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In this work, poly(ethylene-alt-propylene)–silica nanocomposites, constitutinga model nanocomposite system with mostly nonattractive interactions,are studied by means of oscillatory shear rheology. Two differentmolecular weights were used in order to consider both the effect ofnanoparticle presence on the relaxation of short as well as long polymermatrices. An increase of the particle fraction leads on the one handto the observation of typical characteristics of colloidal rheologysuch as mechanical reinforcement and the formation of a particle gel.On the other hand and in the focus of our analysis, the increasingparticle presence also directly affects the relaxation of the polymerchains. In particular, a shift of the polymer loss maximum in G″(ω) is found in the entangled matrices, whereasanomalous flow behavior is evidenced in the rheology data of highlyfilled short matrices. We succeeded to explain these macroscopic observationsfrom the rheology experiments by considering small-angle neutron scatteringand neutron spin echo results on the same samples, which yield detailedinsight into the molecular circumstances responsible for the observedmacroscopic property changes. [ABSTRACT FROM AUTHOR]

Acetaminophen (APAP) or paracetamol, despite its wide and common use for pain and fever symptoms, shows a variety of side effects, toxic effects, and overdose effects. The most common form of toxic effects of APAP is in the liver where phosphatidylcholine is the major component of the cell membrane with additional associated functionalities. Although this is the case, the effects of APAP on pure phospholipid membranes have been largely ignored. Here, we used 1,2-di-(octadecenoyl)- sn -glycero-3-phosphocholine (DOPC), a commonly found phospholipid in mammalian cell membranes, to synthesize large unilamellar vesicles to investigate how the incorporation of APAP changes the pure lipid vesicle structure, morphology, and fluidity at different concentrations. We used a combination of dynamic light scattering, small-angle neutron and X-ray scattering (SANS, SAXS), and cryo-TEM for structural characterization, and neutron spin-echo (NSE) spectroscopy to investigate the dynamics. We showed that the incorporation of APAP in the lipid bilayer significantly impacts the spherical phospholipid self-assembly in terms of its morphology and influences the lipid content in the bilayer, causing a decrease in bending rigidity. We observe a decrease in the number of lipids per vesicle by almost 28% (0.06 wt % APAP) and 19% (0.12 wt % APAP) compared to the pure DOPC (0 wt % APAP). Our results showed that the incorporation of APAP reduces the membrane rigidity by almost 50% and changes the spherical unilamellar vesicles into much more irregularly shaped vesicles. Although the bilayer structure did not show much change when observed by SAXS, NSE and cryo-TEM results showed the lipid dynamics change with the addition of APAP in the bilayer, which causes the overall decreased membrane rigidity. A strong effect on the lipid tail motion showed that the space explored by the lipid tails increases by a factor of 1.45 (for 0.06 wt % APAP) and 1.75 (for 0.12 wt % APAP) compared to DOPC without the drug.

The understanding of materials requires access to the dynamics over many orders of magnitude in time; however, single analytical techniques are restricted in their respective time ranges. Assuming a functional relationship between time and temperature is one viable tool to overcome these limits. Despite its frequent usage, a breakdown of this assertion at the glass-transition temperature is common. Here, we take advantage of time- and length-scale information in neutron spectroscopy to show that the separation of different processes is the minimum requirement toward a more universal picture at, and even below, the glass transition for our systems. This is illustrated by constructing the full proton mean-square displacement for three bottlebrush polymers from femto- to nanoseconds, with simultaneous information on the partial contributions from segmental relaxation, methyl group rotation, and vibrations. The information can be used for a better analysis of results from numerous techniques and samples, improving the overall understanding of materials properties.

We investigated the influence of an n -alkyl-PEO polymer on the structure and dynamics of phospholipid vesicles. Multilayer formation and about a 9% increase in the size in vesicles were observed by cryogenic transmission electron microscopy (cryo-TEM), dynamic light scattering (DLS), and small-angle neutron/X-ray scattering (SANS/SAXS). The results indicate a change in the lamellar structure of the vesicles by a partial disruption caused by polymer chains, which seems to correlate with about a 30% reduction in bending rigidity per unit bilayer, as revealed by neutron spin echo (NSE) spectroscopy. Also, a strong change in lipid tail relaxation was observed. Our results point to opportunities using synthetic polymers to control the structure and dynamics of membranes, with possible applications in technical materials and also in drug and nutraceutical delivery.

