(6′RS,8′RS,2E)- und (6′RS,8′SR,2E)-3-Methyl-3-(2y,2′,6′-trimethyl-7′-oxabicyclo[4.3.0]non-9′-en-8′-yl)-2-propenal ([(5RS,8RS)- und (5RS,8SR)-5,8-Epoxy-5,8-dihydro-ionyloinden]acetaldehyd): Synthese und Röntgenstrukturanalyse

Synthesis and X-Ray Structure of (6′RS,8′RS,2E)- and (6′RS,8′SR,2E)-3-Methyl-3-(2′,2′,6′-trimethyl-7′-oxabicyclo[4.3.0]non-9′-en-8′-yl)-2-propenal ([(5RS,8RS)- and (5RS,8SR)-5,8-Epoxy-5,8-dihydro-ionylidene]acetaldehyde) To check our previous spectroscopic assignments of the structures of trans- and cis-substituted furanoid end groups of carotenoid-5,8-epoxides, we now have synthesized the title compounds. An X-ray structure determination of a single crystal of the trans-isomer (±)- -10A is in agreement with the ¹ H-NMR spectroscopic arguments: isomers with Δδ (H? C(7), H? C(8)) = 0.15–0.22 ppm and J > 1.4 for H? C(7) belong to the cis-series; Δδ in trans-compounds is < 0.07 ppm, and H? C(7) appears as a broad singulett.     

Thiosemicarbazide-Substituted Coumarins as Selective Inhibitors of the Tumor Associated Human Carbonic Anhydrases IX and XII

A novel series of thiosemicarbazide-substituted coumarins was synthesized and the inhibitory effects against four physiologically relevant carbonic anhydrase isoforms I, II, IX and XII showed selective activities on the tumor-associated IX and XII isozymes. Molecular modeling studies on selected compounds 14a and 22a were performed. The binding modes of such compounds were determined assuming their enzymatically active structures (i.e., cinnamic acid) in the thermodynamically favored, and not previously explored, E geometry. Molecular modelling suggests multiple interactions within the enzymatic cavity and may explain the high potency and selectivity reported for the hCAs IX and XII.     

A stability preserved time-integration method for nonlinear advection–diffusion-reaction processes

Journal of Mathematical Chemistry - A new implicit-explicit local differential transform method (IELDTM) is derived here for time integration of the nonlinear (2?+?1)-dimensional...     

Synthese von enantiomerenreinen Violaxanthinen und verwandten Verbindungen

Syntheses of Enantiomerically Pure Violaxanthins and Related Compounds The epoxides 16 and ent- 16 , prepared by Sharpless-Katsuki oxidation of 15 in excellent yield and very high enantiomeric purity, were used as synthons for the preparation of (+)-(S)-didehydrovomifoliol (45) , (+)-(6S, 7E, 9E)-abscisic ester 46 , (+)-(6S, 7E, 9Z)-abscsic ester 47 , (?)-(3S, 7E, 9E)-xanthoxin (49) , (?)-(3R, 7E, 9E)-xanthoxin (50) , (3S, 5R, 6S, 3′S,5′R, 6′S, all-E)-violaxanthin (1) (3R, 5R,6S,3′R,5′R,6′S, all-E)-violaxanthin (55) and their (9Z) (see 53 , 57 ), (13Z) (see 54 , 58 ), and (15Z) (see 60 ) isomers. The novel violadione ( 61 ) was prepared from 1 by oxidation with DMSO/Ac₂O. By base treatment, 61 was converted into violadienedione (62) , a potential precursor of carotenoids with phenolic end groups.     

Model of diffusion-drift charge carrier transport in layers with a fractal structure

A new theoretical (semiempirical) model of diffusion-drift charge carrier transport in layers with a fractal structure based on a partial differential equation with a fractional time derivative has been proposed. It has been shown by numerical calculations that a decrease in the order of the fractional derivative in the presence of the external electric field leads to broadening and asymmetry of the spatial distributions of charge carriers, which physically corresponds to intensification of scattering processes.     

