Connecting structure, dynamics and viscosity in sheared soft colloidal liquids: a medley of anisotropic fluctuations.

Structural distortion and relaxation are central to any liquid flow. Their full understanding requires simultaneous probing of the mechanical as well as structural and dynamical response. We provide the first full dynamical measurement of the transient structure using combined coherent X-ray scattering and rheology on electrostatically interacting colloidal fluids. We find a stress overshoot during the start-up of shear which is due to the strong anisotropic overstretching and compression of nearest-neighbor distances. The rheological response is reflected in uncorrelated entropy-driven intensity fluctuations. While the structural distortion under steady shear is well described by Smoluchowski theory, we find an increase of the particle dynamics beyond the trivial contribution of flow. After the cessation of shear, the full fluid microstructure and dynamics are restored, both on the structural relaxation timescale. We thus find unique structure-dynamics relations in liquid flow, responsible for the macroscopic rheological behavior of the system.

Sharp symmetry-change marks the mechanical failure transition of glasses.

Glasses acquire their solid-like properties by cooling from the supercooled liquid via a continuous transition known as the glass transition. Recent research on soft glasses indicates that besides temperature, another route to liquify glasses is by application of stress that drives relaxation and flow. Here, we show that unlike the continuous glass transition, the failure of glasses to applied stress occurs by a sharp symmetry change that reminds of first-order equilibrium transitions. Using simultaneous x-ray scattering during the oscillatory rheology of a colloidal glass, we identify a sharp symmetry change from anisotropic solid to isotropic liquid structure at the crossing of the storage and loss moduli. Concomitantly, intensity fluctuations sharply acquire Gaussian distributions characteristic of liquids. Our observations and theoretical framework identify mechanical failure as a sharp atomic affine-to-nonaffine transition, providing a new conceptual paradigm of the oscillatory yielding of this technologically important class of materials, and offering new perspectives on the glass transition.

Shear-induced breaking of cages in colloidal glasses: Scattering experiments and mode coupling theory.

We employ x-ray scattering on sheared colloidal suspensions and mode coupling theory to study structure factor distortions of glass-forming systems under shear. We find a transition from quadrupolar elastic distortion at small strains to quadrupolar and hexadecupolar modes in the stationary state. The latter are interpreted as signatures of plastic rearrangements in homogeneous, thermalized systems. From their transient evolution with strain, we identify characteristic strain and length-scale values where these plastic rearrangements dominate. This characteristic strain coincides with the maximum of the shear stress versus strain curve, indicating the proliferation of plastic flow. The hexadecupolar modes dominate at the wavevector of the principal peak of the equilibrium structure factor that is related to the cage-effect in mode coupling theory. We hence identify the structural signature of plastic flow of glasses.

Carbohydrate conformation and lipid condensation in monolayers containing glycosphingolipid Gb3: influence of acyl chain structure.

Globotriaosylceramide (Gb3), a glycosphingolipid found in the plasma membrane of animal cells, is the endocytic receptor of the bacterial Shiga toxin. Using x-ray reflectivity (XR) and grazing incidence x-ray diffraction (GIXD), lipid monolayers containing Gb3 were investigated at the air-water interface. XR probed Gb3 carbohydrate conformation normal to the interface, whereas GIXD precisely characterized Gb3's influence on acyl chain in-plane packing and area per molecule (APM). Two phospholipids, 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) and 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine (DPPE), were used to study Gb3 packing in different lipid environments. Furthermore, the impact on monolayer structure of a naturally extracted Gb3 mixture was compared to synthetic Gb3 species with uniquely defined acyl chain structures. XR results showed that lipid environment and Gb3 acyl chain structure impact carbohydrate conformation with greater solvent accessibility observed for smaller phospholipid headgroups and long Gb3 acyl chains. In general, GIXD showed that Gb3 condensed phospholipid packing resulting in smaller APM than predicted by ideal mixing. Gb3's capacity to condense APM was larger for DSPC monolayers and exhibited different dependencies on acyl chain structure depending on the lipid environment. The interplay between Gb3-induced changes in lipid packing and the lipid environment's impact on carbohydrate conformation has broad implications for glycosphingolipid macromolecule recognition and ligand binding.

Drying of a charge-stabilized colloidal suspension in situ monitored by vertical small-angle X-ray scattering.

We report a first application of vertical small-angle X-ray scattering to investigate the drying process of a colloidal suspension by overcoming gravity related restrictions. From the observation of the drying behavior of charge-stabilized colloidal silica in situ, we find the solidification of the colloidal particles exhibits an initial ordering, followed by a sudden aggregation when they overcome an electrostatic energy barrier. The aggregation can be driven not only by capillary pressure but also by thermal motion of the particles. The dominating contribution is determined by the magnitude of the energy barrier at the transition, which significantly decreases during drying due to an increased ionic strength.

