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Pattern formation is a frequent phenomenon occurring in animate and inanimate systems. The interplay between the mass transport of the chemical species and the underlying chemical reaction networks generates most patterns in chemical systems. Periodic precipitation is an emblematic example of reaction-diffusion patterns, in which the process generates a spatial periodic structure in porous media. Here, we use the dormant reagent method to produce colloidal particles of Prussian blue (PB) and PB analogues at the liquid-gel interface. The generated particles produced a stable periodic stratification pattern in time in the liquid phase placed on top of the solid hydrogel. The phenomenon is governed by periodic swelling of the gel driven by the osmotic stress and stability of the formed particles. To illustrate the phenomenon, we developed an extended reaction-diffusion model, which incorporated the gel swelling and sedimentation effect of the formed colloids and could qualitatively reproduce the pattern formation in the liquid phase.
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Liesegang patterns that develop as a result of reaction-diffusion can simultaneously form products with slightly different sizes spatially separated in a single medium. We show here a reaction-diffusion method using a dormant reagent (citrate) for developing Liesegang patterns of cobalt hexacyanoferrate Prussian Blue analog (PBA) particle libraries. This method slows the precipitation reaction and produces different-sized particles in a gel medium at different locations. The gel-embedded particles are still catalytically active. Finally, the applicability of the new method to other PBAs and 2D systems is presented. The method proves promising for obtaining similar inorganic framework libraries with catalytic abilities.
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This article reports a new family of functional side-chain phenolic polymers derived from lignin monomers, displaying a combination of properties that are usually mutually exclusive within a single material. This includes a well-defined molecular structure, transparency, antioxidant activity, and antistatic properties. Our design strategy is based on the lignin-derived bioaromatic monomer dihydroconiferyl alcohol (DCA), a promising and yet largely unexplored asymmetrical diol bearing one aliphatic and one phenolic hydroxyl group. A lipase-catalyzed (meth)acrylation protocol was developed to selectively functionalize the aliphatic hydroxy group of DCA while preserving its phenolic group responsible for its radical scavenging properties. The resulting mono-(meth)acrylated monomers were then directly copolymerized using reversible addition-fragmentation chain-transfer (RAFT) polymerization without any protection of the phenolic side chains. Kinetics studies revealed that, under select conditions, these unprotected phenolic groups surprisingly did not inhibit the radical polymerization and lead to polymers with defined molar masses, low dispersities, and block copolymers. Finally, applications of these new radical scavenging polymers were demonstrated using an antioxidant assay and antistatic experiments. This research opens the door to the direct incorporation of natural antioxidants within the synthetic polymer backbones, increasing the biobased content and limiting the leaching of potentially harmful additives.
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Antioxidantes , Metanfetamina , Lignina , Cinética , PolímerosRESUMO
Mechanical pulling of adhesive tape creates radicals on the tape's surface. These radicals are capable of reducing metal salts to the corresponding metal nanoparticles. In this way, the mechanically activated tape can be decorated with various types of nanoparticles, including Au, Ag, Pd, or Cu. While retaining their mechanical properties and remaining "sticky," the tapes can exhibit new properties derived from the presence of metal nanoparticles (e.g., bacteriostaticity, increased electrical conductivity). They can also be patterned with nanoparticles only at selective locations of mechanical activation.
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Fenômenos Mecânicos , Nanopartículas Metálicas/química , Adesividade , Adsorção , Propriedades de SuperfícieRESUMO
Mechanical treatment of polymers produces surface cations and anions which, as demonstrated here for the first time, can drive chemical reactions. In particular, it is shown that such a mechanical treatment transforms nonconductive polyaniline into its conductive form. These results provide a mechanical means of patterning conductive polymers and also coating small polymer objects with conductive polyaniline films preventing accumulation of static electricity.
