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- ItemLiquefaction of Biopolymers: Solvent-free Liquids and Liquid Crystals from Nucleic Acids and Proteins(Washington, DC : ACS Publications, 2017) Liu, Kai; Ma, Chao; Göstl, Robert; Zhang, Lei; Herrmann, AndreasConspectusBiomacromolecules, such as nucleic acids, proteins, and virus particles, are persistent molecular entities with dimensions that exceed the range of their intermolecular forces hence undergoing degradation by thermally induced bond-scission upon heating. Consequently, for this type of molecule, the absence of a liquid phase can be regarded as a general phenomenon. However, certain advantageous properties usually associated with the liquid state of matter, such as processability, flowability, or molecular mobility, are highly sought-after features for biomacromolecules in a solvent-free environment. Here, we provide an overview over the design principles and synthetic pathways to obtain solvent-free liquids of biomacromolecular architectures approaching the topic from our own perspective of research. We will highlight the milestones in synthesis, including a recently developed general surfactant complexation method applicable to a large variety of biomacromolecules as well as other synthetic principles granting access to electrostatically complexed proteins and DNA.These synthetic pathways retain the function and structure of the biomacromolecules even under extreme, nonphysiological conditions at high temperatures in water-free melts challenging the existing paradigm on the role of hydration in structural biology. Under these conditions, the resulting complexes reveal their true potential for previously unthinkable applications. Moreover, these protocols open a pathway toward the assembly of anisotropic architectures, enabling the formation of solvent-free biomacromolecular thermotropic liquid crystals. These ordered biomaterials exhibit vastly different mechanical properties when compared to the individual building blocks. Beyond the preparative aspects, we will shine light on the unique potential applications and technologies resulting from solvent-free biomacromolecular fluids: From charge transport in dehydrated liquids to DNA electrochromism to biocatalysis in the absence of a protein hydration shell. Moreover, solvent-free biological liquids containing viruses can be used as novel storage and process media serving as a formulation technology for the delivery of highly concentrated bioactive compounds. We are confident that this new class of hybrid biomaterials will fuel further studies and applications of biomacromolecules beyond water and other solvents and in a much broader context than just the traditional physiological conditions. © 2017 American Chemical Society.
- ItemReversibly Photo-Modulating Mechanical Stiffness and Toughness of Bioengineered Protein Fibers(Weinheim : Wiley-VCH, 2020) Sun, Jing; Ma, Chao; Maity, Sourav; Wang, Fan; Zhou, Yu; Portale, Giuseppe; Göstl, Robert; Roos, Wouter H.; Zhang, Hongjie; Liu, Kai; Herrmann, AndreasLight-responsive materials have been extensively studied due to the attractive possibility of manipulating their properties with high spatiotemporal control in a non-invasive fashion. This stimulated the development of a series of photo-deformable smart devices. However, it remained a challenge to reversibly modulate the stiffness and toughness of bulk materials. Here, we present bioengineered protein fibers and their optomechanical manipulation by employing electrostatic interactions between supercharged polypeptides (SUPs) and an azobenzene (Azo)-based surfactant. Photo-isomerization of the Azo moiety from the E- to Z-form reversibly triggered the modulation of tensile strength, stiffness, and toughness of the bulk protein fiber. Specifically, the photo-induced rearrangement into the Z-form of Azo possibly strengthened cation–π interactions within the fiber material, resulting in an around twofold increase in the fiber's mechanical performance. The outstanding mechanical and responsive properties open a path towards the development of SUP-Azo fibers as smart stimuli-responsive mechano-biomaterials. © 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH
