Ring transformations of heterocyclic compounds. XIV . Ring transformations of pyrylium and thiopyrylium salts with anhydro-bases derived from 1H-benzimidazolium and benzothiazolium salts: An easy access to 2-(2,4,6-triarylphenyl) 1H-benzimidazolium and benzothiazolium derivatives

The preparation of former unknown 2-(2,4,6-triarylphenyl) substituted 1H-benzimidazolium perchlorates 7 and benzothiazolium perchlorates 8 from 2-methyl substituted derivatives 5/6 by a 2,6-[C₅+C] ring transformation of 2,4,6-triarylpyrylium and 2,4,6-triarylthiopyrylium salts 1/9 in the presence of an appropriate base ( 7 : sodium ethoxide, 8 : sodium acetate) is reported. Spectroscopic data of the transformation products and their mode of formation via anhydrobases of the salts 5/6 are discussed.     

Anionic polymerization of butadiene: A MNDO study of the potential energy surface of the propagation reaction in polar and non-polar media

The anionic polymerization of butadiene, to both the 1,2- and 1,4-addition products, is an important industrial process. It is known that the reaction can be steered to either the 1,2- or 1,4-product by the addition, or absence, of a complexing solvent such as ether. The goals of the current study were to map the MNDO Potential Energy Surfaces (PES) of the propagation reactions both in the presence and absence of dimethyl ether to gain insight into the factors influencing the reaction's selectivity. Single point ab initio calculations at the DZP level were run on all reactants, products and transition states as a cross check on the MNDO results.     

Investigation,by single photon ionisation (SPI)–time-of-flight mass spectrometry (TOFMS), of the effect of different cigarette-lighting devices on the chemical composition of the first cigarette puff

Soft single-photon ionisation (SPI)–time-of-flight mass spectrometry (TOFMS) has been used to investigate the effect of different cigarette-lighting devices on the chemical composition of the mainstream smoke from the first cigarette puff. Lighting devices examined were a Borgwaldt electric lighter, a propane/butane gas lighter, a match, a candle, and the burning zone of another cigarette. To eliminate the effects of the different masses of tobacco burnt by use of the different lighting methods a normalisation procedure was performed which enabled investigation of changes in the chemical patterns of the resulting smoke. When another cigarette was used as the lighting device, elevated levels of ammonia and other nitrogen-containing substances were observed. These are high in the sidestream smoke of the cigarette used for lighting and would be drawn into the mainstream smoke of the cigarette being lit. In contrast, smoke from the cigarette lit by the electric lighter contained slightly higher normalised amounts of isoprene. Lighting the cigarette by use of a candle resulted in larger amounts of substances, e.g. benzene, which most probably originated from thermal decomposition of wax. The composition of the first puff of smoke obtained by use of the three lighting methods with open flames (gas lighter, match, and candle) was usually similar whereas the composition of the smoke produced by use of the electric lighter and the cigarette as the lighter were more unique. The chemical patterns generated by the different lighting devices could, however, be separated by principal-component analyses. Two additional test series were also studied. In the first the cigarette was lit with an electric lighter, then extinguished, the ash was cut off, and the cigarette was re-lit. In the second the cigarette was heated in an oven to 80 °C for 5 min before being lit. These treatments did not result in changes in the chemical composition compared with cigarettes lit in the ordinary way. Figure Time-of-flight mass spectrometry (TOFMS) has been used to investigate the effect of different cigarette-lighting devices on the chemical composition of the mainstream smoke from the first cigarette puff     

Impact of hyperthermic regional perfusion therapy on cell metabolism of malignant melanoma monitored by 31P MR spectroscopy

For the first time, the influence of hyperthermic regional perfusion therapy on tumor cell metabolism has been monitored by means of 31P MR spectroscopy. Shortly after treatment, a complete depletion of high energy phosphates, a significant increase of inorganic phosphate, phosphomono- and phosphodiester resonances and a decrease of pH have been observed. Healthy muscle tissue showed only minor effects caused by this aggressive therapy. The time course of the transient variation of phosphate metabolite concentrations is explained in the framework of a simple pathophysiological model. The results demonstrate that the imediate effect of chemotherapy on tumor tissue can be detected by 31P MRS before any clinical signs of tumor response are visible.     

Modification of carbon electrodes by vitamin B12-polymers

New types of electroactive polymers consisting of derivatives of vitamin B₁₂ and epoxy resins have been synthesized. Surface modification of carbon (carbon felt or basal plane pyrolytic graphite) has been achieved by thermal curing of the monomers on the electrodes. Electrochemical response from the Co (II)/Co (I) redox couple has been observed from sub-mono to multilayer coverages. The influence of the size of the epoxy spacer on charge propagation in the polymer has been studied. The B₁₂-modified electrodes have been applied to electrosynthesis and electroanalysis: They catalyze the reductive cross-coupling of alkyl halides and activated olefins and they are efficient sensors for alkylating agents.     

The Use of Constituent Spectra and Weighting in Extended Multiplicative Signal Correction in Infrared Spectroscopy

Extended multiplicative signal correction (EMSC) is a widely used preprocessing technique in infrared spectroscopy. EMSC is a model-based method favored for its flexibility and versatility. The model can be extended by adding constituent spectra to explicitly model-known analytes or interferents. This paper addresses the use of constituent spectra and demonstrates common pitfalls. It clarifies the difference between analyte and interferent spectra, and the importance of orthogonality between model spectra. Different normalization approaches are discussed, and the importance of weighting in the EMSC is demonstrated. The paper illustrates how constituent analyte spectra can be estimated, and how they can be used to extract additional information from spectral features. It is shown that the EMSC parameters can be used in both regression tasks and segmentation tasks.     

微波消解-ICP-AES测定鄱阳湖流域沉积物中微量元素

为了研究鄱阳湖沉积物中微量元素近几年来随季节、年度及沿程的变化情况,对2003年和2005年不同季节采集的鄱阳湖流域各采样点底泥进行了ICP-AES测定.结果表明,鄱阳湖沉积物中各元素的含量随着季节和年度变化而发生一定改变,枯水期普遍大于丰水期;南矶山2005年Cu和Pb含量较2003年有所降低;蔡家湾则与南矶山相反;姚公渡2005年Cu含量也较2003年低,Pb含量则高于2003年;与鄱阳湖流域底泥背景值相比,所测几个样点的Cu,Pb,Cr和Zn含量均在一定程度上超标;除大坞河外,其余各样点As含量均在背景值范围内;从饶河到鄱阳湖入湖口处,各元素含量呈逐渐降低趋势.文章提出的研究方法操作简便,效率高,劳动强度低.