Iodination of PEGylated Polymers Counteracts the Inhibition of Fibrinogen Adsorption by PEG.

Poly(ethylene glycol), PEG, known to inhibit protein adsorption, is widely used on the surfaces of biomedical devices when biofilm formation is undesirable. Poly(desaminotyrosyl-tyrosine ethyl ester carbonate), PDTEC, PC for short, has been a promising coating polymer for insertion devices, and it has been anticipated that PEG plays a similar role if it is copolymerized with PC. Earlier studies show that no fibrinogen (Fg) is adsorbed onto PC polymers with PEG beyond the threshold weight percentage. This is attributed to the phase separation of PEG. Further, iodination of the PC units in the PC polymer, (I2PC), has been found to counteract this Fg-repulsive effect by PEG. In this study, we employ surface-sensitive X-ray techniques to demonstrate the surface affinity of Fg toward the air-water interface, particularly in the presence of self-assembled PC-based film, in which its constituent polymer units are assumed to be much more mobile as a free-standing film. Fg is found to form a Gibbs monolayer with its long axis parallel to the aqueous surface, thus maximizing its interactions with hydrophobic interfaces. It influences the amount of insoluble, surface-bound I2PC likely due to the desorption of the formed Fg-I2PC complex and/or the penetration of Fg onto the I2PC film. The results show that the phase behavior at the liquid-polymer interface shall be taken into account for the surface behavior of bulk polymers surrounded by tissue. The ability of PEG units rearranging into a protein-blocking layer, rather than its mere presence in the polymer, is the key to antifouling characteristics desired for polymeric coating on insertion devices.

Effect of Polymer Chain Length on the Superlattice Assembly of Functionalized Gold Nanoparticles.

We report on the assembly of gold nanoparticle (AuNPs) superlattices at the liquid/vapor interface and in the bulk of their suspensions. Interparticle distances in the assemblies are achieved on multiple length scales by varying chain lengths of surface grafted AuNPs by polyethylene glycol (PEG) with molecular weights in the range 2000-40,000 Da. Crystal structures and lattice constants in both 2D and 3D assemblies are determined by synchrotron-based surface-sensitive and small-angle X-ray scattering. Assuming knowledge of grafting density, we show that experimentally determined interparticle distances are adequately modeled by spherical brushes close to the θ point (Flory-Huggins parameter, χ≈12) for 2D superlattices at a liquid interface and a nonsolvent (χ = ∞) for the 3D dry superlattices.

Unusual Effect of Iodine Ions on the Self-Assembly of Poly(ethylene glycol)-Capped Gold Nanoparticles.

We use synchrotron X-ray reflectivity and grazing incidence small-angle X-ray scattering to investigate the surface assembly of the poly(ethylene glycol) (PEG)-grafted gold nanoparticles (PEG-AuNPs) induced by different salts. We find that NaCl and CsCl behave as many other electrolytes, namely, drive the PEG-AuNPs to the vapor/suspension interface to form a layer of single-particle depth and organize them into very high-quality two-dimensional (2D) hexagonal crystals. By contrast, NaI induces the migration of PEG-AuNPs to the aqueous surface at much higher surface densities than the other salts (at similar concentrations). The resulting 2D ordering at moderate NaI concentrations is very short ranged, and at a higher NaI concentration, the high-density monolayer is amorphous. Considering NaCl, CsCl and the majority of salts behave similarly, this implicates the anomaly of iodine ion (I-) in this unusual surface population. We argue that the influence of most electrolytes on the PEG corona preserves the polymer in the θ-point with sufficient flexibility to settle into a highly ordered state, whereas I- has a much more severe effect on the corona by collapsing it. The collapsed PEG renders the grafted AuNP a nonspherical shaped complex that, although packs at high density, cannot organize into a 2D ordered arrangement.

Effect of (Poly)electrolytes on the Interfacial Assembly of Poly(ethylene glycol)-Functionalized Gold Nanoparticles.

