Synthesis of New Fluorinated Derivatives of Quinolinecarboxylic Acids

Ethyl esters of 1-(7-Z-1-ethyl-6-fluoro-4-oxo-1,4-dihydroquinoline-3-carbamoyl)-5-X-6,7,8-trifluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acids (X = H, F; Z = pyrrolidino-, piperidino-, hexamethylenimino-, morpholino-, thiomorpholino-) have been synthesized by the interaction of quinolone-3-carboxylic acid hydrazides with ethyl esters of 3-ethoxy-2-(polyfluorobenzoyl)acrylic acid . It was shown possible to cyclize intramolecularly the esters obtained with the formation of 1,3,4-oxadiazino[6,5,4-i,j]quinoline derivatives.     

Thermal oxidative degradation of additive-free polypropylene pellets investigated by multichannel Fourier-transform chemiluminescence spectroscopy

Thermal oxidative degradation of additive-free polypropylene pellets heated isothermally in dry air at 150 and 180 °C (below and above the melting point of 163 °C) was investigated by multichannel Fourier-transform chemiluminescence spectroscopy. The initial peak wavelength of chemiluminescence emission at 490 nm remained constant during the early stages of thermal degradation, but new emissions developed with time in the red spectral region over an extended oxidation period. The time-dependent luminescence spectra were deconvoluted into three emission bands by least-squares fitting using Gaussian curves. We concluded that at least three groups of luminescent species (luminophores), having different conjugation lengths, were generated by thermal oxidation over extended periods and show luminescence around 490, 660, and 740 nm.     

阴阳离子菁染料超快荧光动力学特性研究

采用飞秒荧光上转换技术,研究了阴阳离子菁染料及对应的阴离子和阳离子菁染料吸附在立方型和T型溴碘化银表面上形成J-聚集体的荧光衰减时间分辨特性,分析了几种菁染料增感体系的超快电子转移动力学过程及其对增感效率的影响.通过比较几种菁染料增感体系的荧光衰减特性,两种阴阳离子染料要明显快于阴离子染料、阳离子染料及二者的加合,说明阴阳离子染料聚集体到溴碘化银的电子注入速率较快,增感效果更好.对两种阴阳离子染料聚集体荧光衰减特性的比较,可以看出染料在T型颗粒溴碘化银上形成聚集体的荧光寿命更短,因而对T型颗粒的增感效果更好.染料Dye2的荧光衰减要快于染料Dye1,说明染料Dye2到溴碘化银的电子注入速率更快,增感效率更高.     

Spectral Studies on Some Pyrimidine Derivatives in Different Solvents

The electronic absorption spectra of 2-aminopyrimidine (compound I), 2-amino-4-methylpyrimidine (compound II), 2-amino-4,6-dimethylpyrimidine (compound III), 2-amino-4,6-dimethoxypyrimidine (compound IV), 4-amino-2,6-dimethylpyrimidine (compound V), and 4,5-diamopyrimidine (compound VI) have been measured in water and in a series of different organic solvents. The solvent effects on the spectra are discussed and the solvent induced spectral shifts are analyzed in terms of different solute–solvent interaction mechanisms, using the multiple linear regression technique.     

卤化银乳剂颗粒上不对称菁染料J-聚体荧光的研究

光谱增感机理的研究是感光科学中的一个重要课题Gilman^[1]和Kuhn等^[2]曾经提出光谱增感的电子转移和能量传递理论。随着现代谱学手段的出现,为人们了解光谱增感的初始过程提供了条件。近年来,电子转移的机理已被广泛接受,并用来解释与光谱增感有关的各种现象。但在ns~ps范围内的光谱增感动力学方面的研究还不多见。Dahne认为光谱增感不仅决定于染料与卤化银的能级关系,而且是由动力学控制的^[3],激发态染料向卤化银导带注人电子的电子转移过程与辐射及其他无辐射去活过程是竞争的^[4]我们通过对两种不对称的苯并咪哇唾碳著染料在AgBrI乳剂颗粒上吸附形成的J一聚体的荧光性质的研究,以求深人了解光谱增感的电子转移机理及其动力学过程,无疑是有重要意义的。     

Spectral and non-spectral interferences in inductively coupled plasma mass-spectrometry

