Fiber formation and properties of polyester/lignin blends

Thermotropic liquid crystalline polyesters with varied chemical structure are synthesized by melt transesterification polycondensation. They are employed as matrix for blends with lignin materials to obtain melt-spinnable precursors for carbon fibers. The lignin samples are carefully purified by fractionation, enzymatic removal of reducing sugars, and subsequent modification of the terminal OH groups. Effective melt blending is achieved with liquid-crystalline aromatic–aliphatic polyesters having melting ranges that match the softening temperature of the lignin fractions, which is necessary to prevent thermal decomposition of the lignin. Polyester/lignin blends are partially compatibilized, phase-separated materials. The polyester/lignin materials are melt-spun successfully. The fiber properties depend on the lignin purification process. X-ray scattering reveals that orientation in lignin-containing fibers is maintained. First experiments show that the fibers can be converted successfully to carbon fibers by thermal annealing procedures. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48257.     

Determination of polycyclic aromatic hydrocarbons in smoked pork by effect-directed bioassay with confirmation by chemical analysis

Polycyclic aromatic hydrocarbons (PAHs) are generated during smoke curing and other heating treatments of food and represent a large class of chemical pollutants including a number of carcinogens. At present, PAHs are frequently detected by costly and time-consuming chemical analysis. Effect-directed in vitro cell-based bioassays of contaminants can offer a rapid, sensitive, and relatively inexpensive alternative for screening of contaminants in comparison to instrumental analysis. They enable estimation of total biological activity of all compounds acting through the same mode of binding. The aryl hydrocarbon receptor as a binding site plays an important role in PAH-induced carcinogenesis. The in vitro chemical-activated luciferase expression assay (using conditions to detect PAH) was investigated for its applicability for effect-directed analysis of PAH levels in smoked meat. There was an intra-assay variability of 0 to 15% and a mean coefficient of variation of 25% (3 to 50%) for the cleanup and bioassay analysis of the smoked pork samples. There was a correlation between the total responses of the bioassay and the individual amounts of the PAHs with a high molecular weight. The comparison of 2,3,7,8-tetrachlorodibenzo-p-dioxin and benzo[k]fluoranthene used as standard in the in vitro chemical-activated luciferase expression assay resulted in benzo[k]fluoranthene being able to be used as an alternative, nontoxic standard in the bioassay. This bioassay is an applicable effect-directed functional prescreening method for the analysis of PAHs in smoked meat and appears to have potential in being used for food control in the future.     

Development of Biarylalkyl Carboxylic Acid Amides with Improved Anti-schistosomal Activity

The parasitic disease schistosomiasis is the cause of more than 200 000 human deaths per year. Although the disease is treatable, there is one major shortcoming: praziquantel has been the only drug used to combat these parasites since 1977. The risk of the emergence of resistant schistosomes is known to be increasing, as a reduced sensitivity of these parasites toward praziquantel has been observed. We developed a new class of substances, which are derived from inhibitors of human aldose reductase, and which showed promising activity against Schistosoma mansoni couples in vitro. Further optimisation of the compounds led to an increase in anti-schistosomal activity with observed phenotypes such as reduced egg production, vitality, and motility as well as tegumental damage and gut dilatation. Here, we performed structure–activity relationship studies on the carboxylic acid moiety of biarylalkyl carboxylic acids. Out of 82 carboxylic acid amides, we identified 10 compounds that are active against S. mansoni at 25 μm . The best five compounds showed an anti-schistosomal activity up to 10 μm and induced severe phenotypes. Cytotoxicity tests in human cell lines showed that two derivatives had no cytotoxicity at 50 or 100 μm . These compounds are promising candidates for further optimisation toward the new anti-schistosomal agents.     

Structure-Activity Relationship and Crystallographic Studies on 4-Hydroxypyrimidine HIF Prolyl Hydroxylase Domain Inhibitors

The 2-oxoglutarate-dependent hypoxia inducible factor prolyl hydroxylases (PHDs) are targets for treatment of a variety of diseases including anaemia. One PHD inhibitor is approved for use for the treatment of renal anaemia and others are in late stage clinical trials. The number of reported templates for PHD inhibition is limited. We report structure–activity relationship and crystallographic studies on a promising class of 4-hydroxypyrimidine-containing PHD inhibitors.     

Translational Read-Through Therapy of RPGR Nonsense Mutations

X-chromosomal retinitis pigmentosa (RP) frequently is caused by mutations in the retinitis pigmentosa GTPase regulator (RPGR) gene. We evaluated the potential of PTC124 (Ataluren, Translama^TM) treatment to promote ribosomal read-through of premature termination codons (PTC) in RPGR. Expression constructs in HEK293T cells showed that the efficacy of read-through reagents is higher for UGA than UAA PTCs. We identified the novel hemizygous nonsense mutation c.1154T > A, p.Leu385* ({"type":"entrez-nucleotide","attrs":{"text":"NM_000328.3","term_id":"1677500221"}}NM_000328.3) causing a UAA PTC in RPGR and generated patient-derived fibroblasts. Immunocytochemistry of serum-starved control fibroblasts showed the RPGR protein in a dot-like expression pattern along the primary cilium. In contrast, RPGR was no longer detectable at the primary cilium in patient-derived cells. Applying PTC124 restored RPGR at the cilium in approximately 8% of patient-derived cells. RT-PCR and Western blot assays verified the pathogenic mechanisms underlying the nonsense variant. Immunofluorescence stainings confirmed the successful PTC124 treatment. Our results showed for the first time that PTC124 induces read-through of PTCs in RPGR and restores the localization of the RPGR protein at the primary cilium in patient-derived cells. These results may provide a promising new treatment option for patients suffering from nonsense mutations in RPGR or other genetic diseases.     

