Total synthesis of TMS-ent-bisabolangelone

The absolute configuration of bisabolangelone has been established by an eleven step total synthesis of the corresponding TMS protected antipode starting from (R)-(+)-pulegone. Comparison of the TMS-derivatives by GC on a chiral column, allowed us to assign the absolute configuration of the synthetic compound and thus of the corresponding natural product. The latter has been confirmed by the Mosher's ester analysis of the known secondary carbinol derivative.     

Dimethylsulfoxide as a kinetic booster for the chemical generation of singlet oxygen in methanol

The kinetic booster effect of dimethylsulfoxide on the chemical generation of singlet oxygen, ¹O₂, from the disproportionation of hydrogen peroxide catalyzed by molybdate ions in methanol has been evidenced by detection of the IR luminescence of ¹O₂ at 1270 nm and by ⁹⁵Mo NMR spectroscopy. DMSO interacts rapidly, through a direct oxygen transfer with the stable tetraperoxomolybdate , leading to DMSO₂ and to the unstable triperoxomolybdate , which releases ¹O₂. The procedure was applied to accelerate the dark singlet oxygenation of β-citronellol and α-terpinene.     

Supercritical fluid chromatography hyphenated with twin comprehensive two-dimensional gas chromatography for ultimate analysis of middle distillates

This paper reports the conditions of online hyphenation of supercritical fluid chromatography (SFC) with twin comprehensive two-dimensional gas chromatography (twin-GC × GC) for detailed characterization of middle distillates; this is essential for a better understanding of reactions involved in refining processes. In this configuration, saturated and unsaturated compounds that have been fractionated by SFC are transferred on two different GC × GC columns sets (twin-GC × GC) placed in the same GC oven. Cryogenic focusing is used for transfer of fractions into the first dimension columns before simultaneous GC × GC analysis of both saturated and unsaturated fractions. The benefits of SFC–twin-GC × GC are demonstrated for the extended alkane, iso-alkane, alkene, naphthenes and aromatics analysis (so-called PIONA analysis) of diesel samples which can be achieved in one single injection. For that purpose, saturated and unsaturated compounds have been separated by SFC using a silver loaded silica column prior to GC × GC analysis. Alkenes and naphthenes are quantitatively recovered in the unsaturated and saturated fractions, respectively, allowing their identification in various diesel samples. Thus, resolution between each class of compounds is significantly improved compared to a single GC × GC run, and for the first time, an extended PIONA analysis of diesel samples is presented.     

Public understanding of science and the perception of nanotechnology: the roles of interest in science,methodological knowledge,epistemological beliefs,and beliefs about science

In this article, we report data from an online questionnaire study with 587 respondents, representative for the adult U.S. population in terms of age, gender, and level of education. The aim of this study was to assess how interest in science and knowledge as well as beliefs about science are associated with risk and benefit perceptions of nanotechnology. The findings suggest that the U.S. public is still rather unfamiliar with nanotechnology. Those who have some knowledge mainly have gotten it from TV and the Internet. The content of current media reports is perceived as fairly positive. Knowledge of scientific methods is unrelated to benefit and risk perceptions, at least when other predictors are controlled. In contrast, positive beliefs about science (e.g., its impact on economy or health) and more sophisticated epistemological beliefs about the nature of scientific knowledge are moderately linked to more positive perceptions of nanotechnology. The only exception is the perception of scientific uncertainty: This is associated with less positive evaluations. Finally, higher engagement with science is associated with higher risk perceptions. These findings show that laypersons who are engaged with science and who are aware of the inherent uncertainty of scientific evidence might perceive nanotechnology in a somewhat more differentiated way, contrary to how it is portrayed in the media today.     

Characterization and functionalization of cellulose microbeads for extracorporeal blood purification

In the frame of this work, cellulose microbeads with an average particle size of 2.3 μm were characterized with respect to porosity using a batch solute exclusion method and two groups of model substances, namely proteins and polystyrene sulfonates. The pores of the microbeads were almost completely accessible to proteins with Stokes radii below 2.5 nm. More than 60% of the pores were accessible to albumin, which is relevant for the application in blood purification, since many target substances are albumin bound. Activation of the microbeads with increasing amounts of sodium metaperiodate yielded matrices with dialdehyde contents between 100 and 1,000 μmol/g. The activated beads were well suited for the covalent attachment of functional ligands, such as antibodies. Immobilization of antibodies against the pro-inflammatory cytokine TNF-α resulted in efficient TNF-α adsorbents which possess application potential in extracorporeal blood purification, e.g. for the modulation of cytokine levels as supportive therapy for sepsis and other inflammatory disorders.     

A partition relation for partially ordered sets

We introduce a partition relation which is an alternate for measuring how badly the ordinary partition relation fails, we develop its corresponding partition calculus and we determine its status for various typical partially ordered sets.