Photolyse von Monophenylphosphat und e aq − -Bildung in wäßriger Lösung

At photolysis (253.7 nm) of monophenylphosphate (10^?3 m) in O₂-free neutral aqueous solution were determined: orthophosphate (Φ=0.006), phenol (Φ=0.0029), besides of small amounts of phosphorous acid, benzene, 2.2′-dihydroxybiphenyl and traces of 2.4′- and 4.4′-dihydroxybiphenyl. The yield of the main products is smaller at pH 2 and 12. Polymers were formed at u.v.-doses >2·10¹⁹ hv/ml. The electron yield determined by means of N₂O increases from Φ (N₂)= Φ(e _aq ^? )=0.012 to 0.019 changing the ester concentration from 0.001 to 0.1m. Φ (N₂)-value rises by addition of methanol or increasing pH. As electron ejecting state an excited complex is postulated. The effective ionization potential of phenylphosphate in aqueous solution is ≦4.9 e.v.     

L p -Estimates for the Navier–Stokes Equations for Steady Compressible Flow

We consider the Navier–Stokes equations for compressible isentropic flow in the steady three-dimensional case. The pressure and the kinetic energy are estimated uniformly in L^q with being the density. This is an improvement of known estimates in the case Mathematics Subject Classification (2000): 35Q30, 76N10     

Hydrolysis of Cutin by PET-Hydrolases

Functionalisation of synthetic polymers by using enzymes has been recently demonstrated. The major advantage of enzymes over chemical processes lies in their surface specific and endo-wise mode of action. Surface hydrophilisation of PET with lipases and cutinases leads to a dramatic increase of the surfacial acid and hydroxyl group content while conventional chemical treatment does not cause any change. However, this PET-hydrolysing activity by enzymes from distinct classes has not yet been correlated to activity on natural polyesters. Here, we show that lipases, cutinases and a PHA-depolymerase are all capable of hydrolysing PET, while only lipases and cutinases also hydrolysed cutin to various degrees. Lipases showed a higher specificity for terminal fatty acids while the cutinases preferred hydroxy fatty acids during cutin hydrolysis.     

Functional Additive Mixed Models

We propose an extensive framework for additive regression models for correlated functional responses, allowing for multiple partially nested or crossed functional random effects with flexible correlation structures for, for example, spatial, temporal, or longitudinal functional data. Additionally, our framework includes linear and nonlinear effects of functional and scalar covariates that may vary smoothly over the index of the functional response. It accommodates densely or sparsely observed functional responses and predictors which may be observed with additional error and includes both spline-based and functional principal component-based terms. Estimation and inference in this framework is based on standard additive mixed models, allowing us to take advantage of established methods and robust, flexible algorithms. We provide easy-to-use open source software in the pffr() function for the R package refund. Simulations show that the proposed method recovers relevant effects reliably, handles small sample sizes well, and also scales to larger datasets. Applications with spatially and longitudinally observed functional data demonstrate the flexibility in modeling and interpretability of results of our approach.     

Application of affinity capillary electrophoresis for charge heterogeneity profiling of biopharmaceuticals

Charge heterogeneity profiling is important for the quality control (QC) of biopharmaceuticals. Because of the increasing complexity of these therapeutic entities [1], the development of alternative analytical techniques is needed. In this work, flow‐through partial‐filling affinity capillary electrophoresis (FTPFACE) has been established as a method for the analysis of a mixture of two similar monoclonal antibodies (mAbs). The addition of a specific ligand results in the complexation of one mAb in the co‐formulation, thus changing its migration time in the electric field. This allows the characterization of the charged variants of the non‐shifted mAb without interferences. Adsorption of proteins to the inner capillary wall has been circumvented by rinsing with guanidine hydrochloride before each injection. The presented FTPFACE approach requires only very small amounts of ligands and provides complete comparability with a standard CZE of a single mAb.     

Design,Synthesis, and Phenotypic Profiling of Pyrano‐Furo‐Pyridone Pseudo Natural Products

Natural products (NPs) inspire the design and synthesis of novel biologically relevant chemical matter, for instance through biology‐oriented synthesis (BIOS). However, BIOS is limited by the partial coverage of NP‐like chemical space by the guiding NPs. The design and synthesis of “pseudo NPs” overcomes these limitations by combining NP‐inspired strategies with fragment‐based compound design through de novo combination of NP‐derived fragments to unprecedented compound classes not accessible through biosynthesis. We describe the development and biological evaluation of pyrano‐furo‐pyridone (PFP) pseudo NPs, which combine pyridone‐ and dihydropyran NP fragments in three isomeric arrangements. Cheminformatic analysis indicates that the PFPs reside in an area of NP‐like chemical space not covered by existing NPs but rather by drugs and related compounds. Phenotypic profiling in a target‐agnostic “cell painting” assay revealed that PFPs induce formation of reactive oxygen species and are structurally novel inhibitors of mitochondrial complex I.