Synthesis of selenylfullerene with selenium-containing dibenzo[b,g]cyclooctane moiety

The photochemical reaction of C₆₀ with selenium-containing bicyclooctanes affords for the first time the selenylfullerenes. The derivatives were characterized by mass, UV-vis absorption, NMR spectroscopy, and X-ray crystallographic analysis.     

Photochemical electrocyclization of α,β-unsaturated anilides to give zwitterionic intermediates which eliminate carboxylate and phenolate leaving groups

α,β-Unsaturated anilides bearing allylic leaving groups undergo photochemical electrocyclic ring closure to produce zwitterionic intermediates which eliminate carboxylate and phenolate leaving groups.     

肿瘤靶向PEI包覆磁性纳米凝胶的光化学制备及表征

以聚乙烯亚胺(Polyethyleneimine, PEI)为预聚体, H2O2为抽氢剂, 采用光化学方法制备了PEI包覆的磁性纳米凝胶(PEI-Fe3O4), 在PEI-Fe3O4表面共价偶联具有肿瘤靶向作用的叶酸分子(Folate, FA), 制备得到肿瘤靶向PEI包覆磁性纳米凝胶(FA-PEI- Fe3O4). 采用多种手段对PEI-Fe3O4及FA-PEI-Fe3O4进行了表征. 结果表明, FA-PEI-Fe3O4平均粒径为140 nm, 形状规则, 具有超顺磁性, 磁含量达到22.4%, 饱和磁化强度达65.6 A·m2·kg-1, 磁性纳米凝胶较高的磁响应性能和具有肿瘤靶向作用的叶酸分子的修饰, 为其作为潜在的肿瘤靶向载体奠定了基础.     

An enantioselective synthesis of (S)-4-fluorohistidine

We report a new synthesis of enantiomerically pure (S)-4-fluorohisitidine based on diastereoselective alkylation of MOM-protected 4-fluoro-5-bromomethyl imidazole using the Schöllkopf bis-lactim amino acid synthesis. Improvements in procedures for preparation of key intermediates are also described. (S)-4-Fluorohisitidine prepared by this new method was identical in all respects to material prepared by previous procedures.     

Synthesis, spectroscopic properties and crystal structure determination of 2-(2-pyridin-4-yl-vinyl)-1H-benzimidazole derivatives

Substituted 2-(2-pyridin-4-yl-vinyl)-1H-benzimidazole derivatives 2, 3 and 6 were synthesized. 2-(2-Pyridin-4-yl-vinyl)-1H-benzimidazole 2 and 6-methyl-2-(2-pyridin-4-yl-vinyl)-1H-benzimidazole 3 were prepared by condensation reaction from 3-pyridin-4-yl-acrylic acid and corresponding 1,2-phenylenediamines in polyphosporic acid (PPA). 2,7,11-b-Triaza-benzo[c]fluorene 4 was prepared by photochemical dehydrocyclization reaction of ethanolic solution of 2-(2-pyridin-4-yl-vinyl)-1H-benzimidazole 2. 2-(2-Pyridin-4-yl-vinyl)-3H-benzimidazole-6-carbonitrile 6 was prepared by condensation reaction from 3-pyridin-4-yl-propenal and 4-cyano-1,2-phenylenediamine using p-benzoquinone as oxidants. The structure of novel benzimidazole derivatives has been studied by ¹H and ¹³C NMR, IR, MS, UV/Vis and fluorescence spectroscopy. The structure of 2-(2-pyridin-4-yl-vinyl)-1H-benzimidazole 2 was confirmed by X-ray single crystal structure analysis. The conformation of the molecule is E in regard to substituents position around vinyl double C=C bond. The non-planar molecules are mutually connected via the N–H···N and C–H···N type of intermolecular hydrogen bonds into infinite chains spreading along y axis.     

Flow injection-photoinduced-chemiluminescence determination of ziram and zineb

A simple, sensitive and rapid method for the determination of the pesticides ziram and zineb was described. This new method was based on the coupling of FIA methodology and direct chemiluminescent detection; this approach had not been used up to now with these pesticides. The additional use of an ‘on line’ photochemical reaction, which was performed by using a photoreactor consisting of a long piece of PTFE helically coiled around a 15 W low-pressure lamp, increased by a factor >20 the chemiluminometric response of the pesticides. An additional 3-fold improvement in the analytical signal was also achieved by using quinine as sensitizer. The obtained throughputs were very high (121 and 101 h⁻¹ for ziram and zineb, respectively); this feature together with its low limit of detection (1 ng mL⁻¹) makes this method particularly well suited to routine analyses of environmental samples. On the other hand, its applicability to two members of the dithiocarbamate family of pesticides, makes it promising for the determination of the rest of the members of this family. The method was demonstrated by application to spiked water samples from different origins (ground, river and irrigation).     

Laboratory simulation of Hg<Superscript>0</Superscript> emissions from a snowpack

Snow surfaces play an important role in the biogeochemical cycle of mercury in high-latitude regions. Snowpacks act both as sources and sinks for gaseous compounds. Surprisingly, the roles of each environmental parameter that can govern the air–surface exchange over snow are not well understood owing to the lack of systematic studies. A laboratory system called the laboratory flux measurement system was used to study the emission of gaseous elemental mercury from a natural snowpack under controlled conditions. The first results from three snowpacks originating from alpine, urban and polar areas are presented. Consistent with observations in the field, we were able to reproduce gaseous mercury emissions and showed that they are mainly driven by solar radiation and especially UV-B radiation. From these laboratory experiments, we derived kinetic constants which show that divalent mercury can have a short natural lifetime of about 4–6 h in snow.     

光化学荧光分析法研究(Ⅵ)——混合色素的光化学速差动力学荧光分析法测定

以光化学荧光衍生化法测定苋菜红(AM)和直接耐晒嫩黄5GL(DY)2种偶氮色素,研究了同时测定这2种色素混合物的光化学速差动力学荧光分析的原理和方法。AM和DY的浓度分别在0～220ng/mL和0～120ng/mL范围内呈良好的线性关系,相关系数皆为0.999,检出限为0.64ng/mLAM和0.045ng/mLDY。相对标准偏差分别为1.6%(n=8)和1.8%(n=7)。该法用于人工合成混合样品的测定效果良好。     

Studies on the Determination of the Micro Components by Photochemical Kinetics

The iodides can be oxidated to iodine by O_2 in air because of their lower redox potential. In an acidic solution, this reaction can be accelerated by ultraviolet light. Because the iodine yielded from potassium iodide by light irradiating solution can react with other oxidizer components, the iodine is constantly consumed. When it arrives the terminal points of the reaction, the iodine appears. According to the reaction time of the iodine appearing the quantities of the components are determined. And the terminal points can be pointed out by the blue of the iodine-starch or potentiometric     

偶氮苯的光化学顺反异构化反应及其在光强测定中的应用

本文叙述了用偶氮苯露光计测定光强的原理。本方法也同样可用于测定A<﹦>B型光化学异构化反应的量子产率,设计了专用的计算机程序来处理在光强和量子产率的测定中的各种有关数据。