Persistent Organic Pollutants – Are Our Methods Sensitive and Selective Enough?

Due to the exponential growth of the world population and a strong worldwide economic development, humans are increasingly exposed to chemicals. This is particularly true for persistent, toxic chemicals that accumulate in organisms including humans. The presence of these persistent organic pollutants (POPs) has been reported since the 1960s. Analytical methods developed for the determination of POPs in wildlife, food, feed, sediments, dust, air, and humans have seen a tremendous improvement in sensitivity and selectivity. Detection limits of 0.1 mg/kg for pesticides in the 1960s have decreased down to < 0.1 ng/kg for dioxins presently. On the other hand, due to new toxicological insights, authorities nowadays often demand much lower detection limits than in the early days of discovery. This paper compares the lowest effectual levels of a number of POPs with the analytical capabilities of modern laboratories in terms of sensitivity and selectivity. Methods discussed are gas chromatography (GC), including multi-dimensional GC and liquid chromatography (LC), combined with electron capture detection (for GC) or with different mass spectrometric detectors. The conclusion is that the still improving sensitivity of current methods is sufficient to allow detection of POPs at a level clearly below the lowest observable adverse effect levels. Selectivity has also improved, but given the high complexity of some of the POPs and the multitude of POPs and other chemicals to which we are exposed, further developments in selectivity are still badly needed. To limit and focus the information for regulators, an effect-directed analysis is proposed as an alternative approach.     

Selectivity Control in Micellar Electrokinetic Chromatography by Modification of Micellar Surface with Cyclohexanol

Abstract

The effect of cyclohexanol added to the micellar solution of sodium dodecyl sulfate in the micellar electrokinetic chromatography of several aromatic compounds was investigated. Cyclohexanol (0.05–-0.10 M) diminished the capacity factors (k') of the solutes possessing hydrophilic functional groups which were solubilized near the micellar surface, whereas little changed the k' of the hydrophobic solutes solubilized in the micellar core. This selective effect was ascribed to the saturation of the micellar surface with cyclohexanol.     

Study of the selective catalysis of metalloporphyrins for 2-methyl-butane oxidation with PhIO under mild conditions

Nine ironporphyrins and eight manganeseporphyrins were synthesized, and their selective catalysis for the oxidation of the secondary and tertiary carbon–hydrogen bonds of 2-methyl-butane with PhIO was studied. The proportion of the oxidation product of tertiary carbon–hydrogen bond to the one of secondary carbon–hydrogen bond was 3:1 when ironporphyrins were used as catalysts, and 2.3:1 when manganeseporphyrins were used as catalysts. The research showed that the substituting groups on the porphyrin rings influenced the catalytic selectivity of metalloporphyrins for the oxidation of the secondary and tertiary carbon–hydrogen bonds as well as the reaction yields. The electron-attracting groups on benzene rings of ironporphyrins increased the catalytic selectivity of ironporphyrins for the tertiary carbon–hydrogen bond oxidation and the reaction speeds, and the electron-releasing groups increased the catalytic selectivity for secondary carbon–hydrogen bond oxidation and reduced the reaction speeds. Both electron-attracting and -releasing groups on benzene rings of manganeseporphyrins enhanced the catalytic selectivity of manganeseporphyrins for the secondary carbon–hydrogen bond oxidation.     

Pressure drop effects on selectivity and resolution in packed column supercritical fluid chromatography

The influence of pressure drop on retention, selectivity, plate height and resolution was investigated systematically in packed supercritical fluid chromatography (SFC) using pure carbon dioxide as the mobile phase. Numerical methods developed previously which enabled the prediction of pressure gradients, diffusivities, capacity factors, plate heights and resolutions along the length of the column were used for the model calculations. The effects of inlet pressure and supercritical fluid flow rate on selectivity and resolution are studied. In packed column SFC with pure carbon dioxide as the mobile phase, the pressure drop can have a significant effect on resolution. The flow rate is shown to have a larger effect than generally realized. The calculated data are shown to be in good agreement with the experimental results. Finally, the variation of the chromatographic parameters along a 5.5 meter long model SFC column is illustrated. The possibilities and limitations of using long packed columns in SFC are discussed. It is demonstrated that long columns with large plate numbers do not necessarily yield better separations.     

