Condensation of ethyl phenylpropiolate with some cyanoacetyl and cyanomethylene heterocycles

N-Cyanoacetyl pyrrolidine, piperidine and morpholine reacted with ethyl phenylpropiolate to give the rearranged Michael addition products III. Some interesting results obtained from the bromination, hydrolysis and reduction of III are reported. 2-Thiophene and 2-furaneaceto-nitriles reacted with ethyl phenylpropiolate to give the Claisen addition products XVIII. Reaction of either III or XVIII with hydrazine hydrate, phenylhydrazine and hydroxylamine hydrochloride afforded 3-phenylpyrazol-5-one, 1,3-diphenylpyrazol-5-one and 3-phenylisoxazol-5-one together with the appropriate starting cyanoacetyl or cyanomethylene compounds, respectively. The mechanism for the formation of the various reaction products beside the ir and nmr spectral results are discussed.     

Comparison of cellulose nanocrystal (CNC) filler on chemical,mechanical, and corrosion properties of epoxy-Zn protective coatings for mild steel in 3.5% NaCl solution

Cellulose - This present work evaluated the influence of oil palm frond cellulose nanocrystal (OPF-CNC) as a nanofiller to improve the barrier protection of the epoxy-Zn coating to lessen the...     

An enhanced performance of hybrid supercapacitor based on polyaniline-manganese phosphate binary composite

Journal of Solid State Electrochemistry - Manganese phosphate (Mn3(PO4)2) particles decorated polyaniline (PANI) have been proposed as a promising electrode material for supercapacitors. Mn3(PO4)2...     

Assemblies of supramolecular porphyrin dimers in pentagonal and hexagonal arrays exhibiting light-harvesting antenna function

Porphyrin-based supramolecular macrocyclic arrays were synthesized as mimics of photosynthetic light-harvesting (LH) antennae. Pentameric and hexameric macrocyclic porphyrin arrays EP5 and EP6 were constructed by complementary coordination of m-bis(ethynylene)phenylene-linked zinc-imidazolylporphyrin Zn-EP-Zn. The proton NMR spectra of noncovalently linked N-EP5 and N-EP6 indicate fast rotation of the porphyrin moieties along the ethyne axis. These macrocycles were covalently linked and identified as C-EP5 (6832 Da) and C-EP6 (8199 Da) by mass spectrometry. Fluorescence quantum yields of C-EP2 (10.0%), C-EP5 (10.1%), and C-EP6 (11.0%), even larger than that of the unit coordination dimer C-EP1 (9.3%), were significantly increased from those of the series without the ethynylene linkage. The order of increasing fluorescence quantum yields was parallel to that of decreasing fluorescence lifetimes (C-EP1 (1.65 ns), C-EP2 (1.45 ns), C-EP5 (1.42 ns), and C-EP6 (1.38 ns)), indicating that the radiative decay rate kF increased relative to the other decay rates with an increase in the number of ring components. Based on the exciton-exciton annihilation and anisotropy depolarization times, the excitation energy hopping (EEH) times in these macrocyclic systems were obtained as 21 ps for C-EP5 and 12.8 ps for C-EP6. EEH times depend strongly on the orientation factor of the component transition dipoles in the macrocyclic arrays. The hexagonal macrocyclic array with an orientation of better transition dipole coupling resulted in faster EEH time compared to the pentagonal one.     

Silver nanoclusters doped in zeolite to decontaminate water resources from the quinalphos pesticide

Ag (I) nanoclusters doped in mordenite zeolite were prepared and spectroscopically analyzed. Strong luminescence emission that is dependent on the excitation wavelength was observed. These variations in the emission modes are due to the site selective luminescence where various luminophores might be excited upon selecting the proper excitation wavelength. The selected material was found to have strong affinity to remove the quinalphos pesticide, which is widely used for the protection of several vegetable and fruit crops, from water bodies. HPLC and GC–MS techniques were used to follow the kinetic data and to identify the photodecomposition products, respectively. The photodecomposition of quinalphos in the presence of the silver doped mordenite catalyst gives different products compared to the irradiation of quinalphos without catalyst. The presence of the Ag-mordenite catalyst not only adsorbs the quinalphos from the solution but it also reduces its toxic effect as tested on the fruit fly (Drosophila melanogaster).     

