A novel tandem cyclization of condensed 2,3-dialkynylpyrazines into [1,2,3]triazolo[1′,5′;1,2]pyrido[3,4-b]pyrazines promoted by sodium azide

6,7-Dialkynyl-1,3-dimethylpteridine-2,4(1H,3H)-diones and 2,3-dialkynylquinoxalines have been shown to react with sodium azide in DMF at room temperature giving rise 9,11-dimethyl-[1,2,3]triazolo[1′,5′;1,2]pyrido[4,3-g]pteridine-8,10(9H,11H)-diones and [1,2,3]triazolo[1′,5′;1,2]pyrido[3,4-b]quinoxalines. A novel tandem cyclization involves 1,3-dipolar cycloaddition of an azide ion to the carbon-carbon triple bond followed by intramolecular nucleophilic addition of the intermediate 1,2,3-triazole N-anion to another CC bond.     

An oxacalix[2]arene[2]pyrimidine-bis(Zn-porphyrin) tweezer as a selective receptor towards fullerene C70

An oxacalix[2]arene[2]pyrimidine-bis(Zn^II-porphyrin) conjugate was readily prepared via nucleophilic aromatic substitution of a phenolic AB₃-Zn-porphyrin on the upper rim of a (1,3-alternate) 5,17-bis(methylsulfonyl)oxacalix[4]arene precursor. Efficient 1:1 complex formation between the ‘jaws’ bisporphyrin tweezer and fullerene C₇₀ was evidenced by ¹H NMR titrations (K = 3.0 × 10⁴ M⁻¹), while no detectable complexation could be observed with C₆₀. On the other hand, an analogous oxacalix[4]arene-bis(Cu-corrole) conjugate did not show any measurable (C₆₀ or C₇₀) fullerene binding.     

Effects of Ultraviolet A-1 Radiation on Calcineurin Activity and Cytokine Production in (Skin) Cell Cultures†

Calcineurin (Cn) is the target of immunosuppressive drugs used for maintenance therapy of transplant patients. UV radiation is also known to be immunosuppressive and, like the Cn inhibitors, UV has been shown to positively influence various inflammatory skin diseases. Recently, Cn activity has been demonstrated in skin and skin cell cultures. In the present study we have investigated the effects of UV(A-1) irradiation on Cn activity in skin. In total skin we found a significant reduction in Cn activity after exposure to 450 kJ m⁻² of UVA-1 (340–400 nm). In repeated experiments cultures of fibroblasts and keratinocytes also showed dose-dependent and selective reduction in Cn activity after UVA-1 irradiation. UVB irradiation caused a decrease in the Cn activity of one of two fibroblast cultures and was ineffective in keratinocytes. In Jurkat cells and PBMC UVA-1 reduced Cn activity and also the production of cytokines such as interleukin (IL)-2, γ-interferon, IL-4 and IL-10 that are controlled by the Ca²⁺–Cn pathway. These results indicate that UV(A-1) irradiation may lead to inactivation of Cn in the skin and thus suppress the skin immune system in a similar fashion to the Cn inhibitors.     

In situ measurement of biaxial modulus of Si anode for Li-ion batteries

We report in situ measurement of biaxial moduli of a Si thin-film electrode as a function of its lithium concentration. During lithiation, biaxial compressive stress is induced in the Si film and it undergoes plastic flow. At any state-of-charge (SOC), a relatively small delithiation–relithiation sequence unloads and reloads the film elastically. From the stress and strain changes during a delithiation–relithiation cycle, the biaxial modulus of the film is calculated. Stress change is obtained by measuring the change in substrate curvature using a Multi-beam Optical Sensor; the elastic strain change is obtained from the change in SOC. By repeating these measurements at several different values of SOC, the biaxial modulus was seen to decrease from ca. 70 GPa for Li_0.32Si to ca. 35 GPa for Li_3.0Si. Such a significant reduction in elastic modulus has important implications for modeling stress evolution and mechanical degradation in Si-based anodes.     

