An ab initio molecular orbital study of intramolecular H-bonding: 1,3 propanediol

An ab initio molecular orbital calculation has been carried out for three different conformations of 1,3 propanediol, one of which permits intramolecular H-bond studied by ab initio quantum mechanical methods. The ΔE for H-bonding formation is compated to be 0.9 kcal/mole and the charge redistributions and molecular orbital energy changes are compared to those found in intermolecular H-bonds.     

Genes encoding enzymes responsible for biosynthesis of L-lyxose and attachment of eurekanate during avilamycin biosynthesis

The oligosaccharide antibiotic avilamycin A is composed of a polyketide-derived dichloroisoeverninic acid moiety attached to a heptasaccharide chain consisting of six hexoses and one unusual pentose moiety. We describe the generation of mutant strains of the avilamycin producer defective in different sugar biosynthetic genes. Inactivation of two genes (aviD and aviE2) resulted in the breakdown of the avilamycin biosynthesis. In contrast, avilamycin production was not influenced in an aviP mutant. Inactivation of aviGT4 resulted in a mutant that accumulated a novel avilamycin derivative lacking the terminal eurekanate residue. Finally, AviE2 was expressed in Escherichia coli and the gene product was characterized biochemically. AviE2 was shown to convert UDP-D-glucuronic acid to UDP-D-xylose, indicating that the pentose residue of avilamycin A is derived from D-glucose and not from D-ribose. Here we report a UDP-D-glucuronic acid decarboxylase in actinomycetes.     

A flow-through cell for differential pulse anodic stripping voltammetry

A flow-through voltammetric cell with a hanging mercury drop electrode has been developed to fit the static mercury drop electrode (PAR 303). The design has resulted in a linear increase of sensitivity with flow rate and an enhancement of sensitivity by the wall-jet effect. The cell is used in a flow injection system in which samples are introduced with a R??i?ka—Hansen injector. The mercury drop is held at plating potentials while the sample peak passes through the cell. Stripping is done under stopped flow conditions, to reduce noise, after the sample has been washed completely from the cell. The stripping thus takes place into the carrier electrolyte which always has a constant composition independent of sample constituents. Film-forming interfering species will, however, remain on the surface of the mercury drop. The effect of medium exchange on films produced by l-cysteine is reported. The flow-through medium exchange simplifies deaeration, speeds up analysis and reduces contamination.     

Time-resolved and steady-state fluorescence spectroscopic studies of the human lens with comparison to argpyrimidine,pentosidine and 3-OH-kynurenine

The intrinsic fluorescence from the human lens on excitation in the UV region, referred to as blue lens autofluorescence, increases with age or in the presence of diabetes. The present study reveals that the relative contribution of compounds responsible for the blue autofluorescence appears to be a constant with age. Three potential candidates for the blue fluorescence were also studied with respect to fluorescence spectroscopic properties. These were argpyrimidine and pentosidine, both advanced glycation end products, and 3-hydroxykynurenine (3-OH-kynurenine), a photooxidative derivative of tryptophan. It was shown that the spectral properties of argpyrimidine and pentosidine are compatible with the observed blue fluorescence of the human lens, whereas the fluorescence from 3-OH-kynurenine is negligible.     

On the theoretical determination of the electron affinity of ozone

Summary Multiconfigurational electron correlation methods have been analyzed in order to theoretically compute the electron affinity (EA) of ozone. The near-degeneracy correlation effects, which are so important in O₃ and O ₃ ^– , have been described using complete active space (CAS) SCF wave functions. Remaining dynamic correlation effects are computed using second-order perturbation theory (the CASPT2 method). The best calculated adiabatic value (including zero-point energy corrections), 2.19 eV, is about 0.09 eV larger than the experimental value. Comparative studies using size-consistent coupled pair functional approaches (CPF and ACPF) have also been performed. The harmonic frequencies in O ₃ ^– have been determined to be: ₁=992, ₂=572, and ₃=879 cm^–1, which gives a zero-point energy of 0.151 eV.     

Azines possessing strong push-pull donors/acceptors

Azines (R(2)C[double bond, length as m-dash]N-N[double bond, length as m-dash]CR(2)) are 2,3-diaza analogues of 1,3-butadiene. In this report we show that strong polarisation of the azine imparts structural features consistent with delocalization within the azine fragment; NLO properties for the azines are also reported.     

Regio- and Stereoselective Reactions of 17-Phenyl-18,19,20-trinorprostaglandin F(2)(alpha) Isopropyl Ester

Novel prostaglandin F(2)(alpha) derivatives, functionalized at C13 and C14, have been prepared. 17-Phenyl-18,19,20-trinorprostaglandin F(2)(alpha) isopropyl ester [(15S)-1] and its epimer [(15R)-1] were stereoselectively epoxidized, using Sharpless conditions, to produce each of the four diastereomeric epoxides (15S)-2, (15S)-3, (15R)-2, and (15R)-3. Treatment of the four epoxides with LiOH stereospecifically-produced the pentahydroxy substituted analogues 12 and 13. Alternatively, epoxides 2 and 3were allowed to react with thiophenolate ion. The attack of the sulfur nucleophile on the epoxide occurred at either C13 or C14 depending on the stereochemistry of the epoxide and of C15.     

Fluoride determination with a micro flow-calorimeter

Fluoride is determined by an integration technique with a flow calorimeter. All samples are absorbed on an anion-exchange resin before being brought into the calorimetric system. The reaction between hydrofluoric add and sodium hydroxide is used in the determinations. The method is applied to samples with between 7 mug and 5 mg of fluoride. The confidence limit is +/-2-5 mug for small samples and +/-25 mug for large samples. The enthalpy of the reaction H(+) + F(-) --> HF((aq)) was found to be 13.77 +/- 0.08 kJ mole .     

On-line enzymatic reaction,extraction, and chromatography of fatty acids and triglycerides with supercritical carbon dioxide

Supercritical carbon dioxide can be utilized both as an introduction solvent in capillary SFC and as a reaction medium; both possibilities are illustrated in this study. An off-line SFE unit was modified for on-line SFE-SFC. To facilitate rapid depressurization of the extraction cell and to prevent memory effects, a 6-port valve was installed at the outlet line of the extraction unit. An increased background signal was obtained when PEEK polymer was used in the construction of the extraction vessel; when stainless steel was used, the blanks improved. The synthesis of methyl esters and butyl esters of fatty acids from triglycerides in edible fat was examined using an immobilized lipase as a catalyst in on-line SFE-SFC. As a result of 30 minutes reaction – extraction time, high yields of fatty acid esters were obtained at a pressure of 150 bar and a temperature of 50°C.     

Synthesis,characterization, and curing of hyperbranched allyl ether–maleate functional ester resins

A model two-step synthesis of a saturated hyperbranched hydroxyl-terminated ester has been developed to show a synthesis route. Three different series of hyperbranched esters with different terminations have been synthesized to relate some of their properties to their structures. This route has then been used to synthesize three different allyl ethermaleate functional hyperbranched ester resins in a two-step procedure. The resins have been characterized with respect to rheology, structure, and properties, and the differences are discussed. The allyl ether-maleate functional resins have also been studied with respect to curing performance and final film properties. © 1993 John Wiley & Sons, Inc.