We report on the effect of interpolymer complexes (IPCs) of poly(acrylic acid) (PAA) with poly(ethylene glycol)-functionalized Au nanoparticles (PEG-AuNPs) as they assemble at the vapor-liquid interface, using surface-sensitive synchrotron X-ray scattering techniques. Depending on the suspension pH, PAA functions both as a weak polyelectrolyte and a hydrogen bond donor, and these two roles affect the interfacial assembly of PEG-AuNPs differently. Above its isoelectric point, we find that PAA leads to the formation of a PEG-AuNP monolayer at the interface with a hexagonal structure. In the presence of high concentration of HCl (i.e., below the isoelectric point), at which PAA forms IPCs with PEG, the hexagonal structure at the interface appears to deteriorate, concurrent with aggregation in the bulk. Thus, while the electrolytic behavior of PAA induces interfacial assembly, the hydrogen bonding behavior, as PAA becomes neutral, favors the formation of 3D assemblies. For comparison, we also report on the formation of PEG-AuNP monolayers (in the absence of PAA) with strong electrolytes such as HCl, H2SO4, and NaOH that lead to a high degree of crystallinity.

Temperature-Activated PEG Surface Segregation Controls the Protein Repellency of Polymers.

Poly(ethylene glycol) (PEG) is widely used to modulate the hydration states of biomaterials and is often applied to produce nonfouling surfaces. Here, we present X-ray scattering data, which show that it is the surface segregation of PEG, not just its presence in the bulk, that makes this happen by influencing the hydrophilicity of PEG-containing substrates. We demonstrate a temperature-dependent trigger that transforms a PEG-containing substrate from a protein-adsorbing to a protein-repelling state. On films of poly(desaminotyrosyl-tyrosine-co-PEG carbonate) with high (20 wt %) PEG content, in which very little protein adsorption is expected, quartz crystal microbalance data showed significant adsorption of fibrinogen and bovine serum albumin at 8 °C. The surface became protein-repellent at 37.5 °C. When the same polymer was iodinated, the polymer was protein-adsorbent, even when 37 wt % PEG was incorporated into the polymer backbone. This demonstrates that high PEG content by itself is not sufficient to repel proteins. By inhibiting phase separation either with iodine or by lowering the temperature, we show that PEG must phase-separate and bloom to the surface to create an antifouling surface. These results suggest an opportunity to design materials with high PEG content that can be switched from a protein-attractant to a protein-repellent state by inducing phase separation through brief exposure to temperatures above their glass transition temperature.

Superlattice assembly by interpolymer complexation.

We present a coarse grained model for a system where nanocrystals are functionalized with a polymer that is a hydrogen bond acceptor, such as polyethylene glycol (PEG), and are dispersed in a solution with a polymer whose monomers consist of a hydrogen bond donor, such as polyacrylic acid (PAA) at low pH (interpolymer complexation). We determine the minimum concentration of the polymer donor to induce aggregation and the structure and dynamics of the induced (fcc) superlattice. Our results are compared to previous and new experiments.

Two-Dimensional Crystallization of Poly( N-isopropylacrylamide)-Capped Gold Nanoparticles.

Surface-sensitive X-ray reflectivity and grazing incidence small-angle X-ray scattering reveal the structure of polymer-capped-gold nanoparticles (AuNPs that are grafted with poly( N-isopropylacrylamide); PNIPAM-AuNPs) as they self-assemble and crystallize at the aqueous suspension/vapor interface. Citrate-stabilized AuNPs (5 and 10 nm in nominal diameter) are ligand-exchanged by 6 kDa PNIPAM-thiol to form corona brushes around the AuNPs that are highly stable and dispersed in aqueous suspensions. Surprisingly, no clear evidence of thermosensitive effect on surface enrichment or self-assembly of the PNIPAM-AuNPs is observed in the 10-35 °C temperature range. However, addition of simple salts (in this case, NaCl) to the suspension induces migration of the PNIPAM-AuNPs to the aqueous surface, and above a threshold salt concentration, two-dimensional crystals are formed. The 10 nm PNIPAM-AuNPs form a highly ordered single layer with in-plane triangular structure, whereas the 5 nm capped NPs form short-range triangular structure that gradually becomes denser as salt concentration increases.

