Photochemistry of β, γ-unsaturated ketones-V: The direct irradiation of some γ-phenyl β, γ-enones

The photochemistry of some members of the two series of γ-phenyl substituted acyclic β, γ-unsaturated ketones 1 and 2 upon direct irradiation with γ 310nm has been investigated, viz 1c–1h and 2b+2c.The alkyl substituted (E)-5-phenyl-4-penten-2-ones 1c–1h yield the corresponding 1,3-acyl shift products and (Z)-isomers, and 1g and 1h in addition two decarbonylated products. 2b only yields the (Z)-isomer and some benzaldehyde, but 2c yields the 1,3-acyl shift product, the ODPM product, three hydrocarbons formed by disproportionation of the allyl radical, and some benzaldehyde. The β-phenyl β, γ-UK 3a proved to be photostable. The 1,3-acyl shift products of 1c–1h result mainly from the singlet excited state in a cage radical process. The exclusive formation of the (E)-configuration of the 1,3-acyl shift product is explained in terms of conformational preference of the intermediate allyl radical. It is proposed that the formation of the (Z)-isomer proceeds from ¹T(π -π^*) which is populated according to

. Evidence is presented which supports the proposed mechanism.The β,γ-UK 2b containing a benzoyl moiety leads to a higher degree of (E)-(Z) isomerization than the corresponding 1d which has an acetyl moiety.The triplet energies of (E)- and (Z)-1h are 56 and ca 70 kcal/mol respectively.     

Determination of butyltins in environmental samples using sodium tetraethylborate derivatisation: characterisation and minimisation of interferences

Interferences affecting the determination of butyltin species by sodium tetraethylborate (STEB) derivatisation followed by purge-trap preconcentration were systematically studied using synthetic solutions, natural water samples and sediment extracts. Substances that did not cause interferences included most common cations (apart from those metal ions listed below), anions, metalloids and polar organic compounds. Natural organic matter (NOM) specifically interfered with tributyltin (TBT) due to a mechanism involving partitioning of the butyltin to the hydrophobic portions of the NOM. The metal ions Ag(I) (≥2 μM), Cd(II) (≥2 μM), Cu(II) (≥0.5 μM) interfered predominantly with the determination of monobutyltin (MBT) due to catalytic degradation of the STEB reagent. Pb(II) (≥14 μM) interfered with butyltin determination by an unknown mechanism. Other interferences to the purge-trap method were shown to occur in the presence of chelating agents (e.g. EDTA) or hydrophobic liquids such as diesel fuel. A mixture comprising methanol (MeOH), EDTA and Mn(II) was used to partially mask the effect of interfering NOM and metals. Spike recoveries (mean±S.D. of n=7 different samples) of MBT, dibutyltin (DBT) and TBT in contaminated natural water samples were improved from 70±36,90±11 and 91±24 to 102±10,98±3 and 98±4%, respectively. Spike recoveries (mean±S.D. of n=5 different samples) of MBT, DBT and TBT in aliquots of sediment extracts were improved from 86±17,79±18 and 59±32 to 97±6.2,103±3.6 and 103±5.0%, respectively. The ability to analyse larger aliquots of sediment extracts in the presence of the masking mixture improved the detection limit four-fold if MBT and DBT determination was required and 10-fold if only TBT determination was required.     

有机试液的电感耦合等离子体原子发射光谱分析 Ⅰ.实际应用的若干方面

本文从七个方面介绍了ICP-AES在有机试液直接分析中的应用:(1) 油类样品分析;(2) 酒样直接分析;(3) 溶剂萃取分离富集-ICP光谱分析;(4) 基于生成挥发性金属有机化合物的ICP进样方法;(5) 有机试液分析中的其它进样方法;(6) 有机介质中非金属元素的ICP-AES测定;(7) ICP-AES作为色谱法的检测器。     

Determination of polycyclic aromatic hydrocarbons (PAHs) in particulate matter collected with low volume samplers

