Comparative study of materials-binding peptide interactions with gold and silver surfaces and nanostructures : A thermodynamic basis for biological selectivity of inorganic materials

Controllable 3D assembly of multicomponent inorganic nanomaterials by precisely positioning two or more types of nanoparticles to modulate their interactions and achieve multifunctionality remains a major challenge. The diverse chemical and structural features of biomolecules can generate the compositionally specific organic/inorganic interactions needed to create such assemblies. Toward this aim, we studied the materials-specific binding of peptides selected based upon affinity for Ag (AgBP1 and AgBP2) and Au (AuBP1 and AuBP2) surfaces, combining experimental binding measurements, advanced molecular simulation, and nanomaterial synthesis. This reveals, for the first time, different modes of binding on the chemically similar Au and Ag surfaces. Molecular simulations showed flatter configurations on Au and a greater variety of 3D adsorbed conformations on Ag, reflecting primarily enthalpically driven binding on Au and entropically driven binding on Ag. This may arise from differences in the interfacial solvent structure. On Au, direct interaction of peptide residues with the metal surface is dominant, while on Ag, solvent-mediated interactions are more important. Experimentally, AgBP1 is found to be selective for Ag over Au, while the other sequences have strong and comparable affinities for both surfaces, despite differences in binding modes. Finally, we show for the first time the impact of these differences on peptide mediated synthesis of nanoparticles, leading to significant variation in particle morphology, size, and aggregation state. Because the degree of contact with the metal surface affects the peptide's ability to cap the nanoparticles and thereby control growth and aggregation, the peptides with the least direct contact (AgBP1 and AgBP2 on Ag) produced relatively polydispersed and aggregated nanoparticles. Overall, we show that thermodynamically different binding modes at metallic interfaces can enable selective binding on very similar inorganic surfaces and can provide control over nanoparticle nucleation and growth. This supports the promise of bionanocombinatoric approaches that rely upon materials recognition.

Building surfaces and their effect on the urban thermal environment

Use of high reflectance surfaces reduces the amount of solar radiation absorbed through building envelopes and urban structures and thus keeping their surfaces cooler. The cooling energy savings by using high reflectance surfaces have been well documented. Higher surface temperatures add to increasing the ambient temperature as convection intensity is higher. Such temperature increase has significant impacts on the air conditioning energy utilization in hot climates. This study makes use of numerical simulations to analyze the effect of commonly used building materials on the air temperature. A part of the existing CBD (Central Business District) area of Singapore was selected for the study. A series of Computational Fluid Dynamics (CFD) simulations have been carried out using the software CFX-5.6. It was found that at low wind speeds, the effect of materials on the air temperature was significant and the temperature at the middle of a narrow canyon increased up to 2.5[degrees]C with the facade material having lower reflectance.

Degradation of the strength of porous titanium after alkali and heat treatment

Porous titanium with a porosity of 75% was fabricated by space-holder sintering through powder metallurgy. The effect of the alkali and heat treatment on the strength of the porous titanium was investigated. Results indicated that the alkali and heat treatment led to a significant decrease in the strength of the porous titanium, whichwas causedby the degradation due to corrosion of the struts of the porous titanium with a layer of the reaction products, grain pullout and micro-cracks.

Surfaces and depths : evaluating the theoretical assumptions of cognitive skills programmes

Cognitive skills programmes for offenders such as Reasoning and Rehabilitation (R & R) have been around now for over 20 years and were developed in part to address their poor reasoning and decision-making skills. In this paper we critically examine the theoretical underpinnings of the R & R programme in light of current theoretical developments and research from cognitive neuroscience, philosophy, biology, and psychology. After considering recent theoretical and empirical research on rationality, emotions, distributed cognition, and embodiment we conclude with some thoughts about how to fine-tune cognitive skills programmes such as R & R in light of this research.

