Consensus structure elucidation combining GC/EI-MS, structure generation, and calculated properties

This article explores consensus structure elucidation on the basis of GC/EI-MS, structure generation, and calculated properties for unknown compounds. Candidate structures were generated using the molecular formula and substructure information obtained from GC/EI-MS spectra. Calculated properties were then used to score candidates according to a consensus approach, rather than filtering or exclusion. Two mass spectral match calculations (MOLGEN-MS and MetFrag), retention behavior (Lee retention index/boiling point correlation, NIST Kovat's retention index), octanol-water partitioning behavior (log K(ow)), and finally steric energy calculations were used to select candidates. A simple consensus scoring function was developed and tested on two unknown spectra detected in a mutagenic subfraction of a water sample from the Elbe River using GC/EI-MS. The top candidates proposed using the consensus scoring technique were purchased and confirmed analytically using GC/EI-MS and LC/MS/MS. Although the compounds identified were not responsible for the sample mutagenicity, the structure-generation-based identification for GC/EI-MS using calculated properties and consensus scoring was demonstrated to be applicable to real-world unknowns and suggests that the development of a similar strategy for multidimensional high-resolution MS could improve the outcomes of environmental and metabolomics studies.     

Investigation of the utility of laser-secondary neutral mass spectrometry for the detection of polyaromatic hydrocarbons in individual atmospheric aerosol particles

The distribution of polyaromatic hydrocarbons (PAHs) in ambient aerosol particles is of importance to both human health and climate forcing. Although time-of-flight secondary ion mass spectrometry (ToF-SIMS) has proven useful for studying the distribution of organic compounds in individual aerosol particles, it is difficult to detect PAHs at relevant concentrations in individual aerosol particles because of their low ion yield. In this study, we explore the potential of using laser secondary neutral mass spectrometry (Laser-SNMS) to study three PAHs: pyrene, anthracene, and naphthalene. Because of the high volatility of PAHs, a cryostage was required for the analysis to prevent sublimation of the molecules into the vacuum chamber. We studied two laser systems, a 157 nm excimer laser, which is capable of single-photon ionization of the PAHs, and a 193 nm laser, which requires multiphoton ionization. Under optimized conditions for laser power density and primary ion pulse length, 193 nm postionization resulted in a 2-50-fold increase in ion yield over ToF-SIMS. Using the 157 nm laser, the yield was increased by more than 3 orders of magnitude for all 3 PAHs studied. The single-photon postionization process proved superior in terms of both yield enhancement and reduced fragmentation. By using the optimized 157 nm laser system and a cryostage, we were able to detect PAHs on the surface of 2 μm diameter ambient aerosol particles.     

Manufacture and characterization of optical coatings with incorporated copper island films

Copper island films have been prepared by thermal evaporation in vacuum and characterized by in situ as well as ex situ spectrophotometry. The parallel investigation of the island morphology by means of transmission electron microscopy allowed us to establish a clear correlation between film structure and optical properties. The effective optical constants of the copper island films could be determined by means of a fit of their ex situ transmission and reflection spectra. The effective optical constants have been used for designing and preparing optical multilayer coatings applicable for attenuator or color filter specifications. Measured characteristics of the multilayer coatings are in very good agreement with the calculated spectra.     

Decision support for rehabilitation hospital scheduling

We present a detailed analysis of the patient and resource scheduling problem in rehabilitation hospitals. In practice, the predominantly therapeutical treatments and activities which are prescribed for the patients are typically scheduled manually. This leads to rigid and inefficient schedules which can have negative effects on the quality of care and the patients’ satisfaction. We outline the conceptual framework of a decision support system for the scheduling process that is based on formal optimization models. To this end, we first develop a large-scale monolithic optimization model. Then we derive a numerically tractable hierarchical model system in order to deal with problem instances of realistic sizes. We report numerical results with respect to solution times, model sizes and solution quality.     

Control aspects of quantum computing using pure and mixed states

Steering quantum dynamics such that the target states solve classically hard problems is paramount to quantum simulation and computation. And beyond, quantum control is also essential to pave the way to quantum technologies. Here, important control techniques are reviewed and presented in a unified frame covering quantum computational gate synthesis and spectroscopic state transfer alike. We emphasize that it does not matter whether the quantum states of interest are pure or not. While pure states underly the design of quantum circuits, ensemble mixtures of quantum states can be exploited in a more recent class of algorithms: it is illustrated by characterizing the Jones polynomial in order to distinguish between different (classes of) knots. Further applications include Josephson elements, cavity grids, ion traps and nitrogen vacancy centres in scenarios of closed as well as open quantum systems.     

