Mechanical and thermal properties of green polylactide composites with natural fillers

Green composites of PLA with micropowders derived from agricultural by-products such as oat husks, cocoa shells, and apple solids that remain after pressing have been prepared by melt mixing. The thermal and mechanical properties of the composites, including the effect of matrix crystallization and plasticization with poly(propylene glycol), have been studied. All fillers nucleated PLA crystallization and decreased the cold-crystallization temperature. They also affected the mechanical properties of the compositions, increasing the modulus of elasticity but decreasing the elongation at break and tensile impact strength although with few exceptions. Plasticization of the PLA matrix improved the ductility of the composites.     

Direct Trifluoromethylation of Alcohols Using a Hypervalent Iodosulfoximine Reagent

The direct trifluoromethylation of a variety of aliphatic alcohols using a hypervalent iodosulfoximine reagent afforded the corresponding ethers in moderate to good yields (14–72 %). Primary, secondary, and even tertiary alcohols, including examples derived from natural products, underwent this transformation in the presence of catalytic amounts of zinc bis(triflimide). Typical reaction conditions involved a neat mixture of 6.0 equivalents of the alcohol with 1.0 equivalent of the reagent, with the majority of reactions complete within 2 h with 2.5 mol % of the Lewis acid catalyst. Furthermore, experimental evidence was provided that the C−O bond-forming process occurred via the coordination of the alcohol to the iodine atom and subsequent reductive elimination.     

Directing Polymorphism in the Helical Nanofilament Phase

Herein, it is reported that the polymorphism in the helical nanofilament (HNF, B₄) liquid-crystalline phase depends on the fabrication methods, that is, UV-driven formation and template-assisted self-assembly in the nanoconfined geometry. As a result, uniaxially oriented HNFs with different helical structures were obtained, in which generation of the twisted-ribbon and cylindrical-ribbon polymorphs showed that even the molecular lattice has a different orientation. The detailed structures were directly observed by SEM and grazing-incidence X-ray diffraction with synchrotron radiation. The resultant polymorphs could be used in chiro-optical applications due to the capability for fine control of the helical structures.     

Understanding the role of carbamate reactivity in fatty acid amide hydrolase inhibition by QM/MM mechanistic modelling

QM/MM modelling of FAAH inactivation by O-biphenyl-3-yl carbamates identifies the deprotonation of Ser241 as the key reaction step, explaining why FAAH is insensitive to the electron-donor effect of conjugated substituents; this may aid design of new inhibitors with improved selectivity and in vivo potency.     

Kinetic studies on H<Superscript>+</Superscript>-catalysed aquation of chromium(III)-oxalato-asparaginato and chromium(III)-oxalato-histidinato complexes

Three chromium(III) complexes with asparagine (Asn) and histidine (His) of the [Cr(ox)₂(Aa)]²⁻ type, where Aa = N,O–Asn, N,O–His or N,N′–His, were obtained and characterized in solution. The complexes with N,O–Aa undergo acid-catalysed aquation to give a free amino acid and cis-[Cr(ox)₂(H₂O)₂]⁻, whereas the complex with N,N′–His undergoes parallel reaction paths: (1) isomerization to the N,O–His complex and (2) liberation of an oxalate ligand. Kinetics of the N,O–Aa complexes in HClO₄ media were studied spectrophotometrically under pseudo-first-order conditions. The absorbance changes were attributed to the chelate ring opening at the Cr–N bond. The linear dependence of rate constants on [H⁺] was established, and a mechanism for the chelate ring cleavage was postulated. The existence of a metastable intermediate with O-monodentate Aa ligand was proved experimentally. Effect of [Cr(ox)₂(Aa)]²⁻ on 3T3 fibroblasts proliferation was studied. The tests revealed low cytotoxicity of the complexes. Complexes with Ala, His and Cys are good candidates for biochromium sources.     

Powerful connection of laccase and carbon nanotubes: Material for mediator-free electron transport on the enzymatic cathode of the biobattery

We describe the preparation of laccase/single-walled carbon nanotube bioconjugates, their application for the modification of electrodes and application of the electrodes as cathodes for the catalytic reduction of oxygen in a hybrid biofuel cell with Zn anode. Carbon nanotubes functionalized with aminoethyl residues, activated and reacted with laccase show high bioelectrocatalytic activity and are promising for the biofuel cell applications. The power density of the cell was 1 mW cm^− 2 at working voltage of 0.8 V. The open circuit voltage of this hybrid cell was as high as 1.5 V.     

