed by anion-exchange. These results emphasise the often overlooked pH contribution provided by ILs for biomolecule solubilisation whilst providing experimental insights into the structure of aqueous solutions of ionic liquids and the role it plays in the formation of IL-salt aggregates.

Rationalizing the Design of Pluronics-Surfactant Mixed Micelles through Molecular Simulations and Experiments.

Aqueous systems comprising polymers and surfactants are technologically important complex fluids with tunable features dependent on the chemical nature of each constituent, overall composition in mixed systems, and solution conditions. The phase behavior and self-assembly of amphiphilic polymers can be changed drastically in the presence of conventional ionic surfactants and need to be clearly understood. Here, the self-aggregation dynamics of a triblock copolymer (Pluronics L81, EO3PO43EO3) in the presence of three cationic surfactants (with a 12C long alkyl chain but with different structural features), viz., dodecyltrimethylammonium bromide (DTAB), didodecyldimethylammonium bromide (DDAB), and ethanediyl-1,2-bis(dimethyldodecylammonium bromide) (12-2-12), were investigated in an aqueous solution environment. The nanoscale micellar size expressed as hydrodynamic diameter (Dh) of copolymer-surfactant mixed aggregates was evaluated using dynamic light scattering, while the presence of a varied micellar geometry of L81-cationic surfactant mixed micelles were probed using small-angle neutron scattering. The obtained findings were further validated from molecular dynamics (MD) simulations, employing a simple and transferable coarse-grained molecular model based on the MARTINI force field. L81 remained molecularly dissolved up to ∼20 °C but phase separated, forming turbid/translucent dispersion, close to its cloud point (CP) and existed as unstable vesicles. However, it exhibited interesting solution behavior expressed in terms of the blue point (BP) and the double CP in the presence of different surfactants, leading to mixed micellar systems with a triggered morphology transition from unstable vesicles to polymer-rich micelles and cationic surfactant-rich micelles. Such an amendment in the morphology of copolymer nanoaggregates in the presence of cationic surfactants has been well observed from scattering data. This is further rationalized employing the MD approach, which validated the effective interactions between Pluronics-cationic surfactant mixed micelles. Thus, our experimental results integrated with MD yield a deep insight into the nanoscale interactions controlling the micellar aggregation (Pluronics-rich micelles and surfactant-rich micelles) in the investigated mixed system.

Assessing the hydrotropic effect in the presence of electrolytes: competition between solute salting-out and salt-induced hydrotrope aggregation.

Water solubility enhancement is a long-standing challenge in a multitude of chemistry-related fields. Hydrotropy is a simple and efficient method to improve the solubility of hydrophobic molecules in aqueous media. However, the mechanism behind this phenomenon remains controversial. Herein the impact of salt doping on the hydrotropy phenomenon is determined experimentally using the ionic liquid (IL) 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) as a hydrotope and vanillin as a solute. Hydrophobic interactions were found to be central to the aggregation of the hydrotrope around the solute, and seem to drive hydrotropy. Furthermore, 1H-NMR analysis indicates that hydrotrope-solute interactions present a degree of site-specificity. The addition of chloride salts in the presence of higher IL concentrations promotes a greater relative decrease of the vanillin solubility than in the corresponding system without the IL. This was assigned to the negative impact of increased hydrotrope pre-aggregation in the presence of inorganic salts. The results were rationalised using statistical thermodynamics through which hydrotrope aggregation prior to solute addition is shown to be detrimental to the hydrotropic effect, seemingly confirming solute-induced clustering of the hydrotrope to be the predominant mechanism of hydrotropy.

A Comprehensive Descriptive Epidemiological and Clinical Analysis of SARS-CoV-2 in West-Mexico during COVID-19 Pandemic 2020.

