The cyclodimerisation of 3-methyl-2-butenenitrile

3-Methyl-2-butenenitrile (1) cyclodimerised on treatment with lithium diisopropylamide in dimethoxyethane at temperatures between ?78°C and 0°C to 3-amino-4-cyano-1,5,5-trimethyl-1,3-cyclohexadiene (2) the structure of which was established by acid hydrolysis to the known 4-cyano-1,5,5-trimethyl-1-cyclohexene-3-one (3).     

Sulphur distribution in the products of waste tire pyrolysis

The aim of the presented work was to investigate the distribution of sulphur in tire pyrolysis products as well as the influence of process parameters (temperature and residence time) on sulphur distribution due to environmental concerns. Among modern methods used for waste tire recycling, pyrolysis is one of the most reasonable alternatives meeting current environmental standards. However, waste tire sulphur content can be a potential drawback for pyrolysis products utilisation as fuels. Sulphur is present in tires in different concentrations, depending on the type and age of the tires. Typical sulphur content in tires is about 1.6 mass %. In this paper, the distribution of sulphur in tire pyrolysis products was investigated. Tire pyrolysis yields three different products: liquid, gaseous, and solid residue composed mostly of carbon black (chars). Temperature and residence time are the two most important parameters affecting the yield and composition of the volatile fraction and they are therefore expected to affect the sulphur content in residues. Pyrolysis experiments were carried out in a laboratory pyrolysis reaction unit in the temperature range of 650°C to 750°C at different residence times: 88.6 s, 80.2 s, and 73.9 s. Liquid and solid products were analysed by elemental analysis and the distribution of total sulphur in tire pyrolysis products was calculated.     

Conical parametric scattering of a single extraordinary beam in BaTiO3 crystal

In this paper, the parametric scattering of a single extraordinary polarized beam of laser in BaTiO₃ photorefractive crystal has been investigated experimentally and theoretically. The resulting pattern consists of beam fanning, isotropic ring, and anisotropic one. Among all parts of scattering pattern, isotropic ring has not been studied as much as beam fanning and anisotropic ring, and there still are some differences in reports about it. Therefore, the study has mainly focused on this part. In this experimental configuration, isotropic ring is just visible in positive angles although the other parts of parametric scattering pattern can be visible from behind and in front of the crystal. In addition to steady state pattern in forward and backward directions, its transient behavior with the rotation of crystal has been studied. The results of experiments have been analyzed carefully, and their theoretical explanations have been presented based on the standard theory of parametric scattering in photorefractive crystals. It has been shown that this configuration corresponds to the so called parametric B-process scattering.     

C18 tetraynoic fatty acids and essential oil composition of Mkilua fragrans

The fatty acids 17,18-dihydroxyoctadeca-9,11,13,15-tetraynoic acid (mkiluaynoic acid A) and 18-hydroxyoctadeca-9,11,13,15-tetraynoic acid (mkiluaynoic acid B), 5,7,3',4'-tetrahydroxyflavanol, 3,4-dihydroxybenzoic acid and a mixture of stearic and oleic acids were isolated from fruits and stem barks of Mkilua fragrans (Annonaceae). Mkiluaynoic acid A exhibited antifungal activity against Candida albicans comparable with that of the standard antifungal agent Ketoconazole. Structural determination was achieved by analysis of spectroscopic data. The flower stalks yielded essential oils that mainly consisted of sesquiterpenoids as revealed by GC-MS analysis, whereby 14 sesquiterpenes and four other compounds were identified.     

Pore structure of pyrolyzed scrap tires

Internal structure of carbon black produced by pyrolysis (CBp) of rubber samples from the top and bottom parts of sidewall and tread of a passenger car tire was investigated in nitrogen flow at different temperatures. The pore structure (specific surface area, pore size distribution, and porosity) of CBp and commercial CB, was compared. The development of pore structure and the increase of the specific surface area were most intensive during the thermal decomposition at temperatures ranging from 300°C to 500°C. This is caused by the intensive release of volatiles during the pyrolysis. After the pyrolysis was finished, at temperatures above 500°C, further decomposition of solid matter was associated with a slight increase of the specific surface area. Presented at the 34th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 21–25 May 2007.     

Using metal-catalyzed oxidation reactions and mass spectrometry to identify amino acid residues within 10 Å of the metal in Cu-binding proteins

Metal-catalyzed oxidation (MCO) reactions and mass spectrometry (MS) can be used together to determine the amino acids bound to Cu in a metalloprotein. Selective oxidation of only amino acids bound to Cu during the MCO/MS approach relies on proper choice of the types and concentrations of the reducing and oxidizing agents. We show here that if these MCO reagent concentrations are "detuned" or varied slightly from optimal conditions, nonmetal-bound amino acids close to Cu can also be oxidized in a controlled manner. Using Cu/Zn superoxide dismutase as a model system, we demonstrate that amino acids up to 10 A from Cu can be modified as long as they are readily accessible to diffusing reactive oxygen species. UV/VIS spectroscopy and measurements of oxidation kinetics provide evidence that the protein's structural integrity around Cu is maintained during the detuned MCO reactions. Because this method can identify amino acids around Cu that have low solvent accessibility, it should complement other radical-based protein surface-mapping techniques.     

Ce激活氯化钠在真空紫外光激发下的发光性质

采用水热蒸发法制备了NaCl∶Ce3+荧光粉,并通过X射线衍射(XRD)研究了材料的晶体结构。测量并分析材料在室温下的真空紫外激发光谱及相应的发射光谱。结果表明309和324nm的发射峰,对应于Ce3+离子的5d→4f(2 F5/2,2 F7/2)跃迁;激发谱显示6个峰,峰位分别为148,190,205,216,232和247nm。148nm的激发峰是基质吸收引起的;190,205,216,232和247nm是Ce3+的4f→5d跃迁引起的。     

Enzymatic kinetic resolution of Morita-Baylis-Hillman acetates

Racemic Morita-Baylis-Hillman adducts derived from the reaction of acrylonitrile with benzaldehyde, cinnamaldehyde and hydrocinnamaldehyde have been successfully resolved by means of enzymatic kinetic resolution. The (+)-alcohol products were isolated with 94–97% ee after lipase-mediated enantioselective hydrolysis of the corresponding acetates. Mosher’s double derivatisation protocol was applied to these isolated products and the absolute configuration of the alcohols was found to be (S) for all three substrates.     

Self-chemical ionization of diethylzinc

The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd.     

Kinetics of pyrolysis and properties of carbon black from a scrap tire

The pyrolysis of rubber from the sidewall and tread of a passenger car tire was carried out in a nitrogen flow at a wide range of final temperatures. Derivative thermogravimetric analysis (DTG) was applied to examine the kinetics at the different process conditions of completed pyrolysis. Two characteristic stages were observed in the DTG curves. The first stage corresponded to the decomposition of processing oil, plastifier, and additives, whereas the rubber polymer was decomposed in the second stage. Several properties of the carbon black formed by the pyrolysis such as ash content, specific surface area, and pore size distribution were determined. A change of the internal structure of the rubber particle in the meso-and macroregions of the pore size was observed. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.