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    Enlightening Materials with Photoswitches
    (Weinheim : Wiley-VCH, 2020) Goulet-Hanssens, Alexis; Eisenreich, Fabian; Hecht, Stefan
    Incorporating molecular photoswitches into various materials provides unique opportunities for controlling their properties and functions with high spatiotemporal resolution using remote optical stimuli. The great and largely still untapped potential of these photoresponsive systems has not yet been fully exploited due to the fundamental challenges in harnessing geometrical and electronic changes on the molecular level to modulate macroscopic and bulk material properties. Herein, progress made during the past decade in the field of photoswitchable materials is highlighted. After pointing to some general design principles, materials with an increasing order of the integrated photoswitchable units are discussed, spanning the range from amorphous settings over surfaces/interfaces and supramolecular ensembles, to liquid crystalline and crystalline phases. Finally, some potential future directions are pointed out in the conclusion. In view of the exciting recent achievements in the field, the future emergence and further development of light-driven and optically programmable (inter)active materials and systems are eagerly anticipated. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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    Supercharged Proteins and Polypeptides
    (Weinheim : Wiley-VCH, 2020) Ma, Chao; Malessa, Anke; Boersma, Arnold J.; Liu, Kai; Herrmann, Andreas
    Electrostatic interactions play a vital role in nature. Biomacromolecules such as proteins are orchestrated by electrostatics, among other intermolecular forces, to assemble and organize biochemistry. Natural proteins with a high net charge exist in a folded state or are unstructured and can be an inspiration for scientists to artificially supercharge other protein entities. Recent findings show that supercharging proteins allows for control of their properties such as temperature resistance and catalytic activity. One elegant method to transfer the favorable properties of supercharged proteins to other proteins is the fabrication of fusions. Genetically engineered, supercharged unstructured polypeptides (SUPs) are just one promising fusion tool. SUPs can also be complexed with artificial entities to yield thermotropic and lyotropic liquid crystals and liquids. These architectures represent novel bulk materials that are sensitive to external stimuli. Interestingly, SUPs undergo fluid–fluid phase separation to form coacervates. These coacervates can even be directly generated in living cells or can be combined with dissipative fiber assemblies that induce life-like features. Supercharged proteins and SUPs are developed into exciting classes of materials. Their synthesis, structures, and properties are summarized. Moreover, potential applications are highlighted and challenges are discussed. © 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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    Wet-Spun PEDOT/CNT Composite Hollow Fibers as Flexible Electrodes for H2O2 Production
    (Weinheim : Wiley-VCH, 2021) Cui, Qing; Bell, Daniel Josef; Wang, Siqi; Mohseni, Mojtaba; Felder, Daniel; Lölsberg, Jonas; Wessling, Matthias
    The electrochemical synthesis of hydrogen peroxide (H2O2) using the oxygen reduction reaction (ORR) requires highly catalytic active, selective, and stable electrode materials to realize a green and efficient process. The present publication shows for the first time the application of a facile one-step bottom-up wet-spinning approach for the continuous fabrication of stable and flexible tubular poly(3,4-ethylene dioxythiophene) (PEDOT : PSS) and PEDOT : PSS/carbon nanotube (CNT) hollow fibers. Additionally, electrochemical experiments reveal the catalytic activity of acid-treated PEDOT : PSS and its composites in the ORR forming hydrogen peroxide for the first time. Under optimized conditions, the composite electrodes with 40 wt % CNT loading could achieve a high production rate of 0.01 mg/min/cm2 and a current efficiency of up to 54 %. In addition to the high production rate, the composite hollow fiber has proven its long-term stability with 95 % current retention after 20 h of hydrogen peroxide production. © 2021 The Authors. ChemElectroChem published by Wiley-VCH GmbH
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    Digitally Fabricated and Naturally Augmented In Vitro Tissues
    (Weinheim : Wiley-VCH, 2020) Duarte Campos, Daniela F.; De Laporte, Laura
