Calcium adsorption and displacement: characterization of lipid monolayers and their interaction with membrane-active peptides/proteins

Background  

The first target of antimicrobial peptides (AMPs) is the bacterial membrane. In the case of Gram-negative bacteria this is the outer membrane (OM), the lipid composition of which is extremely asymmetric: Whereas the inner leaflet is composed of a phospholipid mixture, the outer leaflet is made up solely from lipopolysaccharides (LPSs). LPS, therefore, represents the first target of AMPs. The binding and intercalation of polycationic AMPs is driven by the number and position of negatively charged groups of the LPS. Also, proteins other than cationic AMPs can interact with LPS, e.g. leading eventually to a neutralization of the endotoxic effects of LPS. We compared different biophysical techniques to gain insight into the properties of the electrical surface potentials of lipid monolayers and aggregates composed of LPSs and various phospholipids and their interaction with peptides and proteins.     

Number ofKekulé structures of single-chain aromatics

The number ofKekulé structures is derived for an arbitrary single-chain aromatic. This class of molecules consists of condensed aromatics where the line through the centers of the fused benzene rings is a single (unbranched) line.     

Molecular dynamics simulation of the renin inhibitor H142 in water

Summary H142 is a synthetic decapeptide designed to inhibit renin, an enzyme acting in the regulation of blood pressure. The inhibiting effect of H142 is caused by a reduction of a-Leu-Val-peptide bond (i. e. C(=O)-NHCH₂-NH). The conformational and dynamical properties of H142 and its unreduced counterpart (H142n) was modelled by means of molecular dynamics simulations. Water was either included explicitly in the simulations or as a dielectric continuum. When water molecules surround the peptides, they remain in a more or less extended conformation through the simulation. If water is replaced by a dielectric continuum, the peptides undergo a conformational change from an extended to a folded state. It is not clear whether this difference is a consequence of a too short simulation time for the water simulations, a force-field artifact promoting extended conformations, or if the extended conformation represents the true conformational state of the peptide. A number of dynamic properties were evaluated as well, such as overall rotation, translational diffusion, side-chain dynamics and hydrogen bonding.     

Comparison of the protein adsorption selectivity of salt-promoted agarose-based adsorbents: Hydrophobic, thiophilic and electron donor–acceptor adsorbents

Protein adsorption of human serum onto six different agarose-based chromatographic gels that were representative of the salt-promoted adsorbent family [octyl- and phenyl-Sepharose, mercaptoethanol–divinyl sulfone agarose (T gel), mercaptomethylene pyridine-derivatized agarose gel (MP gel), tricyanoaminopropene–divinyl sulfone agarose (DVS–TCP gel), tricyanoamino-propene–bisoxirane agarose (bisoxirane–TCP gel)] was studied in the presence of moderate or high concentrations of the water structuring salt, sodium sulfate. Study of the protein adsorption selectivity by two-dimensional gel electrophoresis revealed an opposed selectivity for hydrophobic interaction adsorbents and electron donor–acceptor adsorbents. The T gel, MP gel and TCP gels belonged to the electron donor–acceptor adsorbents, displaying a main selectivity for immunoglobulins, whereas octyl-Sepharose belonged to the hydrophobic adsorbents, displaying a main selectivity for ‘hydrophobic' proteins. Phenyl-Sepharose for its part was described as an example of a composite selectivity of both families. The conclusion of this work is two-fold: (1) hydrophobic interaction chromatography (HIC) and electron donor–acceptor chromatography (EDAC) have opposed protein selectivities and are both salt-promoted. As a main consequence, it means that high concentrations of a water-structuring salt can promote different types of weak molecular interactions, resulting in different protein adsorption selectivities: (2) thiophilic adsorption chromatography (TAC) should be renamed EDAC as similar protein selectivity is demonstrated for electron donor–acceptor ligand devoid of sulfur atoms.     

Thermal decomposition of synthetic hydrotalcites reevesite and pyroaurite

A combination of high resolution thermogravimetric analysis coupled to a gas evolution mass spectrometer has been used to study the thermal decomposition of synthetic hydrotalcites reevesite (Ni₆Fe₂(CO₃)(OH)₁₆·4H₂O) and pyroaurite (Mg₆Fe₂(SO₄,CO₃)(OH)₁₆·4H₂O) and the cationic mixtures of the two minerals. XRD patterns show the hydrotalcites are layered structures with interspacing distances of around 8.0. Å. A linear relationship is observed for the d(001) spacing as Ni is replaced by Mg in the progression from reevesite to pyroaurite. The significance of this result means the interlayer spacing in these hydrotalcites is cation dependent. High resolution thermal analysis shows the decomposition takes place in 3 steps. A mechanism for the thermal decomposition is proposed based upon the loss of water, hydroxyl units, oxygen and carbon dioxide.     

