The time-evolutions of nanoparticle hydrodynamic radius and aggregate fractal dimension during the aggregation of fullerene (C(60)) nanoparticles (FNPs) were measured via simultaneous multiangle static and dynamic light scattering. The FNP aggregation behavior was determined as a function of monovalent (NaCl) and divalent (CaCl(2)) electrolyte concentration, and the impact of addition of dissolved natural organic matter (humic acid) to the solution was also investigated. In the absence of humic acid, the fractal dimension decreased over time with monovalent and divalent salts, suggesting that aggregates become slightly more open and less compact as they grow. Although the aggregates become slightly more open, the magnitude of the fractal dimension suggests intermediate aggregation between the diffusion- and reaction-limited regimes. We observed different aggregation behavior with monovalent and divalent salts upon the addition of humic acid to the solution. For NaCl-induced aggregation, the introduction of humic acid significantly suppressed the aggregation rate of FNPs at NaCl concentrations lower than 150mM. In this case, the aggregation was intermediate or reaction-limited even at NaCl concentrations as high as 500mM, giving rise to aggregates with a fractal dimension of 2.0. For CaCl(2)-induced aggregation, the introduction of humic acid enhanced the aggregation of FNPs at CaCl(2) concentrations greater than about 5mM due to calcium complexation and bridging effects. Humic acid also had an impact on the FNP aggregate structure in the presence of CaCl(2), resulting in a fractal dimension of 1.6 for the diffusion-limited aggregation regime. Our results with CaCl(2) indicate that in the presence of humic acid, FNP aggregates have a more open and loose structure than in the absence of humic acid. The aggregation results presented in this paper have important implications for the transport, chemical reactivity, and toxicity of engineered nanoparticles in aquatic environments.
Understanding the role of kinetics in fiber network microstructure formation is of considerable importance in engineering gel materials to achieve their optimized performances/functionalities. In this work, we present a new approach for kinetic-structure analysis for fibrous gel materials. In this method, kinetic data is acquired using a rheology technique and is analyzed in terms of an extended Dickinson model in which the scaling behaviors of dynamic rheological properties in the gelation process are taken into account. It enables us to extract the structural parameter, i.e. the fractal dimension, of a fibrous gel from the dynamic rheological measurement of the gelation process, and to establish the kinetic-structure relationship suitable for both dilute and concentrated gelling systems. In comparison to the fractal analysis method reported in a previous study, our method is advantageous due to its general validity for a wide range of fractal structures of fibrous gels, from a highly compact network of the spherulitic domains to an open fibrous network structure. With such a kinetic-structure analysis, we can gain a quantitative understanding of the role of kinetic control in engineering the microstructure of the fiber network in gel materials.
A fractal nanostructure having a high surface area is potentially useful in sensors, catalysts, functional coatings, and biomedical and electronic applications. Preparation of fractal nanostructures on solid substrates has been reported using various inorganic or organic compounds. However, achieving such a process using polymers in solution has been extremely challenging. Here, we report a simple one-shot preparation of polymer fractal nanostructures in solution via an unprecedented assembly mechanism controlled by polymerization and self-assembly kinetics. This was possible only because one monomer was significantly more reactive than the other, thereby easily forming a diblock copolymer microstructure. Then, the second insoluble block containing poly(p-phenylenevinylene) (PPV) without any side chains spontaneously underwent self-assembly during polymerization by an in situ nanoparticlization of conjugated polymers (INCP) method. The formation of fractal structures in solution was confirmed by various imaging techniques such as atomic force microscopy, transmission electron microscopy (TEM), and cryogenic TEM. The diffusion-limited aggregation theory was adopted to explain the branching patterns of the fractal nanostructures according to the changes in polymerization conditions such as the monomer concentration and the presence of additives. Finally, after detailed kinetic analyses, we proposed a plausible mechanism for the formation of unique fractal nanostructures, where the gradual formation and continuous growth of micelles in a chain-growth-like manner were accounted for.
As a fractal geometry, Sierpinski triangle has attracted increasing attention in science, technology, engineering, math and art. Herein, three generations of metallo-trigonal supramolecular architectures, metallo-triangles, were assembled using terpyridine (tpy) complexes. The first generation (G1) of mononuclear metallo-triangle was directly obtained by reacting a 60o-orientated bisterpyridinyl ligand and Zn(II) ion. A modular strategy based on the connectivity of
Animal behaviour exhibits fractal structure in space and time. Fractal properties in animal space-use have been explored extensively under the Lévy flight foraging hypothesis, but studies of behaviour change itself through time are rarer, have typically used shorter sequences generated in the laboratory, and generally lack critical assessment of their results. We thus performed an in-depth analysis of fractal time in binary dive sequences collected via bio-logging from free-ranging little penguins (Eudyptula minor) across full-day foraging trips (2(16) data points; 4 orders of temporal magnitude). Results from 4 fractal methods show that dive sequences are long-range dependent and persistent across ca. 2 orders of magnitude. This fractal structure correlated with trip length and time spent underwater, but individual traits had little effect. Fractal time is a fundamental characteristic of penguin foraging behaviour, and its investigation is thus a promising avenue for research on interactions between animals and their environments.
