Solvent-dependent oxidations of 5- and 6-azaindoles to trioxopyrrolopyridines and functionalised azaindoles

A regioselective synthesis of 4,7-dimethoxy 5- and 6-azaindoles 2 has been achieved, based on the appropriate choice of ortho-directing or ortho-repulsing groups in the formylation of a pyridine ring. Studies on the regioselectivity of the formylation step and on the preparation of azidoacrylate intermediates 4 are described in this paper. The reactivity of the 5- and 6-azaindole structures towards BBr3-mediated selective monodemethylation and oxidative demethylation reactions were also investigated. The regioselectivity of the deprotection was confirmed using a chemical approach. Oxidation reactions were then carried out on either dimethoxy- or hydroxymethoxyazaindoles, in different solvents, using [bis(trifluoroacetoxy)iodo]benzene. In acetonitrile-water, trioxopyrrolopyridines 12 were obtained, whereas the formation of functionalised azaindoles 17 was observed in acetonitrile-methanol. The tautomeric structure of the trioxopyrrolopyridines was proved by X-ray diffraction analysis.     

Numerical simulations of a transport-aircraft configuration

An implicit low-cost Navier–Stokes solver combined with a multigrid algorithm and wall functions has been developed for efficient numerical simulations on a realistic wing-body aircraft configuration. A study of the behaviour of different transport-equation turbulence models is given. Comparisons are made with experimental data. The structure of the three-dimensional flow separation predicted by computations is described and its topological coherence is checked.     

Early contrast enhancement of the liver: exact description of subphases using MRI

Purpose

The purpose of this study was to describe the subphases of early post-contrast enhancement of the liver, using vessel enhancement patterns, and correlate these findings with enhancement patterns of abdominal organs.

Materials and Methods

A total of 114 patients who underwent gadolinium-enhanced abdominal magnetic resonance imaging examinations constituted the final study group, of which 56 were women (age range, 3–94 years; mean, 50 years) and 58 were men (age range, 6–85 years; mean, 54 years). Early post-contrast sequences in all patients were evaluated retrospectively by two reviewers for the determination of the presence of contrast enhancement in predetermined major vessels of the abdomen and qualitative and quantitative extent of enhancement of the renal cortex, spleen, pancreas and liver. Based on the overall findings, subphases of early contrast enhancement of the liver were described and quantitative extent of enhancement of organs was correlated with subphases of early contrast enhancement of the liver. Mann–Whitney U test and one-way unbalanced analysis of variance tests were used for the comparisons.

Results

Early hepatic arterial phase was observed in 14/114 patients, mid-hepatic arterial phase in 23/114 patients, late hepatic arterial phase in 33/114 patients, splenic vein only hepatic arterial dominant phase in 20/114 patients and hepatic arterial dominant phase in 24/114 patients. There was an overall association between the subphases of enhancement and the quantitative extent of enhancement for all studied organs (P<.0001).

Conclusion

The evaluation of vessel and organ enhancement patterns has allowed the characterization of five different subphases in early post-contrast enhancement of the liver. The quantitative extent of enhancement of abdominal organs also demonstrated significant correlation with these five subphases.     

Standard dilution analysis of beverages by microwave-induced plasma optical emission spectrometry

In this work, standard dilution analysis (SDA) is combined with microwave-induced plasma optical emission spectrometry (MIP OES) to determine seven elements in coffee, green tea, energy drink, beer, whiskey and cachaça (Brazilian hard liquor). No sample preparation other than simple dilution in HNO₃ 1% v v⁻¹ is required. Due to relatively low plasma temperatures, matrix effects may compromise accuracies in MIP OES analyzes of complex samples. The method of standard additions (SA) offers enhanced accuracies, but is time-consuming and labor intensive. SDA offers a simpler, faster approach, with improved accuracies for complex matrices. In this work, SDA's efficiency is evaluated by spike experiments, and the results are compared to the traditional methods of external calibration (EC), internal standard (IS), and standard additions (SA). SDA is comparable to the traditional calibration methods, and it provides superior accuracies for applications involving ethanol-containing beverage samples. The SDA-MIP OES procedure is effective. Using only two calibration solutions, it may be easily automated for accurate and high sample throughput routine applications.     