The determination of polycyclic aromatic hydrocarbons (PAHs) contained in samples of particulate matter (PM), collected with low volume pumps, were carried out with an high sensitivity method that comes from several revisions of a previous method. The present work describes how, by using programmable temperature vaporization (PTV) and a mass selective detector with inert ionic source for the GC-MS analysis and the modifications of microwave-assisted extraction (MAE), the sensitivity of the method can be increased.The PAHs chosen for testing the method are: benzo[a]anthracene (BaA), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1,2,3-cd]pyrene (Ip) and dibenzo[a,h]anthracene (DbA). They, in fact, belong to that group of substances that are the most harmful for human health for their carcinogenicity.PAHs recoveries for spiked standard solutions at different concentrations were between 95 and 100% with relative standard deviation ranging from 1 to 3%. The revised method was validated using a 1649a urban dust standard reference material (SRM). The results obtained were in good agreement with certified values. The high sensitivity of the method allows to carry out analyses using only a half of the sampled filter (usually 47 mm diameter membranes). In this way, the other half can be used for the characterization of the other components of PM (heavy metals, organic carbon, ions, etc). The last step has been constituted by application of the optimized method on real samples collected in two cities located in Southern Italy (Bari and Taranto).     

原初连续功率谱宇宙模型下暗物质晕的质量函数

最近的宇宙学观测结果给出了一个具有原初连续谱功率指数(RSI-CDM)的ΛCDM冷暗物质宇宙模型,而不是标准的尺度无关谱(PL-CDM).基于这个结果,应用半解析近似,对Jenkins et al(J01)质量方程进行了研究,同时在各个连续谱指数暗能量宇宙学模型下计算出这些模型对应的宇宙中最大暗物质晕的位里质量.结果表明,PL-CDM和RSI-CDM宇宙学模型在低红移处有微小差别.与PL-CDM相比, RSI-CDM在低红移处小质量暗晕的质量丰度较大,但在大结构质量晕中两者差别不明显, 而且这个差异随着红移降低而增大.RSI-CDM在高红移处压低了任何尺度的暗晕质量丰度.关于最大位里质量,平坦空间ΛCDM宇宙学模型在PL-CDM和RSI-CDM都给出更多大质量天体.因此,对PL-CDM和RSI-CDM功率谱模型,都可以用最大位里质量来区别不同的宇宙学模型.     

初论熊琏《澹仙词》

熊琏是清代杰出的女词人，其澹仙词内涵丰富，个性鲜明。主要表现在感怀词活现词人心灵，咏物词寄托意蕴深远，题画词深刻发明画意，悼亡词震撼读者心魄。论其审美价值，澹仙词具有感人肺腑的真情美，妙语天成的自然美，写貌传神的形象美，情景浑融的意境美，以及沉郁凄婉的风格美。     

浅论权利质权的设定

简要介绍了权利质权的概念及特点，阐明了权利质权的设定因其标的物的不同而不同。债权质权、股权质权、知识产权和其他权利质权的设定除受权利质权设定一般原则的约束外，还受与其标的相适应的个别规则的约束。     

颗粒聚集体的崩塌性质研究

考察和分析了一般颗粒物质堆积体中崩塌的主要特征，概述了目前对颗粒物质崩塌研究所涉及的相关模型以及理论，并对其适用范围和局限性进行了分析，指出了他们的成功之处及不足，提出了对颗粒物质堆积体崩塌机理进行深入研究的一些思路。     

半挥发性有机物质的固相萃取技术在松花江水有机毒物检测中的应用

通过对不同类型的化合物在多种固相萃取柱上的回收率进行评价，对影响萃取效率的各参数进行了测定，确定了测定不同水样以及不同组分的最佳萃取条件，建立了系统的半挥发物富集方案，为松花江水中有机毒物的分析测定提供了有效的样品处理方法和测定方法。     

环境大气可吸入颗粒物的矿物学研究

首先介绍了可吸入颗粒物中矿物颗粒的研究意义，随后对国内外矿物颗粒的研究现状和研究方向进行了详细论述；使用X射线衍射(XRD)和带能谱的扫描电镜(SEM/EDX)对北京春季可吸入颗粒物中矿物组分进行了初步研究，结果表明，北京春季可吸入颗粒物中的矿物有石英、粘土矿物、硅铝酸盐矿物、硫酸盐矿物等，以硅铝酸盐矿物为主，同时存在新生的矿物颗粒，新生矿物的存在表明有活跃的大气化学反应发生；在研究的基础上，对今后开展矿物颗粒的研究提出了建议。