- ItemSignificant Upregulation of Alzheimer's β-Amyloid Levels in a Living System Induced by Extracellular Elastin Polypeptides(Weinheim : Wiley-VCH, 2019) Ma, Chao; Su, Juanjuan; Sun, Yao; Feng, Yang; Shen, Nolan; Li, Bo; Liang, Yingxia; Yang, Xintong; Wu, Hui; Zhang, Hongjie; Herrmann, Andreas; Tanzi, Rudolph E.; Liu, Kai; Zhang, CanAlzheimer's disease (AD) is a neurodegenerative disorder and the primary cause of age-related dementia. The etiology of AD is complex and has not been completely elucidated. Herein, we report that treatment with elastin-like polypeptides (ELPs), a component of the brain extracellular matrix (ECM), significantly increased the levels of AD-related amyloid-β peptides (Aβ) both in vitro and in vivo. Regarding the molecular mechanism(s), the upregulation of Aβ levels was related to increased proteolytic processing of the amyloid precursor protein. Furthermore, nesting tests demonstrated that the ELP-treated animals showed significant neurobehavioral deficits with cognitive impairment. These results suggest that the elastin is associated with AD-related pathological and behavioral changes. This finding presents a new aspect for Alzheimer's amyloidosis event and provides a great promise in developing ELP-based model systems to better understand the pathogenesis of AD. © 2019
- ItemThe Cyclostratigraphy Intercomparison Project (CIP): consistency, merits and pitfalls(Amsterdam [u.a.] : Elsevier, 2019) Sinnesael, Matthias; De Vleeschouwer, David; Zeeden, Christian; Batenburg, Sietske J.; Da Silva, Anne-Christine; de Winter, Niels J.; Dinarès-Turell, Jaume; Drury, Anna Joy; Gambacorta, Gabriele; Hilgen, Frederik J.; Hinnov, Linda A.; Hudson, Alexander J.L.; Kemp, David B.; Lantink, Margriet L.; Laurin, Jiří; Li, Mingsong; Liebrand, Diederik; Ma, Chao; Meyers, Stephen R.; Monkenbusch, Johannes; Montanari, Alessandro; Nohl, Theresa; Pälike, Heiko; Pas, Damien; Ruhl, Micha; Thibault, Nicolas; Vahlenkamp, Maximilian; Valero, Luis; Wouters, Sébastien; Wu, Huaichun; Claeys, PhilippeCyclostratigraphy is an important tool for understanding astronomical climate forcing and reading geological time in sedimentary sequences, provided that an imprint of insolation variations caused by Earth’s orbital eccentricity, obliquity and/or precession is preserved (Milankovitch forcing). Numerous stratigraphic and paleoclimate studies have applied cyclostratigraphy, but the robustness of the methodology and its dependence on the investigator have not been systematically evaluated. We developed the Cyclostratigraphy Intercomparison Project (CIP) to assess the robustness of cyclostratigraphic methods using an experimental design of three artificial cyclostratigraphic case studies with known input parameters. Each case study is designed to address specific challenges that are relevant to cyclostratigraphy. Case 1 represents an offshore research vessel environment, as only a drill-core photo and the approximate position of a late Miocene stage boundary are available for analysis. In Case 2, the Pleistocene proxy record displays clear nonlinear cyclical patterns and the interpretation is complicated by the presence of a hiatus. Case 3 represents a Late Devonian proxy record with a low signal-to-noise ratio with no specific theoretical astronomical solution available for this age. Each case was analyzed by a test group of 17-20 participants, with varying experience levels, methodological preferences and dedicated analysis time. During the CIP 2018 meeting in Brussels, Belgium, the ensuing analyses and discussion demonstrated that most participants did not arrive at a perfect solution, which may be partly explained by the limited amount of time spent on the exercises (∼4.5 hours per case). However, in all three cases, the median solution of all submitted analyses accurately approached the correct result and several participants obtained the exact correct answers. Interestingly, systematically better performances were obtained for cases that represented the data type and stratigraphic age that were closest to the individual participants’ experience. This experiment demonstrates that cyclostratigraphy is a powerful tool for deciphering time in sedimentary successions and, importantly, that it is a trainable skill. Finally, we emphasize the importance of an integrated stratigraphic approach and provide flexible guidelines on what good practices in cyclostratigraphy should include. Our case studies provide valuable insight into current common practices in cyclostratigraphy, their potential merits and pitfalls. Our work does not provide a quantitative measure of reliability and uncertainty of cyclostratigraphy, but rather constitutes a starting point for further discussions on how to move the maturing field of cyclostratigraphy forward.
