Aromatic volatile organic compounds absorption with phenyl-based deep eutectic solvents: A molecular thermodynamics and dynamics study

The suitability of phenyl-based deep eutectic solvents (DESs) as absorbents for toluene absorption was investigated by means of thermodynamic modeling and molecular dynamics (MD). The thermodynamic models perturbed-chain statistical associating fluid theory (PC-SAFT) and conductor-like screening model for real solvents (COSMO-RS) were used to predict the vapor–liquid equilibrium of DES–toluene systems. PC-SAFT yielded quantitative results even without using any binary fitting parameters. Among the five DESs studied in this work, [TEBAC][PhOH] consisting of triethyl benzyl ammonium chloride (TEBAC) and phenol (PhOH), was considered as the most suitable absorbent. Systems with [TEBAC][PhOH] had lowest equilibrium pressures of the considered DES–toluene mixtures, the best thermodynamic characteristics (i.e., Henry's law constant, excess enthalpy, Gibbs free energy of solvation of toluene), and the highest self-diffusion coefficient of toluene. The molecular-level mechanism was explored by MD simulations, indicating that [TEBAC][PhOH] has the strongest interaction of DES–toluene compared to the other DESs under study. This work provides guidance to rationally design novel DESs for efficient aromatic volatile organic compounds absorption.     

Surface modification of polyacrylonitrile staple fibers via alkaline hydrolysis for superabsorbent applications

The alkaline hydrolysis of polyacrylonitrile staple fibers was investigated for evaluation as superabsorbent materials. Studies were performed to analyze the hydrolysis of fibers and the quantification of the developed functional groups, such as carboxyl and amide groups as well as changes in the nitrile content by means of Micro‐ATR. Dyeing of the samples with methylene blue was carried out to monitor the carboxyl groups formed during the hydrolysis. A gradual decrease in the nitrile groups and built up of the carboxyl and the amide groups was observed during the hydrolysis. Microscopic investigation carried out to investigate the surface structure of hydrolyzed fibers. Hydrolysis led to surface nonhomogeneity and erosion that was dependent on the hydrolysis conditions. The fibers showed good water retention behavior, making them superabsorbent materials. The dyeing showed more intense coloration in the surface region of the modified fibers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3127–3133, 2004     

Variation of Brominated Indoles and Terpenoids Within Single and Different Colonies of the Marine Bryozoan Flustra foliacea

The variation of the brominated indole and diterpenoid content within single and different colonies of the bryozoan Flustra foliacea was investigated. The secondary metabolite profile and concentrations of individual components of F. foliacea samples were established using GC-MS. Samples from 17 different collecting sites were analyzed. The alkaloid and diterpene composition of F. foliacea varied greatly depending upon the site of collection. Investigation of F. foliacea samples from a single site (Helgoland, North Sea) over a period of time showed that the alkaloid and diterpenoid profile remained constant, however concentrations of individual components varied significantly. The alkaloid and diterpenoid composition of different segments of a single colony was found to be constant. Only small differences could be detected in the essential oil composition of different colonies and segments of single colonies of F. foliacea. Two of the F. foliacea alkaloids were found in the gastropods Hydrobia ulva and Gibbula cinerea, and one alkaloid in the common starfish Asteria rubens, all collected from the surface of the bryozoan.     

Geranylgeraniol and Neurological Impairment: Involvement of Apoptosis and Mitochondrial Morphology

Deregulation of the cholesterol pathway is an anomaly observed in human diseases, many of which have in common neurological involvement and unknown pathogenesis. In this study we have used Mevalonate Kinase Deficiency (MKD) as a disease-model in order to investigate the link between the deregulation of the mevalonate pathway and the consequent neurodegeneration. The blocking of the mevalonate pathway in a neuronal cell line (Daoy), using statins or mevalonate, induced an increase in the expression of the inflammasome gene (NLRP3) and programmed cell death related to mitochondrial dysfunction. The morphology of the mitochondria changed, clearly showing the damage induced by oxidative stress and the decreased membrane potential associated with the alterations of the mitochondrial function. The co-administration of geranylgeraniol (GGOH) reduced the inflammatory marker and the damage of the mitochondria, maintaining its shape and components. Our data allow us to speculate about the mechanism by which isoprenoids are able to rescue the inflammatory marker in neuronal cells, independently from the block of the mevalonate pathway, and about the fact that cell death is mitochondria-related.     

