Recruitment of class I hydrophobins to the air : water interface initiates a multi-step process of functional amyloid formation

Class I fungal hydrophobins form amphipathic monolayers composed of amyloid rodlets. This is a remarkable case of functional amyloid formation in that a hydrophobic:hydrophilic interface is required to trigger the self-assembly of the proteins. The mechanism of rodlet formation and the role of the interface in this process have not been well understood. Here, we have studied the effect of a range of additives, including ionic liquids, alcohols, and detergents, on rodlet formation by two class I hydrophobins, EAS and DewA. Although the conformation of the hydrophobins in these different solutions is not altered, we observe that the rate of rodlet formation is slowed as the surface tension of the solution is decreased, regardless of the nature of the additive. These results suggest that interface properties are of critical importance for the recruitment, alignment, and structural rearrangement of the amphipathic hydrophobin monomers. This work gives insight into the forces that drive macromolecular assembly of this unique family of proteins and allows us to propose a three-stage model for the interface-driven formation of rodlets.

Formation of dynamic duolayer systems at the air/water interface by using non-ionic hydrophilic polymers

The inclusion of a water-soluble polymer, poly(vinyl pyrrolidone) (PVP), into a surface active film composition before application to the water surface leads to the formation of a dynamic duolayer; a novel surface film system. This duolayer shows improved surface viscosity over the monolayer compound alone, while the addition of polymer maintains other film properties such as evaporation control and equilibrium spreading pressure. Brewster Angle Microscopy shows that the duolayer film undergoes a different formation mechanism upon film compression, and the resultant surface pressure/area isotherm is different at lower surface pressures indicating the PVP is present on the water surface at these pressures and squeezed out to the water subphase at higher pressures. The addition of water-soluble polymers to form a dynamic duolayer provides a unique way to produce defect-free and tightly packed films while polymer is associated with the film. This finding provides new knowledge for the design of surface films with improved properties with potential applications in many areas.

The influence of fine ferrite formation on the γ/α interface, fine bainite and retained austenite in a thermomechanically-processed transformation induced plasticity steel

An Fe-0.26C-1.96Si-2Mn with 0.31Mo (wt%) steel was subjected to a novel thermomechanical processing route to produce fine ferrite with different volume fractions, bainite, and retained austenite. Two types of fine ferrites were found to be: (i) formed along prior austenite grain boundaries, and (ii) formed intragranularly in the interior of austenite grains. An increase in the volume fraction of fine ferrite led to the preferential formation of blocky retained austenite with low stability, and to a decrease in the volume fraction of bainite with stable layers of retained austenite. The difference in the morphology of the bainitic ferrite and the retained austenite after different isothermal ferrite times was found to be responsible for the deterioration of the mechanical properties. The segregation of Mn, Mo, and C at distances of 2-2.5 nm from the ferrite and retained austenite/martensite interface on the retained austenite/martensite site was observed after 2700 s of isothermal hold. It was suggested that the segregation occurred during the austenite-to-ferrite transformation, and that this would decrease the interface mobility, which affects the austenite-to-ferrite transformation and ferrite grain size.

In situ observation of the aggregated morphology and interaction of dialkyldimethylammonium bromide with DNA at air/water interface by Brewster angle microscopy

The adsorption of DNA on the Langmuir film of a cationic surfactant, dioctadecyldimethylammonium bromide (DODA·Br), and the change of the aggregation morphology of the composite monolayer with respect to surface pressure have been investigated by Brewster angle microscopy (BAM). In contrast with the case of DODA·Br on pure water subphase, when DNA was dispersed into subphase, its adsorption to the interface monolayer through electrostatic interaction decreases the charge density and therefore promotes the formation of domain at low surface pressure. In addition, the electrostatic interaction changed the phase morphology of DODA·Br Langmuir monolayer under different surface pressure, that is, from flower-shaped crystalline domain on the pure water subphase to circular domain on the subphase dispersed with DNA. The result also shows that the monolayer of the composite at air/water interface under the high pressure is not homogeneous, but consists of incompletely fused domains. For the Langmuir film of the surfactant with shorter alkyl-chains, similar morphology can be observed both under the high and low surface pressure. But the tight-stacked circular domain is no longer observed.

