Organic Charge Transfer Cocrystals as Additives for Dissipation of Contact Charges on Polymers.

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.

Mechanical Control of Periodic Precipitation in Stretchable Gels to Retrieve Information on Elastic Deformation and for the Complex Patterning of Matter.

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.

Control of triboelectric charges on common polymers by photoexcitation of organic dyes.

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.

Minimizing friction, wear, and energy losses by eliminating contact charging.

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.

The Charging Events in Contact-Separation Electrification.

Contact electrification (CE)-charging of surfaces that are contacted and separated, is a common phenomenon, however it is not completely understood yet. Recent studies using surface imaging techniques and chemical analysis revealed a 'spatial' bipolar distribution of charges at the nano dimension, which made a paradigm shift in the field. However, such analyses can only provide information about the charges that remained on the surface after the separation, providing limited information about the actual course of the CE event. Tapping common polymers and metal surfaces to each other and detecting the electrical potential produced on these surfaces 'in-situ' in individual events of contact and separation, we show that, charges are generated and transferred between the surfaces in both events; the measured potential is bipolar in contact and unipolar in separation. We show, the 'contact-charges' on the surfaces are indeed the net charges that results after the separation process, and a large contribution to tribocharge harvesting comes, in fact, from the electrostatic induction resulting from the generated CE charges. Our results refine the mechanism of CE providing information for rethinking the conventional ranking of materials' charging abilities, charge harvesting, and charge prevention.

Artificial Heliotropism and Nyctinasty Based on Optomechanical Feedback and No Electronics.

Although plants are typically not considered an inspiration for designing motile robots, they do perform a variety of intricate motion patterns, including diurnal cycles of sun tracking (heliotropism) and leaf opening (nyctinasty). In real plants, these motions are controlled by complex, feedback-based biological mechanisms that, to date, have been mimicked only in computer-controlled artificial systems. This work demonstrates both heliotropism and nyctinasty in a system in which few simple, but strategically positioned thermo-responsive springs and lenses form a feedback loop controlling these motions and substantiating a behavioral analogy to "plants." In particular, this feedback allows the "artificial plant" to reach and stabilize at a metastable position in which the solar flux on the "plants" and the solar power "leaves" are maximized. Unlike many soft robotic systems, our "plants" are completely autonomous, in that, they do not require any external controls or power sources. Bioinspired designs such as this could be of interest for soft robotic systems in which materials alone-rather than power-consuming electronic circuitry-control the motions.

Mechanochemical activation and patterning of an adhesive surface toward nanoparticle deposition.

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.

Mechanically driven activation of polyaniline into its conductive form.

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.

Control of surface charges by radicals as a principle of antistatic polymers protecting electronic circuitry.

Even minute quantities of electric charge accumulating on polymer surfaces can cause shocks, explosions, and multibillion-dollar losses to electronic circuitry. This paper demonstrates that to remove static electricity, it is not at all necessary to "target" the charges themselves. Instead, the way to discharge a polymer is to remove radicals from its surface. These radicals colocalize with and stabilize the charges; when they are scavenged, the surfaces discharge rapidly. This radical-charge interplay allows for controlling static electricity by doping common polymers with small amounts of radical-scavenging molecules, including the familiar vitamin E. The effectiveness of this approach is demonstrated by rendering common polymers dust-mitigating and also by using them as coatings that prevent the failure of electronic circuitry.

What really drives chemical reactions on contact charged surfaces?

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.

Material transfer and polarity reversal in contact charging.

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.

Dendrimer disassembly in the gas phase: a cascade fragmentation reaction of Fréchet dendrons.

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.

Characterization of self-assembled metallodendrimers in solution, in the gas phase, and at air/solid interfaces.

It is found that 4,4'-bipyridines functionalized in their 3,3'-positions with Fréchet dendrons of 0th to 3rd generation self-assemble with (dppp)M(II) triflates (dppp: bis-(diphenylphosphino)propane; M = Pd, Pt) into metallo-supramolecular squares. They bear a nanometer-sized cavity inside an unpolar dendritic shell. A total of eight amide groups decorate the rims of the cavity connecting the dendrons to the square. Evidence for their formation up to the third generation comes from ESI-FTICR mass spectrometry and NMR experiments. Based on these results, the presence of significant amounts of other polygons or open-chain oligomers can be excluded. Exchange processes have been studied by variable-temperature NMR spectroscopy and by following the ligand exchanges between different squares by mass spectrometry. The ligand exchange is much slower for the Pt(II) squares as compared to their Pd(II) analogs. Visualization of films of these dendrimers using atomic force microscopy (AFM) provides information on their molecular dimensions. After deposition of a square monolayer on the surface, a slow reorganization within this layer is observed which leads to the formation of "tower-like" aggregates and multi-layer formation. The interplay of interactions between the dendrimers and the surface and interactions between different dendrimers are invoked to rationalize the observations.

Mass spectrometric studies of non-covalent compounds: why supramolecular chemistry in the gas phase?

Supramolecular chemistry has progressed quite a long way in recent decades. The examination of non-covalent bonds became the focus of research once the paradigm that the observed properties of a molecule are due to the molecule itself was revised, and researchers became aware of the often quite significant influence of the environment. Mass spectrometry and gas-phase chemistry are ideally suited to study the intrinsic properties of a molecule or a complex without interfering effects from the environment, such as solvation and the effects of counterions present in solution. A comparison of data from the gas phase, i.e. the intrinsic properties, with results from condensed phase, i.e. the properties influenced by the surroundings of the molecule, can consequently contribute significantly to the understanding of non-covalent bonds. This review provides insight into the often-underestimated power of mass spectrometry for the investigation of supramolecules. Through example studies, several aspects are discussed, including determination of structure in solution and the gas phase, ion mobility studies to reveal the formation of zwitterionic structures, stereochemical issues, analysis of reactivity of supramolecular compounds in the condensed and in the gas phase, and the determination of thermochemical data.