Yuri Roiter

Interaction of nanoparticles with lipid membrane.

A nanoscale range of surface feature curvatures where lipid membranes lose integrity and form pores has been found experimentally. The pores were experimentally observed in the l-alpha-dimyristoyl phosphatidylcholine membrane around 1.2-22 nm polar nanoparticles deposited on mica surface. Lipid bilayer envelops or closely follows surface features with the curvatures outside of that region. This finding provides essential information for the understanding of nanoparticle-lipid membrane interaction, cytotoxicity, preparation of biomolecular templates and supported lipid membranes on rough and patterned surfaces.

Interaction of lipid membrane with nanostructured surfaces.

Tiny details of the phospholipid (DMPC) membrane morphology in close vicinity to nanostructured silica surfaces have been discovered in the atomic force microscopy experiments. The structural features of the silica surface were varied in the experiments by the deposition of silica nanoparticles of different diameter on plane and smooth silica substrates. It was found that, due to the barrier function of the lipid membrane, only particles larger than 22 nm in diameter with a smooth surface were completely enveloped by the lipid membrane. However, nanoparticles with bumpy surfaces (curvature diameter of bumps as that of particles <22 nm) were only partially enveloped by the lipid bilayer. For the range of nanostructure dimensions between 1.2 and 22 nm, the lipid membrane underwent structural rearrangements by forming pores (holes). The nanoparticles were accommodated into the pores but not enveloped by the lipid bilayer. The study also found that the lipid membrane conformed to the substrate with surface structures of dimensions less than 1.2 nm without losing the membrane integrity. The experimental results are in accord with the analytical free energy model, which describes the membrane coverage, and numerical simulations which evaluate adhesion of the membrane and dynamics as a function of surface topology. The results obtained in this study are useful for the selection of dimensions and shapes for drug-delivery cargo and for the substrate for supported lipid bilayers. They also help in qualitative understanding the role of length scales involved in the mechanisms of endocytosis and cytotoxicity of nanoparticles. These findings provide a new approach for patterning supported lipid membranes with well-defined features in the 1.2-22 nm range.

Field-Directed Self-Assembly with Locking Nanoparticles

A reversible locking mechanism is established for the generation of anisotropic nanostructures by a magnetic field pulse in liquid matrices by balancing the thermal energy, short-range attractive and long-range repulsive forces, and dipole-dipole interactions using a specially tailored polymer shell of nanoparticles. The locking mechanism is used to precisely regulate the dimensions of self-assembled magnetic nanoparticle chains and to generate and disintegrate three-dimensional (3D) nanostructured materials in solvents and polymers.

Single molecule experiments visualizing adsorbed polyelectrolyte molecules in the full range of mono- and divalent counterion concentrations.

This work provides direct experimental verification (on the level of single molecules) for the behavior of hydrophobic polyelectrolyte chains adsorbed at a solid-liquid interface in the full range of possible salt concentrations: (a) in a dilute salt solution, PE chains possess an extended coil conformation visualized as adsorbed 2D-equilibrated coils; (b) in a moderate salt concentration range, the polymer coil shrinks and approaches the dimensions of a polymer coil under θ-conditions and the chains are visualized as adsorbed 3D-projected coils; (c) at high salt concentrations, the polymer coils reexpand and the molecules are visualized as 2D-equilibrated extended coils; however, (d) reexpansion is limited in the presence of multivalent counterions, presumably due to the bridging of the polymer coils by the counterions.

AFM imaging of adsorbed Nafion polymer on mica and graphite at molecular level.

Perfluorosulfonic acid ionomer (PFSA, specifically Nafion at EW = 975 g/mol) was visualized at the single molecule level using atomic force microscopy (AFM) in liquid. The diluted commercial Nafion dispersion shows an apparent M(w) = 1430 kg/mol and M(w)/M(n) = 3.81, which is assigned to chain aggregation. PFSA aggregates, imaged on mica and HOPG during adsorption from EtOH-H(2)O solvent at pH(e) 3.0 (below isoelectric point), showed a stable, segmented rod-like conformation. This structure is consistent with earlier NMR, SAXS/SANS, and TEM results that support a stiff helical Nafion conformation with long persistence length, a sharp solvent-polymer interface, and an extension of the sulfonated side chain into solution. Adsorption of Nafion structures on HOPG was observed at even higher pH(e) from EtOH due to screening of the repulsive electrostatic interaction in lower dielectric constant solvent, while the chain adopted an expanded coil conformation. These measurements provided direct evidence of the chain aggregation in EtOH-H(2)O solution and revealed their equilibrium conformations for adsorption on two model surfaces, highly ordered pyrolitic graphite (HOPG) and mica. The commercial Nafion dispersion was autoclaved at 0.10% w/w in nPrOH/H(2)O = 4:1 v/v solvent at 230 °C for 6 h to give a single-chain dispersion with M(w) = 310 kg/mol and M(w)/M(n) = 1.60. The autoclaved chains adopt an electrostatically stabilized compact globule conformation as observed by AFM imaging of the single PFSA molecules after rapid deposition on mica and HOPG at a low surface coverage.

Phase behavior and self-assembly of PSn(P2VP-b-PAA)n multiarmed multisegmented star terpolymers with ampholytic arms

We report on the phase behavior and self-assembly phenomena of (polystyrene)n(poly(2-vinylpyridine)-b-poly(acrylic acid))n, PSn(P2VP-b-PAA)n, heteroarm star block terpolymers, in DMF/water solvent mixture. The stars were prepared using a one-pot, four-step anionic polymerization method following the “in–out” approach. These multiarmed, multisegmented star terpolymers self-assemble in selective media exhibiting pH responsiveness owing to the ampholytic nature of their diblock copolymer arms. Two soluble and two insoluble states were observed depending upon the pH of the medium. At low pH (pH 1.0), core–shell unimolecular micelles, with a hydrophobic PS core and P2VP, PAA segments in the shell, were formed. At pH 3.0, H-bonding and electrostatic interactions between the P2VP and PAA segments led to compact spheres. Finally, at pH 8.0 the stars were transformed from a bis-hydrophilic state to bis-hydrophobic state, leading to a network-like intermicellar assembly.

