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  1. Abstract

    It has been proposed that biologically generated turbulence plays an important role in material transport and ocean mixing. Both experimental and numerical studies have reported evidence of the nonnegligible mixing by moderate Reynolds number swimmers, such as zooplankton, in quiescent water, especially at aggregation scales. However, the interaction between biologically generated agitation and the background flow, as a key factor in biologically generated turbulence that could reshape our previous knowledge of biologically generated turbulence, has long been ignored. Here, we show that the geometry between the biologically generated agitation and the background hydrodynamic shear can determine both the intensity and direction of biologically generated turbulent energy flux. Measuring the migration of a centimeter-scale swimmer—as represented by the brine shrimp Artemia salina—in a shear flow and verifying through an analog experiment with an artificial jet revealed that different geometries between the biologically generated agitation and the background shear can result in spectral energy transferring toward larger or smaller scales, which consequently intensifies or attenuates the large-scale hydrodynamic shear. Our results suggest that the long ignored geometry between the biologically generated agitation and the background flow field is an important factor that should be taken into consideration in future studies of biologically generated turbulence.

     
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  2. Ladder-type structures can impart exceptional stability to polymeric electronic materials. This article introduces a new class of conductive polymers featuring a fully ladder-type backbone. A judicious molecular design strategy enables the synthesis of a low-defect ladder polymer, which can be efficiently oxidized and acid-doped to achieve its conductive state. The structural elucidation of this polymer and the characterization of its open-shell nature are facilitated with the assistance of studies on small molecular models. An autonomous robotic system is used to optimize the conductivity of the polymer thin film, achieving over 7 mS cm^−1. Impressively, this polymer demonstrates unparalleled stability in strong acid and under harsh UV-irradiation, significantly surpassing commercial benchmarks like PEDOT:PSS and polyaniline. Moreover, it displays superior durability across numerous redox cycles as the active material in an electrochromic device and as the pseudocapacitive material in a supercapacitor device. This work provides structural design guidance for durable conductive polymers for long-term device operation. 
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    Free, publicly-accessible full text available July 14, 2024
  3. Conjugated polymers have been widely investigated where ladder-type conjugated polymers receive more attention due to their rigid backbones and extraordinary properties. However, the understanding of how the rigid conformation of ladder polymers translates to material properties is still limited. Here, we systematically investigated the solution aggregation properties of a carbazole-derived conjugated ladder polymer (LP) and its analogous non-ladder control polymer (CP) via light scattering, neutron scattering, and UV-vis absorption spectroscopy characterization techniques, revealing a highly robust, temperature-insensitive aggregation behavior of the LP. The experimental findings were further validated by computational molecular dynamics simulations. We found that the peak positions and intensities of the UV spectra of the LP remained constant between 20 °C and 120 °C in chlorobenzene solution. The polymer also showed a stable hydrodynamic radius measured by dynamic light scattering from 20 °C to 70 °C in the chlorobenzene solution. Using small-angle neutron scattering, no Guinier region was reached in the measured q range down to 0.008 Å −1 , even at elevated temperature. In contrast, the non-ladder control polymer CP was fully soluble in the chlorobenzene solvent without the observation of any notable aggregates. The Brownian dynamics simulation showed that during polymer aggregation, the entropy change of the LP was significantly less negative than that of the non-ladder control polymer. These findings revealed the low entropy nature of rigid conjugated ladder polymers and the low entropy penalty for their aggregation, which is promising for highly robust intermolecular interactions at high temperatures. Such a unique thermodynamic feature of rigid ladder polymers can be leveraged in the design and application of next-generation electronic and optoelectronic devices that function under unconventional high temperature conditions. 
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  4. Low-cost and scalable superhydrophobic coating methods provide viable approaches for energy-efficient separation of immiscible liquid/liquid mixtures. A scalable photopolymerization method is developed to functionalize porous substrates with a hybrid coating of tetrapodal ZnO (T-ZnO) and polymethacrylate, which exhibits simultaneous superhydrophobicity and superoleophilicity. Here, T-ZnO serves dual purposes by (i) initiating radical photopolymerization during the fabrication process through a hole-mediated pathway and (ii) providing a hierarchical surface roughness to amplify wettability characteristics and suspend liquid droplets in the metastable Cassie—Baxter regime. Photopolymerization provides a means to finely control the conversion and spatial distribution of the formed polymer, whilst allowing for facile large-area fabrication and potential coating on heat-sensitive substrates. Coated stainless-steel meshes and filter papers with desired superhydrophobic/superoleophilic properties exhibit excellent performance in separating stratified oil/water, oil/ionic-liquid, and water/ionic-liquid mixtures as well as water-in-oil emulsions. The hybrid coating demonstrates desired mechanical robustness and chemical resistance for their long-term application in large-scale energy-efficient separation of immiscible liquid/liquid mixtures. 
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  5. Electrochemical stability and delocalization of states critically impact the functions and practical applications of electronically active polymers. Incorporation of a ladder-type constitution into these polymers represents a promising strategy to enhance the aforementioned properties from a fundamental structural perspective. A series of ladder-type polyaniline-analogous polymers are designed as models to test this hypothesis and are synthesized through a facile and scalable route. Chemical and electrochemical interconversions between the fully oxidized pernigraniline state and the fully reduced leucoemeraldine state are both achieved in a highly reversible and robust manner. The protonated pernigraniline form of the ladder polymer exhibits unprecedented electrochemical stability under highly acidic and oxidative conditions, enabling the access of a near-infrared light-absorbing material with extended polaron delocalization in the solid-state. An electrochromic device composed of this ladder polymer shows distinct switching between UV- and near-infrared-absorbing states with a remarkable cyclability, meanwhile tolerating a wide operating window of 4 volts. Taken together, these results demonstrate the principle of employing a ladder-type backbone constitution to impart superior electrochemical properties into electronically active polymers. 
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