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Nagao, Michihiro

Publications and source records attributed to Nagao, Michihiro.

7 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Antivesiculation and Complete Unbinding of Tail-Tethered Lipids

Here, we report the effect of tail-tethering on vesiculation and complete unbinding of bilayered membranes. Amphiphilic molecules of a bolalipid, resembling the tail-tethered molecular structure of archaeal lipids, with two identical zwitterionic phosphatidylcholine headgroups self-assemble into a large flat lamellar membrane, in contrast to the multilamellar vesicles (MLVs) observed in its counterpart, monopolar nontethered zwitterionic lipids. The antivesiculation is confirmed by small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cyro-TEM). With the net charge of zero and higher bending rigidity of the membrane (confirmed by neutron spin echo (NSE) spectroscopy), the current membrane theory would predict that membranes should stack with each other (aka “bind”) due to dominant van der Waals attraction, while the outcome of the nonstacking (“unbinding”) membrane suggests that the theory needs to include entropic contribution for the nonvesicular structures. This report pioneers an understanding of how the tail-tethering of amphiphiles affects the structure, enabling better control over the final nanoscale morphology.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Structural and Dynamical Roles of Bound Polymer Chains in Rubber Reinforcement

The addition of nanofillers to rubber matrices is a powerful route to improve the mechanical properties. Here, we focus on a molecular understanding of basic mechanisms that are important for the reinforcement in rubbers. The key role in this process is ascribed to bound rubber (BR) that engages with the matrix as well as with adjacent nanofillers. To date, this understanding has been impeded by the lack of experimental tools to directly probe the BR chains buried in a polymer matrix composed of the same polymer. To tackle this challenge, we combine neutron scattering/spectroscopy techniques with isotope-labeling and molecular dynamics simulations. The system is a simplified carbon-black-filled polybutadiene. The combined experimental and computational results provide new insights into the local structural and dynamical heterogeneities of BR chains and their interactions with the matrix polymer, highlighting (i) the structural partition of the bound chains into three components (i.e., trains, loops, and tails) and their fractions; (ii) their dynamical hierarchies, i.e., the trains that remain immobile on the filler surface, the loops that are fairly large and hence allow the interdigitation of matrix chains, and the tails with their unique characteristics to reach far out into the matrix and entangle with matrix chains. These multiple roles of the constituent components of the BR chains promote the formation of a well-developed adhesive polymer–filler interface, enhancing the elastic property of a filled rubber. Finally, the comprehensive understanding derived and validated by the model rubber will be translatable to many other polymer nanocomposites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Relevance of hydrogen bonded associates to the transport properties and nanoscale dynamics of liquid and supercooled 2-propanol

2-Propanol was investigated, in both the liquid and supercooled states, as a model system to study how hydrogen bonds affect the structural relaxation and the dynamics of mesoscale structures, of approximately several Ångstroms, employing static and quasi-elastic neutron scattering and molecular dynamics simulation. Dynamic neutron scattering measurements were performed over an exchanged wave-vector range encompassing the pre-peak, indicative of the presence of H-bonding associates, and the main peak. The dynamics observed at the pre-peak is associated with the formation and disaggregation of the H-bonded associates and is measured to be at least one order of magnitude slower than the dynamics at the main peak, which is identified as the structural relaxation. Additionally, the measurements indicate that the macroscopic shear viscosity has a similar temperature dependence as the dynamics of the H-bonded associates, which highlights the important role played by these structures, together with the structural relaxation, in defining the macroscopic rheological properties of the system. Importantly, the characteristic relaxation time at the pre-peak follows an Arrhenius temperature dependence whereas at the main peak it exhibits a non-Arrhenius behavior on approaching the supercooled state. The origin of this differing behavior is attributed to an increased structuring of the hydrophobic domains of 2-propanol accommodating a more and more encompassing H-bond network, and a consequent set in of dynamic cooperativity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Scaling relationships for the elastic moduli and viscosity of mixed lipid membranes

The elastic and viscous properties of biological membranes play a vital role in controlling cell functions that require local reorganization of the membrane components as well as dramatic shape changes such as endocytosis, vesicular trafficking, and cell division. These properties are widely acknowledged to depend on the unique composition of lipids within the membrane, yet the effects of lipid mixing on the membrane biophysical properties remain poorly understood. Here, we present a comprehensive characterization of the structural, elastic, and viscous properties of fluid membranes composed of binary mixtures of lipids with different tail lengths. We show that the mixed lipid membrane properties are not simply additive quantities of the single-component analogs. Instead, the mixed membranes are more dynamic than either of their constituents, quantified as a decrease in their bending modulus, area compressibility modulus, and viscosity. While the enhanced dynamics are seemingly unexpected, we show that the measured moduli and viscosity for both the mixed and single-component bilayers all scale with the area per lipid and collapse onto respective master curves. This scaling links the increase in dynamics to mixing-induced changes in the lipid packing and membrane structure. More importantly, the results show that the membrane properties can be manipulated through lipid composition the same way bimodal blends of surfactants, liquid crystals, and polymers are used to engineer the mechanical properties of soft materials, with broad implications for understanding how lipid diversity relates to biomembrane function.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Hierarchical Membrane Dynamics in Phase-Separated Model Membranes

Lipid membranes, the primary matrix of cell membranes, exhibit a hierarchy of dynamics from molecular motions to collective undulations, which control spatiotemporal membrane phenomena and regulate various cellular functions. Thus, understanding how various dynamic modes influence membrane behavior is crucial to uncovering the design rules of cell membranes and implementing them in future technologies. Previous membrane dynamics studies using neutron spin-echo spectroscopy (NSE) have shed light on the dependence of collective membrane fluctuations on viscoelastic membrane properties, demonstrating that thickness fluctuation modes (100ns) are dictated by membrane viscosity, which directly governs fast (ps) molecular diffusive motions. Here, we focus on phase-separating lipid membranes, composed of DMPC:DSPC mixtures, to understand the effect of domain formation/growth on hierarchical matrix dynamics using selective lipid deuteration and different neutron spectroscopy techniques. NSE measurements on DMPC:DSPC-d83 (70:30 mol%) show that bending rigidity of the DMPC-rich matrix graduallyincreases with decreasing temperature - as the fully-fluid membrane approaches the upper phase transition (i.e. with the formation of transient DSPC clusters) - and increases further in the phase coexistence region with the growth of DSPC domains. Comparatively, NSE measurements on DMPC-d54:DSPC-d83 vesicles show pronounced matrix thickness fluctuations in the fully-fluid phase and drastic suppression of this fluctuation mode in the gel-fluid coexistence phase, even when the DMPC-rich matrix is still in its fluid phase. This suppression in fluctuations suggests an increase in the matrix viscosity with the growth of gel DSPC domains, which is further investigated by selectively measuring lipid diffusion in the DMPC-rich matrix using neutron backscattering spectroscopy. Comparisons of the experimental results with coarse-grained MD simulationsillustrate the underlying coupling mechanisms. Overall, these observations indicate a clear mechanical and viscoelastic coupling betweenlipid domains and their host matrix, suggesting that domain formation influences membrane properties beyond local effects.

Carrillo, Jan Michael↗