N,S-Substituted Dienes from Mono(arylthio)substituted- and S-, S,S-Substituted Dienes

Mono(thio)substituted dienes 1a-1b gave compounds 3a-c and 5d-g with piperazine and piperidine derivatives in dichloromethane. Compounds 8 , 9 , and 10 were obtained from the reactions of perchlorobutadiene ( 6 ) with 1,4-butanedithiol ( 7 ) in ethanol in the presence of sodium hydroxide. Compounds 12a-b , 13a-b were obtained from the reactions of perchlorobutadiene ( 6 ) with allylmercaptan (CH 2 =CH--CH 2 --SH) and mercaptoethanol (HO--CH 2 --CH 2 --SH).     

Investigation of metal activation of a partially purified polyphenol oxidase enzyme electrode

Biosensors can be developed using different biological materials and immobilization technologies. Enzymes are generally used in biosensor construction, and some enzymes need metal ions or small organic molecules as a cofactor for their activation. Polyphenol oxidases can be activated by several metal ions such as Cu²⁺, Mg²⁺, Zn²⁺, Mn²⁺, and Ni²⁺. In this study, a new measurement method has been developed that is based on the metal ion activation of the polyphenol oxidase enzyme used in the biosensor preparation, especially to determine the concentration of Mg²⁺ ions. Polyphenol oxidase (PPO) (EC 1.10.3.1) was partially purified from potato (Solanum tuberosum) by using (NH₄)₂SO₄ precipitation, dialysis, and lyophylization processes. As a result of this processes, approximately 30-fold purification was achieved for PPO. For construction of the biosensor, the enzyme was immobilized on the dissolved oxygen probe membrane using gelatin and glutaraldehyde (2.5%). Using the biosensor, we obtained responses for catechol in the absence and presence of Mg²⁺ ions. Differences between the biosensor responses were related to the concentration of Mg²⁺ ions. The biosensor response depends linearly on concentration of Mg²⁺ ions between 0.05 and 7.5?mM. In the optimization studies, phosphate buffer (pH 7.0, 50?mM) and 35°C were determined to be the optimum conditions. This project will be a novel biosensor study and it might bring a new term, ‘activation based biosensor’ into the biosensor area.     

A novel (E,E)-dioxime and its mono-, di- and trinuclear complexes bearing tetradentate octyl sulfanyl phenylamino substituents. Synthesis,characterization and electrochemical properties of its transition metal complexes

A new vic-dioxime, 13,14-bis-(hydroxyimino)-9,12,15,18-diazadithiaoctacosane, has been synthesized from 2-octylsulfanylaminobenzene and (E,E)-dichloroglyoxime. Mononuclear transition metal complexes of Ni^II, Cu^II, Co^II and Fe^II have been prepared and were found to have a metal–ligand ratio of 1:2. The synthesis of di- and trinuclear complexes was achieved with U^IVO₂ and Cu^II depending on the stoichiometry of the reactants. The complexes were characterized by elemental analysis, ¹H-n.m.r., u.v.–vis, i.r., f.a.b.-m.s. and by cyclic voltammetry.     

Synthesis and characterization of new 4,5-dihydropyrazol-1-yl derivatives

In this study, first, a series of chalcone compounds S1–S6 were synthesized from various acetophenone derivatives (acetophenone, p-methyl acetophenone, and p-methoxy acetophenone) and aromatic aldehyde derivatives (benzaldehyde, p-methyl benzaldehyde, and p-methoxy benzaldehyde) by the Claisen–Schmidt condensation reaction. These S1–S6 compounds were then used in the preparation of 4,5-dihydropyrazol-1-yl derivatives S7–S15. Finally, four new compounds S16–S19 were synthesized from compound (S7, S8, S9, and S12) and 2,4-dinitrophenylhydrazine. Therefore, three known and ten new heterocyclic compounds were synthesized and completely characterized using ¹H NMR, ¹³C NMR, IR, and elemental analysis.     

An experimental and theoretical approach to the molecular structure of 3‐{[4‐(3‐Methyl‐3‐phenyl‐cyclobutyl)‐thiazol‐2‐yl]‐hydrazono}‐1,3‐dihydro‐ indol‐2‐one

