Chemiluminescence from the oxidation of urea and ammonia with hypobromite and N-bromosuccinimide

The spectral distribution for the chemiluminescent oxidation of ammonia with hypobromite is significantly different to that for the oxidation of ammonia with N-bromosuccinimide. Therefore, in contrast to the assumptions of several authors, the action of N-bromosuccinimide is not solely derived from the in situ formation of hypobromite. Neither the oxidation of urea with hypobromite nor the oxidation of urea with N-bromosuccinimide involves an initial hydrolysis of urea to ammonia in the alkaline solution. However, these two reactions lead to a common emitter. The addition of xanthene dyes, such as dichlorofluorescein, enhance the chemiluminescence intensity by energy transfer to the efficient fluorophore, but reaction between the sensitiser and hypobromite can result in a significant increase in the background signal. A list of potential interferences has been compiled; particular attention was paid to guanidino compounds, as the chemiluminescence accompanying the oxidation of this functional group has not been previously discussed.     

Non-radiative decay processes in isolated SO2 molecules excited within the first allowed absorption band (2500–3200 Å)

New and previously published SO₂ fluorescence emission data related to non-radiative decay processes are considered in light of the recent observations of Brus and McDonald. All the present data are consistent with the previous conclusion of Mettee that non-radiative processes in SO₂ singlet photochemistry are unimportant. It appears that any small inefficiency in the emission of light quanta for SO₂ excited at short wavelengths (2650 A) is largely due to the population of a second very short-lived state which is quenched effectively even at pressures down to 1 μ. The very low efficiency of quanta production which we observed at long wavelengths (3020 Å) appears to have its origin not only in the second easily quenched state, but more importantly, in the diffusional loss of the long-lived singlet which for these conditions has a 20-fold greated lifetime than was expected previously.     

Germacrene A is a product of the aristolochene synthase-mediated conversion of farnesylpyrophosphate to aristolochene

The biosynthesis of several sesquiterpenes has been proposed to proceed via germacrene A. However, to date, the production of germacrene A has not been proven directly for any of the sesquiterpene synthases for which it was postulated as an intermediate. We demonstrate here for the first time that significant amounts of germacrene A (7.5% of the total amount of products) are indeed released from wild-type aristolochene synthase (AS) from Penicillium roqueforti. Germacrene A was identified through direct GC-MS comparison to an authentic sample and through production of beta-elemene in a thermal Cope rearrangement. AS also produced a small amount of valencene through deprotonation of C6 rather than C8 in the final step of the reaction. On the basis of the X-ray structure of AS, Tyr 92 was postulated to be the active-site acid responsible for protonation of germacrene A (Caruthers, J. M.; Kang, I.; Rynkiewicz, M. J.; Cane, D. E.; Christianson, D. W. J. Biol. Chem. 2000, 275, 25533-25539). The CD spectra of a mutant protein, ASY92F, in which Tyr 92 was replaced by Phe, and of AS were very similar. ASY92F was approximately 0.1% as active as nonmutated recombinant AS. The steady-state kinetic parameters were measured as 0.138 min(-1) and 0.189 mM for k(cat) and K(M), respectively. Similar to a mutant protein of 5-epi-aristolochene (Rising, K. A.; Starks, C. M.; Noel, J. P.; Chappell, J. J. Am. Chem. Soc. 2000, 122, 1861-1866), the mutant released significant amounts of germacrene A (approximately 29%). ASY92F also produced various amounts of a further five hydrocarbons of molecular weight 204, valencene, beta-(E)-farnesene, alpha- and beta-selinene, and selina-4,11-diene.     

