Flow Metal‐Free Ar?C Bond Formation via Photogenerated Phenyl Cations

A convenient photochemical flow protocol for the formation of aryl‐carbon bonds via photogenerated phenyl cations has been developed. A wide range of phenylated products, including biaryls, allylarenes, 2‐arylacetals and benzyl γ‐lactones, was smoothly synthesized in satisfactory yields under metal‐free conditions. The adoption of a flow reactor often allowed us to adopt higher concentrations of substrates and shorter irradiation times compared to those usually employed in batch systems.

     

Dual formation of carpets of large carbon nanofibers and thin crystalline carbon nanotubes from the same catalyst-underlayer system

A dense, micron-tall layer of carbon nanofibers (CNFs) was grown above a layer of carbon nanotubes (CNTs) during the same synthesis using a thick cobalt catalyst (15 nm). The CNFs had large diameters (100 nm) and were amorphous while the CNTs had small diameter (10–20 nm) and were crystalline. Base growth mechanism was at play for both the nanofibers and the nanotubes. High-resolution transmission electron microscopy characterization suggested that the main mechanisms leading to the growth of the two structures were based on the dewetting of the catalyst layer and its subsequent alloying with the Ta underlayer. We can extend these principles to grow diverse carbon nanostructures during the same synthesis using appropriate multilayer thin films for different applications, especially for electrochemical cells and supercapacitors.     

Insights into the physics of spray coating of SWNT films

Spray coating is a scalable and high-throughput process for fabrication of transparent and conducting coatings (TCCs) composed of single-walled carbon nanotubes (SWNTs). Presently the fundamentals of this process are not well understood. We show that suppression of coalescence of spray droplets by sufficiently rapid heat- and mass-transfer yields homogeneous SWNT films by preventing the formation of ‘coffee stains’ of larger length scale. Such heat and mass transfer is driven by differential evaporation between the top and edges of the drops, whereas thermal and compositional effects on surface tension and buoyancy are weak. Ultrasonic spraying ensures that the droplets are deposited without significant splashing, and delayed splashing at higher Weber number is evidenced. We find that the performance of spray-coated TCCs made from HiPCO SWNTs is limited by bundle diameter rather than length of the constituent SWNTs and bundes. Vapor acid doping with concentrated sulfuric acid roughly doubles the conductivity of the TCCs.     

Modeling and biological investigations of an unusual behavior of novel synthesized acridine-based polyamine ligands in the binding of double helix and G-quadruplex DNA

Three novel 2,7-substituted acridine derivatives were designed and synthesized to investigate the effect of this functionalization on their interaction with double-stranded and G-quadruplex DNA. Detailed investigations of their ability to bind both forms of DNA were carried out by using spectrophotometric, electrophoretic, and computational approaches. The ligands in this study are characterized by an open-chain (L1) or a macrocyclic (L2, L3) framework. The aliphatic amine groups in the macrocycles are joined by ethylene (L2) or propylene chains (L3). L1 behaved similarly to the lead compound m-AMSA, efficiently intercalating into dsDNA, but stabilizing G-quadruplex structures poorly, probably due to the modest stabilization effect exerted by its protonated polyamine chains. L2 and L3, containing small polyamine macrocyclic frameworks, are known to adopt a rather bent and rigid conformation; thus they are generally expected to be sterically impeded from recognizing dsDNA according to an intercalative binding mode. This was confirmed to be true for L3. Nevertheless, we show that L2 can give rise to efficient π-π and H-bonding interactions with dsDNA. Additionally, stacking interactions allowed L2 to stabilize the G-quadruplex structure: using the human telomeric sequence, we observed the preferential induction of tetrameric G-quadruplex forms. Thus, the presence of short ethylene spacers seems to be essential for obtaining a correct match between the binding sites of L2 and the nucleobases on both DNA forms investigated. Furthermore, current modeling methodologies, including docking and MD simulations and free energy calculations, provide structural evidence of an interaction mode for L2 that is different from that of L3; this could explain the unusual stabilizing ability of the ligands (L2>L3>L1) toward G-quadruplex that was observed in this study.     