Automated high resolution measurement of heliostat slope errors

A new optical measurement method that simplifies and optimizes the mounting and canting of heliostats and helps to assure their optical quality before commissioning of the solar field was developed. This method is based on the reflection of regular patterns in the mirror surface and their distortions due to mirror surface errors. The measurement has a resolution of about 1 million points per heliostat with a measurement uncertainty of less than 0.2 mrad and a measurement time of about 1 min per heliostat. The system is completely automated and allows the automatic measurement of an entire heliostat field during one night. It was extensively tested at the CESA-1 heliostat field at the Plataforma Solar de Almería. Comparisons of flux simulations based on the measurement results with real flux density measurements were performed. They showed an excellent agreement and demonstrated in a striking manner the high measurement accuracy and high grade of detail in the simulation achieved by this technique.     

Filtration performance at high temperatures and analysis of ceramic filter elements during biomass gasification

During the CHRISGAS project, various experimental campaigns were performed with the aim to study the hot gas filtration process during steam-O₂ biomass gasification at Delft University of Technology. The test-rig consists of a 100 kW thermal atmospheric circulating fluidized-bed gasifier and a high temperature filter unit which contains 3 rigid ceramic candles with an outer diameter of 60 mm, 10 mm wall thickness and a length of 1520 mm. This paper gives an overview of tests performed with different fuels (A-wood, B-wood, miscanthus) and with sand and magnesite used as bed materials. Dia-Schumalith¹ candles were operated in the temperature range between 600 °C and 800 °C for more than 50 h. The filtration performance was studied through continuous observation of the increasing differential pressure while the filter cake formed on the surface of the candles. Gas face velocities ranged between 3 cm s^?1 and 5 cm s^?1. Stable filtration was achieved during some tests. Dust cake analysis indicated formation of calcium phosphates and silicates and potassium silicates.     

Mechanical properties of anatase and semi-metallic TiO2 nanotubes

We report for the first time on mechanical properties of anodically formed, self-organized TiO₂ nanotube layers on titanium. We compare their behavior in their virgin state and after conversion to their semi-metallic form by an acetylene treatment. We show that the acetylene treatment leads to significant enhanced hardness, tensile strength and friction behavior.     

Climate policies for road transport revisited (II): Closing the policy gap with cap-and-trade

Current policies in the road transport sector fail to deliver consistent and efficient incentives for greenhouse gas abatement (see companion article by Creutzig et al., in press). Market-based instruments such as cap-and-trade systems close this policy gap and complement traditional policies that are required where specific market failures arise. Even in presence of strong existing non-market policies, cap-and-trade delivers additional abatement and efficiency by incentivizing demand side abatement options. This paper analyzes generic design options and economic impacts of including the European road transport sector into the EU ETS. Suitable points of regulation are up- and midstream in the fuel chain to ensure effectiveness (cover all emissions and avoid double-counting), efficiency (incentivize all abatement options) and low transaction costs. Based on year 2020 marginal abatement cost curves from different models and current EU climate policy objectives we show that in contrast to conventional wisdom, road transport inclusion would not change the EU ETS allowance price. Hence, industrial carbon leakage induced by adding road transport to the EU ETS may be less important than previously estimated.     

STT and DTT Diagrams of Austenitic Cr–Mn–Ni As‐Cast Steels and Crucial Thermodynamic Aspects of γ → α′ Transformation

The mechanical behavior and microstructure evolution during deformation of novel austenitic Cr–Mn–Ni as‐cast steels with varied Ni content were investigated at various temperatures using static tensile tests, optical microscopy, and the magnetic scale for the detection of ferromagnetic phase fraction. To summarize all knowledge about the deformation‐induced processes, the STT and DTT diagrams were developed for Cr–Mn–Ni steels. The diagrams illustrate the different deformation mechanisms depending on temperature and tension load, and quantify the elongation of the deformation mechanisms. The deformation‐induced ε‐ and α' martensite formation and twinning – the TRIP and TWIP effects – occur in the Cr–Mn–Ni steels depending on the chemical composition and temperature. The differences of deformation‐induced processes depend on thermodynamics and are confirmed by thermodynamic calculations. The nucleation threshold of γ → α′ transformation was determined for the investigated Cr–Mn–Ni steels.