How preparation and modification parameters affect PB‐PEO polymersome properties in aqueous solution

The effect of formation and modification methods on the physical properties of polymersomes is critical for their use in applications relying on their ability to mimic functional properties of biological membranes. In this study, we compared two formation methods for polymersomes made from polybutadiene‐polyethylene oxide diblock copolymers: detergent‐mediated film rehydration (DFR) and solvent evaporation (SE). DFR‐prepared polymersomes showed a three times higher permeability compared to SE‐prepared polymersomes as revealed by stopped‐flow light scattering. SE‐prepared polymersomes broke down faster to structures <50 nm diameter when processed with extrusion, which was more pronounced at 5 mg mL^?1, compared to 10, 20, and 25 mg mL^?1. Our results indicate that the bilayer of SE‐prepared polymersomes has a lower apparent fluidity. We also investigated the role of n‐octyl‐β‐d ‐glucopyranoside (OG), a detergent typically used for reconstitution of membrane proteins into lipid bilayers. Specifically, we compared dialysis and biobeads for OG removal to investigate the influence of these methods on bilayer conformation and polymer rearrangement following detergent removal. There was no significant difference found between method, temperature, or time within each method. Our findings provide insight on how biocompatible polymersome production affects the physical properties of the resulting polymersomes. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1581–1592     

Solid-phase synthesis of an apoptosis-inducing tetrapeptide mimicking the Smac protein

An approach for the solid-phase synthesis of apoptosis-inducing Smac peptidomimetics is presented. Using a Rink linker strategy, tetrapeptides mimicking the N-4-terminal residue of the Smac protein [(N-Me)AVPF sequence] were synthesized on PEGA resin in excellent purities and yields. Following two synthetic routes, a known tetrapeptide, incorporating a substituted proline, previously shown to exhibit excellent biological activity in vitro as well as low toxicity, was synthesized effectively on a solid support.     

Transition‐Metal‐Free Cross‐Coupling of Benzothiophenes and Styrenes in a Stereoselective Synthesis of Substituted (E,Z)‐1,3‐Dienes

A transition metal‐free one‐pot stereoselective approach to substituted (E,Z)‐1,3‐dienes was developed by using an interrupted Pummerer reaction/ligand‐coupling strategy. Readily available benzothiophene S‐oxides, which can be conveniently prepared by oxidation of the parent benzothiophenes, undergo Pummerer coupling with styrenes. Reaction of the resultant sulfonium salts with alkyllithium/magnesium reagents generates underexploited hypervalent sulfurane intermediates that undergo selective ligand coupling, resulting in dismantling of the benzothiophene motif and the formation of decorated (E,Z)‐1,3‐dienes.     

Environmental exposure assessment framework for nanoparticles in solid waste

Information related to the potential environmental exposure of engineered nanomaterials (ENMs) in the solid waste management phase is extremely scarce. In this paper, we define nanowaste as separately collected or collectable waste materials which are or contain ENMs, and we present a five-step framework for the systematic assessment of ENM exposure during nanowaste management. The framework includes deriving EOL nanoproducts and evaluating the physicochemical properties of the nanostructure, matrix properties and nanowaste treatment processes as well as transformation processes and environment releases, eventually leading to a final assessment of potential ENM exposure. The proposed framework was applied to three selected nanoproducts: nanosilver polyester textile, nanoTiO₂ sunscreen lotion and carbon nanotube tennis racquets. We found that the potential global environmental exposure of ENMs associated with these three products was an estimated 0.5–143 Mg/year, which can also be characterised qualitatively as medium, medium, low, respectively. Specific challenges remain and should be subject to further research: (1) analytical techniques for the characterisation of nanowaste and its transformation during waste treatment processes, (2) mechanisms for the release of ENMs, (3) the quantification of nanowaste amounts at the regional scale, (4) a definition of acceptable limit values for exposure to ENMs from nanowaste and (5) the reporting of nanowaste generation data.     

Aquatic Ecotoxicity Testing of Nanoparticles—The Quest To Disclose Nanoparticle Effects

The number of products on the market containing engineered nanoparticles (ENPs) has increased significantly, and concerns have been raised regarding their ecotoxicological effects. Environmental safety assessments as well as relevant and reliable ecotoxicological data are required for the safe and sustainable use of ENPs. Although the number of publications on the ecotoxicological effects and uptake of ENPs is rapidly expanding, the applicability of the reported data for hazard assessment is questionable. A major knowledge gap is whether nanoparticle effects occur when test organisms are exposed to ENPs in aquatic test systems. Filling this gap is not straightforward, because of the broad range of ENPs and the different behavior of ENPs compared to “ordinary” (dissolved) chemicals in the ecotoxicity test systems. The risk of generating false negatives, and false positives, in the currently used tests is high, and in most cases difficult to assess. This Review outlines some of the pitfalls in the aquatic toxicity testing of ENPs which may lead to misinterpretation of test results. Response types are also proposed to reveal potential nanoparticle effects in the aquatic test organisms.     

