The reactions of Wittig–Horner reagents with 1,3-dioxo-Δ2,α-indanmalononitrile

Wittig–Horner reagents ( 1a–e ) react with 1,3-dioxo-Δ^2,α-indanmalononitrile ( 2 ) to give the phosphonate adducts 3, 4, 5, 6, and 7 , respectively. Structural reasoning for the new products was based on compatible analytical and spectral data (IR, ¹H, ³¹P NMR, and MS). The mechanism that accounts for the formation of the new adducts is discussed. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8 : 253–257, 1997.     

Study on In-Situ Compatibilization of the PP/PA6 Blends in Twin Screw Extruders

The in-situ compatibilization of PP/PA6 blend was studied in a twin screw extruder. The maleic anhydride (MA) content, peroxide concentration, shear rate and feeding order were among the variables investigated. Degree of grafting of samples collected prior to feeding of PA6 into the extruder was measured using titration combined with FTIR technique. From the SEM results it was found that the increasing of initial MA concentration led to larger PA particle size which could be related to secondary reactions between excess MA and PA. The melt linear viscoelastic measurements performed on the blend samples and the obtained relaxation time spectra showed shorter form relaxation time and interfacial relaxation time for one-step compatibilized sample compared to the sample prepared by the two-step method with the same degree of grafting. This was attributed to the stronger interfacial interaction of the one-step compatibilized blend samples which could be resulted from greater efficiency of grafting and/or compatibilization. These results were supported by SEM results which showed smaller particle size for the one-step compatibilized samples. It was demonstrated that melt linear viscoelastic measurement could provide a great insight into understanding the compatibilization process in twin screw extruder.     

One-pot synthesis of 2,3,5-substituted 1H-pyrroles via the reaction of terminal acetylenes with nitriles and EtAlCl2 catalyzed by Сp2TiCl2

A new one pot method for the synthesis of 2,3,5-substituted 1H-pyrroles in moderate to good yields (58–77%) based on multicomponent reaction of terminal acetylenes with nitriles and EtAlCl₂ in the presence of Сp₂TiCl₂ catalyst and metallic magnesium has been developed. The possible mechanistic pathway to substituted pyrroles is discussed.     

Electronic structure and optical properties of isolated and TiO2-grafted free base porphyrins for water oxidation: A challenging test case for DFT and TD-DFT

Seven free base porphyrins employed in dye-sensitized photoelectrosynthetic cells are investigated with the aim of benchmarking the ability of different density functional theory (DFT) and time-dependent DFT approaches in reproducing their structure, vertical, and E_0-0 excitation energies and the energy levels alignment (red-ox properties) at the interface with the TiO₂. We find that both vertical and E_0-0 excitation energies are accurately reproduced by range-separated functionals, among which the ω B97X-D delivers the lowest absolute deviations from experiments. When the dye/TiO₂ interface is modeled, the physical interfacial energetics is only obtained when the B3LYP functional is employed; on the other hand, M06-2X (54% of exchange) and the two long-range corrected approaches tested (CAM-B3LYP and ω B97X-D) excessively destabilize the semiconductor conduction band levels with respect to the dye's lowest unoccupied molecular orbitals (LUMOs), predicting no pathway for electron injection. © 2019 Wiley Periodicals, Inc.     

Glutathione and pH‐responsive fluorescent nanogels for cell imaging and targeted methotrexate delivery

Cancer is one of the health problems that lead to death in the world, and nanotechnology was shown to have a unique potential to improve the therapeutic efficacy of anticancer agents. The nanosized drug delivery systems (DDSs) have been offered for targeting tumor tissue because of enhanced drug bioavailability and long circulation time. In this context, we reported a facial approach to prepare a novel pH and glutathione‐responsive nanogel. After that, the nanocarriers coupled with highly fluorescent quantum dots were developed. Then methotrexate (MTX) was loaded into and on the surface of nanogels by ionic interaction so that the triggered MTX release ability of the synthesized nanocarriers was verified through the assessment of in vitro drug release at simulated tumor tissue condition. The improved efficiency of the developed nanogels and their targeted performance via conjugation of MTX (as target ligand of folate receptors) were investigated through the various cell cytotoxicity studies such as 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide (MTT) assay, 4′6‐diamidino‐2‐phenylindole (DAPI) staining, and flow cytometry. The results of various cell cytotoxicity studies concluded that the developed smart nanogels have many promising abilities for the targeted MTX delivery to cancer tissues.     