Inductively coupled plasma mass spectrometry of environmental and biological samples is often hampered by spectral and non-spectral interferences. Spectral interferences, caused by the limited resolution of the quadrupole mass spectrometer, can be eliminated in a variety of ways. For their identification inspection of a signal versus carrier gas flowrate is useful. Anion exchange allows the removal of most S and Cl containing compounds, which are at the origin of the majority of spectral interferences. Matrix modification, for example the addition of ethanol and subsequent optimization of the gas flow rates in a number of cases enables the reduction of the interferences to insignificant values. Often a mathematical correction based on isotopic signal ratios can be applied. Non-spectral interferences can be divided in reversible, that is occurring while the sample is being measured, and irreversible matrix effects, that is clogging of the nebulizer and sampling orifices or deposition on the torch or in the ion lens stack. The errors associated with non-spectral interferences can be eliminated by appropriate calibration procedures, adapted sample preparation or limitation of the amount of sample delivered to nebulizer, plasma and sampling devices, for example by the application of flow injection. Applications of all the elimination procedures are described for the analysis of sea-water, estuarine water, soil and sewage extracts, percolate water, urine, serum and wine.     

New Diterpenoid Alkaloids from Delphinium Souliei Franch

Inourpreviouspapers'-',wehavereportedtheisolationandelucidationofaseriesofnewditerpenoidalkaloidsfromDelphinillnlsolllieiFranch.ContinuedphytochemcalinvestigationsontheconstituentsofthisplanthaveledtotheisolationoftwoothernewditerpenoidalkaloidssoulineE(l)andsoulineF(2).SoulineE(2.6mg)wasobtainedascolorlesscrystals,mpf77-78'C(fromethanol).[a]."8.0(c=0.05,CHCI;).itsmolecularformulaC,=H;,NO,wasderivedfromHkEIMS(M-f361.2613,cafe.361.2608).TheiHnmrspectrum(400MHz)exhibitedthefollowingsign…     

Oxiranyl β-Aminovinyl Ketones. 7. Synthesis of 5-Hydroxy-3-(1-oxo-2,3-epoxyalkyl)benzofurans

5-Hydroxy-3-(1-oxo-2,3-epoxyalkyl)benzofurans were obtained with yields of up to 81% by the reaction of p-benzoquinone with oxiranyl -dimethylaminovinyl ketones in acetic acid.     

电感耦合等离子体原子发射光谱法测定镍基单晶高温合金中Mo、W、Ta、Re、Ru时元素之间相互干扰的消除与校正的研究

称取镍基单晶高温合金0.100 0g于聚四氟乙烯烧杯中,先令其与盐酸9mL和硝酸1mL加热反应,待反应缓慢时滴加氢氟酸2mL并继续加热使样品完全溶解。加入500g·L^-1酒石酸溶液2mL,冷却至室温,在塑料容量瓶中加水定容至100.0mL。按仪器工作条件采用电感耦合等离子体原子发射光谱法测定其中5种合金元素(Mo、W、Ta、Re、Ru)的含量,选择分析谱线依次为204.598,207.911,240.063,197.312,240.272nm。结果发现:除了Re外,其余4种元素的测定中均受共存元素的光谱干扰,严重影响了测定结果的准确性。为克服其干扰,除了采用基体匹配法消除镍的基体干扰外,试验采用混合校正系数矩阵法对测定结果进行校准。通过一系列试验计算得到混合校准系数矩阵K,并应用于模拟样品的分析。结果表明:经过矩阵K的校准,所测定的5种元素的准确度显著提高,达到了消除共存元素之间光谱干扰的目的。通过精密度试验,测得上述5种元素测定值的相对标准偏差(n=11)均在1.5%以下,并通过标准加入法进行回收试验,测得5种元素的回收率为97.0%~105%。     

Spectral density distribution moments of a Hamiltonian of N coupled Morse oscillators: The large‐N limit

The expressions for moments of spectral density distribution of a Hamiltonian representing a system of N coupled Morse oscillators are reduced to the large‐N limit. The effect of the values of coupling constants on the spectral density distribution is analyzed. For the values of coupling constants within the pertinent range for real molecules, the relations between moments appear to be close to those for a Gaussian distribution. Outside this range, the deviations from the normal distribution are substantial. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002