Transfer hydrogenation of aryl ketones with homogeneous ruthenium catalysts containing diazafluorene ligands

Novel cationic ruthenium(II) complexes bearing a 4,5‐diazafluorene unit and p‐cymene as ligands have been synthesised. The complexes were characterised based on elemental analysis and Fourier transform infrared and nuclear magnetic resonance spectroscopies. The synthesised Ru(II) complexes were employed as pre‐catalysts for the transfer hydrogenation of aromatic ketones using 2‐propanol as both hydrogen source and solvent in the presence of NaOH. All complexes showed high catalytic activity as catalysts in the reduction of substituted acetophenones to corresponding secondary alcohols. The products of catalysis were obtained with conversion rates of between 80 and 99%. Among the seven new complexes investigated, the most efficient catalyst showed turnover frequencies in the range 255–291 h^?1 corresponding to 85 to 97% conversion, respectively. Copyright © 2016 John Wiley & Sons, Ltd.     

Occupational prolonged organic solvent exposure in shoemakers: brain MR spectroscopy findings

Our purpose was to investigate, by magnetic resonance (MR) spectroscopy, the metabolite changes in the brains of subjects in the shoemaking industry who had been chronically exposed to organic solvents. A total of 49 male subjects and 30 age-matched healthy volunteers underwent detailed neurological and psychiatric examinations. All subjects had long-echo [repetition time (TR) 2000 ms, echo time (TE) 136 ms] single-voxel MR spectroscopy. Voxels (15 x 15 x 15 mm(3)) were placed in the parietal white matter, thalamus, and basal ganglia. N-acetylaspartate (NAA)/creatine (Cr) and choline (Cho)/Cr ratios were calculated. There was no significant difference between the study subjects and the control group in NAA/Cr ratios obtained from thalamus, basal ganglia, and parietal white matter. Cho/Cr ratios in thalamus, basal ganglia, and parietal white matter were found to be significantly increased compared to controls. There was a positive correlation between basal ganglia Cho/Cr ratio and duration of exposure (r = 0.63). MR spectroscopy should be performed to reveal metabolite changes and determine the degree of brain involvement in solvent-related industry workers.     

Effects of heavy metals and oxalate on the zeta potential of magnetite

Zeta potential is a function of surface coverage by charged species at a given pH, and it is theoretically determined by the activity of the species in solution. The zeta potentials of particles occurring in soils, such as clay and iron oxide minerals, directly affect the efficiency of the electrokinetic soil remediation. In this study, zeta potential of natural magnetite was studied by conducting electrophoretic mobility measurements in single and binary solution systems. It was shown that adsorption of charged species of Co(2+), Ni(2+), Cu(2+), Zn(2+), Pb(2+), and Cd(2+) and precipitation of their hydroxides at the mineral surface are dominant processes in the charging of the surface in high alkaline suspensions. Taking Pb(2+) as an example, three different mechanisms were proposed for its effect on the surface charge: if pH<5, competitive adsorption with H(3)O(+); if 56, precipitation of heavy metal hydroxides prevails. Oxalate anion changed the associated surface charge by neutralizing surface positive charges by complexing with iron at the surface, and ultimately reversed the surface to a negative zeta potential. Therefore the adsorption ability of heavy metal ions ultimately changed in the presence of oxalate ion. The changes in the zeta potentials of the magnetite suspensions with solution pH before and after adsorption were utilized to estimate the adsorption ability of heavy metal ions. The mechanisms for heavy metals and oxalate adsorption on magnetite were discussed in the view of the experimental results and published data.     

The synthesis and characterization of copper(II)–<Emphasis Type="Italic">p</Emphasis>-aminosalicylate complexes with diamine ligands

The complexes were synthesized by the reaction between sodium salt of p-aminosalicylic acid (PAS) and Cu(II) for 1 and corresponding ethylenediamine (en) or its derivatives for 2–6. The complexes were characterized by using elemental analyses, FT-IR, UV–Vis, magnetic moment measurements, and thermal analyses techniques. In complex 1[Cu₂(PA)₄(H₂O)₂], two Cu(II) ions were found as bridged by four μ-O:O′ p-aminosalicylato (PA) ligands, forming a cage structure, and two aqua ligands to form dinuclear square-pyramidal geometry around Cu(II) ions. In the complexes 2–6, the PA (anionic form of p-aminosalicylic acid) coordinated to Cu(II) ions as monodentate manner by using its oxygen atom of deprotonated carboxylic acid and ethylenediamine derivatives coordinated to the Cu(II) ions in bidentate manner to form mononuclear octahedral complexes [Cu(PA)₂(L)₂] (L = ethylendiamine, N,N-dimethylethylendiamine, N,N′-dimethylethylendiamine, N,N,N′,N′-tetramethylethylendiamine, and 1,3-propanediamine, for complexes 2, 3, 4, 5, and 6, respectively). In all the complexes OH and NH₂ groups of PA ligands were not coordinated to metals.