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.     

Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH₂ by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N₂ and H₂O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m² g^?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with ¹H‐²⁷Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.     

Compact spreads and compact translation planes over locally compact fields

We prove that a spread S over a locally compact nondlscrete field F defines a topological translation plane if and only if the spread is compact. For F=R, this is implicit in Breuning's thesis [Bre], cf. [B 2]. For the proof, we describe the point set of the projective translation plane as a quotient space of some projective space, with identifications taking place in one hyperplane. This is new even for F=R.     

Finite Element Solution of Conical Diffraction Problems

This paper is devoted to the numerical study of diffraction by periodic structures of plane waves under oblique incidence. For this situation Maxwell's equations can be reduced to a system of two Helmholtz equations in R ² coupled via quasiperiodic transmission conditions on the piecewise smooth interfaces between different materials. The numerical analysis is based on a strongly elliptic variational formulation of the differential problem in a bounded periodic cell involving nonlocal boundary operators. We obtain existence and uniqueness results for discrete solutions and provide the corresponding error analysis.     

Temporary attachment of carbohydrates to cyclopeptide templates: a new strategy for single-bead analysis of multivalent neoglycopeptides

Employing a cleavable carbohydrate–peptide linker, a new strategy for single-bead analysis of multivalent cyclic neoglycopeptides based on Edman degradation is described. Edman degradation of glycopeptides is hampered by the acid lability of the glycosidic bond and potential incompatibilities of phenylthiohydantoin (PTH) derivatives of glycosylated amino acids with PTH derivatives of the proteinogenic amino acids. To overcome this problem, carbohydrates are detached from the cyclopeptide templates before single-bead analysis, allowing for micro sequencing under routine conditions. With this strategy, application of multivalent cyclic neoglycopeptides in split-mix libraries with a subsequent screening process becomes possible for the first time.     

Microwave-accelerated Claisen rearrangements of allyl tetronates and tetramates

[3,3]-Sigmatropic rearrangements of allyl tetronates and allyl tetramates to give 3-allyltetronic or -tetramic acids, respectively, proceed within 20-60 min under microwave irradiation (300 W, 130-190 °C). Consecutive (homo)sigmatropic [1,5] H-shifts such as oxa-ene reactions are promoted less effectively, which allows the isolation of Claisen intermediates of sigmatropic domino sequences, in contrast to conventional heating.     

Chern numbers for two families of noncommutative Hopf fibrations

We consider noncommutative line bundles associated with the Hopf fibrations of SU_q(2) over all Podle? spheres and with a locally trivial Hopf fibration of S³_pq. These bundles are given as finitely generated projective modules associated via 1-dimensional representations of U(1) with Galois-type extensions encoding the principal fibrations of SU_q(2) and S³_pq. We show that the Chern numbers of these modules coincide with the winding numbers of representations defining them. To cite this article: P.M. Hajac et al., C. R. Acad. Sci. Paris, Ser. I 336 (2003).     

Soliton chaos and lengthscale competition in nonlinear dynamics

Perturbing soliton-bearing completely integrable dynamics can give rise to rich and fascinating behaviour. If the perturbation introduces a lengthscale which is large compared to the spatial extent of the solitons present in the system, the solitons move like particles in an effective potential. Taking into account two-soliton interaction can result in chaotic behaviour called ‘soliton chaos’. In the opposite limit of a small-lengthscale perturbation the solitons acquire a dressing which effectively shields them from the perturbation. If the resulting ‘dressed solitons’ are subject to an additional long-wavelength perturbation they move like renormalised particles. Furthermore they can scatter nearly elastically. If the perturbation contains lengthscales which are comparable to one of the soliton's typical lengthscales then lengthscale competition can occur. Neither the particle approximation nor the dressed-particle approximation for the soliton is valid and complicated spatio-temporal behaviour is observed. We illustrate this scenario by means of the perturbed nonlinear Schrödinger equation. The perturbed sine-Gordon equation and the Ablowitz-Ladik equation are also discussed.