PEEK–WC-Based Mixed Matrix Membranes Containing Polyimine Cages for Gas Separation

Membrane-based processes are taking a more and more prominent position in the search for sustainable and energy-efficient gas separation applications. It is known that the separation performance of pure polymers may significantly be improved by the dispersion of suitable filler materials in the polymer matrix, to produce so-called mixed matrix membranes. In the present work, four different organic cages were dispersed in the poly(ether ether ketone) with cardo group, PEEK-WC. The m-xylyl imine and furanyl imine-based fillers yielded mechanically robust and selective films after silicone coating. Instead, poor dispersion of p-xylyl imine and diphenyl imine cages did not allow the formation of selective films. The H₂, He, O₂, N₂, CH₄, and CO₂ pure gas permeability of the neat polymer and the MMMs were measured, and the effect of filler was compared with the maximum limits expected for infinitely permeable and impermeable fillers, according to the Maxwell model. Time lag measurements allowed the calculation of the diffusion coefficient and demonstrated that 20 wt % of furanyl imine cage strongly increased the diffusion coefficient of the bulkier gases and decreased the diffusion selectivity, whereas the m-xylyl imine cage slightly increased the diffusion coefficient and improved the size-selectivity. The performance and properties of the membranes were discussed in relation to their composition and morphology.     

Accelerated weathering of polypropylene/wood flour composites

Wood-plastic composites (WPCs) have received increasing attention during the last decades, because of many advantages related to their use. Some of their main applications are represented by outdoor furnishing and decking; therefore, it is important to assess their behaviour under UV exposure. In this work, polypropylene/wood flour composites were prepared and their resistance to photooxidation investigated. The composites were prepared by extrusion and compression moulding, and were subjected to mechanical tests, FTIR analysis and molecular weight measurements. The results showed that the composites retained a higher fraction of the original mechanical properties after accelerated weathering; the wood flour did not significantly degrade throughout the irradiation time slot of the investigation and the composites kept a higher percentage of the original molecular weight.     

Rheological and photophysical investigations of chromonic-like supramolecular mesophases formed by luminescent iridium(III) ionic complexes in water

Luminescent complexes with general formula [(C^N)₂Ir(N^N)]OCOCH₃, where C^N = 2-phenylpyridine (ppy) and N^N = 2,2?-bipyridine (bpy), self-assemble into ordered ‘soft’ viscous mesophases of chromonic type. By changing the ancillary ligand with 1,10-phenanthroline (phen), a new mesomorphic complex was obtained. The self-assembly into ordered liquid crystalline phases of chromonic type in water was investigated by comprehensive rheological and photophysical studies. By changing the ancillary ligand bpy with phen, assembly into smaller, more symetric aggregates is favoured, resulting in lower viscosity and more dynamic mesophase.     

High-performance liquid chromatographic determination of N-methylformamide and N-methyl-N-(hydroxymethyl)-formamide in human urine.

A reliable high-performance liquid chromatographic (HPLC) method which allows the determination in human urine of two important metabolites of N,N-dimethylformamide (DMF), namely N-methylformamide (MMF) and N-methyl-N-(hydroxymethyl)formamide (DMFOH), is reported. A single-step rapid purification of urine was performed on a C18 solid-phase extraction column and the eluate was injected directly on to the HPLC column. HPLC was carried out isocratically on Aminex Ion Exclusion HPX-87H column using 7.5.10(-4) M sulphuric acid as the mobile phase with ultraviolet detection at 196 nm. The method is specific, accurate, precise and sufficiently sensitive to be applied to the biological monitoring of MMF and DMFOH in workers exposed to DMF.     

Iridium‐Catalyzed C?H Activation versus Directed ortho Metalation: Complementary Borylation of Aromatics and Heteroaromatics

Systematic studies are presented demonstrating the complementarity of directed ortho metalation (DoM) and Ir‐catalyzed strategies for the provision of borylated aromatics and their subsequent Suzuki–Miyaura coupling reactions. A new concept, the use of the TMS group, readily introduced by DoM, as a latent regiodirective moiety to overcome the otherwise problematic production of isomeric borylated product mixtures is presented. Additional electrophile‐induced ipso‐deborylation and DoM reactions of the Bpin products are described.     