This study aimed to summarize the epidemiological and clinical characteristics of COVID-19 from Western Mexico people during 2020. A retrospective analysis from an electronic database of people visiting a sentinel center for molecular SARS-CoV-2 confirmatory diagnosis by RT-PCR from April to December 2020 was carried out for epidemiological and clinical description of COVID-19. Out of 23,211 patients evaluated, 6918 (29.8%) were confirmed for SARS-CoV-2 infection (mean age 38.5 ± 13.99), mostly females (53.8%). Comorbidities, such as diabetes (34.7%), obesity (31.15%), and hypertension (31.8%), presented an increased odds OR = 1.27, CI = 1.14-1.41; OR = 1.08, CI = 1.01-1.16; and OR = 1.09, CI = 0.99-1.19, respectively, for viral-infection. Moreover, fever, headache, and dry cough were the most frequent symptoms. No infection difference among sex was found. Those patients >60 years old were prone to COVID-19 severity (OR = 3.59, CI = 2.10-6.14), evaluated by the number of manifested symptoms, increasing with age. In conclusion, a high SARS-CoV-2 prevalence was found in Western Mexico. Comorbidities were frequent in infected people; nevertheless, no association with disease outcomes was observed, in contrast with the highest disease severity risk found in older patients; however, continuous monitoring should be carried since comorbidities have been reported as aggravating factors. This study can help the health officials for the elaboration of planning efforts of the disease management and others in the future.

To Trap a Pathogen: Neutrophil Extracellular Traps and Their Role in Mucosal Epithelial and Skin Diseases.

Neutrophils are the most abundant circulating innate immune cells and comprise the first immune defense line, as they are the most rapidly recruited cells at sites of infection or inflammation. Their main microbicidal mechanisms are degranulation, phagocytosis, cytokine secretion and the formation of extracellular traps. Neutrophil extracellular traps (NETs) are a microbicidal mechanism that involves neutrophil death. Since their discovery, in vitro and in vivo neutrophils have been challenged with a range of stimuli capable of inducing or inhibiting NET formation, with the objective to understand its function and regulation in health and disease. These networks composed of DNA and granular components are capable of immobilizing and killing pathogens. They comprise enzymes such as myeloperoxidase, elastase, cathepsin G, acid hydrolases and cationic peptides, all with antimicrobial and antifungal activity. Therefore, the excessive formation of NETs can also lead to tissue damage and promote local and systemic inflammation. Based on this concept, in this review, we focus on the role of NETs in different infectious and inflammatory diseases of the mucosal epithelia and skin.

Unveiling the phase behavior of CiEj non-ionic surfactants in water through coarse-grained molecular dynamics simulations.

Poly(oxyethylene) alkyl ethers, usually denoted by CiEj surfactants, exhibit a rich phase behavior in water, self-assembling to form a variety of 3-D structures with a controllable morphology that find multiple applications across different industrial segments. Hence, being able to describe and understand the effect of molecular structure on the phase behavior of these systems is highly relevant for the efficient design of new materials and their applications. Considering the promising results obtained over the last decade using the MARTINI model to describe ethylene-oxide containing compounds, an extensive assessment of the ability of such a model to describe the phase behavior of CiEj in water was carried out and results are presented here. Given the overall poor temperature transferability of the MARTINI model, mostly due to the lack of an accurate representation of hydrogen bonding, simulations were carried out at a single temperature of 333 K, where most phases are expected to occur according to experiments. Different chain lengths of both the hydrophobic and hydrophilic moieties, spanning a wide range of hydrophilic-lipophilic balance values, were investigated and the phase diagrams of various CiEj surfactants explored over a wide concentration range. The model was able to satisfactorily describe the effect of surfactant structure and concentration on mesophase formation. The stability and dimensions of the obtained phases, and the prediction of some unique features such as the characterization of a singular lamellar phase are presented. The results obtained in this work highlight both the predictive ability and the transferability of the MARTINI forcefield in the description of such systems. Moreover, the model was shown to provide adequate descriptions of the micellar phase in terms of micelle dimensions, critical micelle concentration, and average aggregation number.

