Diastereoselectivity in the Carroll rearrangement of β-keto esters of tertiary allylic alcohols

Carroll rearrangement of β-keto esters derived from tertiary allylic alcohols, for example, 7, under basic conditions followed by decarboxylation of the resulting β-keto acids yielded the expected γ,δ-unsaturated methyl ketones 8 with a range of olefin geometries from 100:0 to 1:1.8 E/Z, depending on the relative steric requirements of the two groups at the allylic center.     

Formation of trinuclear palladium orthometalated complexes with unprecedented asymmetrical (mu 3-S)(mu 3-X) bridges (X = OH, SR, O2CR) from mu 2-hydroxo dimeric complexes and CS2

Complexes [Pd(3)(mu(3)-S)(mu(3)-X)(L)(3)] (L = orthometalated imine), obtained by an unusual reaction of mu(2)-OH dimeric complexes and CS(2), are an unprecedented type of asymmetrical bridges between metallatriangles, which force an all-cis arrangement of the three orthometalated ligands relative to the metallatriangle.     

Absolute Continuity in Periodic Thin Tubes and Strongly Coupled Leaky Wires

Using a perturbative argument, we show that in any finite region containing the lowest transverse eigenmode, the spectrum of a periodically curved smooth Dirichlet tube in two or three dimensions is absolutely continuous provided the tube is sufficiently thin. In a similar way we demonstrate absolute continuity at the bottom of the spectrum for generalized Schrödinger operators with a sufficiently strongly attractive interaction supported by a periodic curve in R^d = 2, 3.     

Detection of nanocellulose in commercial products and its size characterization using asymmetric flow field-flow fractionation

The paper reports on a method for the detection of nanocellulose (NC) in consumer products by making use of a combination of (a) liquid-liquid extraction with an ionic liquid, and (b) size characterization by asymmetric flow field-flow fractionation (AF4) coupled to multi-angle light scattering (MALS) and refractive index (RI) detection. Both AF4 and MALS are viable tools for characterizing the size of the nanofibers. Sample preparation is easy, and the extraction efficiency of the method is 80.9 ± 1.8% (n = 5). It was applied to the detection of NC in toothpaste and coconut foodstuff to verify the practicability of the method.

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Graphical abstract Nanocellulose (NC) monitoring from coconut products and toothpaste and its size characterization by liquid-liquid extraction and asymmetric flow field-flow fractionation equipped with multi-angle light scattering and refractive index detection (AF4-MALS-RI).

     

Structural and functional diversity of glutaredoxins in yeast

Glutaredoxins are defined as thiol disulfide oxidoreductases that reduce disulfide bonds employing reduced glutathione as electron donor. They constitute a complex family of proteins with a diversity of enzymatic and functional properties. Thus, dithiol glutaredoxins are able to reduce disulfide bonds and deglutathionylate mixed disulfides between glutathione and cysteine protein residues. They could act regulating the redox state of sulfhydryl residues of specific proteins, while thioredoxins (another family of thiol disulfide oxidoreductases which employ NADPH as electron donor) would be the general sulfhydryl reductants. Some dithiol glutaredoxins such as human Grx2 form dimers bridged by one iron-sulfur cluster, which acts as a sensor of oxidative stress, therefore regulating the activity of the glutaredoxin. The ability to interact with iron-sulfur clusters as ligands is also characteristic of monothiol glutaredoxins with a CGFS-type active site. These do not display thiol oxidoreductase activity, but have roles in iron homeostasis. The three members of this subfamily in Saccharomyces cerevisiae participate in the synthesis of the iron-sulfur clusters in mitochondria (Grx5), or in signalling the iron status inside the cell for regulation of iron uptake and intracellular iron relocalization (Grx3 and Grx4). Such a role in iron metabolism seems to be evolutionary conserved. Fungal cells also contain membrane-associated glutaredoxins structurally and enzymatically similar to dithiol glutaredoxins, which may act as redox regulators at the early stages of the protein secretory machinery.     

New method for determination of trihalomethanes in exhaled breath: Applications to swimming pool and bath environments

A method for the estimation of the human intake of trihalomethanes (THMs), namely chloroform, bromodichloromethane, dibromochloromethane and bromoform, during showering and bathing is reported. The method is based on the determination of these compounds in exhaled breath that is collected by solid adsorption on Tenax using a device specifically designed for this purpose. Instrumental measurements were performed by automatic thermal desorption coupled to gas chromatography with electron capture detection. THMs in exhaled breath samples were determined during showering and swimming pool attendance. The levels of these compounds in indoor air and water were also determined as reference for interpretation of the exhaled breath results. The THM concentrations in exhaled breath of the volunteers measured before the exposure experiments showed a close correspondence with the THMs levels in indoor air where the sampler was located. Limits of detection in exhaled breath were dependent on THM analytes and experimental sites. They ranged between 170 and 710 ng m⁻³ in the swimming pool studies and between 97 and 460 ng m⁻³ in the showering studies. Application of this method to THMs determination during showering and swimming pool activities revealed statistically significant increases in THMs concentrations when comparing exhaled breath before and after exposure.