Nanoparticles in polyelectrolyte multilayer layer-by-layer (LbL) films and capsules : key enabling components of hybrid coatings

Originally regarded as auxiliary additives, nanoparticles have become important constituents of polyelectrolyte multilayers. They represent the key components to enhance mechanical properties, enable activation by laser light or ultrasound, construct anisotropic and multicompartment structures, and facilitate the development of novel sensors and movable particles. Here, we discuss an increasingly important role of inorganic nanoparticles in the layer-by-layer assembly—effectively leading to the construction of the so-called hybrid coatings. The principles of assembly are discussed together with the properties of nanoparticles and layer-by-layer polymeric assembly essential in building hybrid coatings. Applications and emerging trends in development of such novel materials are also identified

Layered nanomaterials for renewable energy generation and storage

This study focuses on potential applications of two-dimensional (2D) materials in renewable energy research.</jats:p

Mathematical Analysis of a Prototypical Autocatalytic Reaction Network

Network autocatalysis, which is autocatalysis whereby a catalyst is not directly produced in a catalytic cycle, is likely to be more common in chemistry than direct autocatalysis is. Nevertheless, the kinetics of autocatalytic networks often does not exactly follow simple quadratic or cubic rate laws and largely depends on the structure of the network. In this article, we analyzed one of the simplest and most chemically plausible autocatalytic networks where a catalytic cycle is coupled to an ancillary reaction that produces the catalyst. We analytically analyzed deviations in the kinetics of this network from its exponential growth and numerically studied the competition between two networks for common substrates. Our results showed that when quasi-steady-state approximation is applicable for at least one of the components, the deviation from the exponential growth is small. Numerical simulations showed that competition between networks results in the mutual exclusion of autocatalysts; however, the presence of a substantial noncatalytic conversion of substrates will create broad regions where autocatalysts can coexist. Thus, we should avoid the accumulation of intermediates and the noncatalytic conversion of the substrate when designing experimental systems that need autocatalysis as a source of positive feedback or as a source of evolutionary pressure

Mathematical Analysis of a Prototypical Autocatalytic Reaction Network

Network autocatalysis, which is autocatalysis whereby a catalyst is not directly produced in a catalytic cycle, is likely to be more common in chemistry than direct autocatalysis is. Nevertheless, the kinetics of autocatalytic networks often does not exactly follow simple quadratic or cubic rate laws and largely depends on the structure of the network. In this article, we analyzed one of the simplest and most chemically plausible autocatalytic networks where a catalytic cycle is coupled to an ancillary reaction that produces the catalyst. We analytically analyzed deviations in the kinetics of this network from its exponential growth and numerically studied the competition between two networks for common substrates. Our results showed that when quasi-steady-state approximation is applicable for at least one of the components, the deviation from the exponential growth is small. Numerical simulations showed that competition between networks results in the mutual exclusion of autocatalysts; however, the presence of a substantial noncatalytic conversion of substrates will create broad regions where autocatalysts can coexist. Thus, we should avoid the accumulation of intermediates and the noncatalytic conversion of the substrate when designing experimental systems that need autocatalysis as a source of positive feedback or as a source of evolutionary pressure

Topological bio-scaling analysis as a universal measure of protein folding

Scaling relationships for polymeric molecules establish power law dependencies between the number of molecular segments and linear dimensions, such as the radius of gyration. They also establish spatial topological properties of the chains, such as their dimensionality. In the spatial domain, power exponents α = 1 (linear stretched molecule), α = 0.5 (the ideal chain) and α = 0.333 (compact globule) are significant. During folding, the molecule undergoes the transition from the one-dimensional linear to the three-dimensional globular state within a very short time. However, intermediate states with fractional dimensions can be stabilized by modifying the solubility (e.g. by changing the solution temperature). Topological properties, such as dimension, correlate with the interaction energy, and thus by tuning the solubility one can control molecular interaction. We investigate these correlations using the example of a well-studied short model of Trp-cage protein. The radius of gyration is used to estimate the fractal dimension of the chain at different stages of folding. It is expected that the same principle is applicable to much larger molecules and that topological (dimensional) characteristics can provide insights into molecular folding and interactions