Reverse-engineering of graphene on metal surfaces: a case study of embedded ruthenium.

Using scanning tunneling microscopy, x-ray photoelectron spectroscopy, and x-ray absorption spectroscopy, we show that Ru forms metallic nanoislands on graphite, covered by a graphene monolayer. These islands are air-stable, contain 2-4 layers of Ru, and have diameters on the order of 10 nm. To produce these nanoislands two conditions must be met during synthesis. The graphite surface must be ion-bombarded, and subsequently held at an elevated temperature (1000-1180 K) during Ru deposition. A coincidence lattice forms between the graphene overlayer and the Ru island top. Its characteristics-coincidence lattice constant, corrugation amplitude, and variation of carbon lattice appearance within the unit cell-closely resemble the well-established characteristics of single-layer graphene on the (0001) surface of bulk Ru. Quantitative analysis of the graphene lattice in relation to the coincidence lattice on the island tops show that the two-dimensional lattice constant of the underlying metal equals that of bulk Ru(0001), within experimental error. The embedded Ru islands are energetically favored over on-top (adsorbed) islands, based on density-functional-theory calculations for Ru films with 1-3 Ru layers. We propose a formation mechanism in which Ru atoms intercalate via defects that act as entry portals to the carbon galleries, followed by nucleation and growth in the galleries. In this model, high deposition temperature is necessary to prevent blockage of entry portals.

Interfacial Self-Assembly of Polyelectrolyte-Capped Gold Nanoparticles.

We report on pH- and salt-responsive assembly of nanoparticles capped with polyelectrolytes at vapor-liquid interfaces. Two types of alkylthiol-terminated poly(acrylic acid) (PAAs, varying in length) are synthesized and used to functionalize gold nanoparticles (AuNPs) to mimic similar assembly effects of single-stranded DNA-capped AuNPs using synthetic polyelectrolytes. Using surface-sensitive X-ray scattering techniques, including grazing incidence small-angle X-ray scattering (GISAXS) and X-ray reflectivity (XRR), we demonstrate that PAA-AuNPs spontaneously migrate to the vapor-liquid interfaces and form Gibbs monolayers by decreasing the pH of the suspension. The Gibbs monoalyers show chainlike structures of monoparticle thickness. The pH-induced self-assembly is attributed to the protonation of carboxyl groups and to hydrogen bonding between the neighboring PAA-AuNPs. In addition, we show that adding MgCl2 to PAA-AuNP suspensions also induces adsorption at the interface and that the high affinity between magnesium ions and carboxyl groups leads to two- and three-dimensional clusters that yield partial surface coverage and poorer ordering of NPs at the interface. We also examine the assembly of PAA-AuNPs in the presence of a positively charged Langmuir monolayer that promotes the attraction of the negatively charged capped NPs by electrostatic forces. Our results show that synthetic polyelectrolyte-functionalized nanoparticles exhibit interfacial self-assembly behavior similar to that of DNA-functionalized nanoparticles, providing a pathway for nanoparticle assembly in general.

Iron Ion and Iron Hydroxide Adsorption to Charge-Neutral Phosphatidylcholine Templates.