Synthesis and structural characterization of a new heterobimetallic coordination complex of barium and cobalt for use as a precursor for chemical vapor deposition

Ba(dmae)2 (dmaeH=N,N-dimethylaminoethanol, C4H11NO) reacts with Co(acac)2 (acac=2,4-pentanedionate) to produce the trinuclear coordination complex [Ba2Co(acac)4(dmae)3(dmaeH)] in an 85% yield. Spectroscopic and single-crystal X-ray diffraction experiments indicate that the complex possesses a structure in which two barium atoms and a cobalt atom are bridged by acac and dmae groups. The barium centers are eight and nine coordinate with BaO7N and BaO7N2 coordination spheres while the cobalt is a more regular CoO5N octahedron. This 2:1 heterobimetallic molecular complex was investigated as precursor for the deposition of thin film by AACVD. The film was characterized by SEM and XRD. TGA shows that the complex starts thermal decomposition upon heating in nitrogen atmosphere at 105 degrees C to produce barium cobalt oxide material of a Ba2CoO3 composition with an orthorhombic structure. The synthetic approach detailed here represents a unique route to the formation of a heterobimetallic barium cobalt coordination complex.     

The use of charged particle bombardment for studying oxygen self-diffusion in oxides

The various nuclear techniques which have been used to study oxygen self-diffusion in oxides are discussed. Results are given for measurements using resonance capture in the¹⁸O(p, α)¹⁵N and¹⁸O(p, γ)¹⁹F reactions and the different techniques are compared.     

Synthesis of 2,3,9,10,16,17,23,24-Octaalkynylphthalocyanines and the Effects of Concentration and Temperature on Their (1)H NMR Spectra

The syntheses of 3,4- and 4,5-diiodophthalonitriles are described. Coupling of the latter compound with Pd(PPh(3))(2)Cl(2) and 1-octyne, 1-heptyne, 1-hexyne, 1-pentyne, and 3,3-dimethyl-1-butyne gave a series of 4,5-dialkynylphthalonitriles. Hydrogenation of 4,5-bis(1-pentynyl)phthalonitrile and 4,5-bis(3,3-dimethyl-1-butynyl)phthalonitrile gave 4,5-dipentylphthalonitrile and 4,5-bis(3,3-dimethylbutyl)phthalonitriles. Condensation of the dialkynylphthalonitriles with lithium 1-pentoxide in 1-pentanol gave 2,3,9,10,16,17,23,24-octaalkynylphthalocyanines, while intervention of the intermediate dilithium phthalocyanines with zinc acetate gave the related zinc(II) phthalocyanines. (1)H NMR spectroscopy of these octaalkynylphthalocyanines exhibited large chemical shifts (1-2 ppm) of the internal and aromatic protons at concentrations ranging from 10(-)(2) to 10(-)(5) M and at temperatures from 27 to 147 degrees C. The effects of aggregation phenomena are discussed. The importance of reporting concentration and temperature values for NMR spectra of phthalocyanines is stressed.     

Determination of lincomycin and tylosin residues in honey by liquid chromatography/tandem mass spectrometry

A simple and rapid analytical method was developed for the determination of lincomycin and tylosin residues in honey as part of field studies examining the efficacy and target animal safety of these antibiotics to control American foulbrood disease in honey bees. Residues of the antibiotics were determined using liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS). Honey samples were diluted and injected directly into the LC/MS/MS system without additional cleanup by solid-phase extraction or liquid-liquid partitioning. A six-port valve system was utilized to selectively route eluant from the LC column into the mass spectrometer only during a relatively short portion of the chromatographic run corresponding to the elution of the analytes of interest. Minimal contamination of the MS source chamber was observed despite the analysis of large numbers of samples. Using internal standard quantitation, excellent accuracy and precision were obtained with no apparent matrix-to-matrix variation. Based on the analysis of fortified replicates, the mean percent deviation from the theoretical concentration and the percent relative standard deviation were both less than 10% for tylosin over an analytical range of 10-1000 microg/kg. Slightly higher mean percent deviations and relative standard deviations were observed for the analysis of lincomycin in fortified replicate samples. The method detection limits were determined to be 5 and 2 microg/kg for lincomycin and tylosin, respectively.     

