Pyrrole studies part 41. Reactivity of 3,4-diformyl-2,5-dimethylpyrrole with diaminoalkanes. An unusual formation of 2-azafulvenes

3,4-Diformyl-2,5-dimethylpyrrole (1) reacts with ,ω-diamino-alkanes, NH₂(CH₂)_nNH₂t' to form either the potentially tautomeric 2:2 macrocyclic adduct (7a) (8), when N = 2, or the potentially tautomeric 1:1 bicyclic adduct (18) (19), when N = 4, 5, 6, and 12. ¹H and ¹³C N.m.r. spectral data indicate that the 2-azafulvene structures predominate for both types of cycloadducts. Only polymeric material was obtained when N = 3.     

Concurrent Covalent and Supramolecular Polymerization

Covalent and supramolecular polymerizations, both of which offer their own unique advantages, have emerged as popular strategies for making artificial materials. Herein, we describe a concurrent covalent and supramolecular polymerization strategy—namely, one which utilizes 1) a bis‐azide‐functionalized diazaperopyrenium dication that undergoes polymeriation covalently with a bis‐alkyne‐functionalized biphenyl derivative in one dimension as a result of a rapid and efficient β‐cyclodextrin(CD)‐accelerated, cucurbit[6]uril(CB)‐templated azide–alkyne cycloaddition, while 2) the aromatic core of the dication is able to dimerize in a criss‐cross fashion by dint of π–π interactions, enabling simultaneous supramolecular assembly, resulting in an extended polymer network in an orthogonal dimension.     

Computational study on the effects of variable viscosity of micropolar liquids on heat transfer in a channel

Journal of Thermal Analysis and Calorimetry - A numerical model is developed to study the effects of temperature-dependent viscosity on heat transfer in magnetohydrodynamic flow of micropolar fluid...     

Bifurcation diagrams and caustics of simple quasi border singularities

Quasi boundary and quasi corner singularities of functions are discussed. They correspond to the classifications of Lagrangian projections with a boundary or a corner. The geometry of bifurcation diagrams and caustics of simple quasi boundary and quasi corner singularities in R³ and R⁴ are described.     

Acid-Promoted Oxygen-Atom Transfer from a Novel Dihydroisoquinoline-Derived Oxaziridine Substituted at Position 1

N-Alkyl-oxaziridines react in the presence of a nucleophile as an oxygenating agent; in the absence of a nucleophile, an isomerization reaction is observed. This study describes the synthesis of two new dihydroisoquinoline oxaziridines and their reactivity in an acid-promoted reaction in the presence and absence of sulfides.     

Anti-atherosclerotic activity of Betulinic acid loaded polyvinyl alcohol/methylacrylate grafted Lignin polymer in high fat diet induced atherosclerosis model rats

Betulinic acid is one such natural pentacyclic triterpenoid compound, holding various pharmacological properties but its poor bioavailability is the only limitation. One of the biological macromolecules such as Lignin is a plant-derived aromatic, eco-friendly and low-cost polymer that certainly self-assembles into nano-sized colloids. Therefore, onto the current investigation, we increased the bioavailability of betulinic acid by coating on to a nanopolymer prepared with poly vinyl alcohol, lignins and methyl acrylate. Betulinic acid loaded polyvinyl alcohol/ethylacrylate grafted Lignin polymer (PVA/Lig-g-MA) nanoformulation was characterized using FTIR, XRD, SEM and TEM analysis and also the drug entrapment, in vitro drug releasing capacity was done to examine the efficiency of the nanoformulation of a drug. The MTT assay was evaluated the cytotoxicity of synthesized nanoformulation against normal endothelial cells HUVEC and HAPEC to confirm the side effects of the drug. The anti-atherosclerotic property of the nanoformulation was ascertained in both in vitro condition (with HUVEC and HPAEC) and in vivo studies (with Wistar rats). As a result, the characterization studies and in vitro studies clearly confirmed the Betulinic acid loaded PVA/Lig-g-MA nanoformulation is an ideal nanopolymer and it doesn’t cause any cytotoxic effect in normal endothelial cells. It also decreased the lipopolysaccharides induced inflammation through the down-regulation of NFκB and MAP/JNK signaling molecule expressions. Following in vivo results confirmed the synthesized nanoformulation effectively decreased the hyperchlostremia, inflammation and vasoconstriction, which induced over high fat diet. The results of histopathological analysis of cardiac tissues also confirmed the cardioprotective role of synthesized nanoformulation. Overall, both the in vitro and in vivo studies authentically proven the Betulinic acid loaded PVA/Lig-g-MA nanoformulation would be a potent cost effective anti-atherosclerotic nanodrug.     

Mapping of the Photoinduced Electron Traps in TiO2 by Picosecond X‐ray Absorption Spectroscopy

Titanium dioxide (TiO₂) is the most popular material for applications in solar‐energy conversion and photocatalysis, both of which rely on the creation, transport, and trapping of charges (holes and electrons). The nature and lifetime of electron traps at room temperature have so far not been elucidated. Herein, we use picosecond X‐ray absorption spectroscopy at the Ti K‐edge and the Ru L₃‐edge to address this issue for photoexcited bare and N719‐dye‐sensitized anatase and amorphous TiO₂ nanoparticles. Our results show that 100 ps after photoexcitation, the electrons are trapped deep in the defect‐rich surface shell in the case of anatase TiO₂, whereas they are inside the bulk in the case of amorphous TiO₂. In the case of dye‐sensitized anatase or amorphous TiO₂, the electrons are trapped at the outer surface. Only two traps were identified in all cases, with lifetimes in the range of nanoseconds to tens of nanoseconds.     

The Effects of Formulation on Imidacloprid Dissipation in Grapes and Vine Leaves and on Required Pre-Harvest Intervals under Lebanese Climatic Conditions

In this study, imidacloprid, a systemic insecticide, currently having a specified European Commission MRL value for vine leaves (2 mg kg⁻¹), was applied on a Lebanese vineyard under different commercial formulations: as a soluble liquid (SL) and water dispersible granules (WDG). In Lebanon, many commercial formulations of imidacloprid are subject to the same critical good agricultural practice (cGAP). It was, therefore, important to verify the variability in dissipation patterns according to matrix nature and formulation type. Random samplings of grapes and vine leaves were performed starting at 2 days until 18 days after treatment. Residue extractions were performed according to the QuEChERS method and the analytical determination using liquid chromatography coupled to tandem mass spectrometry (LC-MS-MS). The SL formulation yielded significantly higher initial deposit than the WDG formulation on grapes and vine leaves. The formulation type did not significantly affect the dissipation rates; the estimated half-lives in grapes and vine leaves were 0.5 days for all imidacloprid formulations. No pre-harvest intervals were necessary on grapes. PHIs of 3.7 days for the SL formulation and 2.8 days for the WDG formulation were estimated on vine leaves. The results showed that the type of formulation and the morphological and physiological characteristics of the matrix had an effect on the initial deposits, and thus residue levels, but not on the dissipation patterns.