The understanding of the basic physical relationships between nano-scale structural variables and the macroscale properties of polymer nanocomposites remains in its infancy. The primary objective of ...this article is to ascertain the state of the art regarding the understanding and prediction of the macroscale properties of polymers reinforced with nanometer-sized solid inclusions over a wide temperature range. We emphasize that the addition of nanoparticles with large specific surface area to polymer matrices leads to amplification of a number of rather distinct molecular processes resulting from interactions between chains and solid surfaces. This results in a “non-classical” response of these systems to mechanical and electro-optical excitations when measured on the macroscale. For example, nanoparticles are expected to be particularly effective at modifying the intrinsic nano-scale dynamic heterogeneity of polymeric glass-formation and, correspondingly, recent simulations indicate that both the strength of particle interaction with the polymer matrix and the particle concentration can substantially influence the dynamic fragility of polymer glass-formation, a measure of the strength of the temperature dependence of the viscosity or structural relaxation time. Another basic characteristic of nanoparticles in polymer matrices is the tendency for the particles to associate into extended structures that can dominate the rheological, viscoelastic and mechanical properties of the nanocomposite so that thermodynamic factors that effect nanoparticle dispersion can be crucially important. Opportunities to exploit knowledge gained from understanding biomechanics of hierarchical biological protein materials and potential applications in materials design and nanotechnology are among future research challenges. Research on nanocomposites formed from block copolymers and nanoparticles offers huge promise in molecular electronics and photovoltaics. The surface functionalization of nanoparticles by the grafting of polymer brushes is expected to play important role in the designing of novel organic/inorganic nanocomposite materials. The formation of bulk heterojunctions at the nanometer scale leads to efficient dissociation of the charge pairs generated under sunlight. Based on the presentations and discussion, we make recommendations for future work in this area by the physics, chemistry, and engineering communities.
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Despite its ubiquitous presence in the built environment, concrete's molecular-level properties are only recently being explored using experimental and simulation studies. Increasing societal ...concerns about concrete's environmental footprint have provided strong motivation to develop new concrete with greater specific stiffness or strength (for structures with less material). Herein, a combinatorial approach is described to optimize properties of cement hydrates. The method entails screening a computationally generated database of atomic structures of calcium-silicate-hydrate, the binding phase of concrete, against a set of three defect attributes: calcium-to-silicon ratio as compositional index and two correlation distances describing medium-range silicon-oxygen and calcium-oxygen environments. Although structural and mechanical properties correlate well with calcium-to-silicon ratio, the cross-correlation between all three defect attributes reveals an indentation modulus-to-hardness ratio extremum, analogous to identifying optimum network connectivity in glass rheology. We also comment on implications of the present findings for a novel route to optimize the nanoscale mechanical properties of cement hydrate.
Abstract The number of massively multiplayer online games (MMOs) is on the rise worldwide along with the fascination that they inspire. Problems occur when the use of MMOs becomes excessive at the ...expense of other life domains. Although not yet formally included as disorder in common diagnostic systems, internet gaming disorder (IGD) is considered a “condition for further study” in section III of the DSM-5. The current review aims to provide an overview of cognitive and neurobiological data currently available on IGD, with a particular focus on impulsivity, compulsivity, and sensitivity to reward and punishment. Additionally, we also compare these findings on IGD with data from studies on pathological gambling (PG)-so far the only condition officially classified as a behavioral addiction in the DSM-5. Multiple similarities have been observed in the neurobiology of IGD and PG, as measured by alterations in brain function and behavior. Both patients with IGD and those with PG exhibited decreased loss sensitivity; enhanced reactivity to gaming and gambling cues, respectively; enhanced impulsive choice behavior; aberrant reward-based learning; and no changes in cognitive flexibility. In conclusion, the evidence base on the neurobiology of gaming and gambling disorders is beginning to illuminate the similarities between the two. However, as only a few studies have addressed the neurobiological basis of IGD, and some of these studies suffer from significant limitations, more research is required before IGD's inclusion as a second behavioral addiction in the next versions of the ICD and DSM can be justified.
Long-distance migration, and the study of the migrants who undertake these journeys, has fascinated generations of biologists. However, many aspects of the annual cycles of these migrants remain a ...mystery as do many of the driving forces behind the evolution and maintenance of the migrations themselves. In this article we discuss nutritional, energetic, temporal and disease-risk bottlenecks in the annual cycle of long-distance migrants, taking a sandpiper, the red knot Calidris canutus, as a focal species. Red knots have six recognized subspecies each with different migratory routes, well-known patterns of connectivity and contrasting annual cycles. The diversity of red knot annual cycles allows us to discuss the existence and the effects of bottlenecks in a comparative framework. We examine the evidence for bottlenecks focusing on the quality of breeding plumage and the timing of moult as indicators in the six subspecies. In terms of breeding plumage coloration, quality and timing of prealternate body moult (from non-breeding into breeding plumage), the longest migrating knot subspecies, Calidris canutus rogersi and Calidris canutus rufa, show the greatest impact of bottlenecking. The same is true in terms of prebasic body moult (from breeding into non-breeding plumage) which in case of both C. c. rogersi and C. c. rufa overlaps with southward migration and may even commence in the breeding grounds. To close our discussion of bottlenecks in long-distance migrants, we make predictions about how migrants might be impacted via physiological 'trade-offs' throughout the annual cycle, using investment in immune function as an example. We also predict how bottlenecks may affect the distribution of mortality throughout the annual cycle. We hope that this framework will be applicable to other species and types of migrants, thus expanding the comparative database for the future evaluation of seasonal selection pressures and the evolution of annual cycles in long-distance migrants. Furthermore, we hope that this synthesis of recent advancements in the knowledge of red knot annual cycles will prove useful in the ongoing attempts to model annual cycles in migratory birds.