Solution-processed anodes from layer-structure materials for high-efficiency polymer light-emitting diodes

The development of low-cost, large-area electronic applications requires the deposition of active materials in simple and inexpensive techniques at room temperature, properties usually associated with polymer films. In this study, we demonstrate the integration of solution-processed inorganic films in light-emitting diodes. The layered transition metal dichalcogenide (LTMDC) films are deposited through Li intercalation and exfoliation in aqueous solution and partially oxidized in an oxygen plasma generator. The chemical composition and thickness of the LTMDC and corresponding transition metal oxide (TMO) films are investigated by X-ray photoelectron spectroscopy. The morphology and topography of the films are studied by atomic force microscopy. X-ray powder diffraction is used to determine the orientation of the LTMDC film. Finally, the LTMDC and their corresponding oxides are utilized as hole-injecting and electron-blocking materials in polymer light-emitting diodes with the general structure ITO/LTMDC/TMO/polyfluorene/Ca/Al. Efficient hole injection and electron blocking by the inorganic layers result in outstanding device performance and high efficiency.     

An evaluation of the mechanism of nitrous acid formation in the urban atmosphere

Nitrous acid (HONO) has been observed to build in the atmosphere of cities during the nighttime hours and it is suspected that photolysis of HONO may be a significant source of HO radicals early in the day. The sources of HONO are poorly understood, making it difficult to account for nighttime HONO formation in photochemical modeling studies of urban atmospheres, such as modeling of urban O₃ formation. This paper reviews the available information on measurements of HONO in the atmosphere and suggest mechanisms of HONO formation. The most extensive atmospheric measurement databases are used to investigate the relations between HONO and potential precursors. Based on these analyses, the nighttime HONO concentrations are found to correlate best with the product of NO, NO₂ and H₂O concentrations, or possibly the NO, NO₂, H₂O, and aerosol concentrations. A new mechanism for nighttime HONO formation is proposed that is consistent with this precursor relationship, namely, reaction of N₂O₃ with moist aerosols (or other surfaces) to form two HONO molecules. Theoretical considerations of the equilibrium constant for N₂O₃ formation and the theory of gas-particle reactions show that the proposed reaction is a plausible candidate for HONO formation in urban atmospheres. For photochemical modeling purposes, a relation is derived in terms of gas phase species only (i.e., excluding the aerosol concentration): NO + NO₂ + H₂O → 2 HONO with a rate constant of 1.68 x 10^-17 e^6348/T (ppm^-2 min^-1). This rate constant is based on an analysis of ambient measurements of HONO, NO, NO₂ and H₂O, with a temperature dependence from the equilibrium constant for formation of N₂O₃. Photochemical grid modeling is used to investigate the effects of this relation on simulated HONO and O₃ concentrations in Los Angeles, and the results are compared to two alternative sources of nighttime HONO that have been used by modelers. Modeling results show that the proposed relation results in HONO concentrations consistent with ambient measurements. Furthermore, the relation represents a conservative modeling approach because HONO production is effectively confined to the model surface layers in the nighttime hours, the time and place for which ambient data exist to show that HONO formation occurs. The empirical relation derived here should provide a useful tool for modelers until such time as knowledge of the HONO forming mechanisms has improved and more quantitative relations can be derived.     

A Quantum Chemical Study of the Abnormal Reactivity of 2‐Methoxyfuran

The gas‐phase pyrolytic and oxidative chemistry of furans has received much attention recently because of their potential as platform chemicals and biofuels. Typically these compounds exhibit very strong ring carbon to H or CH₃ bonds. 2‐Methoxyfuran had been reported to be exceptionally unstable in comparison to related substituted heterocycles in pyrolytic experiments. The origins of its reactivity are shown to be due to the very weak O–CH₃, which at 189.5 ± 1.9 kJ mol^?1 is some 200 kJ mol^?1 weaker than C–H bonds in the molecule. We show that the reported reactivity is somewhat overestimated but that does not alter the fact that 2‐methoxyfuran is exceptionally unstable. It may prove to be a useful alternative to azomethane as a thermal source of methyl radicals.