Enhancement of muramyldipeptide (MDP) immunostimulatory activity by controlled multimerization on dendrimers

Peptidoglycan is a widespread bacterial PAMP molecule and a powerful initiator of innate immune responses. It consists of repeating units of MDP, which as a monomer is only weakly immunostimulatory. Here, MDP-coupled dendrimers were prepared and investigated for stimulation of pig blood mononuclear cells. Compared to monomeric MDP, MDP-dendrimers induced a markedly enhanced production of IL-12 p40, IL-1β and IL-6 and completely down-regulated surface expression of B7 and MHC class II. These results suggest a possible novel strategy based on controlled multimerization of minimal PAMP motifs on dendrimers for preparing molecularly defined immunostimulators with predictable bioactivities.     

Characterization of barley leaf tissue using direct and indirect desorption electrospray ionization imaging mass spectrometry

Chemical profiling of barley (Hordeum vulgare) leaves was demonstrated using direct and indirect desorption electrospray ionization (DESI) imaging mass spectrometry. Direct DESI analysis of the untreated leaves was not possible despite a significant content of hydroxynitrile glucosides known to reside in the epidermis of the leaves. Instead, the epidermis was stripped off the leaves, thus allowing direct DESI imaging to be performed on the back of the epidermis. Furthermore, indirect DESI imaging was performed by making imprints in porous Teflon of the intact leaves as well as of the stripped epidermis. The DESI images reveal accumulation of hydroxynitrile glucosides in the leaf epidermis, homogeneously distributed throughout the surface. The indirect DESI approach enables relative quantitation, confirming variations of hydroxynitrile glucosides content in primary leaves of three different cultivars of barley seedlings. The study presents an example of how to overcome the morphological barriers from the plant surface and perform rapid and repeatable DESI imaging. In addition, a comparison is made of direct and indirect DESI imaging, contributing to the characterization of the recently developed method of indirect DESI imaging of plant material via porous Teflon imprints.     

Ir-catalysed formation of C-F bonds. From allylic alcohols to α-fluoroketones

A novel iridium-catalysed tandem isomerisation/C-F bond formation from allylic alcohols and Selectfluor? to prepare α-fluorinated ketones as single constitutional isomers is reported.     

Mathematical Tool from Corn Stover TGA to Determine Its Composition

Corn stover was treated by steam explosion process at four different temperatures. A fraction of the four exploded matters was extracted by water. The eight samples (four from steam explosion and four from water extraction of exploded matters) were analysed by wet chemical way to quantify the amount of cellulose, hemicellulose and lignin. Thermogravimetric analysis in air atmosphere was executed on the eight samples. A mathematical tool was developed, using TGA data, to determine the composition of corn stover in terms of cellulose, hemicellulose and lignin. It uses the biomass degradation temperature as multiple linear function of the cellulose, hemicellulose and lignin content of the biomass with interactive terms. The mathematical tool predicted cellulose, hemicellulose and lignin contents with average absolute errors of 1.69, 5.59 and 0.74?%, respectively, compared to the wet chemical method.     

Analogues of a locked nucleic acid with three-carbon 2',4'-linkages: synthesis by ring-closing metathesis and influence on nucleic acid duplex stability and structure

Two bicyclic 2'-deoxynucleoside analogues containing a saturated and an unsaturated three-carbon 2',4'-linkage, respectively, have been synthesized using a ring-closing metathesis-based linear strategy starting from uridine. Both analogues have been incorporated into oligodeoxynucleotide sequences and increased the stability of DNA:RNA hybrid duplexes (DeltaT(m) approximately 2.5-5.0 degrees C per modification) and decreased the stability of dsDNA duplexes (DeltaT(m) approximately 2.5-1.0 degrees C per modification). CD spectroscopy revealed that the bicyclic nucleosides induced formation of A-type-like duplexes albeit to a lesser degree than found for locked nucleic acid (LNA) monomers. From the CD data and UV melting analysis, we propose that the 2'-oxygen atom of the bicyclic moiety is essential for the formation of stabilized A-type-like dsDNA but not for the formation of a stabilized A-type DNA:RNA hybrid.