Experimental and DFT studies of ethyl N′-3-(1H-imidazol-1-yl) propylcarbamoyl benzohydrazonate monohydrate

The Imidazole compound, Ethyl N′-3-(1H-imidazol-1-yl) propylcarbamoyl benzohydrazonate monohydrate, has been synthesized and characterized by IR, NMR, electronic spectroscopy, and X-ray single-crystal determination. Molecular geometry from X-ray experiment of the title compound in the ground state has been compared using the density functional method (B3LYP) with 6-31G+(d) basis set. To determine conformational flexibility, molecular energy profile of the title compound was obtained by DFT calculations with respect to two selected degrees of torsional freedom, which were varied from −180° to +180° in steps of 10°. Besides, molecular electrostatic potential (MEP), natural bond orbitals (NBO), frontier molecular orbitals (FMO), and thermodynamic properties were performed at B3LYP/6-31G+(d) level of theory.     

Microdistillation and analysis of volatiles from eight ornamental Salvia taxa

Volatile compounds from seven Salvia species and one interspecific hybrid growing at the Dallas Arboretum and Botanical Garden, Texas, US. Salvia coccinea, S. farinacea, S. greggii, S. leucantha, S. longispicata x farinacea, S. madrensis, S. roemeriana and S. splendens were investigated for their chemical compositions using a microdistillation technique. Volatiles were analyzed by gas chromatography (GC) and gas chromatography-mass spectrometry (GC/MS). One hundred and twenty seven compounds were identified representing 94.3-99.7% of the oils. The major components in each of the seven species were as follows: S. coccinea (Z)-3-hexenal (31%), viridiflorol (19%); S. farinacea 1-octen-3-ol (30%) and (Z)-3-hexenal (23%); S. greggii 1,8-cineole (22%), borneol (17%), camphene (11%) and alpha-pinene (10%); S. leucantha limonene (35%) and alpha-pinene (17%); S. longispicata x farinacea 1-octen-3-ol (50%) and (Z)-3-hexenal (24%); S. madrensis (Z)-3-hexenal (53%); S. roemeriana limonene (49%) and alpha-pinene (20%); and S. splendens (Z)-3-hexenal (36%), 2,5-dimethoxy-p-cymene (19%) and linalool (11%). The microdistillation method was fast, practical and a useful technique that enabled the isolation of the volatiles in samples when only limited quantities were available.     

Essential oil composition, antimicrobial and cytotoxic activities of two endemic Stachys cretica subspecies (Lamiaceae) from Turkey

The chemical compositions of the water-distilled essential oil of Stachys cretica ssp. lesbiaca Rech. fil. and S. cretica ssp. trapezuntica Rech. fil. were determined by GC and GC-MS. Altogether 63 compounds were identified. The sesquiterpene hydrocarbon, germacrene D (20.3% and 12.9% respectively) was the main component identified in both oils. Furthermore, ethanol, light petroleum, dichloromethane, ethyl acetate and n-butanol extracts prepared from the aerial parts of the plants were tested for their antimicrobial activities against six bacterial strains and the yeast Candida albicans. The extracts exhibited no antibacterial activity, but the light petroleum and n-butanolic fractions showed low antifungal activities. Crude ethanolic extracts of the two subspecies were tested for their ability to inhibit the growth of HL-60 and Ishikawa human tumor cell lines. The IC50 values were 100 microg/mL for the HL-60 cell line and 200 microg/mL for the Ishikawa cell line.     

A computational study on the amine-oxidation mechanism of monoamine oxidase: insight into the polar nucleophilic mechanism

The proposed polar nucleophilic mechanism of MAO was investigated using quantum chemical calculations employing the semi-empirical PM3 method. In order to mimic the reaction at the enzyme's active site, the reactions between the flavin and the p-substituted benzylamine substrate analogs were modeled. Activation energies and rate constants of all the reactions were calculated and compared with the published experimental data. The results showed that electron-withdrawing groups at the para position of benzylamine increase the reaction rate. A good correlation between the log of the calculated rate constants and the electronic parameter (sigma) of the substituent was obtained. These results agree with the previous kinetic experiments on the effect of p-substituents on the reduction of MAO-A by benzylamine analogs. In addition, the calculated rate constants showed a correlation with the rate of reduction of the flavin in MAO-A. In order to verify the results obtained from the PM3 method single-point B3LYP/6-31G*//PM3 calculations were performed. These results demonstrated a strong reduction in the activation energy for the reaction of benzylamine derivatives having electron-withdrawing substituents, which is in agreement with the PM3 calculations and the previous experimental QSAR study. PM3 and B3LYP/6-31G* energy surfaces were obtained for the overall reaction of benzylamine with flavin. Results suggest that PM3 is a reasonable method for studying this kind of reaction. These theoretical findings support the proposed polar nucleophilic mechanism for MAO-A.     