Evaluation of standard and advanced preprocessing methods for the univariate analysis of blood serum 1H-NMR spectra

Proton nuclear magnetic resonance (¹H-NMR)-based metabolomics enables the high-resolution and high-throughput assessment of a broad spectrum of metabolites in biofluids. Despite the straightforward character of the experimental methodology, the analysis of spectral profiles is rather complex, particularly due to the requirement of numerous data preprocessing steps. Here, we evaluate how several of the most common preprocessing procedures affect the subsequent univariate analyses of blood serum spectra, with a particular focus on how the standard methods perform compared to more advanced examples. Carr–Purcell–Meiboom–Gill 1D ¹H spectra were obtained for 240 serum samples from healthy subjects of the Asklepios study. We studied the impact of different preprocessing steps—integral (standard method) and probabilistic quotient normalization; no, equidistant (standard), and adaptive-intelligent binning; mean (standard) and maximum bin intensity data summation—on the resonance intensities of three different types of metabolites: triglycerides, glucose, and creatinine. The effects were evaluated by correlating the differently preprocessed NMR data with the independently measured metabolite concentrations. The analyses revealed that the standard methods performed inferiorly and that a combination of probabilistic quotient normalization after adaptive-intelligent binning and maximum intensity variable definition yielded the best overall results (triglycerides, R = 0.98; glucose, R = 0.76; creatinine, R = 0.70). Therefore, at least in the case of serum metabolomics, these or equivalent methods should be preferred above the standard preprocessing methods, particularly for univariate analyses. Additional optimization of the normalization procedure might further improve the analyses.     

Variable denticity in carboxylate binding to the uranyl coordination complexes

Tris-carboxylate complexes of uranyl [UO₂]²⁺ with acetate and benzoate were generated using electrospray ionization mass spectrometry, and then isolated in a Fourier transform ion cyclotron resonance mass spectrometer. Wavelength-selective infrared multiple photon dissociation (IRMPD) of the tris-acetato uranyl anion resulted in a redox elimination of an acetate radical, which was used to generate an IR spectrum that consisted of six prominent absorption bands. These were interpreted with the aid of density functional theory calculations in terms of symmetric and antisymmetric −CO₂ stretches of the monodentate and bidentate acetate, CH₃ bending and umbrella vibrations, and a uranyl O—U—O asymmetric stretch. The comparison of the calculated and measured IR spectra indicated that the predominant conformer of the tris-acetate complex contained two acetate ligands bound in a bidentate fashion, while the third acetate was monodentate. In similar fashion, the tris-benzoate uranyl anion was formed and photodissociated by loss of a benzoate radical, enabling measurement of the infrared spectrum that was in close agreement with that calculated for a structure containing one monodentate and two bidentate benzoate ligands.     

Molecular conductors with differently oriented conducting layers, (EDT-TTF)3Hg2Br6 and (TMBEDT-TTF)5Hg(SCN)4-xIx

New conducting radical cation salts (EDT-TTF)₃Hg ₂Br6, (TMET) ₅Hg(SCN) _4-xI_x (x≈0.35), and (EDT-TTF)₃Hg(SCN)₃I_0.5(PhCl)_0.5 were synthesized. Their conductivities, ESR and polarized reflectance spectra were studied. It was shown that the organic conductors with differently oriented conducting layers (EDT-TTF)₃Hg₂Br₆ and (TMET)₅Hg(SCN)_4-xI_x (x≈?0.35) are characterized by the quasi-one-dimensional character of electron motion. The conductivity along and across conducting layers has a semiconductive character. It was established by ESR and polarized reflectance spectroscopy that the properties of such conductors are a superposition of the properties of individual conducting layers.     

In situ investigations of vault paintings in the Antwerp cathedral

X-ray fluorescence spectroscopy (XRF) and Raman spectroscopy have been used to examine 15th century mediaeval and 16th century renaissance vault paintings in the Our Lady's Cathedral (Antwerp, Belgium) in view of their restoration. The use of mobile instruments made it possible to work totally non-destructively. This complementary approach yields information on the elemental (XRF) and on the molecular composition (Raman) of the pigments. For the 15th century vault painting the pigments lead–tin yellow (Pb₂SnO₄), lead white (2PbCO₃·Pb(OH)₂), vermilion (HgS), massicot (PbO) and azurite (2CuCO₃·Cu(OH)₂) could be identified. The pigments used for the 16th century vault painting could be identified as red lead (Pb₃O₄), hematite (Fe₂O₃), lead white (2PbCO₃·Pb(OH)₂) and azurite (2CuCO₃·Cu(OH)₂). For both paintings the presence of the strong Raman scatterer calcite (CaCO₃) resulted in a difficult identification of the pigments by Raman spectroscopy. The presence of gypsum (CaSO₄·2H₂O) on the mediaeval vault painting probably indicates that degradation took place.