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- ItemSelf-Regenerating Soft Biophotovoltaic Devices(Washington, DC : ACS Publications, 2018) Qiu, Xinkai; Castañeda Ocampo, Olga; de Vries, Hendrik W.; van Putten, Maikel; Loznik, Mark; Herrmann, Andreas; Chiechi, Ryan C.This paper describes the fabrication of soft, stretchable biophotovoltaic devices that generate photocurrent from photosystem I (PSI) complexes that are self-assembled onto Au electrodes with a preferred orientation. Charge is collected by the direct injection of electrons into the Au electrode and the transport of holes through a redox couple to liquid eutectic gallium-indium (EGaIn) electrodes that are confined to microfluidic pseudochannels by arrays of posts. The pseudochannels are defined in a single fabrication step that leverages the non-Newtonian rheology of EGaIn. This strategy is extended to the fabrication of reticulated electrodes that are inherently stretchable. A simple shadow evaporation technique is used to increase the surface area of the Au electrodes by a factor of approximately 106 compared to planar electrodes. The power conversion efficiency of the biophotovoltaic devices decreases over time, presumably as the PSI complexes denature and/or detach from the Au electrodes. However, by circulating a solution of active PSI complexes the devices self-regenerate by mass action/self-assembly. These devices leverage simple fabrication techniques to produce complex function and prove that photovoltaic devices comprising PSI can retain the ability to regenerate, one of the most important functions of photosynthetic organisms. © 2018 American Chemical Society.
- 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.
- ItemPhonon-Polaritonic Bowtie Nanoantennas: Controlling Infrared Thermal Radiation at the Nanoscale(Washington, DC : ACS Publications, 2017) Wang, Tao; Li, Peining; Chigrin, Dmitry N.; Giles, Alexander J.; Bezares, Francisco J.; Glembocki, Orest J.; Caldwell, Joshua D.; Taubner, ThomasA conventional thermal emitter exhibits a broad emission spectrum with a peak wavelength depending upon the operation temperature. Recently, narrowband thermal emission was realized with periodic gratings or single microstructures of polar crystals supporting distinct optical modes. Here, we exploit the coupling of adjacent phonon-polaritonic nanostructures, demonstrating experimentally that the nanometer-scale gaps can control the thermal emission frequency while retaining emission line widths as narrow as 10 cm-1. This was achieved by using deeply subdiffractional bowtie-shaped silicon carbide nanoantennas. Infrared far-field reflectance spectroscopy, near-field optical nanoimaging, and full-wave electromagnetic simulations were employed to prove that the thermal emission originates from strongly localized surface phonon-polariton resonances of nanoantenna structures. The observed narrow emission line widths and exceptionally small modal volumes provide new opportunities for the user-design of near- and far-field radiation patterns for advancements in infrared spectroscopy, sensing, signaling, communications, coherent thermal emission, and infrared photodetection. © 2017 American Chemical Society.
- ItemPlasmonic Hepatitis B Biosensor for the Analysis of Clinical Saliva(Columbus, Ohio : American Chemical Society, 2017) Riedel, Tomáš; Hageneder, Simone; Surman, František; Pop-Georgievski, Ognen; Noehammer, Christa; Hofner, Manuela; Brynda, Eduard; Rodriguez-Emmenegger, Cesar; Dostálek, JakubA biosensor for the detection of hepatitis B antibodies in clinical saliva was developed. Compared to conventional analysis of blood serum, it offers the advantage of noninvasive collection of samples. Detection of biomarkers in saliva imposes two major challenges associated with the low analyte concentration and increased surface fouling. The detection of minute amounts of hepatitis B antibodies was performed by plasmonically amplified fluorescence sandwich immunoassay. To have access to specific detection, we prevented the nonspecific adsorption of biomolecules present in saliva by brushes of poly[(N-(2-hydroxypropyl) methacrylamide)-co-(carboxybetaine methacrylamide)] grafted from the gold sensor surface and post modified with hepatitis B surface antigen. Obtained results were validated against the response measured with ELISA at a certified laboratory using serum from the same patients. © 2017
- ItemAnti-Stokes Stress Sensing: Mechanochemical Activation of Triplet-Triplet Annihilation Photon Upconversion(Weinheim : Wiley-VCH, 2019) Yildiz, Deniz; Baumann, Christoph; Mikosch, Annabel; Kuehne, Alexander J.C.; Herrmann, Andreas; Göstl, RobertThe development of methods to detect damage in macromolecular materials is of paramount importance to understand their mechanical failure and the structure–property relationships of polymers. Mechanofluorophores are useful and sensitive molecular motifs for this purpose. However, to date, tailoring of their optical properties remains challenging and correlating emission intensity to force induced material damage and the respective events on the molecular level is complicated by intrinsic limitations of fluorescence and its detection techniques. Now, this is tackled by developing the first stress-sensing motif that relies on photon upconversion. By combining the Diels–Alder adduct of a π-extended anthracene with the porphyrin-based triplet sensitizer PtOEP in polymers, triplet–triplet annihilation photon upconversion of green to blue light is mechanochemically activated in solution as well as in the solid state. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
- ItemActively Tunable Collective Localized Surface Plasmons by Responsive Hydrogel Membrane(Weinheim : Wiley-VCH, 2019) Quilis, Nestor Gisbert; van Dongen, Marcel; