Optimized conditions for hydrocarbon group type analysis of base oils by thin-layer chromatography-flame ionisation detection

The results of research on the optimization of the thin-layer chromatography-flame ionisation detection for the determination of group composition of natural base oils, including separation of the aromatics into subgroups, are presented. Neutral base oils obtained in several steps of refining from vacuum distillation petroleum fractions are the most difficult to analyze by hydrocarbon group type analysis (HGTA) because of the high content of aliphatic fragments in their molecules. Factors affecting the accuracy and precision of the results were identified. The paper presents the analytical procedure, including two different calibration methods, as well as the results of studies on the reproducibility of HGTA of typical base oils of different viscosity classes under the optimized conditions. The same conditions were found suitable for HGTA of other high-boiling petroleum fractions by TLC with flame ionisation detection. The paper also introduces a new procedure for reproducible determination of polar fractions in base oils utilizing solid-phase extraction columns, and presents a corrected procedure for the determination of saturated compounds and aromatics (mono-, bi- and polycyclic) in base oils by column liquid chromatography.     

Facts and artifacts about aromatic stability estimation

The stability of a set of 105 five-membered π-electron systems (involving aromatic, non-aromatic and anti-aromatic species) was evaluated using six isodesmic reactions of which two belong to the subclass of homodesmotic reactions, which are based on cyclic and acyclic reference systems. We demonstrate that the ‘Resonance Energies’ derived from isodesmotic schemes have obvious flaws and do not correct or cancel other contributions to the energy, such as the changes of hybridization, homoconjugation of heterosubstituted cyclopentadienes, conjugative interactions of CC or CX (X=N or P) with a π or pseudo π orbital at Y (Y=O, S, NH, PH), strain, etc. as effectively as possible. Likewise, ‘aromatic stabilization energies (ASE)’ derived from homodesmotic schemes based on the acyclic reference compounds do not give satisfactory results. We strongly recommend that only cyclic reference compounds should be used for ASE and other aromaticity evaluations. The analysis is based on ab initio optimized geometries at B3LYP/6-311+G^∗∗.     

Carrier influence on the paramagnetic and catalytic properties of supported titanium complexes

Alumina-silica possessing various Al₂O₃/SiO₂ ratios was used as a carrier of surface titanium complexes. The systems obtained were examined as models for the investigation of the macroligand (inorganic gel) influence on the physicochemical properties of supported transition metal complexes. The titanium complexes were prepared first by the reaction of CpTiCl₃, with the hydroxyl groups of the gel and then reduced by an excess of BuLi. The influence was established of the basic gel properties on: (a) the amount of titanium(IV) and titanium(III) complexes on the alumina-silica gel surfaces; (b) the symmetry of the surface Ti^III surface complexes; (c) the electron density around the surface-Ti^III ions, ionic or covalent bonds character in a complex; and (d) the catalytic activity in olefin hydrogenation.     

Complexes of carbonyl compounds with RnAIX3n compounds : IV. The evidence for the formation of cyclic complexes chloroaluminium compounds

Reasonably stable 1 : 2 complexes are formed by carbonyl compounds with chloroaluminium compounds, usually in equilibrium with a 1: 1 complex, however with trimethylaluminium only a 1 : 1 complex is formed. In the case of complexes with an excess of MeAlCl₂, a disproportionation reaction occurs. Possible structures are discussed in light of PMR and IR spectroscopy, dipole moments and molecular weight determination. The previously proposed cyclic six-membered ring is the most reliable structure for the 1 : 2 complex.     

Carbon-13 kinetic isotope effect of the decarbonylation of oxalic acid

Carbon-13 intramolecular kinetic isotope effects in the decarbonylation of oxalic acid dihydrate of natural isotopic composition by SO₃ and by fuming sulphuric acid at room temperature and decarbonylation of oxalic acid dihydrate by 100% H₃PO₄ in the temperature interval 80–150°C have been determined. The obtained isotopic and kinetic results have been compared with the earlier¹³C experimental and theoretical studies in other solvents.     

Investigations of aromatic polyesters with polynaphthalene systems in the main chain—VI: NMR studies of the structure of the aromatic copolyesters

Nuclear magnetic resonance spectra of several kinds of terephthalic copolyesters of 4,4′dihydroxydinaphthyl 1,1′ and 2,2 bis(4-hydroxyphenyl) propane were recorded. Proton signals of the terephthalic acid unit corresponding to heterolinkages and homolinkages could be observed in the range from 8.23 to 8.53 ppm. The average sequence lengths and the degrees of randomness in the copolyesters were calculated from the intensities of these signals.     