Different polymer architectures behave differently regarding their dynamics. We have used a combination of dielectric spectroscopy, and fast field cycling nuclear magnetic resonance (NMR) to compare the dynamical behavior of two different polymer architectures, with similar overall molecular weight. The systems of interest are a bottlebrush polymer and a linear one, both based on poly(dimethylsiloxane) (PDMS). To verify the structure of the PDMS-g-PDMS bottlebrush in the melt, small-angle neutron scattering was used, yielding a spherical shape. Information about the segmental dynamics was revealed by dielectric spectroscopy and extended to higher temperatures by fast field cycling NMR. One advantage of fast field cycling NMR is the detection of large-scale chain dynamics, which dielectric spectroscopy cannot probe for PDMS. While segmental relaxation seems to be independent of the architecture, the large-scale chain dynamics show substantial differences, as represented by the mean square displacement. Here, two regions are detected for each polymer. The linear polymer shows the Rouse regime, followed by reptation. In contrast, the bottlebrush polymer performs Rouse dynamics and diffusion in the available time window, and entanglement effects are completely missing., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

We investigated the molecular dynamics of unilamellar liposomes by neutron spin echo spectroscopy. We report the first experimental evidence of a short-range motion at the length scale of the size of the headgroup of a lipid. The associated mean squared displacement shows a t 0.26 dependence in the pico- to nanosecond region that indicates another process beyond the predictions of the Zilman-Granek (ZG) model ( t 0.66 ) and translational diffusion ( t 1 ). A comparison with theory shows that the observed low exponent is associated with a non-Gaussian transient trapping of lipid molecules in a local area and supports the continuous time random walk model. The analysis of the mean squared displacement leads to the important conclusion that the friction at the interface between water and liposomes plays a minor role. Center of mass diffusion of liposomes and transient trapping of lipids define the range in which the ZG model can be applied to analyze membrane fluctuations.

Well-defined polypeptoids bearing oligomeric ethylene glycol side chains (PNMe(OEt) n G, n = 1-3) with a controlled molecular weight (3.26-28.6 kg/mol) and narrow molecular weight distribution (polydispersity index, PDI = 1.03-1.10) have been synthesized by ring-opening polymerization of the corresponding N-carboxyanhydrides having oligomeric ethylene glycol side chains (Me(OEt) n -NCA, n = 1-3) using primary amine initiators. Kinetic studies of polymerization revealed a first-order dependence on the monomer concentration, consistent with living polymerization. The obtained PEGylated polypeptoids are highly hydrophilic with good water solubility (>200 mg/mL) and are amorphous, with a glass transition temperature in the -41.1 to +46.4 °C range that increases with increasing molecular weight and decreasing side chain length. DLS and SANS analyses revealed no appreciable adsorption of lysozyme to PNMeOEtG. PNMeOEtG having different molecular weights exhibited minimal cytotoxicity toward HEp2 cells. These combined results suggest the potential use of PEGylated polypeptoids as protein-resistant materials in biomedical and biotechnological fields.

The combination of a set of complementary techniques allows us to construct an unprecedented and comprehensive picture of the internal structure, temperature dependent swelling behavior, and the dependence of these properties on the cross-linker concentration of microgel particles based on N-vinylcaprolactam (VCL). The microgels were synthesized by precipitation polymerization using different amounts of cross-linking agent. Characterization was performed by small-angle neutron scattering (SANS) using two complementary neutron instruments to cover a uniquely broad Q-range with one probe. Additionally we used dynamic light scattering (DLS), atomic force microscopy (AFM), and differential scanning calorimetry (DSC). Previously obtained nuclear magnetic resonance spectroscopy (NMR) results on the same PVCL particles are utilized to round the picture off. Our study shows that both the particle radius and the cross-link density and therefore also the stiffness of the microgels rises with increasing cross-linker content. Hence, more cross-linker reduces the swelling capability distinctly. These findings are supported by SANS and AFM measurements. Independent DLS experiments also found the increase in particle size but suggest an unchanged cross-link density. The reason for the apparent contradiction is the indirect extraction of the parameters via a model in the evaluation of DLS measurements. The more direct approach in AFM by evaluating the cross section profiles of observed microgel particles gives evidence of significantly softer and more deformable particles at lower cross-linker concentrations and therefore verifies the change in cross-link density. DSC data indicate a minor but unexpected shift of the volume phase transition temperature (VPTT) to higher temperatures and exposes a more heterogeneous internal structure of the microgels with increasing cross-link density. Moreover, a change in the total energy transfer during the VPT gives evidence that the strength of hydrogen bonds is significantly affected by the cross-link density. A strong and reproducible deviation of the material density of the cross-linked microgel polymer chains toward a higher value compared to the respective linear chains has yet to be explained.