In nature, fractal structures emerge in a wide variety of systems as a local optimization of entropic and energetic distributions. The fractality of these systems determines many of their physical, chemical and/or biological properties. Thus, to comprehend the mechanisms that originate and control the fractality is highly relevant in many areas of science and technology. In studying clusters grown by aggregation phenomena, simple models have contributed to unveil some of the basic elements that give origin to fractality, however, the specific contribution from each of these elements to fractality has remained hidden in the complex dynamics. Here, we propose a simple and versatile model of particle aggregation that is, on the one hand, able to reveal the specific entropic and energetic contributions to the clusters' fractality and morphology, and, on the other, capable to generate an ample assortment of rich natural-looking aggregates with any prescribed fractal dimension.
- Journal of the Royal Society, Interface / the Royal Society
- Published over 3 years ago
Ordered and chaotic superlattices have been identified in Nature that give rise to a variety of colours reflected by the skin of various organisms. In particular, organisms such as silvery fish possess superlattices that reflect a broad range of light from the visible to the UV. Such superlattices have previously been identified as ‘chaotic’, but we propose that apparent ‘chaotic’ natural structures, which have been previously modelled as completely random structures, should have an underlying fractal geometry. Fractal geometry, often described as the geometry of Nature, can be used to mimic structures found in Nature, but deterministic fractals produce structures that are too ‘perfect’ to appear natural. Introducing variability into fractals produces structures that appear more natural. We suggest that the ‘chaotic’ (purely random) superlattices identified in Nature are more accurately modelled by multi-generator fractals. Furthermore, we introduce fractal random Cantor bars as a candidate for generating both ordered and ‘chaotic’ superlattices, such as the ones found in silvery fish. A genetic algorithm is used to evolve optimal fractal random Cantor bars with multiple generators targeting several desired optical functions in the mid-infrared and the near-infrared. We present optimized superlattices demonstrating broadband reflection as well as single and multiple pass bands in the near-infrared regime.
Globally, there are millions of small lakes, but a small number of large lakes. Most key ecosystem patterns and processes scale with lake size, thus this asymmetry between area and abundance is a fundamental constraint on broad-scale patterns in lake ecology. Nonetheless, descriptions of lake size-distributions are scarce and empirical distributions are rarely evaluated relative to theoretical predictions. Here we develop expectations for Earth’s lake area-distribution based on percolation theory and evaluate these expectations with data from a global lake census. Lake surface areas ≥8.5 km(2) are power-law distributed with a tail exponent (τ = 1.97) and fractal dimension (d = 1.38), similar to theoretical expectations (τ = 2.05; d = 4/3). Lakes <8.5 km(2) are not power-law distributed. An independently developed regional lake census exhibits a similar transition and consistency with theoretical predictions. Small lakes deviate from the power-law distribution because smaller lakes are more susceptible to dynamical change and topographic behavior at sub-kilometer scales is not self-similar. Our results provide a robust characterization and theoretical explanation for the lake size-abundance relationship, and form a fundamental basis for understanding and predicting patterns in lake ecology at broad scales.
Stochastic growth processes give rise to diverse and intricate structures everywhere in nature, often referred to as fractals. In general, these complex structures reflect the non-trivial competition among the interactions that generate them. In particular, the paradigmatic Laplacian-growth model exhibits a characteristic fractal to non-fractal morphological transition as the non-linear effects of its growth dynamics increase. So far, a complete scaling theory for this type of transitions, as well as a general analytical description for their fractal dimensions have been lacking. In this work, we show that despite the enormous variety of shapes, these morphological transitions have clear universal scaling characteristics. Using a statistical approach to fundamental particle-cluster aggregation, we introduce two non-trivial fractal to non-fractal transitions that capture all the main features of fractal growth. By analyzing the respective clusters, in addition to constructing a dynamical model for their fractal dimension, we show that they are well described by a general dimensionality function regardless of their space symmetry-breaking mechanism, including the Laplacian case itself. Moreover, under the appropriate variable transformation this description is universal, i.e., independent of the transition dynamics, the initial cluster configuration, and the embedding Euclidean space.
Fractals, being “exactly the same at every scale or nearly the same at different scales” as defined by Benoit B. Mandelbrot, are complicated yet fascinating patterns that are important in aesthetics, mathematics, science and engineering. Extended molecular fractals formed by the self-assembly of small-molecule components have long been pursued but, to the best of our knowledge, not achieved. To tackle this challenge we designed and made two aromatic bromo compounds (4,4″-dibromo-1,1':3',1″-terphenyl and 4,4‴-dibromo-1,1':3',1″:4″,1‴-quaterphenyl) to serve as building blocks. The formation of synergistic halogen and hydrogen bonds between these molecules is the driving force to assemble successfully a whole series of defect-free molecular fractals, specifically Sierpiński triangles, on a Ag(111) surface below 80 K. Several critical points that govern the preparation of the molecular Sierpiński triangles were scrutinized experimentally and revealed explicitly. This new strategy may be applied to prepare and explore various planar molecular fractals at surfaces.