The Dynamics of the Neuropeptide Y Receptor Type 1 Investigated by Solid-State NMR and Molecular Dynamics Simulation

We report data on the structural dynamics of the neuropeptide Y (NPY) G-protein-coupled receptor (GPCR) type 1 (Y1R), a typical representative of class A peptide ligand GPCRs, using a combination of solid-state NMR and molecular dynamics (MD) simulation. First, the equilibrium dynamics of Y1R were studied using ¹⁵N-NMR and quantitative determination of ¹H-¹³C order parameters through the measurement of dipolar couplings in separated-local-field NMR experiments. Order parameters reporting the amplitudes of the molecular motions of the C-H bond vectors of Y1R in DMPC membranes are 0.57 for the Cα sites and lower in the side chains (0.37 for the CH₂ and 0.18 for the CH₃ groups). Different NMR excitation schemes identify relatively rigid and also dynamic segments of the molecule. In monounsaturated membranes composed of longer lipid chains, Y1R is more rigid, attributed to a higher hydrophobic thickness of the lipid membrane. The presence of an antagonist or NPY has little influence on the amplitude of motions, whereas the addition of agonist and arrestin led to a pronounced rigidization. To investigate Y1R dynamics with site resolution, we conducted extensive all-atom MD simulations of the apo and antagonist-bound state. In each state, three replicas with a length of 20 μs (with one exception, where the trajectory length was 10 μs) were conducted. In these simulations, order parameters of each residue were determined and showed high values in the transmembrane helices, whereas the loops and termini exhibit much lower order. The extracellular helix segments undergo larger amplitude motions than their intracellular counterparts, whereas the opposite is observed for the loops, Helix 8, and termini. Only minor differences in order were observed between the apo and antagonist-bound state, whereas the time scale of the motions is shorter for the apo state. Although these relatively fast motions occurring with correlation times of ns up to a few µs have no direct relevance for receptor activation, it is believed that they represent the prerequisite for larger conformational transitions in proteins.     

Aspects of fatigue failure mechanisms in polymer fuel cell membranes

The swelling‐driven fatigue behavior of polymer fuel cell membranes during relative humidity (RH) cycling is investigated. In particular, swelling‐induced membrane stresses are obtained from a numerical model simulating fuel cell RH cycle tests, and compared to the lifetimes obtained experimentally from tests conducted in the absence of electrochemical effects. A strong correlation between the lifetimes of the membranes in the actual tests and model results is obtained. In general, higher RH (or swelling) amplitude results in larger stress amplitudes and shorter lifetime, that is, fewer cycles to failure. Tensile stresses are needed for forming local cavities in the membrane, which may eventually lead to craze formation. Cavitation is less likely to occur in compressed membrane at high humidities. The stress–lifetime plots for polymer fuel cell membranes exhibit similar features to those observed for other polymers. The crazing criterion for polymers suggests that craze initiation during RH cycling is more likely to occur in the low compression regions, such as under the channels, which is in agreement with experimental observations. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1506–1517, 2011     

Molecular information on the dissolution of polydisperse polymers: Mixtures of long and short poly(ethylene oxide)

A systematic study of the dissolution of dry, polydisperse poly(ethylene oxide) (PEO) samples, obtained from mixtures of low-molecular-weight and high-molecular-weight PEO, was made. During the dissolution process, the individual release of the low- and high-molecular-weight fractions was monitored. The high-molecular-weight/low-molecular-weight ratio controls the release rate, and the fraction of high-molecular-weight polymers dominates the effect on the overall release rate in mixed PEO tablets. Both fractions are released at the same rate during the main part of the dissolution process; however, during the initial dissolution period a fractionation occurs. The release rate is not a unique function of the average molecular weight of the polymer, but also depends on the polydispersity. By contrast, the average dimension of a polymer coil, as given by the intrinsic viscosity, gives a good prediction of the release rate irrespective of the polydispersity or details of the molecular weight distribution.     