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Compostos de Anilina/química , Dimetilpolisiloxanos/química , Polímeros/química , Eletricidade EstáticaRESUMO
Soft robots mimic the agility of living organisms without rigid joints and muscles. Continuum bending (CB) is one type of motion living organisms can display. CB can be achieved using pneumatic, electroactive, or thermal actuators prepared by casting an active layer on a passive layer. The corresponding input actuates only the active layer in the assembly resulting in the bending of the structure. These two different layers must be laminated well during manufacturing. However, the formed bilayer can still delaminate later, and the detachment hampers the actuator's reversible, long-time use. An approach to creating a single material bending actuator was previously reported, for which spatial gradient swelling was used. This authentic approach allows a single material to be manufactured as a bending actuator, allowing easy access to such actuators without lamination. In this study, we show spatial porosity differences in the sponges of polydimethylsiloxane (PDMS) (a common material in soft robotics) can be used to create the required anisotropy for bending. The spongy polymers are manufactured through table sugar templates and actuated by (organic) solvent absorption/desorption. This enables some versatility in the mechanical properties, shape, actuation force, and actuation speed. The one-material system's straightforward production and seamless nature are advantageous for reversible and repetitive bending. This simple method can further be developed in hydrogels and polymers for soft robotics and functional materials.
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Although it is known that contact-electrified polymers can drive chemical reactions, the origin of this phenomenon remains poorly understood. To date, it has been accepted that this effect is due to excess electrons developed on negatively charged surfaces and to the subsequent transfer of these electrons to the reactants in solution. The present study demonstrates that this view is incorrect and, in reality, the reactions are driven by mechanoradicals created during polymer-polymer contact.
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Two rotaxanes with benzyl ether axles and tetralactam wheels were synthesized through an anion template effect. They carry naphthalene chromophores attached to the stopper groups and a pyrene chromophore attached to the wheel. The difference between the two rotaxanes is represented by the connecting unit of the naphthyl chromophore to the rotaxane axle: a triazole or an alkynyl group. Both rotaxanes exhibit excellent light-harvesting properties: excitation of the naphthalene chromophores is followed by energy transfer to the pyrene unit with efficiency higher than 90% in both cases. This represents an example of light-harvesting function among chromophores belonging to mechanically interlocked components, that is, the axle and the wheel of the rotaxanes.
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In touch: the outcome of contact electrification between dielectrics depends not only on the transfer of charge but also on the transfer of material. Although only minute quantities of materials are being exchanged during contact, they can reverse the polarity of dielectrics. The reported results corroborate the mosaic model and suggest that the observations are because of the mechanical softness/hardness of the materials.
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Condutividade Elétrica , Poliestirenos/química , Politetrafluoretileno/química , Transferência de Energia , Microscopia de Força Atômica , Estrutura Molecular , Análise Espectral Raman , Eletricidade Estática , Propriedades de SuperfícieRESUMO
In nature, nonequilibrium systems reflect environmental changes, and these changes are often "recorded" in their solid body as they develop. Periodic precipitation patterns, aka Liesegang patterns (LPs), are visual sums of complex events in nonequilibrium reaction-diffusion processes. Here we aim to achieve an artificial system that "records" the temperature changes in the environment with the concurrent LP formation. We first illustrate the differences in 1-D LPs developing at different temperatures in terms of band spacings, which can demonstrate the time, ramp steepness, and extent of a temperature change. These results are discussed and augmented by a mathematical model. Using scanning electron microscopy, we show that the average size of the CuCrO4 precipitate also reflects the temperature changes. Finally, we show that these changes can also be "recorded" in the 2-D and 3-D LPs, which can have applications in long-term temperature tracking and complex soft material design.
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Common polymers can accumulate surface charges through contact, a phenomenon known since ancient times. This charge accumulation can have detrimental consequences in industry. It causes accidents and yields enormous economic losses. Many empirical methods have been developed to prevent the problems caused by charge accumulation. However, a general chemical approach is still missing in the literature since the charge accumulation and discharging mechanisms have not been completely clarified. The current practice to achieve charge mitigation is to increase materials conductivity by high doping of conductive additives. A recent study showed that using photoexcitation of some organic dyes, charge decay can be started remotely, and the minute amount of additive does not change the material's conductivity. Here, we show the contact charging and charge decay behavior of polydimethylsiloxane doped with a series of organic charge transfer cocrystals (CTC) of TCNQ acceptor and substituted pyrene donors (CTC-PDMS). The results show that the CTC-PDMS are antistatic, and the discharging propensity of the composites follows the calculated charge transfer degree of the complexes. On the other hand, the CTC-PDMS are still insulators, as shown by their high surface resistivities. Kelvin probe force microscopy images of the contact-charged and discharged samples show a quick potential decay in CTC domains upon illumination. Combined with the fast overall decay observed, the antistatic behavior in these insulators can be attributed to an electron transfer between the mechanoions in the polymer and the CTC frontier orbitals. We believe our results will help with the general understanding of the molecular mechanism of contact charging and discharging and help develop insulator antistatics.