Labelling of peptides with <Superscript>99m</Superscript>Tc complexes through the modified C-terminal group

Easy and efficient way to modify of the C-terminus of the peptide using amino acid lysine has been proposed and experimentally verified. The synthesis yield was high (≥85%) and it was found that reactions can be carried out even with microgram amounts of the peptide. Using Fmoc-alanine (as the peptide model) with modified C-terminus the procedure of peptide labelling with monovalent and trivalent ^99mTc complexes has been elaborated.     

The chemical composition of the essential oils of Cirsium palustre and C. rivulare and their antiproliferative effect

The composition of the essential oils of Cirsium palustre and C. rivulare and their antiproliferative activity against breast adenocarcinoma cells (MCF-7 and MDA-MBA-231) were investigated. The essential oils obtained by hydro-distillation from the roots (yield 0.2 and 0.1% v/w, respectively), leaves and inflorescences (yield below 0.01%), were analyzed by gas chromatography coupled with mass spectrometry (GC-MS). The composition of the essential oils in the respective organs of each plant differed considerably. On the other hand, similarities were observed in the composition of root and leaf oils. In C. palustre and C. rivulare root oil, 50 and 39 constituents were identified, accounting for 95.3% and 92.4% of the total content. The main components were aplotaxene and its derivatives, representing 78.6% and 46.6% of the total content. In leaf oils of both species, 59 and 49 compounds, respectively, were identified, representing 67.4% and 78.3% of the total content. The major constituents were beta-damascenone (4.1% and 13.4%, respectively) and beta-ionone (6.7% and 5.3%, respectively). Short-chain saturated and unsaturated aliphatic alcohols and aldehydes constituted another important group of compounds (17.7% and 9.0%, respectively). The essential oils of the roots have moderate anti-proliferative activity, with IC50 values ranging from 110 to 140 microg/mL. These concentrations were below the level able to inhibit the proliferation of healthy cells.     

An unusual nicotinamide derivative, 4-pyridone-3-carboxamide ribonucleoside (4PYR), is a novel endothelial toxin and oncometabolite

Our recent studies identified a novel pathway of nicotinamide metabolism that involves 4-pyridone-3-carboxamide-1-β-D-ribonucleoside (4PYR) and demonstrated its endothelial cytotoxic effect. This study tested the effects of 4PYR and its metabolites in experimental models of breast cancer. Mice were divided into groups: 4T1 (injected with mammary 4T1 cancer cells), 4T1 + 4PYR (4PYR-treated 4T1 mice), and control, maintained for 2 or 21 days. Lung metastasis and endothelial function were analyzed together with blood nucleotides (including 4PYR), plasma amino acids, nicotinamide metabolites, and vascular ectoenzymes of nucleotide catabolism. 4PYR metabolism was also evaluated in cultured 4T1, MDA-MB-231, MCF-7, and T47D cells. An increase in blood 4PYR in 4T1 mice was observed at 2 days. 4PYR and its metabolites were noticed after 21 days in 4T1 only. Higher blood 4PYR was linked with more lung metastases in 4T1 + 4PYR vs. 4T1. Decreased L-arginine, higher asymmetric dimethyl-L-arginine, and higher vascular ecto-adenosine deaminase were observed in 4T1 + 4PYR vs. 4T1 and control. Vascular relaxation caused by flow-dependent endothelial activation in 4PYR-treated mice was significantly lower than in control. The permeability of 4PYR-treated endothelial cells was increased. Decreased nicotinamide but enhanced nicotinamide metabolites were noticed in 4T1 vs. control. Reduced N-methylnicotinamide and a further increase in Met2PY were observed in 4T1 + 4PYR vs. 4T1 and control. In cultured breast cancer cells, estrogen and progesterone receptor antagonists inhibited the production of 4PYR metabolites. 4PYR formation is accelerated in cancer and induces metabolic disturbances that may affect cancer progression and, especially, metastasis, probably through impaired endothelial homeostasis. 4PYR may be considered a new oncometabolite.Subject terms: Mechanisms of disease, Pathogenesis, Breast cancer