Determination of Naphthazarin Derivatives in 16 Alkanna Species by RP-LC Using UV and MS for Detection

As part of our ongoing studies, a new and validated method for analysis of isohexenyl-naphthazarines in Turkish Alkanna species was developed. By using reversed phase material (Synergi MAX RP) it was possible to determine four known isohexenylnaphthazarin-derivatives, namely alkannin, acetylalkannin, deoxyalkannin, and β,β-dimethylacrylalkannin within 25 min in n-hexane extracts of the roots. The quantification of these compounds in 16 Anatolian Alkanna species is described for the first time. In order to assure peak identity LC-MS experiments were performed. Quantitative results revealed that the most dominant compound in the extracts was β,β-dimethylacrylalkannin.     

Zur quantitativen Bestimmung des Isopropylalkohols

Ohne Zusammenfassung     

A biosensor based on urate oxidase-peroxidase coupled enzyme system for uric acid determination in urine

A new amperometric biosensor based on urate oxidase-peroxidase coupled enzyme system for the specific and selective determination of uric acid in urine was developed. Commercially available urate oxidase and peroxidase were immobilized with gelatin by using glutaraldehyde and fixed on a pretreated teflon membrane. The method is based on generation of H₂O₂ from urine uric acid by urate oxidase and its consuming by peroxidase and then measurement of the decreasing of dissolved oxygen concentration by the biosensor. The biosensor response depends linearly on uric acid concentration between 0.1 and 0.5 μM. In the optimization studies of the biosensor, phosphate buffer (pH 7.5; 50 mM) and 35 °C were obtained as the optimum working conditions. In addition, the most suitable enzyme activities were found as 64.9×10⁻³ U cm⁻² for urate oxidase and 512.7 U cm⁻² for peroxidase. And also some characteristic studies of the biosensor such as reproducibility, substrate specificity and storage stability were carried out.     

Bis(triethanolamine)cadmium(II) and -­mercury(II) saccharinates: seven-coordinate complexes containing both tri- and tetradentate triethanolamine ligands

The structures of the title triethanol­amine (tea) complexes of Cd^II and Hg^II saccharinates, bis­(triethanol­amine)-κ³O,N,O′;κ⁴O,N,O′,O′′-cadmium(II) 1,2-benziso­thia­zol-3(2H)-onate 1,1-dioxide, [Cd(C₆H₁₅NO₃)₂](C₇H₄NO₃S)₂, (I), and bis­(tri­ethanol­amine)-κ³O,N,O′;κ⁴O,N,O′,O′′-mercury(II) 1,2-benz­iso­thia­zol-3(2H)-onate 1,1-dioxide, [Hg(C₆H₁₅NO₃)₂](C₇H₄NO₃S)₂, (II), or [M(tea)₂](sac)₂, where M is Cd^II or Hg^II and sac is the saccharinate anion, reveal seven-coordinate metal ions in both complexes. Both complex cations, [M(tea)₂]²⁺, adopt a monocapped trigonal prism geometry in which the two tea ligands exhibit different coordination modes to achieve seven-coordination. One tea ligand acts as a tetradentate ligand using all its donor atoms, while the other behaves as a tridentate O,N,O′-donor ligand, with one of its ethanol groups remaining uncoordinated. The H atoms of the free and coordinated hydroxyl groups of the tea ligands are involved in hydrogen bonding with the amine N atom, and with the carbonyl and sulfonyl O atoms of neighbouring sac ions, forming an infinite three-dimensional network. A weak π–π interaction between the phenyl rings of the sac ions also occurs.     

Comparative Studies on Essential Oil and Phenolic Content with In Vitro Antioxidant,Anticholinesterase, Antimicrobial Activities of Achillea biebersteinii Afan. and A. millefolium subsp. millefolium Afan. L. Growing in Eastern Turkey

The potential applications of Achillea species in various industries have encouraged the examination of their phytochemical components along with their biological potential. In the present study, phenolic contents and essential oil compositions together with the in vitro biological activities of the aerial parts from Achillea biebersteinii Afan. and Achillea millefolium subsp. millefolium Afan. collected from Turkey were evaluated. Different solvent extracts (n-hexane, chloroform, methanol, water) were prepared and their antimicrobial, anticholinesterase, and antioxidant activities were studied. The LC-MS/MS results revealed the presence of 16 different phenolic compounds, including chlorogenic acid, rutin, quercetin, and luteolin glycosides, in methanolic extracts. According to GC-FID and GC/MS results, the primary components of the oils were identified as 1,8-cineole (32.5%), piperitone (14.4%), and camphor (13.7%) in A. biebersteinii and 1,8-cineole (12.3%) and β-eudesmol (8.9%) in A. millefolium subsp. millefolium. The infusion and methanolic extracts of both species were found to be rich in their total phenolic content as well as their antioxidant and anticholinesterase activity. In contrast, the n-hexane and chloroform extracts of both species showed strong antimicrobial activity with MIC values ranging from 15 to 2000 μg/mL. Our findings suggest that the investigated Achillea species could be evaluated as potent natural agents, and further studies into the promising extracts are needed.