[Enzymatic resistance in Pseudomonas aeruginosa, clinical and laboratory aspects]. / Resistencia enzimática en Pseudomonas aeruginosa, aspectos clínicos y de laboratorio.

Pseudomonas aeruginosa is one of the major pathogens causing healthcare-associated infections (HAI). Its capacity of adaptation, dissemination, intrinsic resistance to antimicrobials and of acquiring new mechanisms through mobile genetic elements, make the treatment of infections by this microorganism a challenge for the clinician. Intrinsically, P. aeruginosa, presents a reduced permeability in the external membrane, due to the expression of efflux pumps, and an inducible AmpC-type cephalosporinase. In addition, P. aeruginosa is able to acquire new resistance determinants by horizontal transfer in the form of cassettes located in integrons, and in turn located in transposons or plasmids. Within the enzymatic resistance that P. aeruginosa presents, betalactamases, including extended spectrum (ESBL) and carbapenemases. But also aminoglycoside modifying enzymes, stand out, causing this microorganism to present multi-resistance phenotypes (MDR), extreme resistance (XDR) and pan-resistance (PDR) to the called antipseudomonal antibiotics, including the new cephalosporins with betalactamase inhibitors.

Using coarse-grained molecular dynamics to understand the effect of ionic liquids on the aggregation of Pluronic copolymer solutions.

This study is aimed to enhance the understanding of the interaction between ionic liquids (ILs) and non-ionic Pluronic triblock copolymers in aqueous two-phase micellar systems (ATPMS) used for the selective separation/purification of hydrophobic biomolecules. The ILs allow a precise control of the cloud point phase separation temperature (CPT), particularly important when the stability of the molecule is highly dependent on temperature. The effect of choline-based ILs, with two different counter-anions, chloride and hexanoate, was evaluated using molecular dynamics simulations (MD) for F-68 and L-35 Pluronic aqueous solutions. The simulations revealed the role played by the anions during the Pluronic self-assembly, with choline chloride hindering Pluronic aggregation and the choline hexanoate favouring micelle formation and coalescence, in agreement with the experimental data. A detailed study of the accessible surface area of Pluronic showed a progressive dehydration of the Pluronic hydrophilic micelle corona in choline hexanoate mixtures promoting inter-micelle interactions and, consequently, micelle coalescence. With the addition of choline hexanoate, it was observed that the hydrophilic segments, which form the micelle corona, twisted towards the Pluronic micelle core. The electrostatic interaction is also shown to play a key role in this IL-Pluronic aqueous solution, as the hexanoate anions are accommodated in the Pluronic micelle core, while the choline cations are hosted by the Pluronic micelle corona, with the ions interacting with each other during the self-assembly process. In addition, a comparison study of F-68 and L-35 aqueous solutions shows that the IL impact depends on the length of the Pluronic hydrophilic segment. This work provides a realistic microscopic scenario of the complex interactions between Pluronic copolymers and ILs.

Resistencia enzimática en Pseudomonas aeruginosa, aspectos clínicos y de laboratorio / Enzymatic resistance in Pseudomonas aeruginosa, clinical and laboratory aspects

Resumen Pseudomonas aeruginosa es uno de los principales patógenos que causa infecciones asociadas a la atención en salud (IAAS). Su capacidad de adaptación, diseminación, resistencia intrínseca a los antimicrobianos y de adquirir nuevos mecanismos a través de elementos genéticos móviles, hacen que el tratamiento de las infecciones por este microorganismo sea un desafío para el médico clínico. Intrínsecamente, P. aeruginosa, presenta una reducida permeabilidad en la membrana externa, debido a la expresión de bombas de expulsión, y una cefalosporinasa tipo AmpC inducible. Además, P. aeruginosa es capaz de adquirir nuevos determinantes de resistencia por transferencia horizontal en forma de casetes situados en integrones, y a su vez, localizados en transposones o plásmidos. Dentro de la resistencia enzimática que presenta P. aeruginosa destacan las β-lactamasas, incluyendo aquellas de espectro extendido (BLEE) y las carbapenemasas. Pero también enzimas modificadoras de los aminoglucósidos, haciendo que este microorganismo pueda presentar fenotipos de multi-resistencia (MDR), resistencia extrema (XDR) y panresistencia (PDR) a los antimicrobianos denominados antipseudomonas, incluyendo a las nuevas cefalosporinas con inhibidores de beta-lactamasas.