N,N'-Carbonyldiimidazole-mediated functionalization of superparamagnetic nanoparticles as vaccine carrier

Particulates with specific sizes and characteristics can induce potent immune responses by promoting antigen uptake of appropriate immuno-stimulatory cell types. Magnetite (Fe(3)O(4)) nanoparticles have shown many potential bioapplications due to their biocompatibility and special characteristics. Here, superparamagnetic Fe(3)O(4) nanoparticles (SPIONs) with high magnetization value (70emug(-1)) were stabilized with trisodium citrate and successfully conjugated with a model antigen (ovalbumin, OVA) via N,N'-carbonyldiimidazole (CDI) mediated reaction, to achieve a maximum conjugation capacity at approximately 13 microgmicrom(-2). It was shown that different mechanisms governed the interactions between the OVA molecules and magnetite nanoparticles at different pH conditions. We evaluated as-synthesized SPION against commercially available magnetite nanoparticles. The cytotoxicity of these nanoparticles was investigated using mammalian cells. The reported CDI-mediated reaction can be considered as a potential approach in conjugating biomolecules onto magnetite or other biodegradable nanoparticles for vaccine delivery.     

A study of some quinolizone derivatives

The condensation of methyl 2-pyridylacetate and ethyl phenylpropiolate has been found to be a simple and convenient method for the preparation of 4-quinolizone derivatives. Upon hydrolysis and decarboxylation, the initial condensation product, l-carbethoxy-2-phenyl-4H-quinolizin-4-one (V) was converted to 2-phenyl-4H-quinolizin-4-one (VII). Nitration and bromination of these quinolizones were affected under mild conditions. Nitration of V displaced the carbethoxy group, while bromination did not and 1,3-dinitro-4H-quinolizin-4-one and 1-carbeth-oxy-2-phenyl-3-bromo-4H-quinolizin-4-one were obtained, respectively.     

The Prognostic Value of Histidine-Rich Glycoprotein RNA in Breast Tissue Using Unmodified Gold Nanoparticles Assay

The aim of is this study is to explore the role of tissue histidine-rich glycoprotein (HRG) RNA as a promising clinically useful biomarker for breast cancer patients prognosis using nanogold assay. Expression of the HRG RNA was assessed by gold nanoparticles and conventional RT-PCR after purification by magnetic nanoparticles in breast tissue samples. The study included 120 patients, 60 of which were histologically proven breast carcinoma cases, 30 had benign breast lesions and 30 were healthy individuals who had undergone reductive plastic surgery. ER, PR and HER2 status were also investigated. The prognostic significance of tissue HRG RNA expression in breast cancer was explored. The magnetic nanoparticles coated with specific thiol modified oligonucleotide probe were used successfully in purification of HRG RNA from breast tissue total RNAs with satisfactory yield. The developed HRG AuNPs assay had a sensitivity and a specificity of 90 %, and a detection limit of 1.5 nmol/l. The concordance rate between the HRG AuNPs assay with RT-PCR after RNA purification using magnetic nanoparticles was 93.3 %. The median follow-up period was 60 months. Among traditional prognostic biomarkers, HRG was a significant independent prognostic marker in relapse-free survival (RFS). HRG RNA is an independent prognostic marker for breast cancer and can be detected using gold NPs assay, which is rapid, sensitive, specific, inexpensive to extend the value for breast cancer prognosis.     

Self‐Assembly of Tricuprous Double Helicates: Thermodynamics,Kinetics, and Mechanism

We report in this paper the coordination and kinetic properties of two oligobipyridine strands, which contain three 2,2′‐bipyridine subunits separated by oxydimethylene bridges, the 4,4′‐bis(CONET₂)‐substituted L and the 4,4′‐bis(CO₂Et)‐substituted L ′. Spectrophotometric measurements allowed the characterization of thermodynamic complexes and kinetic intermediates* which are involved in the self‐assembly process of L ₂Cu₃ and L Cu₃ helicates. The reaction presents positive cooperativity for the binding of two 2,2′‐bipyridine strands to the cuprous cations. While reactive kinetic intermediates* present distorted coordination geometries around Cu^I, the final rearrangement of the tricuprous bistranded helicates allows more closely tetrahedral coordination of each cation and reduces the interactions. Differences in the bulkiness and electronic properties of the L and L ′ substituents do not affect significantly the stability of the corresponding helicates, but greatly influence binding rates in the self‐assembly process.