Modeling of Transient Trapping of Fatty Acid Tails in Phospholipids

We present the derivation of a new model to describe neutron spin echo spectroscopy and quasi-elastic neutron scattering data on liposomes. We compare the new model with existing approaches and benchmark it with experimental data. The analysis indicates the importance of including all major contributions into modeling of the intermediate scattering function. Simultaneous analysis of the experimental data on lipids with full contrast and tail contrast matched samples, reveals highly confined lipid tail motion. A comparison of their dynamics demonstrates the statistical independ-ence of tail-motion and height-height correlation of the membrane. A more detailed analysis indi-cates that lipid tails are subject to relaxations in a potential with cylindrical symmetry, in addition to the undulation and diffusive motion of the liposome. Despite substantial differences in the chemis-try of the fatty acid tails, the observation indicates a universal behavior. The analysis of partially deuterated systems confirms the strong contribution of the lipid tail to the intermediate scattering function. Within the time range from 5 to 100 ns, the intermediate scattering function can be de-scribed by the height-height correlation function. The existence of the fast-localized tail motion and the contribution of slow translational diffusion of liposomes determines the intermediate scattering function for t 100 ns, respectively. Taking into account the limited time window lowers the bending moduli by a factor of 1.3 (DOPC) to 2 (DMPC) compared to the full range.Comment: 33 pages, 5 figures, published in Soft Matte

Reduced-mobility layers with high internal mobility in poly(ethylene oxide)-silica nanocomposites

© 2017 Author(s). A series of poly(ethylene oxide) nanocomposites with spherical silica was studied by proton NMR spectroscopy, identifying and characterizing reduced-mobility components arising from either room-temperature lateral adsorption or possibly end-group mediated high-temperature bonding to the silica surface. The study complements earlier neutron-scattering results for some of the samples. The estimated thickness of a layer characterized by significant internal mobility resembling backbone rotation ranges from 2 nm for longer (20 k) chains adsorbed on 42 nm diameter particles to 0.5 nm and below for shorter (2 k) chains on 13 nm particles. In the latter case, even lower adsorbed amounts are found when hydroxy endgroups are replaced by methyl endgroups. Both heating and water addition do not lead to significant changes of the observables, in contrast to other systems such as acrylate polymers adsorbed to silica, where temperature- and solvent-induced softening associated with a glass transition temperature gradient was evidenced. We highlight the actual agreement and complementarity of NMR and neutron scattering results, with the earlier ambiguities mainly arising from different sensitivities to the component fractions and the details of their mobility

Dynamics of PDMS- g-PDMS Bottlebrush Polymers by Broadband Dielectric Spectroscopy

Copyright © 2020 American Chemical Society. Poly(dimethylsiloxane) (PDMS)-based bottlebrush polymers, PDMS-g-PDMS, have been synthesized by anionic polymerization in combination with a condensation-based grafting reaction. Bottlebrush polymers show intriguing features, e.g., extremely low viscosities. Hereby, studies of their dynamics are rare. Therefore, we focus on the segmental relaxation by broadband dielectric spectroscopy. An increasing cross-sectional radius proportional to the increasing side chain length has been observed by small-angle neutron scattering over three samples. A comparison of the segmental relaxation times of the bottlebrushes with the respective linear chains reveals slower dynamics in the former. For longer chains, this effect vanishes

Examination of acid-base properties and structural parameters of thiobarbituric acid

The stepwise proton-ligand stability constant of thiobarbituric acid anion was determined in an aqueous solution via pH-potentiometry at ionic strength I=0,1 and temperature T=20°C. Based on the absorption spectra analysis of thiobarbituric acid (H[2]L, H[2]thioBar) solutions in the UV-region at different pH values, it was shown that H[2]thioBar could exist in di-, mono-, and deprotonated forms. This latter fact is reflected in the particle yield H[2]L diagrams as a function of the aqueous solution pH. Besides, some geometric and physico-chemical characteristics of H2thioBar were described by means of quantum chemical calculations