Formation of iron containing aggregates at the liquid-air interface.

The early stages of the formation of inorganic aggregates, composed of iron compounds at the solution-air interface, were investigated in situ. The properties of the solution-air interface were changed by using different Langmuir layers. In order to get insight into the evolution of the sample system in situ, the processes were studied by X-ray scattering and spectroscopy techniques. The formation of aggregates was detected under cationic as well as under anionic Langmuir layers. The observed compounds lack long range order which indicates the formation of amorphous structures. This is supported by extended X-ray absorption fine structure measurements showing only minor order in the formed aggregates.

Sheet-like assemblies of charged amphiphilic α/ß-peptides at the air-water interface.

There is growing interest in the design of molecules that undergo predictable self-assembly. Bioinspired oligomers with well-defined conformational propensities are attractive from this perspective, since they can be constructed from diverse building blocks, and self-assembly can be directed by the identities and sequence of the subunits. Here we describe the structure of monolayers formed at the air-water interface by amphiphilic α/ß-peptides with 1:1 alternation of α- and ß-amino acid residues along the backbone. Two of the α/ß-peptides, one a dianion and the other a dication, were used to determine differences between self-assemblies of the net negatively and positively charged oligomers. Two additional α/ß-peptides, both zwitterionic, were designed to favor assembly in a 1:1 molar ratio mixture with parallel orientation of neighboring strands. Monolayers formed by these α/ß-peptides at the air-water interface were characterized by surface pressure-area isotherms, grazing incidence X-ray diffraction (GIXD), atomic force microscopy and ATR-FTIR. GIXD data indicate that the α/ß-peptide assemblies exhibited diffraction features similar to those of ß-sheet-forming α-peptides. The diffraction data allowed the construction of a detailed model of an antiparallel α/ß-peptide sheet with a unique pleated structure. One of the α/ß-peptide assemblies displayed high stability, unparalleled among previously studied assemblies of α-peptides. ATR-FTIR data suggest that the 1:1 mixture of zwitterionic α/ß-peptides assembled in a parallel arrangement resembling that of a typical parallel ß-sheet secondary structure formed by α-peptides. This study establishes guidelines for design of amphiphilic α/ß-peptides that assemble in a predictable manner at an air-water interface, with control of interstrand orientation through manipulation of Coulombic interactions along the backbone.

Observation of new states of liquid crystal 8CB under nonlinear shear conditions as observed via a novel and unique rheology/small-angle X-ray scattering combination.

New stable states of liquid crystal 8CB could be induced by nonlinear shear conditions and observed by a newly developed rheology/X-ray scattering setup using synchrotron X-ray radiation. Nonlinear oscillatory shear created a distorted sixth order orientational structure. Even when oscillatory shear is switched off, the induced structure remains stable and can be removed only by heating the system into the isotropic state. We assume the structure to be stabilized by defects that pin the new 6-fold phase.

Sticking polydisperse hydrophobic magnetite nanoparticles to lipid membranes.

The formation of a layer of hydrophobic magnetite (Fe(3)O(4)) nanoparticles stabilized by lauric acid is analyzed by in situ X-ray reflectivity measurements. The data analysis shows that the nanoparticles partially disperse their hydrophobic coating. Consequently, a Langmuir layer was formed by lauric acid molecules that can be compressed into an untilted condensed phase. A majority of the nanoparticles are attached to the Langmuir film integrating lauric acid residue on their surface into the Langmuir film. Hence, the particles at the liquid-gas interface can be identified as so-called Janus beads, which are amphiphilic solids having two sides with different functionality.

Elucidating the mechanism of lipid membrane-induced IAPP fibrillogenesis and its inhibition by the red wine compound resveratrol: a synchrotron X-ray reflectivity study.

The islet amyloid polypeptide (IAPP) or amylin is a pancreatic hormone and crucially involved in the pathogenesis of type-II diabetes mellitus (T2DM). Aggregation and amyloid formation of IAPP is considered as the primary culprit for pancreatic beta-cell loss in T2DM patients. In this study, first X-ray reflectivity (XRR) measurements on IAPP at lipid interfaces have been carried out, providing a molecular level characterization of the first steps of the lipid-induced fibrillation process of IAPP, which is initiated by lipid-induced nucleation, oligomerization, followed by detachment of larger IAPP aggregate structures from the lipid membrane, and terminated by the formation of mature fibrils in the bulk solution. The adsorption process of IAPP at lipid interfaces in the absence and presence of negatively charged lipid has also been studied by complementary ATR-FTIR spectroscopic measurements. The morphological properties were followed by atomic force microscopy (AFM). Moreover, we show that the polyphenolic red wine compound resveratrol is able to inhibit IAPP aggregation also in the presence of aggregation-fostering negatively charged lipid interfaces, revealing its potential as a drug candidate for T2DM.