CHEMILUMINESCENCE OF SOYBEAN SEEDS: SPECTRAL ANALYSIS, TEMPERATURE DEPENDENCE AND EFFECT OF INHIBITORS

Abstract— The spontaneous light emission of soybean seeds is enhanced 4–8 times during the first minute after water imbibition. Other solvents are also effective. The temperature dependence of soybean chemiluminescence identifies two reactions with activation energies of 20 and 68 kJ/mol corresponding to the lipoxygenase reaction and to the autoxidation of unsaturated fatty acids, respectively. Free radical scavengers and lipoxygenase inhibitors decrease soybean photoemission. The singlet oxygen probe 1,4-diazabicyclo-[2,2,2]-octane (DABCO) increases soybean photoemission. The emission spectra of soybean seeds under a variety of conditions show bands between 450 and 720 nm with 50–70% of the emission over 600 nm. The experimental evidence is consistent with singlet oxygen being one of the emitting species, however, due to the complexity of the system it is likely that other chemiluminescent species are also formed.     

Uncommon behavior of the p-GaAs electrode during the reduction of oxygen in liquid acidic ammonia

In liquid acidic ammonia, the mechanism of oxygen reduction begins as in acidic aqueous solutions, by the successive contribution of the conduction band and then of the valence band (doubling effect). However, unlike in the acidic aqueous solutions, soon after the oxygen photoreduction, an activation process of the p-GaAs surface is initiated, tied to the presence of protons in the solution. This activation of the surface allows the passage from a reduction mechanism via a conduction band to a reduction mechanism via a valence band (oxygen reduction in the dark).     

Determination of metals in used lubricating oils by AAS using emulsified samples

An efficient method was developed for the determination of metals in used lubricating oils, by atomic absorption spectrometry. Oil samples were treated with an acid mixture and then emulsified in water (10% w/w) using ethoxy nonylphenol (6% w/w) as surfactant. Emulsion characteristics (oil, surfactant content and acid mixture) were optimized to obtain the best AAS signal. Good agreement was found between calibration curves of aqueous and emulsified standard solutions when a peristaltic pump was used to introduce the solutions into the flame. The emulsion methodology was comparable, within 95% of confidence, to traditional ashing methodologies when a standard reference oil and a used lubricating oil were analyzed. Precision between 0.4 and 5% RSD was obtained when real sample was analyzed using emulsions.     

The conformal anomaly associated with an operator product acting in rank 1 symmetric spaces

The conformal anomaly and a contribution to the one-loop effective action associated with the product of the Laplace operators , p=1,2 acting in irreducible rank 1 symmetric spaces are calculated. The explicit form of the zeta functions and the conformal anomaly of the stress-energy momentum tensor is derived. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 3, 166–171 (10 February 1998) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Uniform molecular analysis using femtosecond laser mass spectrometry

The potential of femtosecond laser time-of-flight mass spectrometry (FLMS) for uniform quantitative analysis of molecules has been investigated. Various samples of molecular gases and vapours have been studied, using ultra-fast ( approximately 50 fs) laser pulses with very high intensity (up to 1.6 x 10(16) Wcm(-2)) for non-resonant multiphoton ionisation/tunnel ionisation. Some of these molecules have high ionisation potentials, requiring up to ten photons for non-resonant ionisation. The relative sensitivity factors (RSF) have been determined as a function of the laser intensity and it has been demonstrated that for molecules with very different masses and ionisation potentials, uniform ionisation has been achieved at the highest laser intensities. Quantitative laser mass spectrometry of molecules is therefore a distinct possibility. Copyright 1999 John Wiley & Sons, Ltd.