Validation of atmospheric VOC measurements by proton-transfer-reaction mass spectrometry using a gas-chromatographic preseparation method

Proton-transfer-reaction mass spectrometry (PTR-MS) has emerged as a useful tool to study volatile organic compounds (VOCs) in the atmosphere. In PTR-MS, proton-transfer reactions with H30+ ions are used to ionize and measure VOCs in air with a high sensitivity and fast time response. Only the masses of the ionized VOCs and their fragments, if any, are determined, and these product ions are not unique indicators of VOC identities. Here, a combination of gas chromatography and PTR-MS (GC-PTR-MS) is used to validate the measurements by PTR-MS of a number of common atmospheric VOCs. We have analyzed 75 VOCs contained in standard mixtures by GC-PTR-MS, which allowed detected masses to be unambiguously related to a specific compound. The calibration factors for PTR-MS and GC-PTR-MS were compared and showed that the loss of VOCs in the sample acquisition and GC system is small. GC-PTR-MS analyses of 56 air samples from an urban site were used to address the specificity of PTR-MS in complex air masses. It is demonstrated that the ions associated with methanol, acetonitrile, acetaldehyde, acetone, benzene, toluene, and higher aromatic VOCs are free from significant interference. A quantitative intercomparison between PTR-MS and GC-PTR-MS measurements of the aforementioned VOCs was performed and shows that they are accurately measured by PTR-MS.     

A proteomics platform combining depletion, multi-lectin affinity chromatography (M-LAC), and isoelectric focusing to study the breast cancer proteome

The discovery of breast cancer associated plasma/serum biomarkers is important for early diagnosis, disease mechanism elucidation, and determination of treatment strategy for the disease. In this study of serum samples, a multidimensional fractionation platform combined with mass spectrometric analysis were used to achieve the identification of medium to lower abundance proteins, as well as to simultaneously detect glycan and abundance changes. Immuno-affinity depletion and multi-lectin chromatography (M-LAC) were integrated into an automated HPLC platform to remove high abundance protein and fractionate glycoproteins. The collected glycoproteomes were then subjected to isoelectric focusing (IEF) separation by a digital ProteomeChip (dPC), followed by in-gel digestion and LC-MS analysis using an Orbitrap mass spectrometer. As a result, the total number of identified proteins increased significantly when the IEF fractionation step was included as part of the platform. Relevant proteins with biological and disease significance were observed and the dynamic range of the serum proteome measurement was extended. In addition, potential glycan changes were indicated by comparing proteins in control and cancer samples in terms of their affinity to the multi-lectin column (M-LAC) and the pI profiles in IEF separation. In conclusion, a proteomics platform including high abundance protein depletion, lectin affinity fractionation, IEF separation, and LC-MS analysis has been applied to discover breast cancer-associated proteins. The following candidates, thrombospondin-1 and 5, alpha-1B-glycoprotein, serum amyloid P-component, and tenascin-X, were selected as promising examples of the use of this platform. They show potential abundance and glycan changes and will be further investigated in future studies.     

Three-dimensional atomic imaging of colloidal core-shell nanocrystals

Colloidal core-shell semiconductor nanocrystals form an important class of optoelectronic materials, in which the exciton wave functions can be tailored by the atomic configuration of the core, the interfacial layers, and the shell. Here, we provide a trustful 3D characterization at the atomic scale of a free-standing PbSe(core)-CdSe(shell) nanocrystal by combining electron microscopy and discrete tomography. Our results yield unique insights for understanding the process of cation exchange, which is widely employed in the synthesis of core-shell nanocrystals. The study that we present is generally applicable to the broad range of colloidal heteronanocrystals that currently emerge as a new class of materials with technological importance.     

Molecular Ordering at the Interface Between Liquid Water and Rutile TiO2(110)

The pivotal importance of TiO₂ as a technological material involves most applications in an aqueous environment, but the single‐crystal TiO₂/bulk‐water interfaces are almost completely unexplored, since up to date solid/liquid interfaces are more difficult to access than surfaces in ultrahigh vacuum (UHV). Only a few techniques (as scanning probe microscopy) offer the opportunity to explore these systems under realistic conditions. The rutile TiO₂(110) surface immersed in high‐purity water is studied by in situ scanning tunneling microscopy. The large‐scale surface morphology as obtained after preparation under UHV conditions remains unchanged upon prolonged exposure to bulk water. Moreover, in contrast to UHV, atomically resolved images show a twofold periodicity along the [001] direction, indicative of an ordered structure resulting from the hydration layer. This is consistent with density‐functional theory based molecular dynamics simulations where neighboring interfacial molecules of the first water layer in contact with the bulk liquid form dimers. By contrast, this dimerization is not observed for a single adsorbed water monolayer, i.e., in the absence of bulk water.     

