Self-organized and cu-coordinated surface linear polymerization.
Ontology highlight
ABSTRACT:
SUBMITTER: Li Q
PROVIDER: S-EPMC3696919 | biostudies-literature |
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:At present, the technological groundwork of atomically thin two-dimensional (2D) hetero-layered structures realized by successive thin film epitaxial growth is in principle constrained by lattice matching prerequisite as well as low yield and expensive production. Here, we artificially coordinate ultrathin 2D hetero-layered metal chalcogenides via a highly scalable self-surface charge exfoliation and electrostatic coupling approach. Specifically, bulk metal chalcogenides are spontaneously exfoliated into ultrathin layers in a surfactant/intercalator-free medium, followed by unconstrained electrostatic coupling with a dissimilar transition metal dichalcogenide, MoSe2, into scalable hetero-layered hybrids. Accordingly, surface and interfacial-dominated photocatalysis reactivity is used as an ideal testbed to verify the reliability of diverse 2D ultrathin hetero-layered materials that reveal high visible-light photoreactivity, efficient charge transfer and intimate contact interface for stable cycling and storage purposes. Such a synthetic approach renders independent thickness and composition control anticipated to advance the development of 'design-and-build' 2D layered heterojunctions for large-scale exploration and applications.
| S-EPMC5296640 | biostudies-literature
Project description:Cyclophane structures can control steric pressure in the otherwise open spaces of square-planar d8 -metal catalysts. This elegant concept was so far limited to symmetrical coordinated metals. We report how a cyclophane motif can be generated in ligands that chelate via two different donors. An ancillary second imine in the versatile κ2 -N,O-salicylaldiminato catalyst type enables ring closure via olefin metathesis and selective double bond hydrogenation to yield a 30-membered ring efficiently. Experimental and theoretical analyses show the ancillary imine is directed away from the active site and inert for catalysis. In ethylene polymerization the cyclophane catalyst is more active and temperature stable vs. an open structure reference, notably also in polar solvents. Increased molecular weights and decreased degrees of branching can be traced to an increased energy of sterically demanding transition states by the encircling cyclophane while chain propagation remains highly efficient.
| S-EPMC8456896 | biostudies-literature
Project description:In this work we propose randomly ordered polydomain nematic liquid crystal polymer networks to reversibly generate notable jagged relief patterns at a polymer coating surface by light illumination. The domain size is controlled by the addition of traces of partly insoluble fluorinated acrylate. The photoresponse of the coating is induced by a small amount of copolymerized azobenzene monomers. Upon exposure to UV light, azobenzene undergoes trans to cis isomerization, resulting in a change in molecular order and packing within each domain. The extent of this effect and its directionality depends on the domain orientation. Localized to domain level, this morphological change forms large 3D spikes at the surface with a modulation amplitude of more than 20% of the initial thickness. The process is reversible; the surface topographical patterns erase within 10 s by stopping the light exposure. A finite element model is applied to simulate the surface topography changes of the polydomain coating. The simulations describe the formation of the topographic features in terms of light absorption and isomerization process as a function of the director orientation. The random director distribution leads to surface structures which were found to be in close agreement with the ones measured by interference microscopy. The effect of domain size on surface roughness and depth modulation was explored and related to the internal mechanical constraints. The use of nematic liquid crystal polydomains confined in a polymer network largely simplifies the fabrication of smart coatings with a prominent triggered topographic response.
| S-EPMC4386378 | biostudies-literature
Project description:When selecting a resource to exploit, an insect colony must take into account at least two constraints: the resource must be abundant enough to sustain the whole group, but not too large to limit exploitation costs, and risks of conflicts with other colonies. Following recent results on cockroaches and ants, we introduce here a behavioral mechanism that satisfies these two constraints. Individuals simply modulate their probability to switch to another resource as a function of the local density of conspecifics locally detected. As a result, the individuals gather at the smallest resource that can host the whole group, hence reducing competition and exploitation costs while fulfilling the overall group's needs. Our analysis reveals that the group becomes better at discriminating between similar resources as it grows in size. Also, the discrimination mechanism is flexible and the group readily switches to a better suited resource as it appears in the environment. The collective decision emerges through the self-organization of individuals, that is, in absence of any centralized control. It also requires a minimal individual cognitive investment, making the proposed mechanism likely to occur in other social species and suitable for the development of distributed decision making tools.
| S-EPMC3097225 | biostudies-literature
Project description:Rapidly self-deoxygenating Cu-RDRP in aqueous media is investigated. The disproportionation of Cu(i)/Me6Tren in water towards Cu(ii) and highly reactive Cu(0) leads to O2-free reaction environments within the first seconds of the reaction, even when the reaction takes place in the open-air. By leveraging this significantly fast O2-reducing activity of the disproportionation reaction, a range of well-defined water-soluble polymers with narrow dispersity are attained in a few minutes or less. This methodology provides the ability to prepare block copolymers via sequential monomer addition with little evidence for chain termination over the lifetime of the polymerization and allows for the synthesis of star-shaped polymers with the use of multi-functional initiators. The mechanism of self-deoxygenation is elucidated with the use of various characterization tools, and the species that participate in the rapid oxygen consumption is identified and discussed in detail.
