485—Spectroelectrochemical evidence for imine-alcohol intermediate formed upon electrochemical oxidation of uric acid

Electrochemical oxidation of uric acid in phosphate-containing supporting electrolytes between pH 3–9 at a reticulated vitreous carbon electrode in a thin-layer spectroelectrochemical cell leads to formation of U.V.-absorbing intermediate species. Electrochemical reduction of the intermediate-containing solution leads to the partial regeneration of uric acid. This behavior provides compelling evidence that an imine-alcohol is one of the U.V.-absorbing intermediate species since only this compound may be expected to be reduced to a species which can regenerate uric acid.     

Manganese(I) poly(mercaptoimidazolyl)borate complexes: spectroscopic and structural characterization of Mn...H-B interactions in solution and in the solid state

The manganese(I) tricarbonyl complexes (Bm(R))Mn(CO)3(R = Me, Bz, But, p-Tol) and (PhBmMe)Mn(CO)3, the first bis(mercaptoimidazolyl)borate derivatives for this metal, have been readily prepared and fully characterized. In particular, the presence of three-center-two-electron Mn...H-B interactions in these species, both in solution and in the solid state, has been investigated using a combination of IR and NMR spectroscopies and, in the case of the methyl-, tert-butyl- and para-tolyl-substituted derivatives, by X-ray crystallography. To complement these synthetic and structural studies, the tris(mercaptoimidazolyl)borate complexes (TmMe)Mn(CO)3(R = Me, Bz, But, p-Tol) and (PhTm(Me))Mn(CO)3, as well as the related pyrazolylbis(mercaptoimidazolyl)borate (pzBmMe)Mn(CO)3, have also been synthesized and characterized by a combination of analytical and spectroscopic techniques.     

Introducing variable cell shape methods in field theory simulations of polymers

We propose a new method for carrying out field-theoretic simulations of polymer systems under conditions of prescribed external stress, allowing for shape changes in the simulation box. A compact expression for the deviatoric stress tensor is derived in terms of the chain propagator, and it is used to monitor changes in the box shape according to a simple relaxation scheme. The method allows fully relaxed, stress free configurations to be obtained even in nontrivial morphologies, and it enables the study of morphology transitions induced by external stresses.     

Microwave traps for cold polar molecules

We discuss the possibility of trapping polar molecules in the standing-wave electromagnetic field of a microwave resonant cavity. Such a trap has several novel features that make it very attractive for the development of ultracold molecule sources. Using commonly available technologies, microwave traps can be built with large depth (up to several Kelvin) and acceptance volume (up to several cm³), suitable for efficient loading with currently available sources of cold polar molecules. Unlike most previous traps for molecules, this technology can be used to confine the strong-field seeking absolute ground state of the molecule, in a free-space maximum of the microwave electric field. Such ground state molecules should be immune to inelastic collisional losses. We calculate elastic collision cross-sections for the trapped molecules, due to the electrical polarization of the molecules at the trap center, and find that they are extraordinarily large. Thus, molecules in a microwave trap should be very amenable to sympathetic and/or evaporative cooling. The combination of these properties seems to open a path to producing large samples of polar molecules at temperatures much lower than has been previously possible.Received: 30 June 2004, Published online: 23 November 2004PACS: 33.80.Ps Optical cooling of molecules; trapping - 34.50.-s Scattering of atoms and molecules - 33.80.-b Photon interactions with molecules - 33.55.Be Zeeman and Stark effects     

Design of a Thin Film Infrared Barcode on a Flexible Substrate

We report the design, fabrication and characterization of an infrared barcode. This barcode is composed of a bilayer of titanium and amorphous silicon on a flexible Kapton substrate. Information encoded in the barcode shows high contrast when viewed with an infrared imaging system in the 8 to 12 m spectral region. The barcode information is concealed under visible viewing conditions, i.e., the barcode appears as an untreated, uniform metal sheet to a detector of visible radiation (400 to 700nm).     