Photosystem I‐based Biophotovoltaics on Nanostructured Hematite

The electronic coupling between a robust red algal photosystem I (PSI) associated with its light harvesting antenna (LHCI) and nanocrystalline n‐type semiconductors, TiO₂ and hematite (α‐Fe₂O₃) is utilized for fabrication of the biohybrid dye‐sensitized solar cells (DSSC). PSI‐LHCI is immobilized as a structured multilayer over both semiconductors organized as highly ordered nanocrystalline arrays, as evidenced by FE‐SEM and XRD spectroscopy. Of all the biohybrid DSSCs examined, α‐Fe₂O₃/PSI‐LHCI biophotoanode operates at a highest quantum efficiency and generates the largest open circuit photo­current compared to the tandem system based on TiO₂/PSI‐LHCI material. This is accomplished by immobilization of the PSI‐LHCI complex with its reducing side towards the hematite surface and nanostructuring of the PSI‐LHCI multilayer in which the subsequent layers of this complex are organized in the head‐to‐tail orientation. The biohybrid PSI‐LHCI‐DSSC is capable of sustained photoelectrochemical H₂ production upon illumination with visible light above 590 nm. Although the solar conversion efficiency of the PSI‐LHCI/hematite DSSC is currently below a practical use, the system provides a blueprint for a genuinely green solar cell that can be used for molecular hydrogen production at a rate of 744 μmoles H₂ mg Chl^?1 h^?1, placing it amongst the best performing biohybrid solar‐to‐fuel nanodevices.     

Highly Stretchable and Tough Hydrogels below Water Freezing Temperature

Hydrogels consist of hydrophilic polymer networks dispersed in water. Many applications of hydrogels rely on their unique combination of solid‐like mechanical behavior and water‐like transport properties. If the temperature is lowered below 0 °C, however, hydrogels freeze and become rigid, brittle, and non‐conductive. Here, a general class of hydrogels that do not freeze at temperatures far below 0 °C, while retaining high stretchability and fracture toughness, is demonstrated. These hydrogels are synthesized by adding a suitable amount of an ionic compound to the hydrogel. The present study focuses on tough polyacrylamide‐alginate double network hydrogels equilibrated with aqueous solutions of calcium chloride. The resulting hydrogels can be cooled to temperatures as low as ?57 °C without freezing. In this temperature range, the hydrogels can still be stretched more than four times their initial length and have a fracture toughness of 5000 J m^?2. It is anticipated that this new class of hydrogels will prove useful in developing new applications operating under a broad range of environmental and atmospheric conditions.     

A comparison of boundary graph grammars and context-free hypergraph grammars

Context-free hypergraph grammars and boundary graph grammars of bounded nonterminal degree have the same power, both for generating sets of graphs and for generating sets of hypergraphs. Arbitrary boundary graph grammars have more graph generating power than context-free hypergraph grammars, but they have the same hypergraph generating power. To obtain these results, several normal forms for boundary graph grammars are given. It is also shown that the class of boundary graph languages is closed under the operation of edge contraction, where the label of the edge indicates whether or not the edge should be contracted.     

Photoswitchable Liquid-to-Solid Transition of Azobenzene-Decorated Polysiloxanes

Having external control over fundamental properties of polymers, such as their physical state, is a crucial yet challenging design criterion for smart materials. Liquifying polymers through photochemical events has significantly advanced various research lines. However, the opposite process of solidifying a polymer that is intrinsically in a liquid state reversibly with light is unattained. Herein, the light-controlled liquid-to-solid transition of polysiloxanes is reported, which are decorated with a small number of azobenzene-functionalized ureidopyrimidinone (Azo-UPy) pendants. The UPy moieties toggle between intra- and intermolecular hydrogen bonding via trans→cis photoisomerization of the azobenzene. This transformation on the molecular level leads to the formation of strong supramolecular cross-links, which, in turn, results in the macroscopic solidification of the material. The photoswitching event enables the post-synthetic tailoring of the polymers’ mechanical properties, thus providing an alternative to the addition of plasticizers or hardeners. Moreover, the adhesion strength of the photochromic material increases by a factor of 6 upon exposure to UV light. In situ illumination during rheological measurements reveals the delicate interplay between wavelength dependent penetration depth and photoswitching efficiency. This conceptually new (de)bonding on demand strategy paves the way for creating light-responsive materials with exciting applications in temporal adhesion, recycling, lithography, and material processing.     

Zum Durchstanzen von Flachdecken nach Eurocode 2

Die Regelungen zur Durchstanzbemessung im Eurocode 2 basieren im Wesentlichen auf den Modellvorstellungen in Model Code 90, der die Durchstanztragfähigkeit auf die Querkrafttragfähigkeit zurückführt. Nach Versuchsauswertungen ist diese Analogie für punktgestützte Platten jedoch nicht in jedem Fall zutreffend. Insbesondere für bügelbewehrte Platten ist bei der Bemessung nach Eurocode 2 ein Sicherheitsdefizit möglich, und es erscheint eine Anpassung der Bemessungsgleichungen zwingend erforderlich. Dieser Beitrag erläutert die Sicherheitsdefizite und schlägt verbesserte Bemessungsgleichungen vor. Punching of Flat Slabs according to Eurocode 2 The punching shear provisions according to Eurocode 2 are based on the design recommendations in Model Code 90 where no differentiation between shear and punching shear design is made. This approach is not fully confirmed by test results for flat slabs. In particular for flat slabs with stirrups as shear reinforcement some design provisions according to Eurocode 2 do not achieve the required safety level. Therefore adjustments to the design equations seem to be necessary. In this paper the Eurocode 2 provisions are critically reviewed and improved design regulations are proposed.