Abstract Pseudomonas aeruginosa is one of the major pathogens causing healthcare-associated infections (HAI). Its capacity of adaptation, dissemination, intrinsic resistance to antimicrobials and of acquiring new mechanisms through mobile genetic elements, make the treatment of infections by this microorganism a challenge for the clinician. Intrinsically, P. aeruginosa, presents a reduced permeability in the external membrane, due to the expression of efflux pumps, and an inducible AmpC-type cephalosporinase. In addition, P. aeruginosa is able to acquire new resistance determinants by horizontal transfer in the form of cassettes located in integrons, and in turn located in transposons or plasmids. Within the enzymatic resistance that P. aeruginosa presents, betalactamases, including extended spectrum (ESBL) and carbapenemases. But also aminoglycoside modifying enzymes, stand out, causing this microorganism to present multi-resistance phenotypes (MDR), extreme resistance (XDR) and pan-resistance (PDR) to the called antipseudomonal antibiotics, including the new cephalosporins with betalactamase inhibitors.

Multifunctionality in an Ion-Exchanged Porous Metal-Organic Framework.

Porous robust materials are typically the primary selection of several industrial processes. Many of these compounds are, however, not robust enough to be used as multifunctional materials. This is typically the case of Metal-Organic Frameworks (MOFs) which rarely combine several different excellent functionalities into the same material. In this report we describe the simple acid-base postsynthetic modification of isotypical porous rare-earth-phosphonate MOFs into a truly multifunctional system, maintaining the original porosity features: [Ln(H3pptd)]·xSolvent [where Ln3+ = Y3+ (1) and (Y0.95Eu0.05)3+ (1_Eu)] are converted into [K3Ln(pptd)]·zSolvent [where Ln3+ = Y3+ (1K) and (Y0.95Eu0.05)3+ (1K_Eu)] by immersing the powder of 1 and 1_Eu into an ethanolic solution of KOH for 48 h. The K+-exchanged Eu3+-based material exhibits a considerable boost in CO2 adsorption, capable of being reused for several consecutive cycles. It can further separate C2H2 from CO2 from a complex ternary gas mixture composed of CH4, CO2, and C2H2. This high adsorption selectivity is, additionally, observed for other gaseous mixtures, such as C3H6 and C3H8, with all these results being supported by detailed theoretical calculations. The incorporation of K+ ions notably increases the electrical conductivity by 4 orders of magnitude in high relative humidity conditions. The conductivity is assumed to be predominantly protonic in nature, rendering this material as one of the best conducting MOFs reported to date.

Using coarse-grained molecular dynamics to rationalize biomolecule solubilization mechanisms in ionic liquid-based colloidal systems.

