Comprehensive Profiling by Non-targeted Stable Isotope Tracing Capillary Electrophoresis-Mass Spectrometry: A New Tool Complementing Metabolomic Analyses of Polar Metabolites

Mass spectrometry (MS) driven metabolomics is a frequently used tool in various areas of life sciences; however, the analysis of polar metabolites is less commonly included. In general, metabolomic analyses lead to the detection of the total amount of all covered metabolites. This is currently a major limitation with respect to metabolites showing high turnover rates, but no changes in their concentration. Such metabolites and pathways could be crucial metabolic nodes (e.g., potential drug targets in cancer metabolism). A stable-isotope tracing capillary electrophoresis–mass spectrometry (CE-MS) metabolomic approach was developed to cover both polar metabolites and isotopologues in a non-targeted way. An in-house developed software enables high throughput processing of complex multidimensional data. The practicability is demonstrated analyzing [U-¹³C]-glucose exposed prostate cancer and non-cancer cells. This CE-MS-driven analytical strategy complements polar metabolite profiles through isotopologue labeling patterns, thereby improving not only the metabolomic coverage, but also the understanding of metabolism.     

Ultraviolet C radiation influences the robustness of RNA integrity measurement

The analytical and clinical validity of analyses of RNA samples destined for clinical diagnosis and therapeutic management is directly impacted by RNA quality. RNA is affected by heat, enzymatic degradation, and Ultraviolet (UV) light. RNA from three eukaryotic cell lines was degraded by heat, RNase, or UV light. RNA integrity values obtained with the benchmark Agilent Bioanalyzer 2100 system were compared with those from the more recent QIAxcel Advanced system. The application of this novel method has allowed us to unravel differences between RNA biophysical and biochemical degradation modes. Agilent RNA integrity number (RIN) and QIAxcel RIS were comparable in heat‐degraded and RNase III‐degraded RNA. Agilent RIN and QIAxcel RIS were comparable at a RIN decision level of 7 in UV‐degraded RNA but not overall. The QIAxcel RIS method was more precise than Agilent RIN for RIN<8, while the inverse was true for RIN≥8. Greater degradation of mRNA and rRNA in UV‐damaged samples hampered the Agilent RIN calculation algorithm. Overall, RIS was more robust than RIN for assessing RNA integrity. The ΔΔCt‐values for heat‐ and UV‐degraded RNA samples showed slightly higher correlation with RIS than with RIN. RNA integrity can be used to categorize RNA samples for suitability for downstream gene expression analyses, independently of the RNA degradation mechanism. The new method QIAxcel is more robust and therefore allows more accurate categorization of compromised RNA samples.     

Biosynthetic insights provided by unusual sesterterpenes from the medicinal herb Aletris farinosa

A series of novel sesterterpenes (2–6) have been isolated from the roots of Aletris farinosa and structurally characterized by MS, NMR, and X-ray crystallography in conjunction with computational modeling. Their structures provide new insights into the mechanisms of sesterterpene biosynthesis. Specifically, we propose with support from density functional theory computations that the configuration at a single stereocenter determines the fate of a key tetracyclic carbocationic intermediate, derived from an oxidogeranylfarnesol precursor. Whereas one epimer of the carbocation undergoes H⁺ elimination to give 6, the other undergoes a spectacular cascade of seven 1,2-methyl and hydride migrations leading to the previously unreported carbon skeleton of 5. Theoretical calculations suggest that the cascade is triggered by substrate preorganization in the enzyme active site.     

Einige Bemerkungen zu einer allgemeinen Klasse von Stoffgesetzen für große elasto-plastische Formänderungen

Übersicht Unter den üblichen Voraussetzungen der phänomenologischen Plastizitätstheorie großer Formänderungen werden die Formulierungsbedingungen und einige spezielle Formulierungsmöglichkeiten für Fließbedingungen einer ziemlich allgemeinen Klasse erörtert, die isotrope und anisotrope Verfestigung umfaßt. Es schließen sich einige Bemerkungen zur Belastungsbedingung und zum zugehörigen Formänderungsgesetz an.

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Summary The restrictions for the formulation of yield conditions belonging to a rather general class comprehending isotropic and anisotropic hardening and some special cases are discussed under the usual assumptions of the phenomenological theory of plasticity at large deformations. Connected with this some remarks are following on the loading condition and the related stress-strain relations.

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Herrn Professor Dr. Dr. h. c. U. Wegner zum 70. Geburtstag.     

Analysis of Unsteady Motion with Respect to Noise Sources in a Gas Turbine Combustor: Isothermal Flow Case

In order to evaluate the direct and indirect contributions to the total combustion noise emission, a combustion chamber consisting of a swirl burner and an exit nozzle of Laval-shape, representing a gas turbine combustor, is investigated by means of experiments and large eddy simulation. Focused on the isothermal flow case first and encouraged by a good overall agreement between the LES and the experimental data for the flow field, a first characterisation of the flow with respect to noise sources is performed. To analyse acoustic properties of the flow, time and length scales are evaluated inside the combustor. Furthermore, the evidence for the existence of a precessing vortex core (PVC), typical for configurations with swirl, is revealed. Finally, the effect of the PVC on the flow inside the Laval nozzle is discussed.     

The formation of biaxial nematic phases in binary mixtures of thermotropic liquid-crystals composed of uniaxial molecules

ABSTRACT

Monte Carlo simulations in the isothermal-isobaric ensemble are used to investigate the formation of an ordered, biaxial nematic phase in a binary mixture of thermotropic liquid crystals. The orientational dependence of the interaction between molecules of each pure component is the same as in the well-known Maier-Saupe model; each pure component of the mixture is therefore capable of forming a uniaxial nematic phase. For the interaction between molecules of different components, we use the same Maier-Saupe model but change the sign of the coupling constant. As a consequence a T-shaped arrangement of these molecules is energetically favoured. The formation of the biaxial phase occurs in two steps. At higher temperatures T, one of the components forms a uniaxial nematic phase whereas the other is in a quasi two-dimensional restricted isotropic liquid state. We develop a simple theoretical model to understand the high degree of (ostensible) nematic order in the latter. At lower T, the second component becomes nematic and then the entire mixture of the two compounds has biaxial symmetry. The biaxial nematic phase does not demix into domains rich in molecules of one or the other species.     

Beyond the x-K relations

Explicit formulae are given for all off-diagonal 1–1 and 2–2 resonance terms in the vibrational hamiltonian following the first contact transformation. Such formulae are needed to test the quantitative accuracy of the generalized x-K relation recently published by Della Valle. These formulae are used in a test calculation for linear HCN and DCN and are found only modestly to improve the predicted energy levels for the former, but dramatically improve those of the latter.