Effect of Cavitation Bubble Collapse on the Modification of Solids: Crystallization Aspects

This review examines the concepts how cavitation bubble collapse affects crystalline structure, the crystallization of newly formed structures, and recrystallization. Although this subject can be discussed in a broad sense across the area of metastable crystallization, our main focus is discussing specific examples of the inorganic solids: metal, intermetallics, metal oxides, and silicon. First, the temperature up to which ultrasound heats solids is discussed. Cavitation-induced changes in the crystal size of intermetallic phases in binary AlNi (50 wt % of Ni) alloys allow an estimation of local temperatures on surfaces and in bulk material. The interplay between atomic solid-state diffusion and recrystallization during bubble collapses in heterogeneous systems is revealed. Furthermore, cavitation triggered red/ox processes at solid/liquid interfaces and their influence on recrystallization are discussed for copper aluminum nanocomposites, zinc, titanium, magnesium-based materials, and silicon. Cavitation-driven highly nonequilibrium conditions can affect the thermodynamics and kinetics of mesoscopic phase formation in heterogeneous systems and in many cases boost the macroscopic performance of composite materials, notably in catalytic alloy and photocatalytic semiconductor oxide properties, corrosion resistance, nanostructured surface biocompatibility, and optical properties. © 2016 American Chemical Society10711sciescopu

Microbubbles trigger oscillation of crystal size in solids

An understanding of the nature and conditions of nonlinear processes in open systems is important for modulation of the microstructure of solids at a new level of complexity. We demonstrate that cavitation generated by high intensity ultrasound (HIUS) triggers nonlinear processes in microparticles and layers of titanium. We reveal a non-monotonic dependence of the size of grains in the treated solids on sonication time, and oscillation of titanium grain sizes vs. time of ultrasonic treatment, indicating the influence of two opposing forces: cavitation driven impact of shock heating and shear stress on surfaces. These nonlinear self-organization processes in solids promise new microstructured materials with applications among others in bio- and geosciences.ope

Local pH Gradient Initiated by Light on TiO2 for Light-Triggered Modulation of Polyhistidine-Tagged Proteins

A new principle of photo-assisted spatial desorption of (poly)histidine-tagged (His-Tag) proteins on a TiO2 surface is suggested. A semiconductor TiO2 surface is decorated by layer-by-layer (LbL) assembly of a strong polyelectrolyte, namely, polystyrene sulfonate (PSS), and nickel-nitrilotriacetic acid (NTA). The PSS/NTA multilayer architecture provides n-fold (nxNTA) binding efficiency for more precise protein recognition in comparison to existing molecular His-Tag protein recognition with one- and threefold multiplication (1xNTA, 3xNTA). Spatially resolved desorption of proteins is regulated by non- photodestructive short-term low-intensity light irradiation (&lt;5mWcm(-2)). The local pH shift on irradiated TiO2 selectively affects the pH-sensitive NTA/protein complex, but not the LbL assembly of PSS and NTA, which is stable in a broad pH range.clos

Scaffold Searching of FDA and EMA-Approved Drugs Identifies Lead Candidates for Drug Repurposing in Alzheimer’s Disease

Clinical trials of novel therapeutics for Alzheimer’s Disease (AD) have consumed a significant amount of time and resources with largely negative results. Repurposing drugs already approved by the Food and Drug Administration (FDA), European Medicines Agency (EMA), or Worldwide for another indication is a more rapid and less expensive option. Therefore, we apply the scaffold searching approach based on known amyloid-beta (Aβ) inhibitor tramiprosate to screen the DrugCentral database (n = 4,642) of clinically tested drugs. As a result, menadione bisulfite and camphotamide substances with protrombogenic and neurostimulation/cardioprotection effects were identified as promising Aβ inhibitors with an improved binding affinity (ΔGbind) and blood-brain barrier permeation (logBB). Finally, the data was also confirmed by molecular dynamics simulations using implicit solvation, in particular as Molecular Mechanics Generalized Born Surface Area (MM-GBSA) model. Overall, the proposed in silico pipeline can be implemented through the early stage rational drug design to nominate some lead candidates for AD, which will be further validated in vitro and in vivo, and, finally, in a clinical trial