Isolation and identification of new anthraquinones from Rhamnus alaternus L and evaluation of their free radical scavenging activity

From the butanolic and the ethyl acetate extracts of Rhamnus alaternus L root bark and leaves, three new anthraquinone glycosides, alaternosides A-C (1,4,6,8 tetrahydroxy-3 methyl anthraquinone 1-O-ß-D-glucopyranosyl-4,6-di-O-α-L-rhamnopyranoside (1); 1,2,6,8 tetrahydroxy-3 methyl anthraquinone 8-O-ß-D-glucopyranoside (2) and 1, 6 dihydroxy-3 methyl 6 [2′-Me (heptoxy)] anthraquinone (3)) were isolated and elucidated together with the two known anthraquinone glycosides, Physcion-8-O-rutinoside (4) and emodin-6-O-α-L-rhamnoside (5) as well as with the known kaempferol-7-methylether (6), β-sitosterol (7) and β-sitosterol-3-O-glycoside (8). Their chemical structures were elucidated using spectroscopic methods (1D-, 2D-NMR and FAB-MS). Free radical scavenging activity of the isolated compounds was evaluated by their ability to scavenge DPPH^. free radicals. Compounds (3), (4) and (6) showed the highest activity with IC₅₀ values of 9.46, 27.68 and 2.35 μg/mL, respectively.     

NMR relaxation interference effects and internal dynamics in gamma-cyclodextrin

Multiple-magnetic field (9.4, 14.1 and 21.1 T) measurements of (13)C spin-lattice and spin-spin relaxation rates, the heteronuclear Overhauser enhancement and cross-correlated relaxation rates (CCRRs) in the methylene groups are reported for gamma-cyclodextrin in water/dimethylsulfoxide solution at 323 and 343K. The CCRRs are obtained from differences in the initial relaxation rates of the components of the CH(2) triplet in the (13)C spectra. The relaxation data are analyzed using the Lipari-Szabo approach and a novel modification of the two-site jump model. According to the latter model, inclusion of the dipolar (CH,CH(')) cross-correlated longitudinal and transverse relaxation is important for estimating the rate of the conformational jumps in the hydroxymethyl group. Using the dynamic information from the jump model, we have also used the differences in the initial relaxation rates for the triplet components to estimate the anisotropy of the chemical shielding tensor.     

A three component one-pot procedure for the synthesis of [1,2,4]triazolo/benzimidazolo-quinazolinone derivatives in the presence of H6P2W18O62 · 18H2O as a green and reusable catalyst

A rapid and efficient one-pot method for the synthesis of quinazolinone derivatives and related heterocycles by condensation of 2-amino benzimidazole and 3-amino-1,2,4-triazole, as amine sources, with dimedone and different aldehydes in the presence of H6P2W18O(62).18H2O as a green and reusable catalyst in refluxing acetonitrile has been developed.     

Implication of the Electron Exchange-Correlation on Fully Nonlinear Quantum Dust Ion-Acoustic Solitons

We examine the effect of the electron exchange-correlation on weak and arbitrary amplitude quantum dust ion-acoustic(QDIA) solitons.The reduced quantum hydrodynamic(QHD) model is used.Carrying out a fully nonlinear analysis,it is found that the effect of the exchange-correlation on the main quantities for solitary-wave propagation can be quite important.In particular,it may be noted that the arbitrary amplitude QDIA soliton experiences a spreading as the phenomenon of exchange-correlation becomes effective.Furthermore,our results show that the exchange-correlation effects inhibit the formation of the flat-bottomed solitons and do not favor their emergence.It turns out that exchangecorrelation and quantum diffraction may act concurrently to set up the conditions for the existence of the QDIA solitary waves.Our results complement and provide new insight into our previously published work on this problem.     

Antioxidant Properties of Gluten-Free Pasta Enriched with Vegetable By-Products

The only therapy for coeliac disease patients is to completely avoid foods containing gluten, a protein complex common in several small-grain cereals. However, many alternative gluten-free foods available on the market present nutritional deficiencies. Therefore, the aim of this research was to evaluate the composition and the antioxidant properties of gluten-free pasta enriched with 10% or 15% of tomato waste or linseed meal, two food industry by-products. The traits analysed were protein, lipid, ash and fibre content, heat damage, tocols, carotenoids and phenolics composition (by HPLC), antioxidant capacity, and pasta fracturability. The enriched pastas contained more fibre and lipids than the control, while the protein and ash values were similar. The addition of tomato and linseed waste improved tocols concentration but had no effect on carotenoids content. The free soluble polyphenols increase was similar for both by-products and proportional to the enrichment percentage, while the bound insoluble polyphenols were higher in linseed-enriched pastas. The samples with linseed meal showed the greatest antioxidant capacity and, at 10% addition, the highest fracturability value. In conclusion, the addition of tomato and linseed by-products significantly increases the presence of bioactive compounds (particularly polyphenols), improving the nutritional value of gluten-free pasta.