Surface-sensitive X-ray scattering and spectroscopy techniques reveal significant adsorption of iron ions and iron-hydroxide (Fe(III)) complexes to a charge-neutral zwitterionic template of phosphatidylcholine (PC). The PC template is formed by a Langmuir monolayer of dipalmitoyl-PC (DPPC) that is spread on the surface of 2 to 40 µM FeCl3 solutions at physiological levels of KCl (100 mM). At 40 µM of Fe(III) as many as ∼3 iron atoms are associated with each PC group. Grazing incidence X-ray diffraction measurements indicate a significant disruption in the in-plane ordering of DPPC molecules upon iron adsorption. The binding of iron-hydroxide complexes to a neutral PC surface is yet another example of nonelectrostatic, presumably covalent bonding to a charge-neutral organic template. The strong binding and the disruption of in-plane lipid structure has biological implications on the integrity of PC-derived lipid membranes, including those based on sphingomyelin.

Insertion of apoLp-III into a lipid monolayer is more favorable for saturated, more ordered, acyl-chains.

Neutral lipid transport in mammals is complicated involving many types of apolipoprotein. The exchangeable apolipoproteins mediate the transfer of hydrophobic lipids between tissues and particles, and bind to cell surface receptors. Amphipathic α-helices form a common structural motif that facilitates their lipid binding and exchangeability. ApoLp-III, the only exchangeable apolipoprotein found in insects, is a model amphipathic α-helix bundle protein and its three dimensional structure and function mimics that of the mammalian proteins apoE and apoAI. Even the intracellular exchangeable lipid droplet protein TIP47/perilipin 3 contains an α-helix bundle domain with high structural similarity to that of apoE and apoLp-III. Here, we investigated the interaction of apoLp-III from Locusta migratoria with lipid monolayers. Consistent with earlier work we find that insertion of apoLp-III into fluid lipid monolayers is highest for diacylglycerol. We observe a preference for saturated and more highly ordered lipids, suggesting a new mode of interaction for amphipathic α-helix bundles. X-ray reflectivity shows that apoLp-III unfolds at a hydrophobic interface and flexible loops connecting the amphipathic α-helices stay in solution. X-ray diffraction indicates that apoLp-III insertion into diacylglycerol monolayers induces additional ordering of saturated acyl-chains. These results thus shed important new insight into the protein-lipid interactions of a model exchangeable apolipoprotein with significant implications for its mammalian counterparts.

Neutron-scattering measurements of spin excitations in LaFeAsO and Ba(Fe(0.953)Co(0.047))(2)As(2): evidence for a sharp enhancement of spin fluctuations by nematic order.

Inelastic neutron scattering is employed to investigate the impact of electronic nematic order on the magnetic spectra of LaFeAsO and Ba(Fe(0.953)Co(0.047))(2)As(2). These materials are ideal to study the paramagnetic-nematic state, since the nematic order, signaled by the tetragonal-to-orthorhombic transition at T(S), sets in well above the stripe antiferromagnetic ordering at T(N). We find that the temperature-dependent dynamic susceptibility displays an anomaly at T(S) followed by a sharp enhancement in the spin-spin correlation length, revealing a strong feedback effect of nematic order on the low-energy magnetic spectrum. Our findings can be consistently described by a model that attributes the structural or nematic transition to magnetic fluctuations, and unveils the key role played by nematic order in promoting the long-range stripe antiferromagnetic order in iron pnictides.

Origin of the Instability of Octadecylamine Langmuir Monolayer at Low pH.

It has been reported that an octadecylamine (ODA) Langmuir monolayer becomes unstable at low pH values with no measurable surface pressure at around pH 3.5, suggesting significant dissolution of the ODA molecule into the subphase solution (Albrecht, Colloids Surf. A 2006, 284-285, 166-174). However, by lowering the pH further, ODA molecules reoccupy the surface, and a full monolayer is recovered at pH 2.5. Using surface sum-frequency spectroscopy and pressure-area isotherms, it is found that the recovered monolayer at very low pH has a larger area per molecule with many gauche defects in the ODA molecules as compared to that at high pH values. This structural change suggests that the reappearance of the monolayer is due to the adsorbed Cl(-) counterions to the protonated amine groups, leading to partial charge neutralization. This proposition is confirmed by intentionally adding monovalent salts (i.e., NaCl, NaBr, or NaI) to the subphase to recover the monolayer at pH 3.5, in which the detailed structure of the monolayer is confirmed by sum frequency spectra and the adsorbed anions by X-ray reflectivity.

