The effect of ring substitution on the O-neophyl rearrangement of 1,1-diarylalkoxyl radicals. A product and time-resolved kinetic study

[reaction: see text] A product and time-resolved kinetic study of the effect of ring substitution on the reactivity of 1,1-diarylalkoxyl radicals has been carried out. The radicals undergo an O-neophyl shift to give the isomeric 1-aryl-1-aryloxyalkyl radicals from which the corresponding aromatic ketones are formed. The rearrangement rate constants are influenced by ring substitution, increasing in the presence of electron-withdrawing substituents and decreasing in the presence of electron-donating ones. From the results of product and kinetic studies, the following migratory aptitudes have been obtained: 4-trifluoromethylphenyl > phenyl approximately = 4-methylphenyl > 4-methoxyphenyl. Excellent Hammett-type correlations between the sigma+ substituent constants and both the visible absorption band maxima and the rearrangement rate constants have been obtained. The experimental results indicate that the rearrangement is governed by electronic effects in the starting 1,1-diarylalkoxyl radicals, whereas the stability of the rearranged carbon-centered radical plays a minor role, in line with a reactant-like transition state, strongly supporting the hypothesis that the O-neophyl rearrangement of 1,1-diarylalkoxyl radicals proceeds through a concerted mechanism.     

Complex formation between phytic acid and divalent metal ions: a solution equilibria and solid state investigation

An investigation on the complex formation equilibria between divalent metal ions Me (with Me=Mn, Co, Ni, Cu, Cd, and Pb) and phytic acid (H(12)L) is presented. Experiments were performed through a potentiometric methodology by measuring, at 25 degrees C, the proton and, in some cases (Cu(2+), Cd(2+), and Pb(2+)), also the metal ion activity at equilibrium in solutions containing, besides the metal and the ligand, 3 M NaClO(4) as the ionic medium. Unhydrolyzed solutions of the metal ion at millimolar concentration levels were titrated with solutions of about 10 mM sodium phytate, until the formation of a solid phase took place (always at pH approximately 2.5, except in the case of Cu(2+), which formed soluble complexes up to pH approximately 3.3). Coulometry was employed to produce very dilute solutions of either Cu(2+), Cd(2+), or Pb(2+) of accurately known composition. The emf data were explained by assuming, in the acidity interval explored, the formation of the complexes of general stoichiometry MeH(5)L(5-) and Me(2)H(3)L(5-). Coordination compounds in the solid state were also synthesized and characterized by elemental analysis, thermal analysis, and ICP spectroscopy. The solids had a general stoichiometry Me(6)H (t)LCl (t). x H(2)O, with the following t and x values for each metal investigated: Me ( t; x) = Mn (4; 2); Co (4; 2); Ni (4; 2); Cu (2; 2.5); Zn (2; 1); Sn (6; 6).     

The mobility and ion structure of protonated aminoazoles

The reduced mobility of protonated pyrazole derivatives was measured by ion mobility spectrometry (IMS) in air, nitrogen, and carbon dioxide, at temperatures between 150 and 250°C. It was found that the mobility of protonated 5-amino-1-phenylpyrazole was higher than that of its 3- and 4-isomers. This was attributed to the fact that in the 5-isomer the preferred site of protonation is on the endocyclic nitrogen, which leads to delocalization of the ionic charge, and thus to a diminished interaction with the drift gas molecules. On the other hand, protonated 5-amino-1-methylpyrazole has a slightly lower mobility than its isomers, which is indicative of a different protonation mechanism.     

Arcs of discrete dynamics and constants of motion

A theorem is proved which may relate the attractors of families of dissipative discrete-time dynamical systems to certain closed orbits of conservative systems. The result is illustrated by an example taken from dynamics defined by mappings.     

Transesterification of Waste Frying Oil and Soybean Oil by <Emphasis Type="Italic">Combi</Emphasis>-<Emphasis Type="Italic">lipases</Emphasis> Under Ultrasound-Assisted Reactions

This work describes the use of an ultrasound system for the enzymatic transesterification of oils using combi-lipases as biocatalyst. The reactions were carried out evaluating the individual use of waste oil and fresh soybean oil, and the immobilized lipases CALB, TLL, and RML were used as biocatalysts. It was performed in a mixture design of three factors to obtain the ideal mixture of lipases according to the composition of fatty acids present in each oil, and the main reaction variables were optimized. After 18 h of reaction, ultrasound provided a biodiesel yield of about 90% when using soybean oil and 70% using the waste oil. The results showed that ultrasound technology, in combination with the application of enzyme mixtures, known as combi-lipases, and the use of waste oil, could be a promising route to reduce the overall process costs of enzymatic production of biodiesel.     