Corrosion inhibition of 7000 series aluminium alloys with cerium diphenyl phosphate

Cerium diphenyl phosphate (Ce(dpp)3) has previously been shown to be a strong corrosion inhibitor for aluminium-copper magnesium alloy AA2024-T3 and AA7075 in chloride solutions. Surface characterisation including SEM and ToF-SIMS coupled with electrochemical impedance spectroscopy (EIS) measurements are used to propose a mechanism of corrosion inhibition which appears to involve the formation of a complex oxide film of aluminium and cerium also incorporating the organophosphate component. The formation of a thin complex film consisting of hydrolysis products of the Ce(dpp)3 compound and aluminium oxide is proposed to lead to the observed inhibition. SEM analysis shows that some intermetallics favour the creation of thicker deposits predominantly containing cerium oxide compounds.

Combined continuous wave and pulsed plasma modes : For more stable interfaces with higher functionality on metal and semiconductor surfaces

A novel approach to producing improved bio-interfaces by combining continuous wave (CW) and pulsed plasma polymerization (PP) modes is reported. This approach has enabled the generation of stable interfaces with a higher density of primary amine functionality on metal, ceramic and semiconductor surfaces. Heptylamine (HA) was used as the amine-precursor. In this new design, a thin CW PPHA layer is introduced to provide strong cross-linking and attachment to the metal or semiconductor surfaces and to provide a good foundation for better bonding a pulsed PPHA layer with high retention of functional groups. The combined mode provides the pulsed mode advantage of a 3-fold higher density of primary amines, while retaining much of the markedly higher stability in aqueous solutions of the continuous mode.

Optical actuation of inorganic/organic interfaces: comparing peptide-azobenzene ligand reconfiguration on gold and silver nanoparticles

Photoresponsive molecules that incorporate peptides capable of material-specific recognition provide a basis for biomolecule-mediated control of the nucleation, growth, organization, and activation of hybrid inorganic/organic nanostructures. These hybrid molecules interact with the inorganic surface through multiple noncovalent interactions which allow reconfiguration in response to optical stimuli. Here, we quantify the binding of azobenzene-peptide conjugates that exhibit optically triggered cis-trans isomerization on Ag surfaces and compare to their behavior on Au. These results demonstrate differences in binding and switching behavior between the Au and Ag surfaces. These molecules can also produce and stabilize Au and Ag nanoparticles in aqueous media where the biointerface can be reproducibly and reversibly switched by optically triggered azobenzene isomerization. Comparisons of switching rates and reversibility on the nanoparticles reveal differences that depend upon whether the azobenzene is attached at the peptide N- or C-terminus, its isomerization state, and the nanoparticle composition. Our integrated experimental and computational investigation shows that the number of ligand anchor sites strongly influences the nanoparticle size. As predicted by our molecular simulations, weaker contact between the hybrid biomolecules and the Ag surface, with fewer anchor residues compared with Au, gives rise to differences in switching kinetics on Ag versus Au. Our findings provide a pathway toward achieving new remotely actuatable nanomaterials for multiple applications from a single system, which remains difficult to achieve using conventional approaches.

Optical actuation of inorganic/organic interfaces: comparing peptide-azobenzene ligand reconfiguration on gold and silver nanoparticles

Photoresponsive molecules that incorporate peptides capable of material-specific recognition provide a basis for biomolecule-mediated control of the nucleation, growth, organization, and activation of hybrid inorganic/organic nanostructures. These hybrid molecules interact with the inorganic surface through multiple noncovalent interactions which allow reconfiguration in response to optical stimuli. Here, we quantify the binding of azobenzene-peptide conjugates that exhibit optically triggered cis-trans isomerization on Ag surfaces and compare to their behavior on Au. These results demonstrate differences in binding and switching behavior between the Au and Ag surfaces. These molecules can also produce and stabilize Au and Ag nanoparticles in aqueous media where the biointerface can be reproducibly and reversibly switched by optically triggered azobenzene isomerization. Comparisons of switching rates and reversibility on the nanoparticles reveal differences that depend upon whether the azobenzene is attached at the peptide N- or C-terminus, its isomerization state, and the nanoparticle composition. Our integrated experimental and computational investigation shows that the number of ligand anchor sites strongly influences the nanoparticle size. As predicted by our molecular simulations, weaker contact between the hybrid biomolecules and the Ag surface, with fewer anchor residues compared with Au, gives rise to differences in switching kinetics on Ag versus Au. Our findings provide a pathway toward achieving new remotely actuatable nanomaterials for multiple applications from a single system, which remains difficult to achieve using conventional approaches.