Proteins constitute the building blocks of biological materials such as tendon, bone, skin, spider silk or cells. An important trait of these materials is that they display highly characteristic ...hierarchical structures, across multiple scales, from nano to macro. Protein materials are intriguing examples of materials that balance multiple tasks, representing some of the most sustainable material solutions that integrate structure and function. Here we review progress in understanding the deformation and fracture mechanisms of hierarchical protein materials by using a materials science approach to develop structure-process-property relations, an effort defined as materiomics. Deformation processes begin with an erratic motion of individual atoms around flaws or defects that quickly evolve into formation of macroscopic fractures as chemical bonds rupture rapidly, eventually compromising the integrity of the structure or the biological system leading to failure. The combination of large-scale atomistic simulation, multi-scale modeling methods, theoretical analyses combined with experimental validation provides a powerful approach in studying deformation and failure phenomena in protein materials. Here we review studies focused on the molecular origin of deformation and fracture processes of three types of protein materials. The review includes studies of collagen – Nature’s super-glue; beta-sheet rich protein structures as found in spider silk – a natural fiber that can reach the strength of a steel cable; as well as intermediate filaments – a class of alpha-helix based structural proteins responsible for the mechanical integrity of eukaryotic cells. The article concludes with a discussion of the significance of universally found structural patterns such as the staggered collagen fibril architecture or the alpha-helical protein motif.
Abstract Autism, an incurable neurodevelopmental brain disorder, is a complex psychopathology in which the affected individual cannot effectively self-regulate their sensory inputs toward coherent ...and focused motor outputs. There have been many hypotheses as to the etiology of autism – genetics, neurotransmitter imbalances, early childhood immunizations, xenobiotic and teratogenic agents, and maternal infection; the disorder can perhaps be studied best under the field of “Psychoneuroimmunology”, which analyzes systemic and psychopathologies from an integrated approach through the combined effects of the nervous, immune, and endocrine systems. Using principles of psychoneuroimmunology along with previously established but yet un-linked scientific principles and observations, this paper proposes a neuroimmune-based mechanistic hypothesis for the etiology of autism that connects elevated levels of maternal pro-inflammatory cytokines to autistic symptoms in her offspring through a logical sequence of events. While both researchers and clinicians often note correlations between pro-inflammatory cytokine levels and autistic symptoms in affected individuals, no specific mechanism has been documented that logically and directly connects the two. I propose that pro-inflammatory cytokines arising from maternal inflammation, infection, and, possibly, autoimmunity, pass through the placenta; enter the fetal circulation; cross the fetal blood–brain barrier (BBB); and cause aberrant neuronal growth and plasticity within the fetal brain via a “cytokine-storm”. Microglia and astrocyte stimulation lead to a positive-feedback loop that also facilitates the development of a chronic inflammatory environment within the fetus, pre-disposing it to lifelong comorbid psychiatric and systemic pathologies. Such a mechanism could account for many of the observed symptoms and behaviors of autistic individuals such as hyper-sensitivity to environmental stimuli, object fixation, echolalia, repetitive physical behaviors, chronic enterocolitis, autoimmune disease, and, at the extreme, savantism. The thiazolidinedione pioglitazone (and possibly rosiglitazone), a non-steroidal anti-inflammatory drug (NSAID), which is commonly used to lower blood glucose levels and associated inflammatory markers in patients with diabetes, and histamine receptor blockers, as well as monitoring and limiting sucrose-containing foods, might prove to be effective preventative therapies for the development of autism in the fetus for pregnant women displaying either a cytokine-induced depression or other elevated systemic inflammatory state conditions.
In contrast to synthetic materials, evolutionary developments in biology have resulted in materials with remarkable structural properties, made out of relatively weak constituents, arranged in ...complex hierarchical patterns. For instance, nacre from seashells is primarily made of a fragile ceramic, yet it exhibits superior levels of strength and toughness. Structural features leading to this performance consist of a microstructure organized in a hierarchical fashion, and the addition of a small volume fraction of biopolymers. A key to this mechanical performance is the cohesion and sliding of
wavy ceramic tablets. Another example is bone, a structural biological material made of a collagen protein phase and nanoscopic mineral platelets, reaching high levels of toughness and strength per weight. The design and fabrication of
de novo synthetic materials that aim to utilize the deformation and hardening mechanism of biological materials such as bone or nacre is an active area of research in mechanics of materials. In this review, our current knowledge on microstructure and mechanics of nacre and bone are described, and a review of the fabrication of nacre-inspired artificial and related materials is presented. Both experimental and simulation approaches are discussed, along with specific examples that illustrate the various approaches. We conclude with a broader discussion of the interplay of size effects and hierarchies in defining mechanical properties of biological materials.
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