Interfacial binding of divalent cations to calixarene-based Langmuir monolayers.

The interactions of Langmuir monolayers produced through the self-assembly of an amphiphilic p-carboxycalix[4]arene (1) with a series of divalent, fourth-period transition metals, at the air-water interface, were investigated. Changes in the interfacial behavior of 1 in response to the presence of CuCl2, CoCl2, MnCl2, and NiCl2 were studied by means of Langmuir compression isotherms and Brewster angle microscopy (BAM). The measurements revealed that the self-assembly properties of 1 are significantly affected by Cu(2+) ions. The interactions of 1-based monolayers with Co(2+) and Cu(2+) ions were further investigated by means of synchrotron radiation-based X-ray reflectivity (XRR), X-ray near-total-reflection fluorescence (XNTRF), and grazing incidence X-ray diffraction (GIXD). XNTRF and XRR analyses revealed that the monolayer of 1 binds more strongly to Cu(2+) than Co(2+) ions. In the presence of relatively high concentrations of Cu(2+) ions in the subphase (1.4 × 10(-3) M), XNTRF exhibited anomalous depth profile behavior and GIXD measurements showed considerably strong diffuse scattering. Both measurements suggest the formation of Cu(2+) clusters contiguous to the monolayer of 1.

Morphological transformations in the magnetite biomineralizing protein Mms6 in iron solutions: a small-angle X-ray scattering study.

Magnetotactic bacteria that produce magnetic nanocrystals of uniform size and well-defined morphologies have inspired the use of biomineralization protein Mms6 to promote formation of uniform magnetic nanocrystals in vitro. Small angle X-ray scattering (SAXS) studies in physiological solutions reveal that Mms6 forms compact globular three-dimensional (3D) micelles (approximately 10 nm in diameter) that are, to a large extent, independent of concentration. In the presence of iron ions in the solutions, the general micellar morphology is preserved, however, with associations among micelles that are induced by iron ions. Compared with Mms6, the m2Mms6 mutant (with the sequence of hydroxyl/carboxyl containing residues in the C-terminal domain shuffled) exhibits subtle morphological changes in the presence of iron ions in solutions. The analysis of the SAXS data is consistent with a hierarchical core-corona micellar structure similar to that found in amphiphilic polymers. The addition of ferric and ferrous iron ions to the protein solution induces morphological changes in the micellar structure by transforming the 3D micelles into objects of reduced dimensionality of 2, with fractal-like characteristics (including Gaussian-chain-like) or, alternatively, platelet-like structures.

Iron near absorption edge X-ray spectroscopy at aqueous-membrane interfaces.

Employing synchrotron X-ray scattering, we systematically determine the absorption near-edge spectra (XANES) of iron in its ferrous (Fe(2+)) and ferric (Fe(3+)) states both as ions in aqueous solutions and as they bind to form a single layer to anionic templates that consist of carboxyl or phosphate groups at aqueous/vapor interfaces. While the XANES of bulk iron ions show that the electronic state and coordination of iron complexes in the bulk are isotropic, the interfacial bound ions show a signature of a broken inversion-symmetry environment. The XANES of Fe(2+) and Fe(3+) in the bulk possess distinct profiles however, upon binding they practically exhibit similar patterns. This indicates that both bound ions settle into a stable electronic and coordination configuration with an effective fractional valence (for example, Fe([2+ν]+), 0 < ν < 1) at charged organic templates. Such two dimensional properties may render interfacial iron, abundant in living organisms, a more efficient and versatile catalytic behavior.

Nanocrystal Assemblies: Current Advances and Open Problems.