Activation of the glmS Ribozyme Confers Bacterial Growth Inhibition

The ever‐growing number of pathogenic bacteria resistant to treatment with antibiotics call for the development of novel compounds with as‐yet unexplored modes of action. Here, we demonstrate the in vivo antibacterial activity of carba‐α‐d ‐glucosamine (CGlcN). In this mode of action study, we provide evidence that CGlcN‐mediated growth inhibition is due to glmS ribozyme activation, and we demonstrate that CGlcN hijacks an endogenous activation pathway, hence utilizing a prodrug mechanism. This is the first report describing antibacterial activity mediated by activating the self‐cleaving properties of a ribozyme. Our results open the path towards a compound class with an entirely novel and distinct molecular mechanism.     

Cover Image,Volume 66, Issue 3

The cover image, by Katia Sparnacci et al., is based on the Research Article High temperature surface neutralization process with random copolymers for block copolymer self‐assembly, DOI: 10.1002/pi.5285 .

     

Electrically insulating polymeric nanocomposites with enhanced thermal conductivity by visible‐light curing of epoxy–boron nitride nanotube formulations

Epoxy–boron nitride nanotube (BNNT) composites were prepared using visible light through a radical‐induced cationic polymerization method activated by camphorquinone. The fully cured films showed an enhancement of glass transition temperature in the presence of the filler. Electrical characterization showed a slight dielectric constant decrease with BNNT content. Finally, thermal conductivity measured using nano‐flash analysis showed a linear increase in the thermal conductivity of the materials with increasing BNNT content in the photocurable formulations. © 2017 Society of Chemical Industry     

Influence of shear thinning and material flow on robotic dispensing of poly(ethylene glycol) diacrylate/poloxamer 407 hydrogels

Robotic dispensing of hydrogels offers a direct way for generating complex hydrogel shapes. For this, there is a general need for hydrogel formulations with suitable rheological properties. In this contribution, hydrogel formulations containing poly(ethylene glycol) diacrylate (PEG‐DA) and Poloxamer 407 are characterized regarding their flow behavior during robotic dispensing. Formulations contain between 15% and 20% PEG‐DA and 22.5% and 25% Poloxamer 407. All formulations show shear thinning which can be described using a power law with a power law index between 0.10 and 0.11 and calculated shear rates at the wall of the dispensing needle of 379 s^?1 with a dispensing speed of 8 mm s^?1 and a dispensing needle inner diameter of 0.51 mm. Thus, facilitating the generation of smooth hydrogel strands, three‐dimensional hydrogel objects can be prepared without flow after robotic dispensing and can be cured afterward to elastic hydrogels, retaining the shape of the dispensed object. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45083.     

Oxidation Catalysts Based on Antimony Mixed Oxides with Rutile-Type Structures

Several authors have correlated catalyst structure to catalytic behavior in selective oxidation reactions. Sleight [1] reviewed the importance of the scheelite structure for the allylic oxidation and ammonoxidation of olefins; Grasselli and co-workers [2–4] extensively examined the relationship between structure and catalytic activity of bismuth-molybdates, uranium-antirnonates, and bismuth-cerium molybdates. Bordes and Courtine [5] correlated the activity in mild oxidation of 1-butene to the properties of the structure of vanadium-phosphorus oxides. However, little attention has been given in the literature to the role of the rutile structure in allylic oxidation reactions even though the high activity and selectivity of antimony oxides stabilized in matrices with rutile structure (SnO₂ and FeSbO₄) in olefins oxidation and ammonoxidation have been known for several years. Furthermore, Tables 1 and 2 indicate that the kinetic and catalytic behavior of antimony-based catalysts in allylic oxidation reactions are very different from that of molybdate-based catalysts. This suggests that antimony- and molybdate-based catalysts are two distinct classes of catalysts of allylic oxidation, in agreement with a recent suggestion by Grasselli et al. [13].     

Selenocarbamates As a Prodrug-Based Approach to Carbonic Anhydrase Inhibition

A study on the activity of selenocarbamates as a novel chemotype acting as carbonic anhydrase (CA, EC 4.2.1.1) inhibitors is reported. Undergoing CA-mediated hydrolysis, selenocarbamates release selenolates behaving as zinc binding groups and effectively inhibiting CAs. A series of selenocarbamates characterised by high molecular diversity and complexity have been studied against different human CA isoforms such as hCA I, II, IX and XII. Selenocarbamates behave as masked selenols with potential biological applications as prodrugs for CAs inhibition-based strategies. X-ray studies provided insights into the binding mode of this novel class of CA inhibitors.