γ-alkylation of α,β-unsaturated ketones: α'-phenylsulfonyl groups as regioselective control elements

The α'-phenylsulfonyl derivative of E-3-penten-2-one ($\text{3}$) undergoes predominant γ-alkylation with a variety of alkyl iodides when first converted into a trilithiated intermediate with excess lithium diisopropylamide in tetrahydrofuran-hexane.     

5- and 7-substituted 2-methyl-8-quinolinols

The synthesis and characterization of the 5- and 7-monosubstituted 2-methyl-8-quinolinols where the substituents are fluorine, chlorine, bromine, iodine, nitro, amino, and sulfonic acid groups were carried out. The bischelates with copper(II) of those ligands containing hydrogen, fluorine, chlorine, bromine, iodine, and nitro are also reported.     

Artifact-free matrix-assisted laser desorption ionization time-of-flight mass spectra of tert.-butyldimethylsilyl ether derivatives of cyclodextrins used for the synthesis of single-isomer, chiral resolving agents for capillary electrophoresis

Artifact-free, high-resolution matrix-assisted laser desorption ionization (MALDI) time-of-flight mass spectra have been obtained for the labile, single-isomer, tert.-butyldimethylsilyl ether derivatives of alpha-, beta- and gamma-cyclodextrins by optimizing the MALDI sample preparation method. 2,5-Dihydroxybenzoic acid, a 3:1 mixture of 2,5-dihydroxybenzoic acid and 1-hydroxyisoquinoline, and 2,4,6-trihydroxyacetophenone were investigated as MALDI matrices with methanol and acetonitrile as matrix solvents. Partial-to-complete loss of the tert.-butyldimethylsilyl groups was observed when the commonly used 2,5-dihydroxybenzoic acid was the MALDI matrix and/or methanol was the solvent, both with and without trifluoroacetic acid as additive. Loss of the labile tert.-butyldimethylsilyl groups was avoided with 2,4,6-trihydroxyacetophenone as MALDI matrix and acetonitrile as matrix solvent. Good ion intensities were achieved for the (M+Na)+ and (M+K)+ quasimolecular ions in the positive-ion mode. Minor byproducts were observed in some of the samples and the information was used to aid the optimization of the synthetic work.     

Lipoide

Ohne Zusammenfassung     

Health risk assessment for nanoparticles: A case for using expert judgment

Uncertainties in conventional quantitative risk assessment typically relate to values of parameters in risk models. For many environmental contaminants, there is a lack of sufficient information about multiple components of the risk assessment framework. In such cases, the use of default assumptions and extrapolations to fill in the data gaps is a common practice. Nanoparticle risks, however, pose a new form of risk assessment challenge. Besides a lack of data, there is deep scientific uncertainty regarding every aspect of the risk assessment framework: (a) particle characteristics that may affect toxicity; (b) their fate and transport through the environment; (c) the routes of exposure and the metrics by which exposure ought to be measured; (d) the mechanisms of translocation to different parts of the body; and (e) the mechanisms of toxicity and disease. In each of these areas, there are multiple and competing models and hypotheses. These are not merely parametric uncertainties but uncertainties about the choice of the causal mechanisms themselves and the proper model variables to be used, i.e., structural uncertainties. While these uncertainties exist for PM2.5 as well, risk assessment for PM2.5 has avoided dealing with these issues because of a plethora of epidemiological studies. However, such studies don’t exist for the case of nanoparticles. Even if such studies are done in the future, they will be very specific to a particular type of engineered nanoparticle and not generalizable to other nanoparticles. Therefore, risk assessment for nanoparticles will have to deal with the various uncertainties that were avoided in the case of PM2.5. Consequently, uncertainties in estimating risks due to nanoparticle exposures may be characterized as ‘extreme’. This paper proposes a methodology by which risk analysts can cope with such extreme uncertainty. One way to make these problems analytically tractable is to use expert judgment approaches to study the degree of consensus and/or disagreement between experts on different parts of the exposure–response paradigm. This can be done by eliciting judgments from a wide range of experts on different parts of the risk causal chain. We also use examples to illustrate how studying expert consensus/disagreement helps in research prioritization and budget allocation exercises. The expert elicitation can be repeated over the course of several years, over which time, the state of scientific knowledge will also improve and uncertainties may possibly reduce. Results from expert the elicitation exercise can be used by risk managers or managers of funding agencies as a tool for research prioritization.     

Inhibition of cell adhesion to fibronectin by oligopeptide-substituted polynorbornenes.

Polynorbornenes substituted with two different peptide sequences from the RGD-containing integrin cell-binding domain of fibronectin are potent inhibitors of human foreskin fibroblast cell adhesion to fibronectin-coated surfaces. Ring-opening metathesis polymerization (ROMP) using Ru==CHPh(Cl)(2)(PCy(3))(DHIMes) (1) as an initiator produced polymers substituted with GRGDS and PHSRN peptide sequences. The inhibitory activity was quantified for these polymers and compared to the free peptides and GRGES-containing controls. A homopolymer substituted with GRGDS peptides was significantly more active than the free GRGDS peptide (IC(50) of 0.18 +/- 0.03 and 1.33 +/- 0.20 mM respectively), and the copolymer containing both GRGDS and PHSRN is the most potent inhibitor (IC(50) of 0.04 +/- 0.01 mM). These results demonstrate that significant enhancements of observed biological activity can be obtained from polymeric materials containing more than one type of multivalent ligand and that ROMP is a useful method to synthesize such well-defined copolymers.     

Satellite observations of electric fields in the innermagnetosphere and their effects in the mid-to-low latitude ionosphere

During geomagnetic disturbances, momentum and energy are transferred in significant quantities from interplanetary space to the magnetosphere-ionosphere system through the mediation of charged particles and electric fields. The most dramatic manifestations occur in the plasma sheet and the conjugate auroral ionosphere. However, electric fields observed during magnetic storms also penetrate the inner magnetosphere that maps to subauroral latitudes in the ionosphere. For example, a sudden commencement shock wave initiating the March 1991 magnetic storm created a new radiation belt within minutes. Particle and field measurements by Combined Release and Radiation Effects Satellite (CRRES) near the equatorial plane of the magnetosphere and by Defense Meteorological Satellite Program (DMSP) satellites in the topside ionosphere during the magnetic storm of June 1991 indicate that penetration electric fields energized the stormtime ring current and rapidly transported plasma within subauroral ion drift (SAID) structures at midlatitudes and in upward drafting plasma bubbles at low latitudes. Through enhanced transport or chemical reactions, the SAIDs dug deep plasma troughs at topside altitudes. Equatorial plasma bubbles developed while the ring current was unable to shield the electric field from the innermost magnetosphere     

Superconductivity pairing induced by two level systems in amorphous metals

From the standard interaction between electrons and two level systems a superconductive pairing is envisaged. The solutions of the Eliashberg equations for the critical temperature as well as the zero temperature gap lead to expressions as exp (?1/√λ₀) instead of exp (?1/λ₀) in the BCS case, which enhances considerably the superconducting properties in the weak coupling case.