Enantiomeric Cyclic Peptides with Different Caco‐2 Permeability Suggest Carrier‐Mediated Transport

Recently, oral absorption of cyclic hexapeptides was improved by N‐methylation of their backbone amides. However, the number and position of N‐methylations or of solvent exposed NHs did not correlate to intestinal permeability, measured in a Caco‐2 model. In this study, we investigate enantiomeric pairs of three polar and two lipophilic peptides to demonstrate the participation of carrier‐mediated transporters. As expected, all the enantiomeric peptides exhibited identical lipophilicity (logD_7.4) and passive transcellular permeability determined by the parallel artificial membrane permeability assay (PAMPA). However, the enantiomeric polar peptides exhibited different Caco‐2 permeability (P_app) in both directions a–b and b–a. The same trend was observed for one of the lipophilic peptide, whereas the second lipophilic enantiomer pair showed identical Caco‐2 permeability (within the errors). These findings provide the first evidence for the involvement of carrier‐mediated transport for peptides, especially for those of polar nature.     

Adiabatic passage Hartmann-Hahn cross polarization in NMR under magic angle sample spinning

We have recently demonstrated that polarization transfer using an adiabatic passage through the Hartmann-Hahn condition (APHH-CP) by a variation of the radio-frequency amplitude can substantially improve the transfer efficiency over Hartmann-Hahn cross polarization. Here we show that APHH-CP can be combined with fast magic angle sample spinning (MAS). The heteronuclear dipolar order, established in the course of the transfer, can indeed be created and preserved.     

Zur Kenntnis der kolloidchemischen Eigenschaften des Humus

Ohne ZusammenfassungMeinem verehrten Lehrer, Herrn Prof. Dr. H. Pallmann — auf dessen Anregung diese Arbeit ausgeführt würde — möchte ich für die mir zuteil gewordene Förderung und die wertvollen Ratschläge bestens danken.     

Metallo‐supramolecular block copolymer micelles: Improved preparation and characterization

Micelles prepared from amphiphilic block copolymers in which a poly(styrene) segment is connected to a poly(ethylene oxide) block via a bis‐(2,2′:6′,2″‐terpyridine‐ruthenium) complex have been intensely studied. In most cases, the micelle populations were found to be strongly heterogeneous in size because of massive micelle/micelle aggregation. In the study reported in this article we tried to improve the homogeneity of the micelle population. The variant preparation procedure developed, which is described here, was used to prepare two “protomer”‐type micelles: PS₂₀‐[Ru]‐PEO₇₀ and PS₂₀‐[Ru]‐PEO₃₇₅. The dropwise addition of water to a solution of the compounds in dimethylformamide was replaced by the controlled addition of water by a syringe pump. The resulting micelles were characterized by sedimentation velocity and sedimentation equilibrium analyses in an analytical ultracentrifuge and by transmission electron microscopy of negatively stained samples. Sedimentation analysis showed virtually unimodal size distributions, in contrast to the findings on micelles prepared previously. PS₂₀‐[Ru]‐PEO₇₀ micelles were found to have an average molar mass of 318,000 g/mol (corresponding to 53 protomers per micelle, which is distinctly less than after micelle preparation by the standard method) and an average hydrodynamic diameter (d_h) of 18 nm. For PS₂₀‐[Ru]‐PEO₃₇₅ micelles, the corresponding values were M = 603,000 g/mol (31 protomers per micelle) and d_h = 34 nm. The latter particles were found to be identical to the “equilibrium” micelles prepared in pure water. Both micelle types had a very narrow molar mass distribution but a much broader distribution of s values and thus of hydrodynamic diameters. This indicates a conformational heterogeneity that is stable on the time scale of sedimentation velocity analysis. The findings from electron microscopy were in disagreement with those from the sedimentation analysis both in average micelle diameter and in the width of the distributions, apparently because of imperfections in the staining procedure. The preparation procedure described also may be useful in micelle formation from other types of protomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4458–4465, 2004     

Solid-State Thin-Film Sensors Based on Chalcogenide Materials Obtained by Planar Technology and Pulsed Laser Deposition

Methods of silicon planar technology and pulsed laser deposition were applied to fabricate fully solid-state chemical sensors for determining ions of copper, lead, cadmium, thallium, and also sulfide and chloride ions on the basis of thin chalcogenide films as ion-sensitive membranes.     

A mixed‐FEM formulation for nonlinear incompressible elasticity in the plane

This article deals with an expanded mixed finite element formulation, based on the Hu‐Washizu principle, for a nonlinear incompressible material in the plane. We follow our related previous works and introduce both the stress and the strain tensors as further unknowns, which yields a two‐fold saddle point operator equation as the corresponding variational formulation. A slight generalization of the classical Babu?ka‐Brezzi's theory is applied to prove unique solvability of the continuous and discrete formulations, and to derive the corresponding a priori error analysis. An extension of the well‐known PEERS space is used to define an stable associated Galerkin scheme. Finally, we provide an a posteriori error analysis based on the classical Bank‐Weiser approach. © 2002 John Wiley & Sons, Inc. Numer Methods Partial Differential Eq 18: 105–128, 2002     

A p-version finite element method for nonlinear elliptic variational inequalities in 2D

This article introduces and analyzes a p-version FEM for variational inequalities resulting from obstacle problems for some quasi-linear elliptic partial differential operators. We approximate the solution by controlling the obstacle condition in images of the Gauss–Lobatto points. We show existence and uniqueness for the discrete solution u _p from the p-version for the obstacle problem. We prove the convergence of u _p towards the solution with respect to the energy norm, and assuming some additional regularity for the solution we derive an a priori error estimate. In numerical experiments the p-version turns out to be superior to the h-version concerning the convergence rate and the number of unknowns needed to achieve a certain exactness of the approximation.