Simulation of the latex particle morphology

A model is presented for the simulation of the structuration of polymer particles under conditions in which the new polymer chains are compatible with the polymer previously formed. The model involves the calculation of the monomer concentration gradients within the particles due to discrepancies in thermodynamic interactions between the monomer and the different polymers present in each part of the polymer particle. In addition, the distribution of free radicals in the latex particle is taken into account. This distribution results from the anchoring of the hydrophilic end-group of the growing polymer chain on the surface of the particle. The model was applied to the simulation of the polymerization of vinyl acetate on a butyl acrylate–vinyl acetate copolymer seed. It was found that the development of the particle morphology was mainly due to the profile of concentration of radicals in the particle. On the other hand, the effect of the monomer–polymer thermodynamic interactions on the particle morphology was found to be negligible. However, it has to be pointed out that this is because, for the system studied, the interaction parameters of vinyl acetate with polyvinyl acetate and polybutyl acrylate are nearly identical.     

Direct immersion solid‐phase microextraction with gas chromatography and mass spectrometry for the determination of specific biomarkers of human sweat in melted snow

To provide a reliable tool for investigating diffusion processes of the specific components of the human odor 3‐hydroxy‐3‐methylhexanoic acid and 3‐methyl‐3‐sulfanylhexan‐1‐ol through the snowpack, we developed and optimized an analytical method based on direct immersion solid‐phase microextraction followed by gas chromatography with mass spectrometry. Direct immersion solid‐phase microextraction was performed using polyacrylate fibers placed in aqueous solutions containing 3‐hydroxy‐3‐methylhexanoic acid and 3‐methyl‐3‐sulfanylhexan‐1‐ol. After optimization, absorption times of 120 min provided a good balance to shorten the analysis time and to obtain suitable amounts of extractable analytes. The extraction efficiency was improved by increasing the ionic strength of the solution. Although the absolute extraction efficiency ranged between 10 and 12% for 3‐hydroxy‐3‐methylhexanoic acid and 2–3% for 3‐methyl‐3‐sulfanylhexan‐1‐ol, this method was suitable for analyzing 3‐hydroxy‐3‐methylhexanoic acid and 3‐methyl‐3‐sulfanylhexan‐1‐ol concentrations of at least 0.04 and 0.20 ng/mL, respectively. The precision of the direct immersion solid‐phase microextraction method ranged between 8 and 16%. The variability within a batch of six fibers was 10–18%. The accuracy of the method provided values of 88–95 and 86–101% for 3‐hydroxy‐3‐methylhexanoic acid and 3‐methyl‐3‐sulfanylhexan‐1‐ol, respectively. The limit of detection (and quantification) was 0.01 ng/mL (0.04 ng/mL) for 3‐hydroxy‐3‐methylhexanoic acid and 0.06 ng/mL (0.20 ng/mL) for 3‐methyl‐3‐sulfanylhexan‐1‐ol. The signal versus concentration was linear for both compounds (r² = 0.973–0.979). The stability of these two compounds showed that 3‐hydroxy‐3‐methylhexanoic acid was more stable in water than 3‐methyl‐3‐sulfanylhexan‐1‐ol. We applied the method to environmental samples in correspondence with an olfactory target buried previously.     

A new sensor architecture based on carbon Printex 6L to the electrochemical determination of ranitidine