A study on the formation of MgAl2O4 and MgO crystals in Al-Mg/quartz composite by differential thermal analysis

The present study has examined the thermodynamics of MgAl₂O₄ and MgO formations in Al–Mg alloy/quartz (>99% crystalline silica) through differential thermal analysis (DTA). The formation of MgAl₂O₄ and MgO is detected as exothermic peaks in the heat flow curve and the reaction is confirmed by the Si dissolution peaks observed during the reheating of samples and SEM analysis of the reacted sample. The presence of MgAl₂O₄ and MgO is confirmed in the XRD analysis of the reacted sample. The study has enabled the production of nano sized MgAl₂O₄ and MgO crystals at the interface of Al–Mg alloy and quartz. The reaction between them is found to be influenced by the oxidation of Mg, which is reduced by increasing heating rates.

Insight into reactions and interface between boron nitride nanotube and aluminium

Nature and mechanism of interfacial reactions between boron nitride nanotubes (BNNTs) and aluminum matrix at high temperature (650 °C) are studied using high-resolution transmission electron microscopy (HRTEM). This study analyzes the feasibility of the use of BNNTs as reinforcement in aluminum matrix composites for structural application, for which interface plays a critical role. Thermodynamic comparison of aluminum (Al)-BNNT with analogous Al-carbon nanotube (Al-CNT) system reveals lesser amount of reaction in the former. Experimental observation also reveals thin (~7 nm) reaction-product formation at Al-BNNT interface even after 120 min of exposure at 650 °C. The spatial distribution of the reaction-product species at the interface is governed by the competitive diffusion of N, Al, and B. Morphology of the reaction products are influenced by their orientation relationship with BNNT walls. A theoretical prediction on Al-BNNT interface in macroscale composite suggests the formation of strong bond between the matrix and reinforcement phase.

Synergistic effects within a C2-symmetric organocatalyst : the potential formation of a chiral catalytic pocket

This study describes the synthesis of five novel C2-symmetric organocatalysts that facilitate the on-water asymmetric aldol reaction at low catalyst loading (1 mol%) without the use of additives. Each catalyst is composed of two diprolinamide units joined by a symmetric alkyl bridging group allowing for systematic modulation of catalytic site proximity. Typically, catalysts in this manuscript which bear the catalytic units in close proximity gave the best reaction outcomes in terms of conversion (up to >99%), diastereomeric ratio (4/96, syn/anti) and enantiomeric excess (up to 97%). This effect has been attributed to the assembly of a chiral pocket, facilitated by hydrogen bonding at the oil-in-water interface.

Laboratory studies on the coupled oscillations between an internal density interface and a shear layer

The results from experiments conducted in a 2m high flow compartment at large Reynolds numbers are reported in this paper. Flow entered the compartment through an opening at the base on one side of the compartment and exited from an opening at the bottom of the opposite wall of the compartment. A shear layer is formed at the boundary between the incoming flow and the ambient fluid in the compartment. The impingement of the shear layer on the opposite wall of the compartment gives rise to periodic vortex formation and highly organized oscillations in the shear layer. When a density interface is present inside the compartment, resonance conditions were set up when the oscillations of the internal standing waves were “locked in” with the shear layer oscillations. Under resonance conditions, internal standing waves with amplitudes of up to 0.1m were observed. The formation of the internal standing waves is linked to the shear layer oscillations. Resonance conditions result when the shear layer is oscillating close to the natural frequency of the stratified fluid system in the compartment. The results of this investigation are applicable for fresh water storage in floating bottom-opened tanks in the sea, where under resonance conditions, entrainment rates could be significantly increased.

