Impact of an Irreversibly Adsorbed Layer on Local Viscosity of Nanoconfined Polymer Melts

We report the origin of the effect of nanoscale confinement on the local viscosity of entangled polystyrene (PS) films at temperatures far above the glass transition temperature. By using marker x-ray photon correlation spectroscopy with gold nanoparticles embedded in the PS films prepared on solid substrates, we have determined the local viscosity as a function of the distance from the polymer-substrate interface. The results show the impact of a very thin adsorbed layer ( 7 nm in thickness) even without specific interactions of the polymer with the substrate, overcoming the effect of a surface mobile layer at the air-polymer interface and thereby resulting in a significant increase in the local viscosity as approaching the substrate interface.T. K. acknowledges the financial support from NSF Grant No. CMMI-084626. Uses of the Advanced Photon Source and the National Synchrotron Light Source were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contracts No. DE-AC02- 06CH11357 and No. DE-AC02-98CH10886, respectively

Tuning Membrane Thickness Fluctuations in Model Lipid Bilayers

AbstractMembrane thickness fluctuations have been associated with a variety of critical membrane phenomena, such as cellular exchange, pore formation, and protein binding, which are intimately related to cell functionality and effective pharmaceuticals. Therefore, understanding how these fluctuations are controlled can remarkably impact medical applications involving selective macromolecule binding and efficient cellular drug intake. Interestingly, previous reports on single-component bilayers show almost identical thickness fluctuation patterns for all investigated lipid tail-lengths, with similar temperature-independent membrane thickness fluctuation amplitude in the fluid phase and a rapid suppression of fluctuations upon transition to the gel phase. Presumably, in vivo functions require a tunability of these parameters, suggesting that more complex model systems are necessary. In this study, we explore lipid tail-length mismatch as a regulator for membrane fluctuations. Unilamellar vesicles of an equimolar mixture of dimyristoylphosphatidylcholine and distearoylphosphatidylcholine molecules, with different tail-lengths and melting transition temperatures, are used as a model system for this next level of complexity. Indeed, this binary system exhibits a significant response of membrane dynamics to thermal variations. The system also suggests a decoupling of the amplitude and the relaxation time of the membrane thickness fluctuations, implying a potential for independent control of these two key parameters

Confinement Effect on Surface Melting in Polymer Thin Films : Grazlng-incidence X-ray Scattering Studies

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Chain Trajectory and Crystallization Mechanism of a Semicrystalline Polymer in Melt- and Solution-Grown Crystals As Studied Using 13C–13C Double-Quantum NMR

The re-entrance sites, successive chain-folding number ⟨n⟩, and chain-folding fraction ⟨F⟩ of the chain-folding (CF) structure of 13C CH3-labeled isotactic poly(1-butene) (iPB1) with an weight-averaged molecular weight (⟨Mw⟩ = 37 K g/mol) in solution- and melt-grown crystals as a function of crystallization temperature (Tc) were determined using solid-state (SS) NMR. The solution- and melt-grown crystals possessed adjacent re-entry structures between the right- and left-handed stems along the (100) and (010) planes, which were invariant as a function of Tc. The adjacent re-entry structures in the former exhibited long-range order (⟨n⟩ ≥ 8) compared with that in the latter (⟨n⟩ ≥ 1.7–2). These results indicated that the concentration and entanglement of polymers play significant roles in the CF process and structural formation during the initial stage of crystallization, whereas kinetics does not. Transmission electron microscopy (TEM) revealed well-defined hexagonal and circular crystals grown from the solution state at Tc = 60 and ∼0 °C, respectively. The morphological and molecular-level structural data demonstrated that kinetics influences the structural formations of polymers differently at different length scales during crystallization. Moreover, SS-NMR, small-angle X-ray scattering (SAXS), and atomic force microscopy (AFM) indicated that the crystallinity (χc) and lamellar thickness (⟨lc⟩) of the melt-grown crystals are highly dependent on Tc, whereas in the solution-grown crystals, these parameters are independent of Tc. The experimental results and molecular dynamics, as reported in the literature, indicated that both χc and ⟨lc⟩ are primarily determined by the molecular dynamics of the stems after deposition of the chains on the growth front (late process)

Peptide–dendron hybrids that adopt sequence-encoded β-sheet conformations

Rational design rules for programming hierarchical organization and function through mutations of monomers in sequence-defined polymers can accelerate the development of novel polymeric and supramolecular materials. Our strategy for designing peptide–dendron hybrids that adopt predictable secondary and quaternary structures in bulk is based on patterning the sites at which dendrons are conjugated to short peptides. To validate this approach, we have designed and characterized a series of β-sheet-forming peptide–dendron hybrids. Spectroscopic studies of the hybrids in films reveal that the peptide portion of the hybrids adopts the intended secondary structure

Reduced Viscosity of the Free Surface in Entangled Polymer Melt Films

By embedding ‘‘dilute’’ gold nanoparticles in single polystyrene thin films as ‘‘markers’’, we probe the local viscosity of the free surface at temperatures far above the glass transition temperature (Tg). The technique used was x-ray photon correlation spectroscopy with resonance-enhanced x-ray scattering. The results clearly showed the surface viscosity is about 30% lower than the rest of the film. We found that this reduction is strongly associated with chain entanglements at the free surface rather than the reduction in Tg.T. K. acknowledges financial support from NSF Grant No. CMMI-0846267 and ChemMatCARS, APS. The use of the APS was supported by the DOE, Office of Basic Energy Science, under Contract No. DE-AC02- 06CH11357

Pathways of cylindrical orientations in PS-b-P4VP diblock copolymer thin films upon solvent vapor annealing

The orientation changes of perpendicular cylindrical microdomains in polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) thin films upon annealing in different solvent vapors were investigated by in situ grazing incidence small-angle X-ray scattering (GISAXS) and ex situ scanning force microscopy (SFM). The swelling of P4VP perpendicular cylinders (C⊥) in chloroform, a non-selective solvent vapor, leads to the reorientation to in-plane cylinders through a disordered state in a particular kinetic pathway in the phase diagram upon drying. On the other hand, the swelling of the P4VP perpendicular cylinders in a selective solvent vapor (i.e., 1,4-dioxane) induces a morphological transition from cylindrical to ellipsoidal as a transient structure to spherical microdomains; subsequent solvent evaporation resulted in shrinkage of the matrix in the vertical direction, merging the ellipsoidal domains into the perpendicularly aligned cylinders. In this paper, we have discussed the mechanism based on the selectivity of the solvent to the constituting blocks that is mainly responsible for the orientation changes