Solubilizing agents are widely used to extract poorly soluble compounds from biological matrices. Aqueous solutions of surfactants and hydrotropes are commonly used as solubilizers, however, the underlying mechanism that determines their action is still roughly understood. Among these, ionic liquids (IL) are often used not only for solubilization of a target compound but in liquid-liquid extraction processes. Molecular dynamics simulations can shed light into this issue by providing a microscopic insight of the interactions between solute and solubilising agents. In this work, a new coarse-grained (CG) model was developed under the MARTINI framework for gallic acid (GA) while the CG models of three quaternary ammonium ionic liquids and salts (QAILS) were obtained from literature. Three QAILS were selected bearing in mind their potential solubilising mechanisms: trimethyl-tetradecylammonium chloride ([N1,1,1,14]Cl) as a surfactant, tetrabutylammonium chloride ([N4,4,4,4]Cl) as a hydrotrope, and tributyl-tetradecylammonium chloride ([N4,4,4,14]Cl) as a system combining the characteristics of the other compounds. Throughout this hydrotrope-to-surfactant spectrum and considering the most prevalent GA species across the pH range, the solvation of GA at two concentration levels in aqueous QAILS solutions were studied and discussed. The results of this study indicate that dispersive interactions between the QAILS and GA are generally the driving force in the GA solubilization. However, electrostatic interactions play an increasingly significant role as the GA becomes deprotonated, affecting their placement within the micelle and ultimately the solvation mechanism. The hydrotropic mechanism seen in [N4,4,4,4]Cl corroborates recent models based on the formation of a hydrotrope-solute aggregates driven by dispersive forces. This work contributes to the application of a transferable approach to partition and solubilization studies using molecular dynamics, which could complement experimental assays and quickly screen molecular candidates for these processes.

Unravelling the Interactions between Surface-Active Ionic Liquids and Triblock Copolymers for the Design of Thermal Responsive Systems.

The tunable properties of surface-active ionic liquids (SAILs) and Pluronics are dramatically magnified by combining them in aqueous solutions. The thermo-controlled character of both, essential in the extraction of valuable compounds, can be fine-tuned by properly selecting the Pluronic and SAIL nature. However, further understanding of the nanoscale interactions directing the aggregation in these complex mixtures is needed to effectively design and control these systems. In this work, a simple and transferable coarse-grained model for molecular dynamics simulations, based on the MARTINI force field, is presented to study the impact of SAILs in Pluronics aggregation in aqueous solutions. The diverse amphiphilic characteristics and micelle morphologies were exemplified by selecting four archetypical nonionic Pluronics-two normal, L-31 and L-35, and two reverse, 10R5 and 31R1. The impact of the alkyl chain length and the headgroup nature were evaluated with the imidazolium-based [C10mim]Cl and [C14mim]Cl and phosphonium-based [P4,4,4,14]Cl SAILs. Cloud point temperature (CPT) measurements at different Pluronic concentrations with 0.3 wt % of SAIL in aqueous solution emphasized the distinct impact of SAIL nature on the thermo-response behavior. The main effect of SAIL addition to nonionic Pluronics aqueous solutions is the formation of Pluronic/SAIL hybrid micelles, where the presence of SAIL molecules introduces a charged character to the micelle surface. Thus, additional energy is necessary to induce micelle aggregation, leading to the observed increase in the experimental CPT curves. The SAIL showed a relatively weak impact in Pluronic micelles with relatively high PPG hydrophobic content, whereas this effect was more evident when the Pluronic hydrophobic/hydrophilic strength is balanced. A detailed analysis of the Pluronic/SAIL micelle density profiles showed that the phosphonium head groups were positioned inside the micelle core, whereas smaller imidazolium head groups were placed much closer to the hydrophilic PEG corona, leading to a distinct effect on the cloud point temperature for those two classes of SAILs. Herein, the phosphonium-based SAIL induces a lower repulsion between neighboring micelles than the imidazolium-based SAILs, resulting in a less pronounced increase of the CPT. The model presented here offers, for the first time, an intuitive and powerful tool to unravel the complex thermo-response behavior of Pluronic and SAIL mixtures and support the design of tailor-made thermal controlled solvents.

Improved coarse-grain model to unravel the phase behavior of 1-alkyl-3-methylimidazolium-based ionic liquids through molecular dynamics simulations.

