Synthesis of Pyrazolo‐[4́,3́:5,6]pyrido[2,3‐d]pyrimidine‐diones Catalyzed by a Nano‐sized Surface‐Grafted Neodymium Complex of the Tungstosilicate via Multicomponent Reaction

An inorganic–organic hybrid based on lanthanide clusters and Keggin type polyoxometalates (POMs) (Na[Nd (pydc‐OH)(H₂O)₄]₃}[SiW₁₂O₄₀]) was used the first time as trinuclear catalyst for one pot synthesis of pyrazolo[4??,3?:5,6]pyrido[2,3‐d]pyrimidine‐diones, via two different four and five‐component reactions involving hydrazine hydrate, ethyl acetoacetate, aryl aldehydes, and 6‐amino‐1,3‐dimethyl uracil or barbituric acid with ammonium acetate as alternative materials in green condition. To evaluate potential application of the as‐made hybrid in adsorption and separation processes, nitrogen adsorption was performed at 77 K through simulation study. The hybrid catalyst was further characterized via powder X‐ray diffraction (PXRD) at room temperature which indicated the good phase purity of the catalyst. The results show that the catalytic activity of the hybrid catalyst has increased relative to each parent component due to the special interaction between Keggin anions and pydc‐OH ligands.     

An analytical strategy for quantitative analysis of sulfite in the presence of nitrite uses carbon paste electrode amplified with acetylferrocene and NiO nanoparticle

The analysis of sulfite and nitrite as two important water pollutants is very important in water and wastewater samples. Therefore, an analytical strategy suggests for analysis of sulfite in the presence of nitrite as two harmful environmental pollutants. For the goal, an electrochemical platform based on carbon paste electrode (CPE) modified with NiO nanoparticles (NiO-NPs) and acetylferrocene (AF) was suggested (CPE/NiO-NPs/AF). The CPE/NiO-NPs/AF showed a good electro-catalytic activity for analysis of sulfite in concentration range 0.005–500 μM with limit of detection 0.001 μM. The electro-catalytic interaction between sulfite and AF at a surface of CPE/NiO-NPs/AF can help to resolving overlapping single of sulfite and nitrite for simultaneous determination of them. The CPE/NiO-NPs/AF showed high performance ability for analysis of sulfite and nitrite in wastewater samples.     

Determination of the isoflavone genistein in soybeans by high-performance liquid chromatography following cloud point extraction

A simple and sensitive method has been developed for preconcentration and determination of genistein in soybeans. This method is based on cloud point extraction (CPE) of genistein from soybeans using ethylene glycol monoalkyl ether (Genapol X-080) as a nonionic surfactant. The concentration of extracted genistein was determined by HPLC with a UV detector. Optimum experimental conditions were established. With 5% Genapol X-080 (v/v), a liquid/solid ratio of 25:1 mL/g, and ultrasonic-assisted extraction at 40 degrees C for 45 min, the extraction percentage of genistein reached its highest value. The preconcentration factor for genistein was about 16.5. The RSD for seven replicate measurements and the LOD were +/- 4.45% and 15.0 ng/mL, respectively. CPE is simple, inexpensive, and suitable for extraction of genistein from soybean. It uses environmentally friendly surfactants and offers a convenient alternative to more conventional extraction systems.     

Structure and vibrational assignment of the enol form of 1,1,1-trifluoro-2,4-pentanedione

Molecular structure of 1,1,1-trifluoro-pentane-2,4-dione, known as trifluoro-acetylacetone (TFAA), has been investigated by means of Density Functional Theory (DFT) calculations and the results were compared with those of acetylacetone (AA) and hexafluoro-acetylacetone (HFAA). The harmonic vibrational frequencies of both stable cis-enol forms were calculated at B3LYP level of theory using 6-31G** and 6-311++G** basis sets. We also calculated the anharmonic frequencies at B3LYP/6-31G** level of theory for both stable cis-enol isomers. The calculated frequencies, Raman and IR intensities, and depolarization ratios were compared with the experimental results. The energy difference between the two stable cis-enol forms, calculated at B3LYP/6-311++G**, is only 5.89 kJ/mol. The observed vibrational frequencies and Raman and IR intensities are in excellent agreement with the corresponding values calculated for the most stable conformation, 2TFAA. According to the theoretical calculations, the hydrogen bond strength for the most stable conformer is 57 kJ/mol, about 9.5kJ/mol less than that of AA and about 14.5 kJ/mol more than that of HFAA. These hydrogen bond strengths are consistent with the frequency shifts for OH/OD stretching and OH/OD out-of-plane bending modes upon substitution of CH(3) groups with CF(3) groups. By comparing the vibrational spectra of both theoretical and experimental data, it was concluded that 2TFAA is the dominant isomer.     

Multiobjective Problems: Enhanced Necessary Conditions and New Constraint Qualifications through Convexificators

In this paper, we study necessary optimality conditions for local Pareto and weak Pareto solutions of multiobjective problems involving inequality and equality constraints in terms of convexificators. We develop the enhanced Karush–Kuhn–Tucker conditions and introduce the associated pseudonormality and quasinormality conditions. We also introduce several other new constraint qualifications which entirely depend on the feasible set. Then a connecting link between these constraint qualifications is presented. Moreover, we provide several examples that clarify the interrelations between the different results that we have established.     

Synthesis of new phosphonato esters by reaction between triphenyl or trialkyl phosphite and acetylenic diesters in the presence of NH‐containing compounds

The reaction between triphenyl or trialkyl phosphite and acetylenic esters in the presence of some heterocyclic or aromatic NH compounds such as thiazolidine‐2,4‐dione, 2‐methyl indole, 5‐bromoisatine, 3‐nitroacetanilide, saccharin, 5,5‐dimethylhydantoin, 2‐nitroaniline, 4‐nitroaniline, benzophenon hydrazine, and anthranilic acid led to the formation of phosphonato esters in high yield. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:630–639, 2011; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.20725     

Stereoselective synthesis of the 1,N-deoxyguanosine adducts of cinnamaldehyde. A stereocontrolled route to deoxyguanosine adducts of α,β-unsaturated aldehydes

α,β-Unsaturated aldehydes (enals) react with deoxyguanosine and have mutagenic potential. For higher enals, the reaction of deoxyguanosine gives diastereomeric 6-substituted 8-hydroxypyrimidopurinone products. These stereoisomers may have different local conformations in DNA, which may have biological consequences. We have developed a stereospecific synthesis of 1,N²-deoxyguanosine adducts of cinnamaldehyde. The key step is the synthesis is a metal-promoted intramolecular C-H insertion reaction of nitrogen of an enantiomerically pure sulfamate ester. The approach may be general for the stereocontrolled synthesis of this class of DNA adducts and can be applied to the preparation of site-specifically adducted oligonucleotides.