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As miscellaneous as the Plant Kingdom is, correspondingly diverse are the opportunities for taking inspiration from plants for innovations in science and engineering. Especially in robotics, properties like growth, adaptation to environments, ingenious materials, sustainability, and energy-effectiveness of plants provide an extremely rich source of inspiration to develop new technologies-and many of them are still in the beginning of being discovered. In the last decade, researchers have begun to reproduce complex plant functions leading to functionality that goes far beyond conventional robotics and this includes sustainability, resource saving, and eco-friendliness. This perspective drawn by specialists in different related disciplines provides a snapshot from the last decade of research in the field and draws conclusions on the current challenges, unanswered questions on plant functions, plant-inspired robots, bioinspired materials, and plant-hybrid systems looking ahead to the future of these research fields.
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Materiais Biomiméticos , Robótica , Plantas , Fenômenos Fisiológicos Vegetais , EngenhariaRESUMO
Liesegang pattern (LP) is one example of self-organized periodic precipitation patterns in nonequilibrium systems. Several studies have demonstrated that the LP morphology can track physicochemical environmental conditions (e.g., temperature); however, the polarity effect has not been explored to date. In this study, a copper chromate system is used to reveal the impact of solvent polarity on the evolving LP structure using water/organic solvent mixtures. In the typical case of using water/dimethyl sulfoxide (DMSO) mixtures, two drastic changes in LP morphology with increasing DMSO contents were found: (i) increasing frequency of the original structure and (ii) formation of a hierarchical pattern with the appearance of another, lower-frequency structure. Furthermore, the simulation model operating with a bimodal size distribution, allowing both homogeneous and heterogeneous precipitations showed good agreement with the experimental results. Therefore, this study demonstrated that LP can be tailored by solvent polarity and can be used for designing hierarchical precipitation patterns in a straightforward manner.
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Cobre , Dimetil Sulfóxido , Solventes/química , Dimetil Sulfóxido/química , Cromatos , Água/químicaRESUMO
Self-regulation (or so-called homeostasis) is a property of all living organisms to maintain an internal stable state through specialized biofeedback mechanisms under varying external and internal conditions. Although these feedback mechanisms in living organisms are complex networks and hard to implement one-to-one in artificial systems, the new approaches in soft robotics may benefit from the concept of self-regulation-especially in the new endeavors of making untethered, autonomous soft robots. In this study, we show a simple system, in which plant robots display heliotropism (sun tracking) and nyctinasty (leaf opening) through artificial self-regulation attained through a bioinspired transpiration mechanism. The feedback involves dehydration/hydration and transpiration events that keep the stem continuously in a metastable position, which maximizes light on plant leaves and the efficiency of light harvesting when solar panels are attached on leaves. We also demonstrate that this artificial feedback can be regulated by doping with light-absorbing chemicals or by changing the geometry of the system, and it can further be expanded to other lightweight systems. Implementing self-regulation into (soft) robots through bioinspired material feedback is beneficial not only for energy efficiency and harvesting but also for achieving embodied intelligence in autonomous soft robots.
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Materiais Biomiméticos , Robótica , Materiais Biomiméticos/química , Fototropismo , Folhas de Planta , Luz SolarRESUMO
Controlled generation of singlet oxygen is very important due to its involvement in scheduled cellular maintenance processes and therapeutic potential. As a consequence, precise manipulation of singlet oxygen release rates under mild conditions, is crucial. In this work, a cross-linked polyacrylate, and a polydimethylsiloxane elastomer incorporating anthracene-endoperoxide modules with chain extensions at the 9,10-positions were synthesized. We now report that on mechanical agitation in cryogenic ball mill, fluorescence emission due to anthracene units in the PMA (polymethacrylate) polymer is enhanced, with a concomitant generation of singlet oxygen as proved by detection with a selective probe. The PDMS (polydimethylsiloxane) elastomer with the anthracene endoperoxide mechanophore, is also similarly sensitive to mechanical force.