HYPOTHESIS: Imidazolium-based ionic liquids (ILs) in water exhibit a surfactant-like behavior that is only partially characterized by experimental techniques with molecular dynamic (MD) simulations emerging as a complimentary tool to study their phase behavior. However, while atomistic models suffer of time and size scale limitations, higher-level models (e.g. coarse-grain) are still of limited applicability, accuracy, and transferability. EXPERIMENTS: A robust and transferable CG model for 1-alkyl-3-methylimidazolium halides [Cnmim][X], using the MARTINI forcefield (FF), was proposed and validated against all-atom (AA) simulations and existing experimental data. A systematic study on the effect of the alkyl chain length, IL concentration, and temperature on the phase behavior of [Cnmim][Cl] aqueous solutions was performed. FINDINGS: At low amphiphile concentrations, the micellar regime extends from the critical micellar concentration (cmc) up to 10-25 wt%, depending on the alkyls chain length, where a sphere-to-rod transition is observed. The aggregation numbers of the spherical micelles were found to be in good agreement with experiments and, as the concentration was increased, a variety of mesophases was observed, providing useful insights into these systems. Furthermore, the segregation of IL moieties into polar and non-polar domains in ILs, possessing short alkyl tails, was demonstrated.

Enhancement of Ethane Selectivity in Ethane-Ethylene Mixtures by Perfluoro Groups in Zr-Based Metal-Organic Frameworks.

A series of zirconium dicarboxylate-based metal-organic frameworks (Zr MOFs) of the UiO-66 (tetrahedral and octahedral cages) or MIL-140 (triangular channels) structure type were investigated for the separation of ethane/ethylene mixtures. The adsorption, investigated both experimentally and computationally, revealed that the size and type of pores have a more pronounced effect on the selectivity than the aromaticity of the linker. The increase in pore size when changing from benzene to naphthalene (NDC) dicarboxylate ligand makes UiO-NDC less selective (1.3-1.4) than UiO-66 (1.75-1.9) within the pressure range (100-1000 kPa), while the three-dimensional (3D) pores of the UiOs favor the adsorption of ethane due to the interactions between ethane with more spacers than in the case of the 1D channels of MIL-140s. The impact of the functionalization revealed a very interesting increase of selectivity when two perfluoro groups are present on the aromatic ring (UiO-66-2CF3) (value of 2.5 up to 1000 kPa). Indeed, UiO-66-2CF3 revealed a unique combination of selectivity and working capacity at high pressures. This is due to a complex adsorption mechanism involving a different distribution of the guest molecules in the different cages associated with changes in the ligand/perfluoro orientation when the pressure increases, favoring the ethane adsorption at high pressures.

Mechanisms of phase separation in temperature-responsive acidic aqueous biphasic systems.

The temperature responsive solubility of ionic liquids with 'bulky' polar regions, such as tributyltetradecyl phosphonium chloride ([P44414]Cl), in acidic aqueous solutions is elucidated through a combined experimental and computational approach. The temperature effect in the acidic aqueous biphasic system HCl/[P44414]Cl/H2O was characterised in the range 273 K to 373 K and was found to significantly deviate from the corresponding aqueous biphasic system with NaCl. A new transferable coarse grained MARTINI model for [P44414]Cl was developed, validated and applied to provide a molecular understanding of the experimental results. It is shown that the presence of large aliphatic moieties around the central phosphorus atoms of [P44414]Cl results in a decrease in the electrostatic repulsion between the cationic moieties, leading the [P44414]+ cation to present a behaviour conventionally associated with non-ionic surfactants. This difference in behaviour between HCl and NaCl was shown to result from the greater interaction of the hydronium cation with the micelle surface, thereby enhancing the [P44414]Cl aggregation.

A novel fluorimetric method for glyphosate and AMPA determination with NBD-Cl and MCR-ALS.