Impact of Local Stiffness on Entropy Driven Microscopic Dynamics of Polythiophene

© 2020, The Author(s). We exploited the high temporal and spatial resolution of neutron spin echo spectroscopy to investigate the large-scale dynamics of semiflexible conjugated polymer chains in solutions. We used a generalized approach of the well-established Zimm model of flexible polymers to describe the relaxation mode spectra of locally stiff polythiophene chains. The Zimm mode analysis confirms the existence of beads with a finite length that corresponds to a reduced number of segmental modes in semiflexible chains. Irrespective of the temperature and the molecular weight of the conjugated polymer, we witness a universal behavior of the local chain stiffness and invariability of the bead length. Our experimental findings indicate possibly minor role of the change in π-electron conjugation length (and therefore conjugated backbone planar to non-planar conformational transition) in the observed thermochromic behavior of polythiophene but instead point on the major role of chain dynamics in this phenomenon. We also obtained the first experimental evidence of an existence of a single-chain glass state in conjugated polymers

SPHERES, J\"ulich's High-Flux Neutron Backscattering Spectrometer at FRM II

SPHERES (SPectrometer with High Energy RESolution) is a third-generation neutron backscattering spectrometer, located at the 20 MW German neutron source FRM II and operated by the Juelich Centre for Neutron Science. It offers an energy resolution (fwhm) better than 0.65 micro-eV, a dynamic range of +-31 micro-eV, and a signal-to-noise ratio of up to 1750:1.Comment: 12 pages, 7 figures, 2 tables. Supplemental material consists of 3 pages, 2 figures, 2 table

Mitral Annulus Segmentation From Three-Dimensional Ultrasound

An accurate and reproducible segmentation of the mitral valve annulus from 3D ultrasound is useful to clinicians and researchers in applications such as pathology diagnosis and mitral valve modeling. Current segmentation methods, however, are based on 2D information, resulting in inaccuracies and a lack of spatial coherence. We present a segmentation algorithm which, given a single user-specified point near the center of the valve, uses maxflow and active contour methods to delineate the annulus geometry in 3D. Preliminary comparisons to manual segmentations and a sensitivity study show the algorithm is both accurate and robust.Engineering and Applied Science

Observations of volcanic clouds in their first few days of atmospheric residence: The 1992 eruptions of crater peak, Mount Spurr volcano, Alaska

Satellite SO2 and ash measurements of Mount Spurr’s three 1992 volcanic clouds are compared with ground‐based observations to develop an understanding of the physical and chemical evolution of volcanic clouds. Each of the three eruptions with ratings of volcanic explosivity index three reached the lower stratosphere (14 km asl), but the clouds were mainly dispersed at the tropopause by moderate to strong (20–40 m/s) tropospheric winds. Three stages of cloud evolution were identified. First, heavy fallout of large (\u3e500 μm) pyroclasts occurred close to the volcano (vent) during and immediately after the eruptions, and the cloud resembled an advected gravity current. Second, a much larger, highly elongated region marked by a secondary‐mass maximum occurred 150–350 km downwind in at least two of the three events. This was the result of aggregate fallout of a bimodal size distribution including fine (\u3c25 \u3eμm) ash that quickly depleted the solid fraction of the volcanic cloud. For the first several hundred kilometers, the cloud spread laterally, first as an intrusive gravity current and then by wind shear and diffusion as downwind cloud transport occurred at the windspeed (during the first 18–24 h). Finally, the clouds continued to move through the upper troposphere but began decreasing in areal extent, eventually disappearing as ash and SO2 were removed by meteorological processes. Total SO2 in each eruption cloud increased by the second day of atmospheric residence, possibly because of oxidation of coerupted H2S or possibly because of the effects of sequestration by ice followed by subsequent SO2 release during fallout and desiccation of ashy hydrometeors. SO2 and volcanic ash travelled together in all the Spurr volcanic clouds. The initial (18–24 h) area expansion of the clouds and the subsequent several days of drifting were successfully mapped by both SO2 (ultraviolet) and ash (infrared) satellite imagery