A glassy carbon electrode (GCE) modified with carbon Printex 6L (Printex6L/GCE) as a novel sensor is proposed. A morphological study was carried out using scanning electron microscopy, and an electrochemical characterization of the proposed electrode was performed by cyclic voltammetry (CV) using [Fe(CN)₆]^4? as a redox probe. With the incorporation of the carbon Printex 6L film onto the GCE surface, the [Fe(CN)₆]^4? analytical signal was substantially increased and the difference between the oxidation and reduction potentials (ΔE _p) decreased, a characteristic of the electrocatalytic effect. Furthermore, the use of carbon Printex 6L film resulted in an 84 % increase in the oxidation current and a 123 % increase in the reduction current. Faster charge transfer was observed at the proposed electrode/electrolyte interface during CV when compared with GCE. The Printex6L/GCE was tested for ranitidine (RNT) sensing and showed a decrease in the working potential and an increase in the analytical signal, when compared with GCE, again demonstrating an electrocatalytic effect. Under optimized experimental conditions, the developed square-wave adsorptive anodic stripping voltammetry (SWAdASV) method presented an analytical curve that was linear in RNT concentration range from 1.98 × 10^?6 to 2.88 × 10^?5 mol L^?1 with a detection limit of 2.44 × 10^?7 mol L^?1. The developed Printex6L/GCE was successfully applied to the determination of RNT concentrations in human body fluid samples (urine and serum).     

Review: Graphene-supported coordination complexes and organometallics: properties and applications

Recent advances in the functionalization of graphene (G) and graphene oxide (GO) using classical coordination complexes, as well as σ- and π-organometallic compounds as precursors, are discussed. Graphene can form hybrids via covalent or non-covalent interactions with metal complexes of carboxylates, amines, polypyridine compounds, a host of N,O-containing ligands, porphyrins, phthalocyanines, carbonyls, cyclopentadienyls, pyrene-containing moieties, and other aromatic structures. The hybrid constructs are interesting for applications in catalysis, energy storage, and corrosion inhibition and present interesting possibilities of modulating the electronic structure of graphene.     

New Insight in Copper‐Ion Binding to Human Islet Amyloid: The Contribution of Metal‐Complex Speciation To Reveal the Polypeptide Toxicity

Type‐2 diabetes (T2D) is considered to be a potential threat on a global level. Recently, T2D has been listed as a misfolding disease, such as Alzheimer's and Parkinson's diseases. Human islet amyloid polypeptide (hIAPP) is a molecule cosecreted in pancreatic β cells and represents the main constituent of an aggregated amyloid found in individuals affected by T2D. The trace‐element serum level is significantly influenced during the development of diabetes. In particular, the dys‐homeostasis of Cu²⁺ ions may adversely affect the course of the disease. Conflicting results have been reported on the protective role played by complex species formed by Cu²⁺ ions with hIAPP or its peptide fragments in vitro. The histidine (His) residue at position 18 represents the main binding site for the metal ion, but contrasting results have been reported on other residues involved in metal‐ion coordination, in particular those toward the N or C terminus. Sequences that encompass regions 17–29 and 14–22 were used to discriminate between the two models of the hIAPP coordination mode. Due to poor solubility in water, poly(ethylene glycol) (PEG) derivatives were synthesized. A peptide fragment that encompasses the 17–29 region of rat amylin (rIAPP) in which the arginine residue at position 18 was substituted by a histidine residue was also obtained to assess that the PEG moiety does not alter the peptide secondary structure. The complex species formed by Cu²⁺ ions with Ac‐PEG‐hIAPP(17–29)‐NH₂, Ac‐rIAPP(17–29)R18H‐NH₂, and Ac‐PEG‐hIAPP(14–22)‐NH₂ were studied by using potentiometric titrations coupled with spectroscopic methods (UV/Vis, circular dichroism, and EPR). The combined thermodynamic and spectroscopic approach allowed us to demonstrate that hIAPP is able to bind Cu²⁺ ions starting from the His18 imidazole nitrogen atom toward the N‐terminus domain. The stability constants of copper(II) complexes with Ac‐PEG‐hIAPP(14–22)‐NH₂ were used to simulate the different experimental conditions under which aggregate formation and oxidative stress of hIAPP has been reported. Speciation unveils: 1) the protective role played by increased amounts of Cu²⁺ ions on the hIAPP fibrillary aggregation, 2) the effect of adventitious trace amounts of Cu²⁺ ions present in phosphate‐buffered saline (PBS), and 3) a reducing fluorogenic probe on H₂O₂ production attributed to the polypeptide alone.