Phosphoinositide signaling; from affinity probes to pharmaceutical targets

Lipid signaling by phosphoinositides (PIP(n)s) involves an array of proteins with lipid recognition, kinase, phosphatase, and phospholipase functions. Understanding PIP(n) pathway signaling requires identification and characterization of PIP(n)-interacting proteins. Moreover, spatiotemporal localization and physiological function of PIP(n)-protein complexes must be elucidated in cellular and organismal contexts. For protein discovery to functional elucidation, reporter-linked phosphoinositides or tethered PIP(n)s have been essential. The phosphoinositide 3-kinase (PI 3-K) signaling pathway has recently emerged as an important source of potential "druggable" therapeutic targets in human pathophysiology in both academic and pharmaceutical environments. This review summarizes the chemistry of PIP(n) affinity probes and their use in identifying macromolecular targets. The process of target validation will be described, i.e., the use of tethered PIP(n)s in determining PIP(n) selectivity in vitro and in establishing the function of PIP(n)-protein complexes in living cells.     

Transference numbers for anhydrous methanol solutions at 10 and 25°C

Transference numbers are reported for LiCl and NaCl in methanol at 25°C and for NaCl, KCl, and Bu₄NBr in methanol at 10°C. The potentiometric moving-boundary method as developed by Kay and Fratiello was employed to give a precision of about 0.05% and an accuracy of at least 0.1% as indicated by two independent determinations of the conductances of the Cl^– and Br^– ions. The data are extrapolated by the Fuoss-Onsager theory, and the magnitude of the electrophoretic effect is calculated as described by Kay and Dye. The agreement with this theory is quite good at both temperatures, although the å value required in the case of Bu₄NBr is considerably larger than that obtained from conductance data. This agreement contrasts with that obtained for ethanol and acetone solutions where the measured electrophoretic effect is considerably larger than the corresponding calculated values. The importance of this fact in the determination of ion-pair association constants is discussed.     

A single extraction method for the analysis by liquid chromatography/tandem mass spectrometry of fumonisins and biomarkers of disrupted sphingolipid metabolism in tissues of maize seedlings

The fungus Fusarium verticillioides is a pathogen of many plants and produces fumonisins. In addition to their well-studied animal toxicoses, these toxins contribute to the development of maize seedling disease in susceptible maize varieties. Fumonisin disruption of sphingolipid biosynthesis occurs during pathogenesis. An extraction method was developed for the simultaneous analysis of fumonisins B₁ (FB₁), B₂ (FB₂) and B₃ (FB₃), free sphingoid bases and sphingoid base 1-phosphates in maize tissues by liquid chromatography/linear ion trap tandem mass spectrometry. The method involved a single extraction using 1:1 acetonitrile:water + 5% formic acid (1 ml per 10 mg tissue). Mean recoveries ranged from approximately 50 to 99 percent, and limits of detection ranged from 10 fg μl⁻¹ to 6900 fg μl⁻¹. To test the efficacy of the method, seeds of a susceptible maize line were inoculated with a pathogenic, fumonisin-producing strain of F. verticillioides. The seedlings were then harvested, and fumonisin content, as well as sphingoid bases and their 1-phosphates, were measured in the leaf and root tissues. Fumonisin accumulation was significantly greater in leaf one compared to leaves two and three. While FB₁, FB₂, and FB₃ were detected in root tissues, FB₁ was preferentially accumulated in leaf tissues. Accumulation of sphingoid bases and their 1-phosphates was evident in roots and leaves of seedlings grown from inoculated seed, with the level of accumulation being similar in leaves 1, 2 and 3. The method developed was effective, fast, and sensitive for use in simultaneously measuring fumonisin in tissues and their effects on sphingolipid metabolite biomarkers of disease. The method should be useful for screening maize cultivars for susceptibility to F. verticillioides-induced seedling diseases. Figure Lesion with chromatography