Residue analysis of 500 high priority pesticides: Better by GC–MS or LC–MS/MS?

This overview evaluates the capabilities of mass spectrometry (MS) in combination with gas chromatography (GC) and liquid chromatography (LC) for the determination of a multitude of pesticides. The selection of pesticides for this assessment is based on the status of production, the existence of regulations on maximum residue levels in food, and the frequency of residue detection. GC-MS with electron impact (EI) ionization and the combination of LC with tandem mass spectrometers (LC-MS/MS) using electrospray ionization (ESI) are identified as techniques most often applied in multi-residue methods for pesticides at present. Therefore, applicability and sensitivity obtained with GC-EI-MS and LC-ESI-MS/MS is individually compared for each of the selected pesticides. Only for one substance class only, the organochlorine pesticides, GC-MS achieves better performance. For all other classes of pesticides, the assessment shows a wider scope and better sensitivity if detection is based on LC-MS.     

Bioactivity evaluation of collagen-based scaffolds containing a series of Sr-doped melt-quench derived phosphate-based glasses

Phosphate-based glasses have been attracting attention due to their possible medical applications arising from unique dissolution characteristics in the human body leading to the possibility of new tissue regeneration. In this study, the leaching kinetics of a series of melt-quenched Sr-doped phosphate glasses are presented. Regardless of the presence of Sr, all the glasses have an initial linear and sustained release of the ions followed by a plateau. To guarantee proper nutritional support to the growing tissue during regeneration and to mimic the 3-dimensional architecture of tissues, organic scaffold systems have been developed. However, their poor mechanical strength has limited their application. To overcome this problem, cross-linkers can be used although this then limits the solubility of the materials. To succeed in dealing with such a limitation, in this paper, by freeze-drying, the aforementioned soluble melt-quenched phosphate glasses were combined as powders with collagen fibres from bovine achilles tendon to make degradable scaffolds. The scaffolds were characterized by SEM, EDX and BET. Changes to the dissolution behaviour of the glasses arising from the presence of collagen interacting with the ions leached were reported. Furthermore, the ability of the scaffolds to induce hydroxyapatite (HA) formation was evaluated: one the elaborated scaffold could grow an HA-like layer after a week in SBF. Based on the results obtained, a possible application in restorative dentistry is proposed for one or more materials.

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Probing the Ni(OH)2 Precursor for LiNiO2 at the Atomic Scale: Insights into the Origin of Structural Defect in a Layered Cathode Active Material

In lithium ion batteries (LIBs), the layered cathode materials of composition LiNi_1−x−yCo_xMn_yO₂ are critical for achieving high energy densities. A high nickel content (>80%) provides an attractive balance between high energy density, long lifetime, and low cost. Consequently, Ni-rich layered oxides cathode active materials (CAMs) are in high demand, and the importance of LiNiO₂ (LNO) as limiting case, is hence paramount. However, achieving perfect stoichiometry is a challenge resulting in various structural issues, which successively impact physicochemical properties and result in the capacity fade of LIBs. To better understand defect formation in LNO, the role of the Ni(OH)₂ precursor morphology in the synthesis of LNO requires in-depth investigation. By employing aberration-corrected scanning transmission electron microscopy, electron energy loss spectroscopy, and precession electron diffraction, a direct observation of defects in the Ni(OH)₂ precursor preparedis reported and the ex situ structural evolution from the precursor to the end product is monitored. During synthesis, the layered Ni(OH)₂ structure transforms to partially lithiated (non-layered) NiO and finally to layered LNO. The results suggest that the defects observed in commercially relevant CAMs originate to a large extent from the precursors, hence care must be taken in tuning the co-precipitation parameters to synthesize defect-free Ni-rich layered oxides CAMs.     

Morphology Transformation Pathway of Block Copolymer-Directed Cooperative Self-Assembly of ZnO Hybrid Films Monitored In Situ during Slot-Die Coating

Cooperative self-assembly (co-assembly) of diblock copolymers (DBCs) and inorganic precursors that takes inspiration from the rich phase separation behavior of DBCs can enable the realization of a broad spectrum of functional nanostructures with the desired sizes. In a DBC assisted sol–gel chemistry approach with polystyrene-block-poly(ethylene oxide) and ZnO, hybrid films are formed with slot-die coating. Pure DBC films are printed as control. In situ grazing-incidence small-angle X-ray scattering measurements are performed to investigate the self-assembly and co-assembly process during the film formation. Combining complementary ex situ characterizations, several distinct regimes are differentiated to describe the morphological transformations from the initially solvent-dispersed to the ultimately solidified films. The comparison of the assembly pathway evidences that the key step in the establishment of the pure DBC film is the coalescence of spherical micelles toward cylindrical domains. Due to the presence of the phase-selective precursor, the formation of cylindrical aggregates in the solution is crucial for the structural development of the hybrid film. The pre-existing cylinders in the ink impede the domain growth of the hybrid film during the subsequent drying process. The precursor reduces the degree of order, prevents crystallization of the PEO block, and introduces additional length scales in the hybrid films.