Self-assembly of organic monolayers below the freezing threshold.

One measure that arctic fish and amphibians use to minimize damage to cellular membranes during cooling and freezing processes is the production of cryo-protective substances. We have mimicked this biological "trick" by using the surface of a cryo-protectant as a liquid subphase for the preparation of organic membranes. Following this innovative approach, quasi two-dimensional amphiphilic monolayers were cooled to -40 degrees C at a liquid/gas interface. To date, the low temperature region of the generic phase diagram for alkane chain molecules has been only "virtually" accessible by tuning the molecular chain length. By extending the temperature range well below the freezing point of water, we gained new insights into membrane stability, morphology, and reorganization at low temperatures. Upon cooling relaxed monolayers at a surface pressure of 4.5 mN/m, we find a transition from a mesophase with tilted chains at ambient temperature toward a crystalline phase with upright chains at low temperatures. Structure factor calculations reveal that the chain alignment in the crystalline phase differs from the classical herringbone configuration.

In situ observation of gamma-Fe2O3 nanoparticle adsorption under different monolayers at the air/water interface.

We studied the adsorption of gamma-Fe 2O 3 nanoparticles from an aqueous solution under different charged Langmuir monolayers (stearic acid, stearyl alcohol, and stearyl amine). The aqueous subphase was composed of a colloidal suspension of gamma-Fe 2O 3 nanoparticles. The average hydrodynamic diameter of the nanoparticles measured by dynamic light scattering measurements was 16 nm. The observed zeta potential of +40 mV (at pH 4) results in a long-term stability of the colloidal dispersion. The behavior of the different monolayer/nanoparticle composites were studied with surface pressure/area (pi/ A) isotherms. The adsorption of the nanoparticles under the different monolayers induced an expansion of the monolayers. These phenomena depended on the charge of the monolayers. After the Langmuir/Blodgett transfer on glass substrates, the nanoparticle/monolayer composite films were studied by means of UV-vis spectroscopy. The spectra pointed to increasing adsorption of the nanoparticles with increasing electronegativity of the monolayers. On the basis of these results, we studied the in situ adsorption of nanoparticles under the different monolayers by X-ray reflectivity measurements. Electron density profiles of the liquid/gas interfaces were obtained from the X-ray reflectivity data. The results gave clear evidence for the presence of electrostatic interaction between the differently charged monolayers and the positively charged nanoparticles. While the adsorption process was favored by the negatively charged stearic acid monolayer, the positively charged layer of stearyl amine prevented the formation of ultrathin nanoparticle layers.

Unaffected microscopic dynamics of macroscopically arrested water in dilute clay gels.

Adequate clay minerals considerably affect the macroscopic mechanical behavior of water even at concentrations of a few percent. Thus when 2 wt. % laponite clay mineral nanoparticles are added to water, the resulting colloidal suspension after some time takes on the semisolid characteristics of a jellylike material at room temperature. Cold neutron time-of-flight spectroscopy data are in agreement with the assumption that notwithstanding this macroscopic change, the mobility of the water molecules on intermolecular and intramolecular length scales remains largely unaffected. This observation is discussed in the context of the properties and the role of water in different more or less dilute ionic environments. The result contributes to the ongoing debate of the properties and role of water in living cells.

Highly packed and oriented DNA mesophases identified using in situ microfluidic X-ray microdiffraction.

DNA condensation in vivo usually requires proteins and/or multivalent salts. Here, we explore the in vitro compaction of DNA by cationic dendrimers having an intermediate size and charge. The dynamic assembly of DNA-dendrimer mesophases is discernible due to the laminar flow in a specially designed X-ray compatible microfluidic device. The setup ensures a nonequilibrium ascent of reactant concentration, and the resulting progression of DNA compaction was detected online using microfocused small-angle X-ray diffraction. The evolution of a DNA-dendrimer columnar square mesophase as a function of increasing dendrimer content is described. Additionally, in regions of maximum shear, an unexpected high-level perpendicular ordering of this phase is recorded. Furthermore, these assemblies are found to be in coexistence with a densely packed DNA-only mesophase in regions of excess DNA. The latter is reminiscent of dense packing found in bacteriophage and chromosomes, although surprisingly, it is not stabilized by direct dendrimer contact.

Visualization of flow-aligned type I collagen self-assembly in tunable pH gradients.