    Human in vitro tissues are extracorporeal 3D cultures of human cells embedded in biomaterials, commonly hydrogels, which recapitulate the heterogeneous, multiscale, and architectural environment of the human body. Contemporary strategies used in 3D tissue and organ engineering integrate the use of automated digital manufacturing methods, such as 3D printing, bioprinting, and biofabrication. Human tissues and organs, and their intra- and interphysiological interplay, are particularly intricate. For this reason, attentiveness is rising to intersect materials science, medicine, and biology with arts and informatics. This report presents advances in computational modeling of bioink polymerization and its compatibility with bioprinting, the use of digital design and fabrication in the development of fluidic culture devices, and the employment of generative algorithms for modeling the natural and biological augmentation of in vitro tissues. As a future direction, the use of serially linked in vitro tissues as human body-mimicking systems and their application in drug pharmacokinetics and metabolism, disease modeling, and diagnostics are discussed. © 2020 The Authors. Advanced Healthcare Materials published by Wiley-VCH GmbH
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    Computer-Assisted Recombination (CompassR) Teaches us How to Recombine Beneficial Substitutions from Directed Evolution Campaigns
    (Weinheim : Wiley-VCH, 2020) Cui, Haiyang; Cao, Hao; Cai, Haiying; Jaeger, Karl-Erich; Davari, Mehdi D.; Schwaneberg, Ulrich
    A main remaining challenge in protein engineering is how to recombine beneficial substitutions. Systematic recombination studies show that poorly performing variants are usually obtained after recombination of 3 to 4 beneficial substitutions. This limits researchers in exploiting nature's potential in generating better enzymes. The Computer-assisted Recombination (CompassR) strategy provides a selection guide for beneficial substitutions that can be recombined to gradually improve enzyme performance by analysis of the relative free energy of folding (ΔΔGfold). The performance of CompassR was evaluated by analysis of 84 recombinants located on 13 positions of Bacillus subtilis lipase A. The finally obtained variant F17S/V54K/D64N/D91E had a 2.7-fold improved specific activity in 18.3 % (v/v) 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]). In essence, the deducted CompassR rule allows recombination of beneficial substitutions in an iterative manner and empowers researchers to generate better enzymes in a time-efficient manner. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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    Advanced Optical Programming of Individual Meta-Atoms Beyond the Effective Medium Approach
    (Weinheim : Wiley-VCH, 2019) Michel, Ann-Katrin U.; Heßler, Andreas; Meyer, Sebastian; Pries, Julian; Yu, Yuan; Kalix, Thomas; Lewin, Martin; Hanss, Julian; De Rose, Angela; Maß, Tobias W.W.; Wuttig, Matthias; Chigrin, Dmitry N.; Taubner, Thomas
    Nanometer-thick active metasurfaces (MSs) based on phase-change materials (PCMs) enable compact photonic components, offering adjustable functionalities for the manipulation of light, such as polarization filtering, lensing, and beam steering. Commonly, they feature multiple operation states by switching the whole PCM fully between two states of drastically different optical properties. Intermediate states of the PCM are also exploited to obtain gradual resonance shifts, which are usually uniform over the whole MS and described by effective medium response. For programmable MSs, however, the ability to selectively address and switch the PCM in individual meta-atoms is required. Here, simultaneous control of size, position, and crystallization depth of the switched phase-change material (PCM) volume within each meta-atom in a proof-of-principle MS consisting of a PCM-covered Al–nanorod antenna array is demonstrated. By modifying optical properties locally, amplitude and light phase can be programmed at the meta-atom scale. As this goes beyond previous effective medium concepts, it will enable small adaptive corrections to external aberrations and fabrication errors or multiple complex functionalities programmable on the same MS. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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    Polymeric Membranes With Sufficient Thermo‐Mechanical Stability to Deploy Temperature Enhanced Backwash