The electrochemical surface forces apparatus : the effect of surface roughness, electrostatic surface potentials, and anodic oxide growth on interaction forces, and friction between dissimilar surfaces in aqueous solutions

We present a newly designed electrochemical surface forces apparatus (EC-SFA) that allows control and measurement of surface potentials and interfacial electrochemical reactions with simultaneous measurement of normal interaction forces (with nN resolution), friction forces (with μN resolution), and distances (with Å resolution) between apposing surfaces. We describe three applications of the developed EC-SFA and discuss the wide-range of potential other applications. In particular, we describe measurements of (1) force–distance profiles between smooth and rough gold surfaces and apposing self-assembled monolayer-covered smooth mica surfaces; (2) the effective changing thickness of anodically growing oxide layers with Å-accuracy on rough and smooth surfaces; and (3) friction forces evolving at a metal–ceramic contact, all as a function of the applied electrochemical potential. Interaction forces between atomically smooth surfaces are well-described using DLVO theory and the Hogg–Healy–Fuerstenau approximation for electric double layer interactions between dissimilar surfaces, which unintuitively predicts the possibility of attractive double layer forces between dissimilar surfaces whose surface potentials have similar sign, and repulsive forces between surfaces whose surface potentials have opposite sign. Surface roughness of the gold electrodes leads to an additional exponentially repulsive force in the force–distance profiles that is qualitatively well described by an extended DLVO model that includes repulsive hydration and steric forces. Comparing the measured thickness of the anodic gold oxide layer and the charge consumed for generating this layer allowed the identification of its chemical structure as a hydrated Au(OH)3 phase formed at the gold surface at high positive potentials. The EC-SFA allows, for the first time, one to look at complex long-term transient effects of dynamic processes (e.g., relaxation times), which are also reflected in friction forces while tuning electrochemical surface potentials.

Fabrication of superhydrophobic surfaces by smoke deposition and application in oil-water separation

 Utilizing the smoke emitted by discarded silicone combustion, a simple method of smoke deposition is presented for fabricating a superhydrophobic surface with outstanding water repellence, which exhibited a water contact angle of 164 ± 0.8° and a sliding angle of lower than 1°. In addition, the as-prepared surface possesses favourable heat, water impact and water immersion stabilities. Oil leakages seriously endanger both the environment and the social economy. By this simple smoke deposition method, a selective-wettability copper mesh has been fabricated to separate oil-water mixtures. The smoke-deposited mesh achieved a high separation efficiency of over 93% for various oils, and showed excellent reusability, maintaining a high separation efficiency over 10 cycles. The water repellence of the used mesh can be refreshed by recoating with silicone and smoke deposition. This work provides a new strategy to utilize discarded silicone to fabricate superhydrophobic surfaces and oil-water separation meshes.

Dynamic characteristics and efficiency of a fluidized bed heat treatment process

The dynamic characteristics of gas bubbles in fluidized beds are important to determine the heat and mass transfer rates at component surfaces and the treated profiles of components. They also have great impact on the components’ structural, mechanical and physical properties. However, it has been very difficult to monitor those characteristics dynamically. In this paper, a specifically designed fluidized bed was introduced to facilitate the capturing of its dynamic characteristics and a new video image processing and analysis algorithm was developed. The algorithm is robust and adaptive in terms of locating both bubbles and components in beds with a single or multiple components. It has many advantages in dynamic characterization of gas bubbles and monitoring component treatment. By using this algorithm, the properties of gas bubbles over any period of time can be accurately obtained. This technology will provide a potential on-line dynamic monitoring and quality control system for the chemical heat treatment processes with fluidized beds.