The title molecule, 3‐{[4‐(3‐methyl‐3‐phenyl‐cyclobutyl)‐thiazol‐2‐yl]‐hydrazono}‐1,3‐dihydro‐indol‐2‐one (C₂₂H₂₀N₄O₁S₁), was prepared and characterized by ¹H NMR, ¹³C NMR, IR, UV–visible, and single‐crystal X‐ray diffraction. The compound crystallizes in the monoclinic space group P21 with a = 8.3401(5), b = 5.6976(3), c = 20.8155(14) Å, and β = 95.144(5)°. Molecular geometry from X‐ray experiment and vibrational frequencies of the title compound in the ground state has been calculated using the Hartree–Fock with 6‐31G(d, p) and density functional method (B3LYP) with 6‐31G(d, p) and 6‐311G(d, p) basis sets, and compared with the experimental data. The calculated results show that optimized geometries can well reproduce the crystal structural parameters, and the theoretical vibrational frequencies values show good agreement with experimental data. Density functional theory calculations of the title compound and thermodynamic properties were performed at B3LYP/6‐31G(d, p) level of theory. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012     

Multicomponent Reactions of Furan‐2,3‐diones: Synthesis and Characterizations of Furo[3,2‐c]pyran‐4‐ones

Furo[3,2‐c]pyran‐4‐ones, which possess a natural‐product skeleton, are synthesized via a simple, one‐pot, three‐component reaction of furan‐2,3‐diones with dialkyl acetylenedicarboxylates and Ph₃P.     

PHA-L lectin and carbohydrate relationship: conjugation with CdSe/CdS nanoparticles, radiolabeling and in vitro affinities on MCF-7 cells

This research aims to investigate the interaction between phytohemagglutinin-L (PHA-L) and sialic acid, which is abundant on the breast cancer cell (MCF-7) surface and displays monosaccharide characteristics, by experimental and computational methods. Experimentally, CdSe/CdS nanoparticles (QDs) were synthesized; PHA-L was conjugated with QDs and labeled with ¹²⁵I. Radiolabeling yield was found to be 97 ± 1.2 %. Afterwards, in vitro bioaffinities of radiolabeled PHA-L conjugated QDs have been investigated on MCF-7 cells and it has been observed that the cell incorporation increased with time. The results indicated that ¹²⁵I labeled QD-PHA-L conjugates represent significant affinity on MCF-7 cells. In the second step of the study, the crystal structure of carbohydrate interaction surface of PHA-L was extracted from the crystal structure of PHA-L. The interactions between this surface and sialic acid were calculated by computational tools. These calculations revealed specific interactions between PHA-L and sialic acid. Semi-empirical methods, PM3 and AM1, were used in these calculations. Significant outcomes have been obtained from the experimental and computational studies and these results demonstrated that PHA-L may be an effective agent for imagining MCF-7 cells.     

Einige Neue N,S-Substituierte 2-Nitrodienverbindungen Aus Reaktionen Von Mono(p-fluorarylthio)substituierten Dienen Mit Aminen

2-Nitrodiene compound 1 was stirred with p-fluorothiophenol for a long time and compound 3 was obtained. Compound 1 gave bis(thio)substituted 2-nitrodiene compound 4 and tris(thio)substituted compound 5 with 2 moles of p-fluorothiophenol in the presence of NaOH in ethanol. The compounds 9a–g have been prepared from 8a–g and 3. Compound 7 was obtained from the reaction of mono(thio)substituted 2-nitrodiene with morpholine. Compound 3 gives 11a–d in the reaction with piperidines in CH₂Cl₂ (or ether). Compound 13a–b have been obtained from the reaction of compound 3 with primary amines 12a–b. Compound 3 gives 15 and 16 in the reaction with 2,5-dimethylpiperazine in CH₂Cl₂.

     

Swelling Characterization of the Superabsorbent Copolymer in the Petroleum-Based Solvent-Water Mixtures

The crosslinked and porous copolymer grains were synthesized by inverse suspension polymerization of acrylamide. The synthesized copolymer was characterized by Fourier Transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). It was achieved to absorbed 418 g water by 1 g copolymer after 5 min waiting time. Moreover, it was seen that about 99% of water was absorbed by 1 g copolymer in the solvent water mixtures (300 mL solvent–200 mL distilled water) after 2.5 min waiting time. The diffusion coefficients of the copolymer in the solvent-water mixtures were found between 8.87 · 10⁴ and 10.64 · 10⁴ cm²s^?1. Furthermore, the copolymer in distilled water achieved to reach a high value of the diffusion coefficient (13.2 · 10⁴ cm²s^?1).     

Synthesis and Metal Ion Recognition Properties of a Novel Chiral Calix[4](azoxa)crown-7

A novel chiral calix[4](azoxa)crown-7 (9) has been synthesized and its metal ion recognition properties investigated. The starting reagents, chiral diamine 5 and calix[4]arene diacid chloride derivative 8, were prepared according to literature methods. ¹H and ¹³C NMR data show that 9 exists in a cone conformation. In liquid–liquid extraction experiments, 9 exhibits selectivity for Li⁺ among the other alkali metals and a good extraction ability for transition metal cations, suggesting its potential use in different fields, such as a sensor for ions as well as for chiral molecules.