Detectability of words and nonwords in two kinds of noise

Recent models of speech perception emphasize the possibility of interactions among different processing levels. There is evidence that the lexical status of an utterance (i.e., whether it is a meaningful word or not) may influence earlier stages of perceptual analysis. To test how far down such "top-down" influences might penetrate, an investigation was conducted to determine whether there is a difference in detectability of words and nonwords masked by amplitude-modulated or unmodulated broadband noise. The results were negative, suggesting either that the stages of perceptual analysis engaged in the detection task are impermeable to lexical top-down effects, or that the lexical level was not sufficiently activated to have any facilitative effect on perception.     

Arc‐Disjoint Directed and Undirected Cycles in Digraphs

The dicycle transversal number of a digraph D is the minimum size of a dicycle transversal of D, that is a set of vertices of D, whose removal from D makes it acyclic. An arc a of a digraph D with at least one cycle is a transversal arc if a is in every directed cycle of D (making acyclic). In [3] and [4], we completely characterized the complexity of following problem: Given a digraph D, decide if there is a dicycle B in D and a cycle C in its underlying undirected graph such that . It turns out that the problem is polynomially solvable for digraphs with a constantly bounded number of transversal vertices (including cases where ). In the remaining case (allowing arbitrarily many transversal vertices) the problem is NP‐complete. In this article, we classify the complexity of the arc‐analog of this problem, where we ask for a dicycle B and a cycle C that are arc‐disjoint, but not necessarily vertex‐disjoint. We prove that the problem is polynomially solvable for strong digraphs and for digraphs with a constantly bounded number of transversal arcs (but possibly an unbounded number of transversal vertices). In the remaining case (allowing arbitrarily many transversal arcs) the problem is NP‐complete.     

Symmetry of solutions to nonlocal nonlinear boundary value problems in radial sets

For open radial sets \({\Omega \subset {\mathbb {R}}^N}\), \({N\geq 2}\) we consider the nonlinear problem

$$(P)\qquad\left\{\begin{array}{ll}I u = f(|x|,u)& \;\, \rm{ in } ~\Omega,\\ u \equiv 0 &\,\,\, \text{on}~ \mathbb{R}^{N}{\setminus} \Omega,\\ \lim_{|x|\to\infty}u(x) = 0,&\end{array}\right.$$

where I is a nonlocal operator and f is a nonlinearity. Under mild symmetry and monotonicity assumptions on I, f and \({\Omega}\) we show that any continuous bounded solution of (P) is axial symmetric once it satisfies a simple reflection inequality with respect to a hyperplane. In the special case where f does not depend on |x|, we show that any nonnegative nontrivial continuous bounded solution of (P) in \({\mathbb {R}^N}\) is radially symmetric (up to translation) and strictly decreasing in its radial direction. Our proves rely on different variants of maximum principles for antisymmetric supersolutions which can be seen as extensions of the results in Jarohs and Weth (Ann Mat Pura Appl 195:273–291, 2016). As an application, we prove an axial symmetry result for minimizers of an energy functional associated to (P).

     

Simultaneous Dual Encoding of Three‐Dimensional Structures by Light‐Induced Modular Ligation

A highly efficient strategy for the simultaneous dual surface encoding of 2D and 3D microscaffolds is reported. The combination of an oligo(ethylene glycol)‐based network with two novel and readily synthesized monomers with photoreactive side chains yields two new photoresists, which can be used for the fabrication of microstructures (by two‐photon polymerization) that exhibit a dual‐photoreactive surface. By combining both functional photoresists into one scaffold, a dual functionalization pattern can be obtained by a single irradiation step in the presence of adequate reaction partners based on a self‐sorting mechanism. The versatility of the approach is shown by the dual patterning of halogenated and fluorescent markers as well as proteins. Furthermore, we introduce a new ToF–SIMS mode (“delayed extraction”) for the characterization of the obtained microstructures that combines high mass resolution with improved lateral resolution.