The Effect of cis-trans Isomerism on the Electronic-vibrational Structure of the Ground and Excited States and Reactivity of 2-(2-Furyl)- and 2-(2-Thienyl)oxazole

The fluorescent properties, structure, and electronic structure of the ground and excited singlet and triplet electronic states of the cis and trans forms of 4,5-dihydro-2-(2-furyl)oxazole, 4,4-dihydro-2-(2-thienyl)oxazole, 2-(2-furyl)oxazole (FO), and 2-(2-thienyl)oxazole (TO) have been studied. The orbital nature of the lower excited singlet and triplet states has been studied by the semiempirical INDO/S (valence approximation) and PPP/S ( approximation) methods. It was shown that for FO and TO molecules the lower triplet state is of the * type, for which delocalization of the electronic excitation on atoms is characteristic. In the singlet excitation state inversion was observed of the energy levels of the delocalized * states and n* states localized over several bonds (for the free TO and FO molecules the lower excited singlet states S₁* were assigned to * and n* types respectively). Owing to the low position of the T * and T _n* levels relative to the singlet level of * type, the rate constant for intercombination conversion is greater than the rate constant for radiative decay. Consequently an efficient population of the triplet states of the molecules occurs under conditions of electronic-vibrational excitation. The direction of reactions during synthesis was compared with the localization indices in the ground state for electrophilic, nucleophilic, and radical substitution, and also with the excitation localization numbers L for a wide selection of electronically excited states. It was concluded that the change in the structure of the azole molecule on replacing an O atom by an S atom, or on changing from a partially hydrogenated to a heteroaromatic system, was the main reason for the change of all the spectral parameters characterizing the electronic-vibrational or the spin-orbital interaction of the most reactive groups of atoms in the molecular structure.     

Reaction of Grignard Reagents with Diethyl Perfluoroacyl (1-Cyanoethyl)phosphonates. Synthesis of Perfluoroalkylated α,β-Unsaturated Nitriles with Predominant Z-Selectivity

ＩｎｔｒｏｄｕｃｔｉｏｎＲｅｃｅｎｔｌｙｍｕｃｈａｔｔｅｎｔｉｏｎｈａｓｂｅｅｎｄｅｖｏｔｅｄｔｏｔｈｅｓｙｎｔｈｅｓｉｓｏｆα ,β ｕｎｓａｔｕｒａｔｅｄｎｉｔｒｉｌｅｓｓｉｎｃｅｔｈｅｙａｒｅｉｍ ｐｏｒｔａｎｔｓｔｒｕｃｔｕｒａｌｆｅａｔｕｒｅｏｆｓｅｖｅｒａｌｎａｔｕｒａｌｌｙｏｃｃｕｒｒｉｎｇｂｉ ｏｌｏｇｉｃａｌｌｙａｃｔｉｖｅｃｏｍｐｏｕｎｄｓ .1,2 Ｔｈｅｉｎｔｒｏｄｕｃｔｉｏｎｏｆｆｌｕｏ ｒｉｎｅｏｒｔｒｉｆｌｕｏｒｏｍｅｔｈｙｌｇｒｏｕｐｉｎｔｏｂｉｏｌｏｇｉｃａｌｌｙａｃｔｉｖ…     

Selective separation of gold from iron ore samples using ion exchange resin

Gold in iron ore samples is separated from iron (major matrix cation), antimony and vanadium using anion exchange resin in (0.2 M) HBr, potassium peroxodisulfate and acetone:water:nitric acid media. The exchangeable anion Cl⁻ of the ion exchanger Dowex 1X 4 is replaced by Br⁻ using (6 M) HBr solution. Certified reference material DGP-M1, spiked ferric magnetic oxide, gold radioactive tracer ¹⁹⁸Au and gold standard solutions are used to study the adsorption efficiency and the yield recovery of tetrabromoaurate AuBr₄⁻ from the resin. Ten eluents have been tried to elute gold from the column, and it has been found that a 10 ml potassium peroxodisulfate and 240 ml acetone:water:nitric acid [125:5:5] solution fulfills the objective. The set up of the separation procedure allows quantitative adsorption of gold by the resin, while the major matrix cation (Fe) and others (Cd, Ag, Cu, V, Sb, Ti) have been passed through the column with the feeding solution (0.2 M) HBr. The resin selectivity coefficient (K) of separating Au from Fe has been found to be K_Fe^Au≈6.4×10¹¹. The eluted Au is treated with K₂S₂O₈ and H₂O₂ for spectrophotometric determination as rhodamine-B complex at 555.6 nm. The linearity, detection limit, precision, and accuracy of the determination method have been found to be up to 2.0 μg g⁻¹, 0.018 μg g⁻¹, 0.009 μg g⁻¹ and 3%, respectively.     

