Acyl migration from N to C in aziridine-2-carboxylic esters

Acyl group migration from N to C in aziridine-2-carboxylates takes place in deprotonation reactions and, as a result, aziridine-2,2-dicarboxylates are formed. Mechanistic studies proved that the observed migration is an intramolecular reaction.     

A parametrization of matrix conjugacy orbit sets as unions of affine planes

The problem of finding a canonical form of complex matrices up to conjugacy with the set of canonical matrices being a union of affine planes in the matrix space is considered. A solution of the problem is given.     

Facile synthesis of coumarin bioisosteres—1,2-benzoxathiine 2,2-dioxides

A simple and reproducible procedure for the synthesis of bioisosteres of coumarin—1,2-benzoxathiine 2,2-dioxide is presented. The developed method is based on the intramolecular aldol cyclization of derivatives of mesylsalicyl aldehydes in the presence of strong organic bases, where best results were obtained with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). It has been shown that depending on the nature of the substituent in the aromatic ring, intermediate aldol adducts (3,4-dihydro-1,2-benzoxathiin-4-ol 2,2-dioxides) in different ratios with title compound are formed. Dehydration of the intermediate aldols with POCl₃ led to full conversion into 1,2-benzoxathiine 2,2-dioxide derivatives. The scaffold of 1,2-benzoxathiine 2,2-dioxide is unequivocally proven by a single-crystal X-ray structure.     

Effect of light polarization on holographic recording in glassy azocompounds and chalcogenides

Light polarization effects on a holographic grating recording in a glassy chalcogenide a-As₄₀S₁₅Se₄₅ film has been experimentally studied and compared with previously studied glassy molecular azobenzene film 8a at 633, using s − s,p − p, CE-1 and CE-2 circular-elliptic recording-beam polarizations (differing by light electric field rotation directions). The azocompound exhibited much higher self-diffraction efficiency (SDE) and diffraction efficiency whereas chalcogenide was more sensitive. Their recording efficiency polarization dependences also were different. SDE up to 45% was achieved in 8a with p − p and up to 2.6% in a-As₄₀S₁₅Se₄₅ with CE-2 polarized recording beams. The polarization changes in the diffraction process were studied as well in these and other materials (11, 16, 19 and a-As₂S₃ film, LiTaO₃:Fe crystal). It was found that light polarization changes in the process of diffraction from gratings recorded vectorially by s−p polarizations depended on chemical composition, wavelength, and exposure time. Vector gratings with SDE up to 25% were recorded in 8a, rotating a linear polarization by 90°. No light polarization changes were found in azobenzene 19 and chalcogenide films and in LiTaO₃:Fe crystal, thus showing a vector recording of scalar holograms. The recording mechanisms in azocompounds and chalcogenides are discussed and compared.     

Point defects related to 260 K thermostimulated luminescence in α-Al2O3

Abstract

Thermo- and photostimulated processes are studied in reduced hydrogen containing α-Al₂O₃ excited by UV light. It is found that UV excitation in F absorption band at 90 K results in a ionization of the F-centers and capture of released electrons at defects thus producing an anisotropy absorption band at 4.2 eV and the dominant thermoluminescence (TL) peak at 260 K. The 260 K TSL peak is accompanied by complete bleaching of the 4.2 eV absorption band and vice versa—by light stimulation in the region of the 4.2 eV band the 260 K TSL peak disappear and released electrons recombine with F⁺-centers. Both the effect of the preliminary high-temperature thermal treatment of samples on formation of 4.2 eV-centers and the observed dichroism characteristics allows to conclude that corresponding complex defect contains hydrogen and can involve vacancy pair.     

Defect assisted intrinsic luminescence in Al2O3 crystals

Abstract

The origin of the luminescence bands at 7.5 eV anv 3.8 eV appearing additionaly to the luminescence of F- and F⁺- centres in pure Al₂O₃ are investigated. The time - resolved luminescence spectra, absorption and luminescence excitation spectra as well as trap spectroscopy data depending on deviation from the stochiometry of crystals are discussed in terms of self - trapping of excitons in two configurations. The role of defects due to annihilation of excitons is considered.     

Modified Baby Milk—Bioelements Composition and Toxic Elements Contamination

Breast milk has the most suitable composition for the proper development in the first year of a child’s life. However, it is often replaced with artificial milk. The aim of the study was to analyze the composition of essential elements: Na, K, Ca, P, Mg, Fe, Zn, Cu, and Mn as well as toxic elements: Ni, Pb, Sr, Li, and In in 18 formulas available in Poland. The daily supply was also estimated. The study was performed by Inductively Coupled Plasma Optical Emission Spectrometry method. The results showed the presence of all essential elements tested, but the content of P and Mn significantly differed from the concentrations declared. Such discrepancies can have significant impact on the daily dose of the bioelements taken. However, the content of elements was within the reference standards established by the EU Directive with exception of P, the amount of which exceeded the norms 5.23–18.80-times. Daily supply of P in tested milk as well as Fe and Mn provided with first and hypoallergenic formula exceeded the adequate intake. Analysis revealed the contamination with harmful elements—Pb, Sr, Li, and In were detected in almost all products. The study confirms the data concerning some discrepancies in composition and the contamination of food and may provide information on the feeding quality of children and estimation of health risk associated with exposure to toxic elements.     

Thermostimulated recombination processes in LiBaF3 crystals

The creation of radiation defects in LiBaF₃ crystals at 10 K and the processes of their thermostimulated recombination are investigated. The methods of optical absorption, thermal bleaching of color centers, thermostimulated luminescence and fractional glow technique are used. The radiation defects anneal in a multi-stage process accompanied with thermo-luminescence at 20, 46, 105, 130, 170, 210 and 270 K. Differences in the optical absorption spectra measured before and after the TSL peaks are obtained and recombination parameters are determined. The TSL peak at 20 K arises from the delocalization of H-centers. The presence of two TSL peaks related to V_K-centers at 105 and 130 K indicates that 60° and 90° migration hops occur.     

Ion diffusion-controlled thermally stimulated processes in x-ray irradiated halide crystals

The ionic and ion diffusion-controlled thermally stimulated relaxation (TSR) processes in CaF₂, BaF₂, LiBaF₃ and KBr crystals were investigated above 290 K by means of the ionic conductivity, ionic thermally stimulated depolarisation current (TSDC) and thermal bleaching techniques. Under a DC field the halide crystals store large ionic space charge. We were able to detect in CaF₂, BaF₂, LiBaF₃ and KBr in the extrinsic ionic conductivity region a series of the ionic defect (the interstitial anion and/or anion vacancies - in fluorides; the cation vacancies - in KBr) release stages: 3-6 wide and overlapping ionic TSDC peaks. The correlated data of the ionic TSDC and the F band thermal show that above 290 K the TSR processes are initiated and controlled by the ionic defect thermal detrapping, migration and interaction with the localised electronic and ionic charges and colour centres. The ion diffusion-controlled TSR processes take place in the above halide crystals.