Thermal and Temporal Aging of Silica Gels in Monomer Solutions

In previous work we have introduced the idea of preparing ambient pressure dried silica aerogels by increasing the wet gels' stiffness by aging in a TEOS solution until shrinkage during drying is almost eliminated. The present work elucidates the possibilities for obtaining ambient pressure dried aerogels employing this idea, however, cheap water soluble sodium silicate (water glass) precursors have been used to increase the economic feasibility of the process.We have shown how the G modulus of water glass based gels can be increased by aging in TEOS solution and gels with a density down to 0.2 g/cm3 can be obtained. These wet gels show a higher reactivity towards TEOS compared to TEOS based gels. We have also introduced the idea of aging wet gels in a solution where the monomers are provided from water glass instead of TEOS and some initial results on G modulus and density are included.     

Acremolin,a new 1H-azirine metabolite from the marine-derived fungus Acremonium strictum

Acremolin (1), a novel modified base, was isolated from the culture broth of the marine fungus Acremonium strictum. Based on combined spectroscopic analyses, the structure of this compound was that of a methyl guanine base containing an isoprene unit. In addition, the presence of a 1H-azirine moiety is unprecedented among natural products. This compound exhibited weak cytotoxicity against an A549 cell line.     

Adamantyl Side Chains as Anti-Aggregating Moieties in Dyes for Dye-Sensitized Solar Cells

Designing and evaluating novel dye concepts is crucial for the development of the field of dye-sensitized solar cells (DSSCs). In our recent report, the novel concept of tethering the anti-aggregation additive chenodeoxycholic acid (CDCA) to dyes for DSSC was introduced. Based on the performance improvements seen for this modification, the aim of this study is to see if a simplified anti-aggregation unit could achieve similar results. The following study reports the synthesis and photovoltaic characterization of two novel dyes decorated with the steric ethyladamantyl moiety on the π-spacer, and on the triarylamine donor. This modification is demonstrated to be successful in increasing the photovoltages in devices employing copper-based electrolytes compared to the non-modified reference dye. The best photovoltaic performance is achieved by a device prepared with the adamantyl decorated donor dye and CDCA, this device achieves a power conversion efficiency of 6.1 % (Short-circuit current=8.3 mA cm⁻², Open-circuit voltage=1054 mV, Fill factor=0.69). The improved photovoltaic performance seen for the adamantyl decorated donor demonstrate the potential of ethyladamantyl side chains as a tool to ensure surface protection of TiO₂.     

Geminal conjugation in disulfides

Some aspects of the spatial and electronic structure of disulfides XSSX (X = H, Alk, Ph, Hal) are considered. It is shown that the growth of the geminal n_s-σ_SX* conjugation efficiency leads to a shortening of the SS bond that is more than three times as large as the simultaneous SX bond lengthening. The positive effective charge on the sulfur atom also increases as a result of this conjugation. These effects increase with the growth of - I and + M abilities of the substituents X. The SK_a line shifts and the HOMO bonding degree (Delta;n_S) have been measured by the X-ray fluorescence spectroscopy method for dialkyl disulfides (Alk = Me, Et, Pr, i-Pr, Bu, i-Bu, t-Bu, C₅H₁₁, C₈H₁₇, H₂NCH₂CH₂, CH₂CH  CH₂, CH₂Ph) and S₈. With the help of Δn_S values that are proportional to the n_S–σ_SC* conjugation efficiency, the sequence of the enhancement of the geminal conjugation efficiency has been established for the disulfides investigated. In the framework of the n_S–σ_SS* geminal conjugations, the shortening of the SS bonds in S₈ is explained. © John Wiley & Sons, Inc.     

X-ray fluorescent spectroscopy study of the charge state of heteroatoms in organic compounds of third row elements. 7. Thiocyanates and isothiocyanates

We propose an x-ray spectral criterion as a characteristic of organic and inorganic thiocyanates and isothiocyanates. We establish the lack of interaction between the level of the unshared electron pair of sulfur and the _cC-orbitals in thiocyanates.Translated from Izvestiya Akademii Nauk SSSR, Seriya, Khimicheskaya, No. 11, pp. 2519–2521, November, 1989.     

Changes in intratumor heterogeneity in blood perfusion in intradermal human melanoma xenografts during tumor growth assessed by DCE-MRI

The purpose of this study was to use dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI) to search for systematic intratumor heterogeneity in blood perfusion in human melanoma xenografts growing intradermally in BALB/c-nu/nu mice. Six xenografted tumors of an amelanotic human melanoma line (A-07) were included in the study. DCE-MRI was performed daily for 5 days by using spoiled-gradient recalled sequences. Tumor images of E.F (E is initial extraction fraction and F is perfusion) were produced by subjecting DCE-MRI data to Kety analysis. E.F was used as a measure of tumor blood perfusion, since comparative studies have shown that E.F is closely related to blood perfusion in A-07 tumors. The E.F images indicated that the intratumor heterogeneity in blood perfusion was similar in all investigated tumors. The blood perfusion was low in the center of the tumors and increased toward the tumor periphery in the dorsal and ventral direction by a factor of 3-4, but not in the lateral and medial direction. The magnitude of the heterogeneity increased by a factor of approximately 2 during tumor growth. In conclusion, intradermal human melanoma xenografts show significant systematic intratumor heterogeneity in blood perfusion.     

Nitrogen isotope analysis of ammonium in aqueous solutions using a perfluorosulfonated ionomer membrane for solid-phase microextraction

The use of custom-made solid-phase microextraction (SPME) fibers coated with a perfluorosulfonated ionomer, Nafion, was investigated for nitrogen isotopic analysis of ammonium in aqueous solutions. Aqueous ammonium was converted to ammonia by addition of a base, followed by absorption from the headspace, desorption in the injection port of a gas chromatograph, and analysis by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Fibers coated with a Nafion tubing were chosen due to a higher fiber-gas distribution constant and a higher Nafion thickness than fibers coated with Nafion solution, both leading to a higher amount of ammonia absorbed at equilibrium. The Nafion membrane-coated fiber absorbed approximately 20 times more than a commercial polydimethylsiloxane (PDMS) fiber. The isotopic fractionation between fiber and gas was 1.0117 +/- 0.0009 (standard deviation, SD, of all measurements) at an initial ammonia gas concentration of 21-210 microM. At 390 microM initial gas concentration it was slightly lower. When sampling from liquid samples, an ammonium concentration of 10 mM was needed to obtain a sufficient amount of ammonia absorbed. Modeling of the absorption at different temperatures showed that the absorption was approximately constant in the temperature range suitable for SPME experiments. Absorption at room temperature was therefore used for simplicity. A pilot study was conducted in which absorption was achieved from a single 9 microL droplet of sample. The preliminary results showed that delta(15)N analysis was possible for only 0.4-0.5 micromol of ammonium with a SD of 0.8 per thousand (n = 5).