Collagen is a major component of the extracellular matrix that exhibits unique hierarchical organization at multiple length scales ranging from nano to macroscale. Despite numerous methods to create collagen-based biomaterials, the self-assembly process of collagen ex vivo is poorly understood. Here, we describe a system that uses a microfluidic method to investigate the dynamics of collagen self-assembly. A main inlet stream of semidilute soluble collagen-I is hydrodynamically focused by two side inlet streams, which gradually increases the pH in the main stream. This enables dynamic nonequilibrium investigation of the self-assembly process simultaneously at different positions and therefore different stages in the assembly process within the same system. The device is designed for in situ monitoring and characterization of collagen assembly using polarization microscopy and X-ray diffraction: the continuous extensional flow provides highly ordered phases of the macromolecules over a large distance in the outlet microchannel and allows for data collection without material damage. We further demonstrate that finite element method simulations provide a good description of our experimental results regarding the diffusive phenomena, flow profile, and pH distribution. Our approach has broad impact, since it provides a powerful means of controlling and investigating the dynamic self-assembly process of biomacromolecules.

In situ study of the growth of nanodots in organic heteroepitaxy.

We report the self-organization of organic nanodots with high crystallinity during the growth of organic heterostructures of Di-indenoperylene (DIP) onto copper-hexadecafluorophthalocyanine (F16CuPc), donor and acceptor molecules, respectively. The process is related to the Stranski-Krastanov growth mode, which is accompanied by a novel type of structural reconstruction of the underlying organic film. This reconstruction affects three monolayers adjacent to the organic interface. In spite of the close resemblance to the formation of semiconductor nanostructures for inorganic heteroepitaxy, the present results conclusively demonstrate a distinctly different growth mechanism for organic heteroepitaxy whose understanding demands further theoretical studies.

Grazing incidence X-ray scattering to probe the self-assembly of phthalocyanine nanorods on a liquid surface.

The structural properties of Langmuir monolayers on aqueous substrates of a metal free phthalocyanine, 2,9,16,23-tetrakis(phenylthio)-29H,31H-phthalocyanine and an Aluminum centered phthalocyanine, Aluminum 2,9,16,23-tetrakis(phenylthio)-29H,31H-phthalocyanine chloride are reported here. Their structure is investigated under progressive lateral compression by grazing incidence diffuse X-ray scattering out of the specular plane to determine specular reflectivity-like information where the phase change of the molecules from "flat-lying" on the surface to "edge-standing" perpendicular to the surface was directly observed. Furthermore grazing incident X-ray diffraction is used to investigate the in-plane ordering of the system where it has been found that at high density states the systems can be considered as monolayers consisting of arrays of side-by-side cofacially aggregated cylindrical rodlike entities.

Long-range molecular organization of an organic monolayer grafted on a mineral substrate.

Structured and functional materials are of the utmost importance for the development of microelectronic technology. We report on a method to obtain a highly ordered organic molecular layer on a mineral substrate. We took advantage of the regular array of reactive sites present at the single-crystal surface of topaz to perform a liquid-phase silanization reaction. The grazing-incidence diffraction technique was used to characterize the bare and covalently coated surfaces. The ordering of the monomolecular organic layer reproduces the perfect single-crystal structure of the cleaved surface over millimeter distances.

Observation of zinc phthalocyanine aggregates on a water surface using grazing incidence X-ray scattering.

Reported here are the structural properties of a zinc 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine Langmuir monolayer on a water surface under progressive lateral compression investigated by grazing incidence X-ray scattering. Grazing incidence diffuse X-ray scattering out of the specular plane (GIXOS) is exploited to determine specular reflectivity-like information where the phase change of flat-lying molecules on the surface to edge-standing molecules perpendicular to the surface is directly observed. Furthermore, grazing incident X-ray diffraction (GIXD) is used to investigate the in-plane ordering of the system where it has been found that in the high-density state (approximately 0.35 nm2 per molecule) the system can be considered to be a monolayer consisting of arrays of side-by-side lying cofacially aggregated cylindrical rodlike entities.

Microfluidics of soft matter investigated by small-angle X-ray scattering.

The combination of X-ray microdiffraction and microfluidics is used to investigate the dynamic behaviour of soft materials. A microfocused X-ray beam enables the observation of the influence of droplet formation on the nanostructure of a smectic liquid crystal in water. Using a hydrodynamic focusing device, the evolution of the intercalation of DNA into multilamellar membranes can be studied. Owing to the elongational flow at the centre of this device, alignment of the material is induced which allows for an improved structural characterization. Furthermore, the influence of strain applied to these materials can be tested.