Conformational equilibria and photoinduced tautomerization in 2-(2′-pyridyl)pyrrole

Depending on the polarity and protic abilities of the solvent, 2-(2′-pyridyl)pyrrole can exist in either syn or anti rotameric forms. In nonpolar solvents, intramolecular excited state single proton transfer is observed, manifested by the appearance of low-energy tautomeric emission. The solvent-assisted excited state double proton transfer reaction is also detected. DFT calculations confirm low barriers for both single and double proton transfer processes in the lowest excited singlet state and show different character of the tautomerization in both cases: in the intramolecular reaction, mutual approach of two nitrogen atoms plays an important role.     

The analysis of the zero-order and the second derivative spectra of retinol acetate, tocopherol acetate and coenzyme Q10 and estimation of their analytical usefulness for their simultaneous determination in synthetic mixtures and pharmaceuticals

The aim of the present work was to develop a simple and rapid method of retinol acetate, tocopherol acetate and coenzyme Q(10) determination in pharmaceuticals without involving any preparation operations like separation or masking. The values of second derivative amplitude at 212 nm for tocopherol, 351 nm for retinol and 222 nm for coenzyme were used for construction of calibration graphs. Beer's law is obeyed in the concentration range 0.5-20, 0.5-7.5 and 0.5-30 microg ml(-1) for retinol acetate, tocopherol acetate and coenzyme, respectively. The elaborated procedures were successfully applied to the simultaneous determination of studied compounds in their binary synthetic mixtures and in commercial preparations with high reliability and repeatability. Spectral properties of retinol acetate allows to determine its contents in ternary mixture which includes Vitamin E and coenzyme Q(10).     

Application of organolithium and related reagents in synthesis,Part XII. Synthesis of phenyl- and pyridylpyridopyridazinones and their derivatives

Summary The preparation of the pyridazinones10a,10b,11a,11b, and12a,12b from the ketoamides7,8, and9 and hydrazine hydrate is described. It was found that from ketoamides8b and9b in addition to the expected pyridopyridazinones11b and12b also aminopyridopyridazines14 and15 were formed and that ketoamide7b gave exclusively aminopyridopyridazine13. The pyridopyridazinones10b,11b, and12b were alkylated with alkyl iodides.

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Anwendungen von Organolithium und verwandten Reagenzien in organischen Synthesen, Teil XII. Synthese von Phenyl- und Pyridylpyridopyridazinonen und ihren Derivaten

Zusammenfassung Die Darstellung der Pyridazinone10a,10b,11a,11b und12a,12b aus Ketoamiden7,8 und9 und Hydrazinhydrat wird beschrieben. Es wurde festgestellt, daß aus Ketoamiden8b und9b außer den erwarteten Pyridopyridazinonen11b und12b auch Aminopyridopyridazine14 und15 enstanden und daß das Ketoamid7b ausschließlich ins Aminopyridopyridazin13 überführt wurde. Die Pyridopyridazinone10b,11b und12b wurden mit Alkyljodiden alkyliert.

     

Electrochemical grafting by reduction of 4-aminoethylbenzenediazonium salt: Application to the immobilization of (bio)molecules

We propose in this study a simple and rapid way to produce stable amino-derivatized conductive surfaces for the subsequent immobilization of (bio)molecules. This was achieved through the use of (4-aminoethyl)benzenediazonium salt (AEBD), which was immobilized on glassy carbon and gold electrodes by its electrochemical reduction. The presence of terminal grafted amino functions was evidenced with XPS by analyzing N1s core level. Besides this conventional surface characterisation, an electrochemical strategy is proposed here to evidence the presence of immobilized amines, in which the chemical reactivity of amines towards 2,4,6-trinitrobenzenesulfonic acid (TNBS) is used. Surface-bound TNBS served as an electrochemical marker and was detected by cyclic voltammetry. Additionally, pre-modified gold electrodes with amino functions can be derivatized with biomolecules such as glutathione (GSH). Glutathione attachment was evidenced by studying the electrochemical behaviour of ferri/ferrocyanide redox before and after its immobilization. The functionalized electrodes were then used for the detection of copper ions in neutral aqueous solutions.