Determination of Pesticides in the Respirable Fraction of Airborne Particulate Matter by High-performance Liquid Chromatography–Tandem Mass Spectrometry

Potential harmful effects of pesticides include risks to human health of workers involved in the wet spray application in cultivated areas. Inhalation exposure depends on several factors including pesticide concentrations in the respirable fraction of airborne particulate matter (PM₄). To ensure a high level of protection, the use of tractors with cabins provides protection against dust, aerosols, and vapors. Since tractors not providing maximum protection are still in use, PM₄ was sampled during spreading operations in agricultural fields inside and outside tractor cabins. Sample preparation technique based on accelerated solvent extraction and solid-phase extraction cleanup was optimized before analysis of nine pesticides in PM₄. Meptyldinocap, deltamethrin, myclobutanil, fluopyram, methoxyfenozide, dimethomorph, fluopicolide, cyflufenamid, and metrafenone were simultaneously determined by high-performance liquid chromatography–electrospray ionization–tandem mass spectrometry (HPLC–ESI–MS–MS). The results demonstrated the efficacy of the tractor cabs used in the sampling sites.     

Chiral Stationary Phases Based on Small Molecules: An Update of the Last 17 Years

A literature survey covering the report on Pirkle-type chiral stationary phases (CSPs) from January 2000 to March 2017 is presented in this review. More than 200 CSPs comprising small molecules as chiral selectors covalently bound to the chromatographic support have been reported in this period. The chemical nature of these new chiral selectors, new insights into the development strategies and their applications in liquid chromatography were emphasized.     

Pharmacokinetic measurements of IDN 5390 using electrospray ionization tandem mass spectrometry: structure characterization and quantification in dog plasma

In this report, electrospray ionization tandem mass spectrometry (ESI-MS/MS) for a pharmacokinetic study of IDN 5390, a novel C-seco taxane derivative, which is under preclinical evaluation, has been investigated. Our results showed that IDN 5390 and other taxanes including paclitaxel and IDN 5109 could ionize well in not only positive-, but also in negative-ion mode. Under collision-induced dissociation (CID) conditions, these compounds could fragment into similar M- (molecular), T- (taxane ring) and S- (side chain) series ions. In positive-ion ESI, the formation of both T- and S-series ions involved the breaking of the C-13 ester bond. In negative-ion ESI, however, while the formation mechanism of S-series ions remained the same, the breaking of the C-1' carboxylic ester bond resulted in T-series ions. At optimum collision energy (CE) values, M-, T- and S-series ions of IDN 5390 in both positive- and negative-ion ESI-MS/MS spectra had good intensity. This phenomenon makes both positive- and negative-ion ESI-MS/MS good methods for IDN 5390 metabolite structural characterization, i.e. to reveal the location of modification groups in IDN 5390 metabolites versus IDN 5390 either on the side chain or the taxane ring. A liquid chromatography (LC)/ESI-MS/MS method using the multiple-reaction monitoring (MRM) technique was thereafter developed to quantify IDN 5390 in dog plasma using paclitaxel as internal standard. The method was validated using a concentration range between 5 and 1000 ng/mL and had a limit of detection of 1 ng/mL. The inter-day %CV (%coefficient of variation) of the calibration standards ranged between 4.36 and 9.64%, the intra-day %CV of the calibration standards between 0.61 and 13.44%, and the mean % accuracy of the quality control samples at the low, middle and high end of the concentration curves were 12.5, 6.8 and 9.6%, respectively.     

[3]Pseudorotaxanes based on the cryptand/monopyridinium salt recognition motif

The first cryptand/monopyridinium salt [3]pseudorotaxanes were prepared from two cryptand hosts and two bispyridinium guests as confirmed by proton NMR characterization, electrospray ionization mass spectrometry, and X-ray analysis. It was found that the two monopyridinium binding sites are independent of each other for the formation of one [3]pseudorotaxane.     

Wheat lipids to discriminate species, varieties, geographical origins and crop years

The knowledge of lipid components of wheat finds a precious information in order to differentiate between Triticum durum (TD) and Triticum aestivum (TA). The determination of the percentages of methyl esters of the differently unsaturated fatty acids with 18-carbon atoms (C₁₈), of sterol fraction and of the other components is of particular weight. In this paper, the classification methods of linear discriminant analysis (LDA) and quadratic discriminant analysis (QDA) were applied in order to measure the classification and prediction abilities of the determined (percentages of the) components of the lipid fraction of wheat in differentiating among species, origins, varieties and crops. By univariate feature selection method (Fisher weights (FW)) and linear discriminant analysis, it was found that the only oleate is able to distinguish between the two species with a prediction rate of 100%. Inside the species Triticum durum, it was obtained a prediction rate of 83.9% while discriminating between the different origins, a prediction rate of 82.2% while discriminating among varieties and a prediction rate of 94.3% among crop years.