二维/二维S-型Bi3NbO7/g-C3N4异质结光催化剂驱动选择性CO2还原制CH4

人工光合作用可直接将二氧化碳转化为一系列碳氢化合物,实现大气中的碳循环,被视为一种既能解决能源短缺又能减少温室气体,进而改善人类生存环境的新型绿色技术.光催化二氧化碳还原体系需要合适的耦合氧化还原反应,以及对外界光源的有效利用以产生足够电子参与反应,因此构建高催化活性和高选择性的催化体系仍然面临着巨大挑战.此外,二维纳米结构(2D)由于具有比表面积大、离子的迁移路径短以及独特的平层电子转移轨道等特性,被证实有利于光催化还原CO₂过程.其中,Bi₃NbO₇特殊的片层结构和合适的能带位置,使其在光催化还原CO₂反应中表现出良好的催化性能.然而,Bi₃NbO₇的光生载流子易复合及反应中光腐蚀严重等缺陷导致其光利用率较低,限制了其实际应用.因此,构建S-型异质结是提高复合材料光催化活性的一种有前途的策略.S-型异质结不仅能有效地分离光生电子和空穴,而且这一电子转移过程赋予了复合物最大的氧化还原能力.同时,S-型光催化体系不仅拥有同样的强氧化和强还原能力,还可显著抑制副反应的发生及副产物的产生,有利于CO₂还原反应的高选择性进行.本文利用简易的溶剂热法制备了一系列S-型Bi₃NbO₇/g-C₃N₄(BNO/UCN)异质结光催化剂,与其纯组分催化剂相比,表现出优异的光催化还原CO₂活性,g-C₃N₄含量为80wt%的BNO/UCN-3光催化剂催化CO₂生成CH₄产率为37.59μmol·g^-1h^-1,是g-C₃N₄的15倍,CH₄选择性为90%;且循环反应10次后仍保持较高的活性及CH4选择性.光催化活性及选择性的显著增强是由于二维分布的纳米结构和S-型电荷转移路径.在可见光照射下,界面内建电场、带边缘弯曲和库仑相互作用协同促进了复合物相对无用的电子和空穴的复合.因此,剩余的电子和空穴具有较高的还原性和氧化性,使复合材料具有较高的氧化还原能力.自由基捕获实验、电子顺磁共振实验和原位X射线光电子能谱实验结果表明,光催化剂中的电子迁移遵循S-型异质结机理.综上,本文不仅为新型S-型异质结CO₂还原光催化剂的设计和制备提供了新方法,而且为未来解决能源短缺及实现碳中和目标提供一定的实验及理论依据.     

Two-mode Fluorescent Detection of Cyanide by a Simple AIE-based Chemosensor with Red Emission

TPE-TCF, a simple TPE-derivative with red-emission was used to detect cyanide in the condition of single dispersion as well as under aggregate state. It could be found that TPE-TCF exhibited excellent fluorescent response to cyanide in both situations, and the mechanism was supposed to be the reaction between cyanide and the double bond in TPE-TCF as well as the aggregation induced emission property of the reacted TPE-TCF molecules. What's more, TPE-TCF could distinguish cyanide with other species, such as common anions and biotiol well, which indicated it as a potential indicator for cyanide with good selectivity and specificity.     

Vorhersage alyotroper Effekte in ternären flüssigen Systemen

Summary After a short introduction into the phenomenon of alyotropism inequalities are derived by use of a general Redlich-Kister statement in the enlargement to ternary systems, recommended by Kohler. This allows to predict alyotropic effects, which is demonstrated on some examples. For the first time, alyotropism can be predicted in this way not only for systems with a continuous miscibility gap, but also for systems with a one-sided miscibility gap.

Herrn Prof. Dr. F. Kohler zu seinem 65. Geburtstag gewidmet     

Applications of Nanopore Sensing in Detection of Toxic Molecules

As a novel analytical method, nanopore sensing is widely applied in many fields such as nucleic acids sequencing, protein/peptides analysis, detection of metal ions and biomacromolecules including virus, bacteria, etc. With the growing public concerns on dietary safety and public security, there has been a greater demand on the detection of toxic molecules. With high sensitivity and selectivity, nanopore sensing is considered as a more powerful assay, and has been reported in many research articles. Accordingly, this paper surveys the application of nanopore sensing in detection of toxic molecules.     