Cholesterol modulates amiodarone-membrane interactions in model and native membranes

The effects of cholesterol, a lipid mostly found in the sarcolemmal membranes, on the interaction of amiodarone with synthetic models of dimyristoylphosphatidylcholine (DMPC) and with native models of mitochondria and brain microsomes was studied. Alterations on the structural order of lipids were assessed by fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene (DPH) probing the bilayer core, and of the propionic acid derivative 3-(p-(6-phenyl)-1,3,5-hexatrienyl)phenylpropionic acid (DPH-PA) probing the outer regions of the bilayer. As detected by the probes and according to classic observations, cholesterol progressively increased the molecular order in the fluid phase of DMPC. Additionally, it modulated the type and extension of amiodarone effects. For low cholesterol concentrations (≤10–15 mol%), amiodarone (50 μM) ordered DMPC bilayers and the effects were almost identical to those observed in pure DMPC. For higher cholesterol concentrations, amiodarone ordering effects decreased slightly and faded for cholesterol concentrations as high as 25 and 30 mol%, when detected by DPH-PA and DPH, respectively. Above these high cholesterol concentrations, a crossover from ordering to disordering effects of amiodarone was apparent, either in the upper region of the bilayer or the hydrophobic core. The effects of amiodarone in native membranes of mitochondria and brain microsomes, in which "native" cholesterol accounts for about 0 and 25 mol%, respectively, correlated reasonably with the results in models of synthetic lipids. There is a close relationship between cholesterol concentration and amiodarone effects, in either synthetic models or native model membranes. Therefore, it may be predicted that the lipid physicochemical properties regulated by cholesterol concentration will also modulate the effects of amiodarone in sarcolemma.     

Synthesis,Crystal Structures and Properties of Two Novel Co（Ⅱ） and Cd（Ⅱ） Complexes of N-AcetyI-L-glutamic Acid and Imidazole Ligands

Two novel complexes {[Co（A-glu）（Im）2]·0.5H2O}n （1） and [Cd（A-glu）（Im）3]n （2） （H2A-glu=N-acetyl-L-glutamic acid, Im=imidazole） have been synthesized from the reaction of H2A-glu with Co（CH3COO）2·4H2O or Cd（CH3COO）2·2H2O in the presence of Im. Both of the complexes display different coordination environment and similar one-dimensional chain structure. The magnetic susceptibility measurements for 1 show a weak antiferromagnetic interaction between two cobalt（Ⅱ） ions bridged by A-glu ligand. The complex 2 exhibits an intense fluorescent emission in solid state at room temperature.     

Facial selectivity of the (R)-1,3-dimethyl-1-cyclohexyl cation in the gas phase

The model reaction between the (R)-1,3-dimethyl-1-cyclohexyl cation (I) and methanol has been investigated under gas-phase radiolytic conditions (750 Torr; 25-120 degrees C) with the aim of evaluating the intrinsic factors that govern the facial selectivity of biased carbocations. The peculiarity of the experimental approach allows the formation of different CH(3) (18)OH.I ionic adducts. Subsequent conversion of these adducts to give the corresponding E/Z covalent products follows different reaction coordinates, which are characterized by their own activation parameters. On the grounds of density functional theory (DFT) results, several [CH(3)OH.I] structures have been located on the relevant potential-energy surface (PES). The experimental results point to a gas-phase facial selectivity, which is mainly governed by entropic factors that arise as a result of the occurrence of different noncovalent ion-molecule "facial adducts" (FA). The formation of FAs may also play an important role in both the reaction dynamics and the positional selectivity. The present results cannot be interpreted by any of the models based on solution-phase experiments.     

Stereoisomeric flavor compounds,part LVIII: The use of heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin as a chiral stationary phase in flavor analysis

The characteristics of the new chiral stationary phase heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)-β-cyclodextrin are outlined and compared with permethyl- and perethyl-β-cyclodextrins.     

Fourier transform infrared spectroscopy study of the effect of pH on anion and cation adsorption onto poly(acrylo‐amidino diethylenediamine)

The role of hydrogen bonding in the chemistry of transition‐metal complexes remains a topic of intense scientific and technological interest. Poly(acrylo‐amidino diethylenediamine) was synthesized to study the effects of hydrogen bonding on complexes at different pHs. The polymer was synthesized through the coupling of diethylene triamine with polyacrylonitrile fiber in the presence of AlCl₃ · 6H₂O addition. The adsorption capacity of this polymer was 11.4 mequiv/g. The ions used for the adsorption test were CrO, PO, Cu²⁺, Ni²⁺, Fe²⁺, and Ag⁺. All experiments were confirmed with Fourier transform infrared. In the study of anion adsorption, at low pHs, only ionic bonds existed, whereas at high pHs, no bonds existed. However, in the middle pH region, both ionic bonds and hydrogen bonds formed between poly(acrylo‐amidino diethylenediamine) and the chromate ion or phosphate ion. When poly(acrylo‐amidino diethylenediamine) and metal ions (Cu²⁺, Ni²⁺, Fe²⁺, and Ag⁺) formed complexes, a hydrogen‐bonding effect was not observed with Fourier transform infrared. The quantity of metal ions adsorbed onto poly(acrylo‐amidino diethylenediamine) followed the order Ag⁺ > Cu²⁺ > Fe²⁺ > Ni²⁺. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2010–2018, 2004     

Synthetic Crystalline Calcium Silicate Hydrate (I): Cation Exchange and Caesium Selectivity

Summary.  Solid crystalline calcium silicate hydrate (I) synthesized from equimolar amounts of Ca and Si under hydrothermal conditions at 120°C shows cation exchange properties towards divalent metal cations such as Ni, Cu, Cd, or Hg. It also exhibits caesium selectivity in the presence of Na⁺. The exchange capacity and selectivity of the solid can be increased by 10 and 28%, respectively, upon substitution of 0.01 mol of the Ca²⁺ in its structure by Na⁺. The ability of metal cation uptake by the solid was found to obey the order Ni²⁺ > Hg²⁺ > Cu²⁺ > Cd²⁺. The different affinities of calcium silicate hydrate (I) towards these ions can be used for their separation from solutions and also in nuclear waste treatment. The mechanism of the exchange reaction is discussed. Received June 11, 2001. Accepted September 10, 2001