We report the development of a new analytical method for the quantification of N-(phosphonomethyl)glycine (glyphosate) and (aminomethyl)phosphonic acid (AMPA) by combining spectrofluorimetry and multivariate calibration. In this study, fluorescence spectroscopy was used to quantify glyphosate and AMPA, which were previously derivatized with the fluorogenic reagent: 4-chloro-7-nitrobenzofurazan (NBD-Cl). Fluorescence excitation-emission matrices (EEM) were recorded by exciting between 400 and 500 nm, and measuring the emission between 500 and 610 nm. The second-order data obtained were processed using the Multivariate Curve Resolution with Alternating Least Square (MCR-ALS) methodology. The developed method was used to predict different concentrations of glyphosate and AMPA in validation samples. In addition, the presence of the herbicide was evaluated in real samples: a commercial formulation and a water sample from a cultivated area. For this purpose, the standard addition method was used to study the matrix effect in each case. The ranges of working concentrations obtained for this new method are in agreement with the amounts found in surface water samples near a direct sowing soybean growing region in Argentina.

Revisión sistemática sobre la suplementación profiláctica de L-carnitina en la nutrición parenteral de recién nacidos pretérmino / A systematic review about prophylactic L-carnitine administration in parenteral nutrition of extremely preterm infants

Objetivo: Los recién nacidos pretérmino con nutrición parenteral total tienen tanto una reducción de la ingesta de L-carnitina como de las reservas tisulares, lo que podría suponer una peor tolerancia de los lípidos paren‑ terales. El objetivo fue revisar la literatura científica en busca de los posibles beneficios clínicos de su administración en la nutrición parenteral. Métodos: Revisión sistemática de los documentos recuperados en las bases de datos MEDLINE/Pubmed, Scopus, The Cochrane Library, British Library EThOS y TESEO. Los términos utilizados como descriptores fueron «Total Parenteral Nutrition» y «Carnitine». La calidad de los artículos se evaluó mediante la escala de Jadad. Resultados: Tras aplicar los criterios de inclusión y exclusión, se seleccionaron para la revisión 18 artículos de las 93 referencias recuperadas, de los cuales 4 fueron descartados al no ser considerados de alta calidad. Casi la totalidad de los estudios coincidían en las variables analíticas medidas (carnitina libre y acilcarnitina, triglicéridos, ácidos grasos libres y cuerpos cetónicos). Además, en algunos se tenían en cuenta otras variables clínicas, como la ganancia ponderal o la apnea. Conclusiones: La suplementación rutinaria en la nutrición parenteral de recién nacidos pretérmino sí parece mejorar los niveles plasmáticos de carnitina, pero sin llegar a demostrar una mejoría significativa en el perfil lipídico, ni aumento de la ganancia ponderal, ni disminución de la morbi-mortalidad o reducción de la estancia hospitalaria. Son necesarios más estudios para demostrar si la suplementación sistemática a recién nacidos pretérmino que requieren nutrición parenteral total durante más de un mes aportaría beneficios clínicos

Objective: Preterm infants with total parenteral nutrition are at particular risk of developing carnitine deficiency with impaired tolerance of parenteral lipids. The objective was to review the scientific literature on potencial benefits of prophylactic L-carnitine administration in parenteral nutrition of preterm newborns. Methods: Selected scientific articles in MEDLINE/PubMed, Scopus, The Cochrane Library, British Library EThOS and TESEO databases were assessed for this systematic review. The terms used as descriptors were «Total Parenteral Nutrition» and «Carnitine». Jadad scale was chosen to evaluate the quality of them. Results: 18 out of the 93 references retrieved were selected for reviewing after applying the inclusion and exclusion criteria, 4 of them were discarded for being considered of low quality. Almost all studies agreed on the analytical variables measured (free carnitine and acylcarnitine, triglycerides, free fatty acids and ketone bodies). Other clinical variables such as weight gain, apnea, or lenght of stay at hospital were also considered. Conclusions: The present results prove that routine supplementation in the parenteral nutrition of preterm newborns may help to increase carnitine levels, but neither a relevant improvement in the lipid profile, or an increase in weight gain, or a decrease in morbimortality or reduction of hospital stay could be demonstrated. More studies are needed in preterm infants to know whether routine supplementation of L-carnitine in neonates requiring total parenteral nutrition for a long time would provide any clinical benefit