整体式三氧化钨/氧化石墨烯气凝胶增强可见光光催化氧化NO性能（英文）

近年来,光催化技术在去除以NO为代表的诸多室内气体污染物方面展现出巨大的潜力.单质铋和铋系氧化物,非金属氧化物以及钙钛矿等众多半导体光催化材料均具有优异的NO降解效率,但很难控制氧化产物.因而会生成大量毒性更强的中间产物NO2造成二次污染.因此,寻求一种清洁、高效,且具有良好选择性的光催化材料成为了亟待解决的问题.六方相三氧化钨(h-WO_3)的价带位置较正,氧化电位较高,具有很强的氧化能力,是一种良好的氧化性光催化半导体材料.然而,WO_3催化材料多为粉末状,不仅容易团聚,难以回收利用并且会堵塞检测气路.同时,WO_3本身存在的电子-空穴复合率高,弱的可见光响应性等问题使其光催化活性较低.因而,制备具有良好可见光响应,高电子-空穴分离效率的一体化WO_3材料是其广泛应用前急需解决的问题.而石墨烯气凝胶是理想的催化剂载体,其较高的比表面积以及多孔状结构可有效地增加催化剂的暴露面积,提升催化剂利用率;更重要的是,氧化石墨烯(GO)具有极高的导电率,可作为电子受体加速电子-空穴对的分离而提升光催化活性.因此,以GO作为基体材料,构建WO_3/GO气凝胶一体化材料有良好的应用前景.然而,现在还鲜见有关宏观WO_3/GO气凝胶光催化降解NO的报道.本文以偏钨酸铵为钨源,利用体积分数为25%的冰醋酸在180ⅹC条件下制备六方相三氧化钨.通过机械搅拌以及冷冻干燥法制备WO_3/GO气凝胶.经光催化氧化NO测试发现其可见光下降解率可达51%,是WO_3粉体的3.3倍,并且NO_2生成率仅为0.5%,远远低于其他相关光催化材料.采用了X射线衍射(XRD),透射电镜(TEM),X射线光电子能谱(XPS),紫外-漫反射分光光度计(UV-DRS),傅里叶红外光谱(FTIR)和荧光光谱(PL)等手段研究了其光催化性能提高的原因.XRD测试显示,复合材料主体为h-WO_3,说明GO的引入并未破坏材料晶体结构;TEM和BET测试发现,在加入GO之后h-WO_3分散性变好,比表面积变大,从而可暴露更多的光催化活性位点.UV-DRS吸收光谱可以看到WO_3/GO气凝胶材料的吸收边发生了显著的红移,其禁带宽度从3.44 eV减小到3.16 eV,这可能是GO影响了WO_3的能带结构所致.同时PL结果表明,引入了GO之后,气凝胶材料的非辐射跃迁程度明显减小表明其电子-空穴对的复合得到了显著抑制,电子迁移显著加强.综合以上结果,可以得到WO_3/GO光催化性能提升以及良好的产物选择性的原因.首先,三维气凝胶材料的结构提升了催化剂的有效利用率,较大的比表面积暴露了更多的活性位点.其次,GO的引入减小了复合材料的禁带宽度,并使其吸光性能有所改善,产生了更多的光生电子和空穴.最后,GO本身极高的导电性,使光生电子-空穴对得以有效的分离,一方面,电子通过GO迅速转移到材料表面来参与光催化反应;另一方面,电子的快速转移抑制了电子-空穴对的复合,进而提高光催化性能,而且较正的价带位置保证了NO较为彻底的氧化为NO3–.因此,相比传统粉末WO_3催化材料,一体化的WO_3/GO气凝胶不仅显著提升了NO降解率,同时严格抑制了毒副产物NO2的生成,同时更具有容易回收利用,不存在二次污染的优点.综上所述,WO_3/GO一体化气凝胶光催化材料有望在环境净化与能源领域表现出良好的应用前景.