| S-EPMC8159280 | biostudies-literature
Project description:Ring/chain competition in oligomerization reactions represents a long-standing topic of synthetic chemistry and was treated extensively for solution reactions but is not well-understood for the two-dimensional confinement of surface reactions. Here, the kinetic and thermodynamic principles of ring/chain competition in on-surface synthesis are addressed by scanning tunneling microscopy, X-ray photoelectron spectroscopy, and Monte Carlo simulations applied to azulene-based organometallic oligomers on Cu(111). Analysis of experiments and simulations reveals how the ring/chain ratio can be controlled through variation of coverage and temperature. At room temperature, non-equilibrium conditions prevail and kinetic control leads to preferential formation of the entropically favored chains. In contrast, high-temperature equilibrium conditions are associated with thermodynamic control, resulting in increased yields of the energetically favored rings. The optimum conditions for ring formation include the lowest possible temperature within the regime of thermodynamic control and a low coverage. The general implications are discussed and compared to the solution case.
| S-EPMC7318695 | biostudies-literature
Project description:Podosomes are self-organized, dynamic, actin-containing structures that adhere to the extracellular matrix via integrins [1-5]. Yet, it is not clear what regulates podosome dynamics and whether podosomes can function as direct mechanosensors, like focal adhesions [6-9]. We show here that myosin-II proteins form circular structures outside and at the podosome actin ring to regulate podosome dynamics. Inhibiting myosin-II-dependent tension dissipated podosome actin rings before dissipating the myosin-ring structure. As podosome rings changed size or shape, tractions underneath the podosomes were exerted onto the substrate and were abolished when myosin-light-chain activity was inhibited. The magnitudes of tractions were comparable to those generated underneath focal adhesions, and they increased with substrate stiffness. The dynamics of podosomes and of focal adhesions were different. Torsional tractions underneath the podosome rings were generated with rotations of podosome rings in a nonmotile, nonrotating cell, suggesting a unique feature of these circular structures. Stresses applied via integrins at the apical surface directly displaced podosomes near the basal surface. Stress-induced podosome displacements increased nonlinearly with applied stresses. Our results suggest that podosomes are dynamic mechanosensors in which interactions of myosin tension and actin dynamics are crucial for regulating these self-organized structures in living cells.
| S-EPMC2605691 | biostudies-literature
Project description:BackgroundThe cause of autoimmunity, which is unknown, is investigated from a different angle, i.e., the defect in immune 'system', to explain the cause of autoimmunity.Methodology/principal findingsRepeated immunization with antigen causes systemic autoimmunity in mice otherwise not prone to spontaneous autoimmune diseases. Overstimulation of CD4(+) T cells led to the development of autoantibody-inducing CD4(+) T (aiCD4(+) T) cell which had undergone T cell receptor (TCR) revision and was capable of inducing autoantibodies. The aiCD4(+) T cell was induced by de novo TCR revision but not by cross-reaction, and subsequently overstimulated CD8(+) T cells, driving them to become antigen-specific cytotoxic T lymphocytes (CTL). These CTLs could be further matured by antigen cross-presentation, after which they caused autoimmune tissue injury akin to systemic lupus erythematosus (SLE).Conclusions/significanceSystemic autoimmunity appears to be the inevitable consequence of over-stimulating the host's immune 'system' by repeated immunization with antigen, to the levels that surpass system's self-organized criticality.
| S-EPMC2795160 | biostudies-literature
Project description:The termite nest is one of the architectural wonders of the living world, built by the collective action of workers in a colony. Each nest has several characteristic structural motifs that allow for efficient ventilation, cooling, and traversal. We use tomography to quantify the nest architecture of the African termite Apicotermes lamani, consisting of regularly spaced floors connected by scattered linear and helicoidal ramps. To understand how these elaborate structures are built and arranged, we formulate a minimal model for the spatiotemporal evolution of three hydrodynamic fields-mud, termites, and pheromones-linking environmental physics to collective building behavior using simple local rules based on experimental observations. We find that floors and ramps emerge as solutions of the governing equations, with statistics consistent with observations of A. lamani nests. Our study demonstrates how a local self-reinforcing biotectonic scheme is capable of generating an architecture that is simultaneously adaptable and functional, and likely to be relevant for a range of other animal-built structures.
| S-EPMC7865135 | biostudies-literature
Project description:Often members of a group benefit from dividing the group's task into separate components, where each member specializes their role so as to accomplish only one of the components. While this division of labor phenomenon has been observed with respect to both manual and cognitive labor, there is no clear understanding of the cognitive mechanisms allowing for its emergence, especially when there are multiple divisions possible and communication is limited. Indeed, maximization of expected utility often does not differentiate between alternative ways in which individuals could divide labor. We developed an iterative two-person game in which there are multiple ways of dividing labor, but in which it is not possible to explicitly negotiate a division. We implemented the game both as a human experimental task and as a computational model. Our results show that the majority of human dyads can finish the game with an efficient division of labor. Moreover, we fitted our computational model to the behavioral data, which allowed us to explain how the perceived similarity between a player's actions and the task's focal points guided the players' choices from one round to the other, thus bridging the group dynamics and its underlying cognitive process. Potential applications of this model outside cognitive science include the improvement of cooperation in human groups, multi-agent systems, as well as human-robot collaboration.
| S-EPMC8289079 | biostudies-literature