We explore the potential of nanocrystals (a term used equivalently to nanoparticles) as building blocks for nanomaterials, and the current advances and open challenges for fundamental science developments and applications. Nanocrystal assemblies are inherently multiscale, and the generation of revolutionary material properties requires a precise understanding of the relationship between structure and function, the former being determined by classical effects and the latter often by quantum effects. With an emphasis on theory and computation, we discuss challenges that hamper current assembly strategies and to what extent nanocrystal assemblies represent thermodynamic equilibrium or kinetically trapped metastable states. We also examine dynamic effects and optimization of assembly protocols. Finally, we discuss promising material functions and examples of their realization with nanocrystal assemblies.

Structure of biodegradable films at aqueous surfaces: X-ray diffraction and spectroscopy studies of polylactides and tyrosine-derived polycarbonates.

Three representative polymers of increasing modulus, poly(d,l-lactic acid), PDLLA, poly(desaminotyrosyl-tyrosine ethyl ester carbonate), PDTEC, and the same polymer with iodinated DTE segments, PI2DTEC, were characterized by surface-pressure versus area (Π-A) isotherms and surface sensitive X-ray diffraction techniques. Films of 10-100 Å thickness were prepared for these studies by spreading dilute polymer solutions at air-water interfaces. The general properties of the isotherms and the Flory exponents, determined from the isotherms, vary in accordance with the increasing modulus of PDLLA, PDTEC, PI2DTEC, respectively. The analysis of in situ X-ray reflectivity and grazing incidence X-ray diffraction (GIXD) measurements from films at aqueous surfaces provides a morphological picture that is consistent with the modulus of the polymers, and to a large extent, with their packing in their dry-bulk state. Large absorption of X-rays by iodine enabled X-ray spectroscopic studies under near-total-reflection conditions to determine the iodine distribution in the PI2DTEC film and complement the structural model derived from reflectivity and GIXD. These structural studies lay the foundation for future studies of polymer-protein interactions at aqueous interfaces.

Role of Magnetic Defects in Tuning Ground States of Magnetic Topological Insulators.

Magnetic defects play an important, but poorly understood, role in magnetic topological insulators (TIs). For example, topological surface transport and bulk magnetic properties are controlled by magnetic defects in Bi2 Se3 -based dilute ferromagnetic (FM) TIs and MnBi2 Te4 (MBT)-based antiferromagnetic (AFM) TIs. Despite its nascent ferromagnetism, the inelastic neutron scattering data show that a fraction of the Mn defects in Sb2 Te3 form strong AFM dimer singlets within a quintuple block. The AFM superexchange coupling occurs via Mn-Te-Mn linear bonds and is identical to the AFM coupling between antisite defects and the FM Mn layer in MBT, establishing common interactions in the two materials classes. It is also found that the FM correlations in (Sb1-x Mnx )2 Te3 are likely driven by magnetic defects in adjacent quintuple blocks across the van der Waals gap. In addition to providing answers to long-standing questions about the evolution of FM order in dilute TI, these results also show that the evolution of global magnetic order from AFM to FM in Sb-substituted MBT is controlled by defect engineering of the intrablock and interblock coupling.

Assembling PNIPAM-Capped Gold Nanoparticles in Aqueous Solutions.

Employing small-angle X-ray scattering (SAXS), we explore the conditions under which assembly of gold nanoparticles (AuNPs) grafted with the thermosensitive polymer poly(N-isopropylacrylamide) (PNIPAM) emerges. We find that short-range order assembly emerges by combining the addition of electrolytes or polyelectrolytes with raising the temperature of the suspensions above the lower-critical solution temperature (LCST) of PNIPAM. Our results show that the longer the PNIPAM chain is, the better organization in the assembled clusters. Interestingly, without added electrolytes, there is no evidence of AuNPs assembly as a function of temperature, although untethered PNIPAM is known to undergo a coil-to-globule transition above its LCST. This study demonstrates another approach to assembling potential thermosensitive nanostructures for devices by leveraging the unique properties of PNIPAM.