Non-positive autoimmune responses against CYP2E1 in refrigeration mechanics exposed to halogenated hydrocarbons

The aim of the study was to determine if occupational exposure to hydrofluorocarbons (HFC) and hydrochlorofluorocarbons (HCFC) generates autoimmune responses against CYP2E1. HFCs and HCFCs have replaced the chlorofluorocarbons (CFC) in e.g. refrigeration installations and air-conditioning systems. During the substitution period, refrigeration mechanics reported symptoms like asthma, influenza-like reactions, and joint troubles. These symptoms resemble those of chronic inflammatory diseases with an autoimmune component. Since exposure to structurally similar chemicals, e.g. halothane, has previously been associated with autoimmune responses and diseases, autoimmunity among the refrigeration mechanics might hypothetically explain the reported inflammatory symptoms. Serum from 44 Swedish men, occupationally exposed to halogenated hydrocarbons, was screened for antibodies against CYP2E1 with enzyme-linked immunosorbent assay. Thirty of the workers had asthma, joint problems or influenza-like symptoms whereas 14 of them had no such symptoms. They were all selected from a cohort of 280 refrigeration mechanics. Unexposed, healthy, Swedish men (n=35) constituted control group. The study was approved by the Ethics Committee at Karolinska Institutet. No increase in autoantibodies against CYP2E1 was detected among the occupationally exposed workers as compared to the unexposed controls. Further, there was no difference in antibody titer between the exposed workers with symptoms and the exposed, asymtomatic workers or the unexposed controls. The present study does not completely exclude a connection between exposure and effect but makes the relation less likely at these exposure levels.     

Soft-Seeded Pomegranate (<Emphasis Type="Italic">Punica granatum</Emphasis> L.) Varieties: Preliminary Characterization and Quality Changes of Minimally Processed Arils During Storage

A preliminary characterization of two new soft-seeded pomegranate varieties (MR-100® and KINGDOM®) based on their main physico-chemical and nutritional parameters was reported. The two varieties showed significant differences (p ≤ 0.05) in polyphenols, anthocyanins and antioxidant activity. Kingdom pomegranate had higher polyphenols (2524.73 mg GAE/L), anthocyanins (752.49 mg C₃gE/L) and antioxidant activity (EC₅₀ 13.58 μL/mL) than MR-100 (1792.74 mg GAE/L, 141.29 mg C₃gE/L and EC₅₀ 47.53 μL/mL, respectively). Moreover, minimally processed arils of the two varieties were packaged in semipermeable and micro-perforated film at 5 °C, and the quality changes that occurred during storage condition (15 days) were investigated. During storage, Kingdom arils exhibited a better performance in terms of antioxidant activity, polyphenols and anthocyanin content with respect to MR-100. Furthermore, the packaging systems did not affect the estimated quality parameters for both varieties. Based on the sensory evaluation and microbial counts, both aril varieties reached, at 15-day storage, suitable values for commercial purpose.     

Photo-Polymerization Damage Protection by Hydrogen Sulfide Donors for 3D-Cell Culture Systems Optimization

Photo-polymerized hydrogels are ideally suited for stem-cell based tissue regeneration and three dimensional (3D) bioprinting because they can be highly biocompatible, injectable, easy to use, and their mechanical and physical properties can be controlled. However, photo-polymerization involves the use of potentially toxic photo-initiators, exposure to ultraviolet light radiation, formation of free radicals that trigger the cross-linking reaction, and other events whose effects on cells are not yet fully understood. The purpose of this study was to examine the effects of hydrogen sulfide (H₂S) in mitigating cellular toxicity of photo-polymerization caused to resident cells during the process of hydrogel formation. H₂S, which is the latest discovered member of the gasotransmitter family of gaseous signalling molecules, has a number of established beneficial properties, including cell protection from oxidative damage both directly (by acting as a scavenger molecule) and indirectly (by inducing the expression of anti-oxidant proteins in the cell). Cells were exposed to slow release H₂S treatment using pre-conditioning with glutathione-conjugated-garlic extract in order to mitigate toxicity during the photo-polymerization process of hydrogel formation. The protective effects of the H₂S treatment were evaluated in both an enzymatic model and a 3D cell culture system using cell viability as a quantitative indicator. The protective effect of H₂S treatment of cells is a promising approach to enhance cell survival in tissue engineering applications requiring photo-polymerized hydrogel scaffolds.     

An inverse analysis procedure for the material parameter identification of elastic–plastic free-standing foils

A model calibration technique is considered for the estimation of material parameters in free-standing thin foils. The experimental apparatus is inspired by bursting strength testers for paper, textile fabrics and polymer coatings such as geo-membranes. The procedure referred to herein consists of the following phases. A controlled fluid pressure is applied to the foil specimen placed on an horizontal plane with a suitably shaped hole. The induced out-of-plane displacements are measured by a laser profilometer. The material parameters are then inferred from these measurements through inverse analysis, by simulation of the test and minimisation of a suitable norm which defines the discrepancy between measured and computed displacements. Potentialities and limitations of the proposed method are assessed on the basis of computer-generated “pseudo-experimental” data, where modelling errors are ruled out. The identifiability of some industrially meaningful material parameters is established.