Tristearin bilayers: structure of the aqueous interface and stability in the presence of surfactants

We report results of atomistic molecular dynamics simulations of an industrially-relevant, exemplar triacylglycerol (TAG), namely tristearin (TS), under aqueous conditions, at different temperatures and in the presence of an anionic surfactant, sodium dodecylbenzene sulphonate (SDBS). We predict the TS bilayers to be stable and in a gel phase at temperatures of 350 K and below. At 370 K the lipid bilayer was able to melt, but does not feature a stable liquid-crystalline phase bilayer at this elevated temperature. We also predict the structural characteristics of TS bilayers in the presence of SDBS molecules under aqueous conditions, where surfactant molecules are found to spontaneously insert into the TS bilayers. We model TS bilayers containing different amounts of SDBS, with the presence of SDBS imparting only a moderate effect on the structure of the system. Our study represents the first step in applying atomistic molecular dynamics simulations to the investigation of TAG-aqueous interfaces. Our results suggest that the CHARMM36 force-field appears suitable for the simulation of such systems, although the phase behaviour of the system may be shifted to lower temperatures than is the case for the actual system. Our findings provide a foundation for further simulation studies of the TS-aqueous interface.

Formation of defects in the graphite oxidization process: a positron study

High-resolution positron annihilation lifetime (PAL) and two-detector coincidence Doppler broadening of annihilation radiation (2D-DBAR) measurements on graphite and its oxide derivatives for defect information, differing in oxidization agents, are reported. Positron measurements were found to be very effective in the investigation of defects in graphite and its derivatives. Positrons are mainly annihilated in vacancy-like defects on the particle surface and in large open-volume holes associated with the interface of graphite and graphite oxide. Different types of defects have been detected for unexfoliated graphite oxide and exfoliated graphene oxide based on 2D-DBAR measurements, namely the vacancy cluster and vacancy-oxygen complexes. It is also interesting to observe that the calculated large open-volume diameter of graphene oxide coincides with the distance between the layers from the XRD investigation, which indicates that the annihilation of the long-lived lifetime component τ3 might take place in the area between the graphene layers; no large open-volume hole has been detected.

Dynamic performance of duolayers at the air/water interface. 1. Experimental analysis

Understanding, and improving, the behavior of thin surface films under exposure to externally applied forces is important for applications such as mimicking biological membranes, water evaporation mitigation, and recovery of oil spills. This paper demonstrates that the incorporation of a water-soluble polymer into the surface film composition, i.e., formation of a three-duolayer system, shows improved performance under an applied dynamic stress, with an evaporation saving of 84% observed after 16 h, compared to 74% for the insoluble three-monolayer alone. Canal viscometry and spreading rate experiments, performed using the same conditions, demonstrated an increased surface viscosity and faster spreading rate for the three-duolayer system, likely contributing to the observed improvement in dynamic performance. Brewster angle microscopy and dye-tagged polymers were used to visualize the system and demonstrated that the duolayer and monolayer system both form a homogeneous film of uniform, single-molecule thickness, with the excess material compacting into small floating reservoirs on the surface. It was also observed that both components have to be applied to the water surface together in order to achieve improved performance under dynamic conditions. These findings have important implications for the use of surface films in various applications where resistance to external disturbance is required.

The distribution of grain boundary and interface plane orientations in transformed microstructures

The properties of interfaces depend not only on the lattice misorientation, but also on the interface plane orientation. Extensive studies of grain boundaries led to the conclusion that in systems evolving by grain growth, the relative areas of different grain boundary planes are inversely correlated to their relative energies. In other words, the low energy grain boundary planes make up a larger part of the population than the higher energy grain boundary planes. The hypothesis of this work is that the interface plane orientation distribution in transformed microstructures depends more on the mechanism of formation than on the relative energy. After a discussion of methods for measuring interface plane orientations, results will be presented for lath martensite in a low carbon steel and for martensite in a Ti-6Al-4V alloy processed in two different ways to promote a displacive transformation in one case and a diffusional transformation in the other.