Gas chromatographic confirmation of amino acid structure via diastereomer preparation.

The partial gas chromatographic (GC) resolution of several amino acid N-trifluoroacetyl 2-butyl ester diastereomeric derivatives on a short packed column has been used to confirm GC peak assignments in analysis of a marine sediment sample.     

Development of xylose-fermenting yeasts for ethanol production at high acetic acid concentrations

Mutants resistant to comparatively high levels of acetic acid were isolated from the xylose-fermenting yeastsCandida shehatae andPichia stipitis by adapting these cultures to increasing concentrations of acetic acid grown in shake-flask cultures. These mutants were tested for their ability to ferment xylose in presence of high acetic acid concentrations, in acid hydrolysates of wood, and in hardwood spent sulfite liquor, and compared with their wild-type counterparts and between themselves. TheP. stipitis mutant exhibited faster fermentation times, better tolerance to acid hydrolysates, and tolerance to lower pH.     

Tautomerism in the 5-pyrazolone series 1(H)-5-pyrazolones and indazolones

Structure (I) is shown to be the correct formulation for the compound hitherto considered to be the “azine” of ethyl acetoacetate; I rearranges to IV. Both IV, 1(H)-3-methyl, and 1(H)-3-phenyl, 5-pyrazolones and related compounds are shown to exist in the enolic form (VII) in the solid state and predominantly so in the solvents in which they are soluble. Similarly the indazolones are found to be represented exclusively by the enolized structure XII. The acetates of both series are reformulated where necessary on the basis of spectroscopic data, and the high frequencies found for the carbonyl groups in the IR are shown to reflect a lack of conjugation with the π-electrons of the heterocyclic ring.     

Experimental and theoretical study of the adsorption of fumaramide [2]rotaxane on Au(111) and Ag(111) surfaces

Thin films of fumaramide [2]rotaxane, a mechanically interlocked molecule composed of a macrocycle and a thread in a "bead and thread" configuration, were prepared by vapor deposition on both Ag(111) and Au(111) substrates. X-ray photoelectron spectroscopy (XPS) and high-resolution electron-energy-loss spectroscopy were used to characterize monolayer and bulklike multilayer films. XPS determination of the relative amounts of carbon, nitrogen, and oxygen indicates that the molecule adsorbs intact. On both metal surfaces, molecules in the first adsorbed layer show an additional component in the C 1s XPS line attributed to chemisorption via amide groups. Molecular-dynamics simulation indicates that the molecule orients two of its eight phenyl rings, one from the macrocycle and one from the thread, in a parallel bonding geometry with respect to the metal surfaces, leaving three amide groups very close to the substrate. In the case of fumaramide [2]rotaxane adsorption on Au(111), the presence of certain out-of-plane phenyl ring and Au-O vibrational modes points to such bonding and a preferential molecular orientation. The theoretical and experimental results imply that the three-dimensional intermolecular configuration permits chemisorption at low coverage to be driven by interactions between the three amide functions of fumaramide [2]rotaxane and the Ag(111) or Au(111) surface.     

Synthesis of 4‐Substituted‐ and 1,4‐Disubstituted‐4‐Hydroxypyrrolidin‐2‐ones

This report describes the synthesis of 4‐substituted‐ and 1,4‐disubstituted‐4‐hydroxypyrrolidin‐2‐ones by cyclization of intermediate γ‐aminoesters prepared from alkylbenzylamines, α‐bromoketones, and lithio ethyl acetate.     

Radiance-based monitoring of the extent of tissue coagulation during laser interstitial thermal therapy

Optical monitoring relates the dynamic changes in measured light intensity to the extent of treatment-induced coagulation that occurs during laser interstitial thermal therapy. We utilized a two-region Monte Carlo simulation to elucidate the nature of the changes in interstitial radiance and fluence that result from the formation of a volume of thermal coagulation surrounding a cylindrical emitter. Using simulation results, we demonstrate that radiance sensors are more sensitive than traditional fluence sensors to coagulation-induced scattering changes. Radiance measurements take advantage of directional detection angles that are more receptive to the onset and passing of the coagulation boundary. We performed experiments with albumen phantoms to demonstrate the practicality of the radiance method for monitoring interstitial laser thermal therapy.