Changes in soil C-isotopic composition in an agroecosystem under Free Air Carbon dioxide Enrichment (FACE) treatment during a crop rotation period

FACE (Free Air Carbon dioxide Enrichment) has been used since 1999 to evaluate the effects of future atmospheric CO(2) concentrations on an arable crop agroecosystem. The experiment conducted at the Institute of Agroecology at the Federal Research Centre in Braunschweig consists of a typical local crop rotation of winter barley, a cover crop, sugar beet and winter wheat. The atmospheric CO2 concentration of ambient air is about 375 ppm with a delta13C value of -7 to -9 per thousand, and 550 ppm (delta13C value = -20.2 per thousand) during daylight hours in the rings fumigated with additional CO2. Thus, the surplus C can be traced in the agricultural system. Over the course of the first experimental period (3-year crop rotation period), the C-isotopic composition and the C concentration in soil were monitored monthly. Plant samples were analysed according to the relevant developmental stages of the crop under cultivation. A 13C depletion was observed in plant parts, as well as in soil samples from the FACE rings under CO2 enrichment, indicating that labelled C has reached both respective ecosystem compartments. Albeit farming management practice (especially ploughing) leads to a mixing of 'old' and 'new' C compounds throughout all soil horizons down to the end of the ploughing layer and resulted in a heterogeneous distribution of newly formed C compounds in the soil, isotope analysis of soil C reflected where the surplus C went.     

An XPS round robin investigation on analysis of wood pulp fibres and filter paper

X-ray photoelectron spectroscopy (XPS) has been applied to pulp and paper research for decades. However, there has been no attempt to standardise or even systematically compare experimental and analysis procedures, even though it is known that fibrous, nature-derived and insulating fibre materials pose remarkable challenges to reliable surface analysis. The experimental problems are mainly linked with neutralisation, energy resolution, contamination and X-ray induced degradation.We have tested applicability, reliability and reproducibility of XPS analysis on real pulp samples with varying lignin and extractives contents in a small round robin investigation. We also tested the instrumental set-ups with an acetone-extracted filter paper, used as a reference sample. The data, collected at four different laboratories with state-of-the-art instruments indicate that reproducible results can be obtained, despite minor differences in experimental and analysis procedures. However, we found that a specified sample handling procedure and limited X-ray exposure are crucial for reproducible, reliable data.Based on the round robin data we recommend dose restricted monochromatic measurements, a cellulosic in situ reference and a consistent sample handling procedure. The data confirms that a paper-based reference material and the correlation of high-resolution C 1s data with O/C atomic ratios can be used in testing instruments and experimental set-ups for pulp and paper materials.     

Photobilin e. Photooxidation von bacteriochlorophyll-e-derivaten

The blue photooxidation products from metall-free derivatives of bacteriochlorophyll e can be purified without decomposition by reversed phase chromatography. They are identified spectroscopically and chemically as open-chain tetrapyrroles and are named photobilins e.     

Zwei metallreiche Phosphide – Die Kristallstrukturen von Mg8Ir23P8 und Mg13Pt26P10

Two Metal‐rich Phosphides – The Crystal Structures of Mg₈Ir₂₃P₈ and Mg₁₃Pt₂₆P₁₀ Mg₈Ir₂₃P₈ (a = 8.586(4), b = 16.998(7), c = 3.959(2) Å) and Mg₁₃Pt₂₆P₁₀ (a = 8.834(2), b = 21.154(4), c = 4.074(1) Å) crystallize in new structure types (Pbam, Z = 1), which were determined by single crystal methods. In the Ir compound four of seven crystallographically different Ir atoms build up cuboctahedra centered by other Ir atoms. The cuboctahedra are connected with each other via common faces to strands along [001] and they are linked with Ir₅ square pyramids centered by P atoms to a three‐dimensional network, in which some of the Ir atoms are part of both polyhedra. The Mg atoms are situated in the holes of the network coordinated by 14 nearest neighbours. The structure of Mg₁₃Pt₂₆P₁₀ is quite similar and contains cuboctahedra too, but they are formed by both kinds of metal atoms building two different polyhedra. The first type is centered by Pt atoms, whereas the centers of the other one are occupied by Mg atoms and P₂ dumb‐bells with a statistical distribution. The cuboctahedra are linked with each other via common faces along [001] and edges along [100] and they are connected with Pt₅ square pyramids centered by P atoms in a similar fashion like in Mg₈Ir₂₃P₈.