    (Weinheim : Wiley-VCH, 2021) Aumeier, Benedikt M.; Vollmer, Fabian; Lenfers, Simon; Yüce, Süleyman; Wessling, Matthias
    The alternative membrane cleaning method Temperature Enhanced Backwash exploits elevated temperatures of typically 125 °C to realize high shear rate. This exceeds usual operating temperatures by far. Therefore, the thermo-mechanical properties of polymeric membranes were investigated. A repeated load cycle testing was suited and sensitive to detect the failure of membrane material and potting. All tested PES membranes showed to be stable during the repeated load cycle testing. The potting adhesive may be decisive, thus, a tensile test at 125 °C is proposed. © 2021 The Authors. Chemie Ingenieur Technik published by Wiley-VCH GmbH
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    Heterolepic β‐Ketoiminate Zinc Phenoxide Complexes as Efficient Catalysts for the Ring Opening Polymerization of Lactide
    (Weinheim : Wiley-VCH, 2019) Ghosh, Swarup; Schäfer, Pascal M.; Dittrich, Dennis; Scheiper, Christoph; Steiniger, Phillip; Fink, Gerhard; Ksiazkiewicz, Agnieszka N.; Tjaberings, Alexander; Wölper, Christoph; Gröschel, André H.; Pich, Andrij; Herres‐Pawlis, Sonja; Schulz, Stephan
    Zinc phenoxide complexes L1ZnOAr 1–4 (L1=Me2NC2H4NC(Me)CHC(Me)O) and L2ZnOAr 5–8 (L2=Me2NC3H6NC(Me)CHC(Me)O) with donor-functionalized β-ketoiminate ligands (L1/2) and OAr substituents (Ar=Ph 1, 5; 2,6-Me2-C6H3 2, 6; 3,5-Me2-C6H3 3, 7; 4-Bu-C6H4 4, 8) with tuneable electronic and steric properties were synthesized and characterized. 1–8 adopt binuclear structures in the solid state except for 5, while they are monomeric in CDCl3 solution. 1–8 are active catalysts for the ring opening polymerization (ROP) of lactide (LA) in CH2Cl2 at ambient temperature and the catalytic activity is controlled by the electronic and steric properties of the OAr substituent, yielding polymers with high average molecular weight (Mn) and moderately controlled molecular weight distribution (MWDs). 1 and 5 showed a living polymerization character and kinetic studies on the ROP of L–LA with 1 and 5 proved first order dependencies on the monomer concentration. Homonuclear decoupled 1H-NMR analyses of polylactic acid (PLA) formed with rac-LA proved isotactic enrichment of the PLA microstructure. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
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    Zwitterionic Nanogels and Microgels: An Overview on Their Synthesis and Applications
    (Weinheim : Wiley-VCH, 2021) Saha, Pabitra; Ganguly, Ritabrata; Li, Xin; Das, Rohan; Singha, Nikhil K.; Pich, Andrij
    Zwitterionic polymers by virtue of their unique chemical and physical attributes have attracted researchers in recent years. The simultaneous presence of positive and negative charges in the same repeat unit renders them of various interesting properties such as superhydrophilicity, which has significantly broadened their scope for being used in different applications. Among polyzwitterions of different architectures, micro- and/or nano-gels have started receiving attention only until recently. These 3D cross-linked colloidal structures show peculiar characteristics in context to their solution properties, which are attributable either to the comonomers present or the presence of different electrolytes and biological specimens. In this review, a concise yet detailed account is provided of the different synthetic techniques and application domains of zwitterion-based micro- and/or nanogels that have been explored in recent years. Here, the focus is kept solely on the “polybetaines,” which have garnered maximum research interest and remain the extensively studied polyzwitterions in literature. While their vast application potential in the biomedical sector is being detailed here, some other areas of scope such as using them as microreactors for the synthesis of metal nanoparticles or making smart membranes for water-treatment are discussed in this minireview as well.
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    Soft Microrobots Employing Nonequilibrium Actuation via Plasmonic Heating
    (Weinheim : Wiley-VCH, 2017) Mourran, Ahmed; Zhang, Hang; Vinokur, Rostislav; Möller, Martin
    A soft microrobot composed of a microgel and driven by the light-controlled nonequilibrium dynamics of volume changes is presented. The photothermal response of the microgel, containing plasmonic gold nanorods, enables fast heating/cooling dynamics. Mastering the nonequilibrium response provides control of the complex motion, which goes beyond what has been so far reported for hydrophilic microgels.