Function-based single and dual point haptic interaction in Cyberworlds

Polygon and point based models dominate virtual reality. These models also affect haptic rendering algorithms, which are often based on collision with polygons. With application to dual point haptic devices for operations like grasping, complex polygon and point based models will make the collision detection procedure slow. This results in the system not able to achieve interactivity for force rendering. To solve this issue, we use mathematical functions to define and implement geometry (curves, surfaces and solid objects), visual appearance (3D colours and geometric textures) and various tangible physical properties (elasticity, friction, viscosity, and force fields). The function definitions are given as analytical formulas (explicit, implicit and parametric), function scripts and procedures. We proposed an algorithm for haptic rendering of virtual scenes including mutually penetrating objects with different sizes and arbitrary location of the observer without a prior knowledge of the scene to be rendered. The algorithm is based on casting multiple haptic rendering rays from the Haptic Interaction Point (HIP), and it builds a stack to keep track on all colliding objects with the HIP. The algorithm uses collision detection based on implicit function representation of the object surfaces. The proposed approach allows us to be flexible when choosing the actual rendering platform, while it can also be easily adopted for dual point haptic collision detection as well as force and torque rendering. The function-defined objects and parts constituting them can be used together with other common definitions of virtual objects such as polygon meshes, point sets, voxel volumes, etc. We implemented an extension of X3D and VRML as well as several standalone application examples to validate the proposed methodology. Experiments show that our concern about fast, accurate rendering as well as compact representation could be fulfilled in various application scenarios and on both single and dual point haptic devices.

School and individual-level characteristics are associated with children's moderate to vigorous intensity physical activity during school recess

Objective: The objective of this study was to identify school environmental characteristics associated with moderate to vigorous physical activity during school recess, including morning and lunch breaks.

Methods: Accelerometry data, child-level characteristics and school physical activity, policy and socio-cultural data were collected from 408 sixth grade children (mean age 11 years) attending 27 metropolitan primary schools in Perth, Western Australia. Hierarchical modelling identified key characteristics associated with children's recess moderate to vigorous physical activity (RMVPA).

Results: Nearly 40% of variability in children's RMVPA was explained by school environment and individual characteristics identified in this study. Children's higher daily RMVPA was associated with newer schools, schools with a higher number of grassed surfaces per child and fewer shaded grassed surfaces, and the physical education coordinator meeting Australian physical activity guidelines.

Conclusions: Characteristics of the school physical and social environments are strongly correlated with children's MPVA during recess.

Urban surface temperature behaviour and heat island effect in a tropical planned city

 Putrajaya is a model city planned with concepts of a "city in the garden" and an "intelligent city" in the tropics. This study presents the behaviour of the surface temperature and the heat island effect of Putrajaya. Findings show that heat island intensity is 2 °C on average at nighttime and negligible at daytime. But high surface temperature values were recorded at the main boulevard due to direct solar radiation incident, street orientation in the direction of northeast and southwest and low building height-to-street width ratio. Buildings facing each other had cooling effect on surfaces during the morning and evening hours; conversely, they had a warming effect at noon. Clustered trees along the street are effective in reducing the surface temperature compared to scattered and isolated trees. Surface temperature of built up areas was highest at noon, while walls and sidewalks facing northwest were hottest later in the day. Walls and sidewalks that face northwest were warmer than those that face southeast. The surface temperatures of the horizontal street surfaces and of vertical façades are at acceptable levels relative to the surface temperature of similar surfaces in mature cities in subtropical, temperate and Mediterranean climates. © 2014 Springer-Verlag Wien.

Relationship between processing, surface energy and bulk properties of ultrafine silk particles

Silk particles of different sizes and shapes were produced by milling and interactions with a series of polar and non-polar gaseous probes were investigated using an inverse gas chromatography technique. The surface energy of all silk materials is mostly determined by long range dispersive interactions such as van der Waals forces. The surface energy increases and surface energy heterogeneity widens after milling. All samples have amphoteric surfaces and the concentration of acidic groups increases after milling while the surfaces remain predominantly basic. We also examined powder compression and flow behaviours using a rheometer. Increase in surface energy, surface area, and static charges in sub-micron air jet milled particles contributed to their aggregation and therefore improved flowability. However they collapse under large pressures and form highly cohesive powder. Alkaline hydrolysis resulted in more crystalline fibres which on milling produced particles with higher density, lower surface energy and improved flowability. The compressibility, bulk density and cohesion of the powders depend on the surface energy as well as on particle size, surface area, aggregation state and the testing conditions, notably the consolidated and unconsolidated states. The study has helped in understanding how surface energy and flowability of particles can be changed via different fabrication approaches.