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Material design using nonequilibrium systems provides straightforward access to complexity levels that are possible through dynamic processes. Pattern formation through nonequilibrium processes and reaction-diffusion can be used to achieve this goal. Liesegang patterns (LPs) are a kind of periodic precipitation patterns formed through reaction-diffusion. So far, it has been shown that the periodic band structure of LPs and the geometry of the pattern can be controlled by experimental conditions and external fields (e.g., electrical or magnetic). However, there are no examples of these systems being used to retrieve information about the changes in the environment as they form, and there are no studies making use of these patterns for complex material preparation. This work shows the formation of LPs by a diffusion-precipitation reaction in a stretchable hydrogel and the control of the obtained patterns by the unprecedented and uncommon method of mechanical input. Additionally, how to use this protocol and how deviations from "LP behavior" of the patterns can be used to "write and store" information about the time, duration, extent, and direction of gel deformation are presented. Finally, an example of using complex patterning to deposit polypyrrole by using precipitation patterns is shown as a template.
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The mass spectrometric characterization of Fréchet-type dendrons is reported. In order to provide the charges necessary for electrospray ionization, dendrons bearing an OH group at the focal point can be deprotonated and observed in the negative ion mode. Alternatively, the corresponding bromides can be converted to quaternary ammonium ions that can easily be detected in the positive mode. If the latter ions are subjected to collision-induced dissociation experiments, a fragmentation cascade begins with the dissociation of the focal amine. The focal benzyl cation quickly decomposes in a fragmentation cascade from the focal point to the periphery until the peripheral benzyl (or naphthylmethyl) cations are formed. Five different mechanisms are discussed in detail, three of which can be excluded based on experimental evidence. The cascade fragmentation is reminiscent of self-immolative dendrimers.
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Dendrímeros/química , Gases , Íons , Estrutura Molecular , Espectrometria de Massas por Ionização por Electrospray , Espectrometria de Massas em TandemRESUMO
Triboelectric charging of insulators, also known as contact charging in which electrical charges develop on surfaces upon contact, is a significant problem that is especially critical for various industries such as polymers, pharmaceuticals, electronics, and space. Several methods of tribocharge mitigation exist in practice; however, none can reach the practicality of using light in the process. Here we show a light-controlled manipulation of triboelectric charges on common polymers, in which the tribocharges are mitigated upon illumination with appropriate wavelengths of light in presence of a mediator organic dye. Our method provides spatial and temporal control of mitigation of static charges on common polymer surfaces by a mechanism that involves photoexcitation of organic dyes, which also allows additional control using wavelength. This control over charge mitigation provides a way to manipulate macroscopic objects by tribocharging followed by light-controlled discharging.
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Tetralactam macrocycles can be functionalized by a variety of cross-coupling reactions. A modular "toolbox" strategy is presented that allows 1) several tetralactam macrocycles to be covalently connected with each other or with a central spacer, 2) the macrocycles to be substituted with or connected to different chromophores, and 3) metal-coordination sites to be attached to the macrocycles. With this approach a series of different oligo-macrocyclic hosts was obtained with great structural diversity and enormous potential for further functionalization. Rotaxanes made on the basis of these macrocycles have been synthesized to demonstrate their utility in building more complex supramolecular architectures.
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Lactamas/síntese química , Compostos Macrocíclicos/síntese química , Cristalografia por Raios X , Ciclização , Lactamas/química , Medições Luminescentes , Compostos Macrocíclicos/química , Conformação Molecular , Estrutura Molecular , Rotaxanos/química , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
One-fourth of the global energy losses result from friction and wear. Although friction and tribocharging were presented to be mutually related, reduction of friction and wear by eliminating tribocharges on common polymers, and decrease of power losses in devices with polymer parts were not shown to date. Here, we demonstrate that for common polymers, friction-which is strongly related to surface charge density-can be notably reduced by various methods of tribocharge mitigation, namely, corona discharging, solvent treatment, or placing a grounded conductor on the backside of one of the shearing materials. In our simple demonstrations, we found that by preventing tribocharge accumulation, a remarkable two-thirds of power loss during operation of simple mechanical devices with common polymers and plastic parts can be saved and wear can be reduced by a factor of 10. These demonstrations indicate important practical ramifications in mechanical systems with insulating parts.