Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis

Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β^2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis.     

A volatolomic approach using cerumen as biofluid to diagnose bovine intoxication by Stryphnodendron rotundifolium

An innovative volatolomic approach employs the detection of biomarkers present in cerumen (earwax) to identify cattle intoxication by Stryphnodendron rotundifolium Mart., Fabaceae (popularly known as barbatimão). S. rotundifolium is a poisonous plant with the toxic compound undefined and widely distributed throughout the Brazilian territory. Cerumen samples from cattle of two local Brazilian breeds (‘Curraleiro Pé-Duro’ and ‘Pantaneiro’) were collected during an experimental intoxication protocol and analyzed using headspace (HS)/GC–MS followed by multivariate analysis (genetic algorithm for a partial least squares, cluster analysis, and classification and regression trees). A total of 106 volatile organic metabolites were identified in the cerumen samples of bovines. The intoxication by S. rotundifolium influenced the cerumen volatolomic profile of the bovines throughout the intoxication protocol. In this way, it was possible to detect biomarkers for cattle intoxication. Among the biomarkers, 2-octyldecanol and 9-tetradecen-1-ol were able to discriminate all samples between intoxicated and nonintoxicated bovines. The cattle intoxication diagnosis by S. rotundifolium was accomplished by applying the cerumen analysis using HS/GC–MS, in an easy, accurate, and noninvasive way. Thus, the proposed bioanalytical chromatography protocol is a useful tool in veterinary applications to determine this kind of intoxication.     

Supercritical CO2 as a superior solvent for the cyclization of diallylmalonate catalyzed by palladium-containing zeolites

Palladium-containing zeolites catalyze the cycloisomerization of diethyl diallylmalonate to dimethylcyclopentenes. When the reaction is carried out in toluene, the performance of the palladium catalyst depends on the pore size of the zeolites. At 60 °C, palladium adsorbed on large pore size Beta zeolite (pore size ∼7.4 Å) is more active than medium pore size ZSM-5 (pore size ∼5.4 Å). This lower activity of ZSM-5 compared to Beta is attributable to the restricted diffusion of reagent and products through the ZSM-5 channels as compared to Beta zeolite. However, due to the gas-like diffusion characteristic of the supercritical state, the activity of ZSM-5 increases and becomes identical to that of Beta zeolite using supercritical CO₂ as medium.     

A versatile protocol for the preparation of substituted 1- and 2-naphthyl piperazines from aminonaphthols

Aminonaphthols are easily transformed into a variety of 1- and 2-naphthyl piperazines using a sequence of diazotization, iodide substitution and Pd(0) catalyzed coupling reactions.     

Predicting automobile claims bodily injury severity with sequential ordered logit models

Despite the large cost of bodily injury (BI) claims in motor insurance, relatively little research has been done in this area. Many companies estimate (and therefore reserve) bodily injury compensation directly from initial medical reports. This practice may underestimate the final cost, because the severity is often assessed during the recovery period. Since the evaluation of this severity is often only qualitative, in this paper we apply an ordered multiple choice model at different moments in the life of a claim reported to an insurance company. We assume that the information available to the insurer does not flow continuously, because it is obtained at different stages. Using a real data set, we show that the application of sequential ordered logit models leads to a significant improvement in the prediction of the BI severity level, compared to the subjective classification that is used in practice. We also show that these results could improve the insurer’s reserves notably.     

Internal standardization for the determination of cadmium,cobalt, chromium and manganese in saline produced water from petroleum industry by inductively coupled plasma optical emission spectrometry after cloud point extraction

In the present paper a procedure is proposed for the determination of traces of Cd, Co, Mn and Cr in petroleum industry produced water by inductively coupled plasma optical emission spectrometry. The procedure is based on cloud point extraction of these metals, as their dithizonate complexes, into the surfactant-rich phase of octylphenoxypolyethoxyethanol surfactant (Triton X-114). Extractions were carried out in solutions with salinities between 10‰ and 70‰. Since residual salinity in the surfactant-rich phase caused differences in its transport to the plasma, yttrium was used as an internal standard to correct for this effect. The simultaneous metal extraction procedure was optimized by response surface methodology using a Doehlert design and desirability function. Enhancement factors of 21, 21, 9 and 19, along with limits of quantification of 0.093, 0.20, 0.73 and 1.2 μg L^− 1, and precision expressed as relative standard deviation (n = 8, 20.0 μg L^− 1) of 5.8, 1.2, 1.7 and 5.7% were obtained for Cd, Co, Mn and Cr, respectively. The accuracy was evaluated by spike recovery tests on the high salinity water samples with salinity of 40 and 63‰.     

Left, right, and inner socles of associative systems

We investigate the basic properties of the different socles that can be considered in not necessarily semiprime associative systems. Among other things, we show that the socle defined as the sum of minimal (or minimal and trivial) inner ideals is always an ideal. When trivial inner ideals are included, this inner socle contains the socles defined in terms of minimal left or right ideals. This revised version was published online in June 2006 with corrections to the Cover Date.     

X-ray diffraction study of some mesogenic copper, nickel and vanadyl complexes

We present a comparative study of various metallomesogenic complexes, using X-ray diffraction methods. For a given ligand linked to different metal atoms (Cu, Ni, VO), the nature of this central atom influences mainly the magnetic susceptibilities of the mesophases. With different ligands, which keep the close neighbourhood of the metal atom unchanged, the apparent length of the mesogenic unit is longer for short ligands than for longer ones. This unexpected behaviour is qualitatively well explained by taking into account the global shape of the different complexes.     

The prediction of coal properties using compressed infrared data from osculating polynomials

Reduction of the representation of infrared spectra from coal samples by osculating polynomials of degree nine is discussed. The reduced representation contains polynomial coefficients of order zero to four. Mathematical models of the original spectra are obtained by linear combination of the coefficients. These compressed models are statistically correlated to coal properties, namely, volatile matter, fixed carbon, ash content, heating value, hydrogen, carbon, sulphur, nitrogen, and maximum vitrinite reflectance, and the results are compared with those previously obtained from second derivatives of the same spectra. The use of compressed data, while giving slightly better correlations for some of the properties, has the advantage of requiring less computational time.