- ItemUltra-strong bio-glue from genetically engineered polypeptides([London] : Nature Publishing Group UK, 2021) Ma, Chao; Sun, Jing; Li, Bo; Feng, Yang; Sun, Yao; Xiang, Li; Wu, Baiheng; Xiao, Lingling; Liu, Baimei; Petrovskii, Vladislav S.; Zhang, Jinrui; Wang, Zili; Li, Hongyan; Zhang, Lei; Li, Jingjing; Wang, Fan; Gӧstl, Robert; Potemkin, Igor I.; Chen, Dong; Zeng, Hongbo; Zhang, Hongjie; Liu, Kai; Herrmann, AndreasThe development of biomedical glues is an important, yet challenging task as seemingly mutually exclusive properties need to be combined in one material, i.e. strong adhesion and adaption to remodeling processes in healing tissue. Here, we report a biocompatible and biodegradable protein-based adhesive with high adhesion strengths. The maximum strength reaches 16.5 ± 2.2 MPa on hard substrates, which is comparable to that of commercial cyanoacrylate superglue and higher than other protein-based adhesives by at least one order of magnitude. Moreover, the strong adhesion on soft tissues qualifies the adhesive as biomedical glue outperforming some commercial products. Robust mechanical properties are realized without covalent bond formation during the adhesion process. A complex consisting of cationic supercharged polypeptides and anionic aromatic surfactants with lysine to surfactant molar ratio of 1:0.9 is driven by multiple supramolecular interactions enabling such strong adhesion. We demonstrate the glue’s robust performance in vitro and in vivo for cosmetic and hemostasis applications and accelerated wound healing by comparison to surgical wound closures.
- ItemSupercharged Proteins and Polypeptides(Weinheim : Wiley-VCH, 2020) Ma, Chao; Malessa, Anke; Boersma, Arnold J.; Liu, Kai; Herrmann, AndreasElectrostatic 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
- ItemOrganic carbon burial is paced by a ∼173-ka obliquity cycle in the middle to high latitudes(Washington, DC [u.a.] : Assoc., 2021) Huang, He; Gao, Yuan; Ma, Chao; Jones, Matthew M.; Zeeden, Christian; Ibarra, Daniel E.; Wu, Huaichun; Wang, ChengshanEarth’s climate system is complex and inherently nonlinear, which can induce some extraneous cycles in paleoclimatic proxies at orbital time scales. The paleoenvironmental consequences of these extraneous cycles are debated owing to their complex origin. Here, we compile high-resolution datasets of total organic carbon (TOC) and stable carbon isotope (δ13Corg) datasets to investigate organic carbon burial processes in middle to high latitudes. Our results document a robust cyclicity of ~173 thousand years (ka) in both TOC and δ13Corg. The ~173-ka obliquity–related forcing signal was amplified by internal climate feedbacks of the carbon cycle under different geographic and climate conditions, which control a series of sensitive climatic processes. In addition, our new and compiled records from multiple proxies confirm the presence of the obliquity amplitude modulation (AM) cycle during the Mesozoic and Cenozoic and indicate the usefulness of the ~173-ka cycle as geochronometer and for paleoclimatic interpretation.
- ItemDe novo rational design of a freestanding, supercharged polypeptide, proton-conducting membrane(Washington : American Association for the Advancement of Science (A A A S), 2020) Ma, Chao; Dong, Jingjin; Viviani, Marco; Tulini, Isotta; Pontillo, Nicola; Maity, Sourav; Zhou, Yu; Roos, Wouter H.; Liu, Kai; Herrmann, Andreas; Portale, GiuseppeProton translocation enables important processes in nature and man-made technologies. However, controlling proton conduction and fabrication of devices exploiting biomaterials remains a challenge. Even more difficult is the design of protein-based bulk materials without any functional starting scaffold for further optimization. Here, we show the rational design of proton-conducting, protein materials exceeding reported proteinaceous systems. The carboxylic acid-rich structures were evolved step by step by exploring various sequences from intrinsically disordered coils over supercharged nanobarrels to hierarchically spider β sheet containing protein-supercharged polypeptide chimeras. The latter material is characterized by interconnected β sheet nanodomains decorated on their surface by carboxylic acid groups, forming self-supportive membranes and allowing for proton conduction in the hydrated state. The membranes showed an extraordinary proton conductivity of 18.5 ± 5 mS/cm at RH = 90%, one magnitude higher than other protein devices. This design paradigm offers great potential for bioprotonic device fabrication interfacing artificial and biological systems. Copyright © 2020 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).