Stimuli-responsive hydrogel hollow capsules by material efficient and robust cross-linking-precipitation synthesis revisited.

Monodisperse stimuli-responsive hydrogel capsules were synthesized in the 100-nm-diameter to 10-μm-diameter range from poly(4-vinylpyridine) (P4VP) and poly(ethyleneimine) (PEI) through a simple, efficient two-step cross-linking-precipitation template method under conditions of a good solvent. In this method, the core-shell particles were obtained by the deposition (heterocoagulation mechanism) of the cross-linked P4VP, PEI, or their mixtures on the surfaces of the template colloidal silica particles in nitromethane (for PEI) or a nitromethane-acetone mixture (for P4VP and P4VP-PEI mixtures) in the presence of cross-linker 1,4-diiodobutane. The cross-linked polymeric shell swollen in a good solvent stabilized the core-shell colloids. This mechanism provided the conditions for the synthesis of core-shell colloids in a submicrometer range of dimensions with an easily adjusted shell thickness (wall of the capsules) ranging from a few to hundreds of nanometers. The chemical composition of the shell was tuned by varying the ratio of co-cross-linked shell-forming polymers (P4VP and PEI). In the second step, the hollow capsules were obtained by etching the silica core in HF solutions. In this step, the colloidal stability of the hollow capsules was provided by ionized P4VP and PEI cross-linked shells. The hollow capsules demonstrate that the pH- and ionic-strength-triggered swelling and shrinking result in size-selective uptake and release properties. Cross-linked via quaternized functional groups, P4VP capsules undergo swelling and shrinking transitions at a physiologically relevant pH of around 6. The 200-nm-diameter hollow capsule with 25-nm-thick walls demonstrated a factor of 2 greater capacity to accommodate cargo molecules than the core-shell particles of the same dimensions because of an internal compartment and a combination of radial and a circumferential swelling modes in the capsules.

Stimuli-responsive properties of peptide-based copolymers studied via directional growth of self-assembled patterns on solid substrate

We studied the self-assembly of peptide-based ABA and CBC triblock-copolymers (obtained by bacterial expression) containing random coiled hydrophilic central B blocks flanked with helical A or C blocks. The A and C blocks were of different compositions with respect to the fraction of lysine residues which provided a higher pH sensitivity of the copolymer solutions. The interchain interactions of the copolymers driven by external stimuli (pH and temperature) were explored in the process of macromolecular self-assembling in the thin films of the copolymer solutions deposited on the solid substrate. The interactions involved in the macromolecular association affected the morphology of the developed patterns. The polypeptide of the B block was not involved in the formation of the secondary structures, while the A and C blocks demonstrated helical folding responsible for the intermolecular association. The mechanism of the responsive behavior of the copolymers is based on the reversible assembling of the helices into coiled-coil structures upon the change of pH or temperature. It was found that at low pH values, when electrostatic repulsion was strong and the A/C blocks unfolded, assembling yielded fractal dendrites. Increasing the pH resulted in the recovery of the helical conformation of the A/C blocks and caused a transition from the fractal to compact structures. An elevation of temperature resulted in the disruption of the dendritic structures. The reported here approach to the evaluation of the intermolecular interactions, based on the analysis of the dendritic patterns, provides a rapid and simple method for the characterization of complex processes of self-assembling biomacromolecules.

Effects of Surfactants and Polyelectrolytes on the Interaction between a Negatively Charged Surface and a Hydrophobic Polymer Surface

We have measured and characterized how three classes of surface-active molecules self-assemble at, and modulate the interfacial forces between, a negatively charged mica surface and a hydrophobic end-grafted polydimethylsiloxane (PDMS) polymer surface in solution. We provide a broad overview of how chemical and structural properties of surfactant molecules result in different self-assembled structures at polymer and mineral surfaces, by studying three characteristic surfactants: (1) an anionic aliphatic surfactant, sodium dodecyl sulfate (SDS), (2) a cationic aliphatic surfactant, myristyltrimethylammonium bromide (MTAB), and (3) a silicone polyelectrolyte with a long-chain PDMS midblock and multiple cationic end groups. Through surface forces apparatus measurements, we show that the separate addition of three surfactants can result in interaction energies ranging from fully attractive to fully repulsive. Specifically, SDS adsorbs at the PDMS surface as a monolayer and modifies the monotonic electrostatic repulsion to a mica surface. MTAB adsorbs at both the PDMS (as a monolayer) and the mica surface (as a monolayer or bilayer), resulting in concentration-dependent interactions, including a long-range electrostatic repulsion, a short-range steric hydration repulsion, and a short-range hydrophobic attraction. The cationic polyelectrolyte adsorbs as a monolayer on the PDMS and causes a long-range electrostatic attraction to mica, which can be modulated to a monotonic repulsion upon further addition of SDS. Therefore, through judicious selection of surfactants, we show how to modify the magnitude and sign of the interaction energy at different separation distances between hydrophobic and hydrophilic surfaces, which govern the static and kinetic stability of colloidal dispersions. Additionally, we demonstrate how the charge density of silicone polyelectrolytes modifies both their self-assembly at polymer interfaces and the robust adhesion of thin PDMS films to target surfaces.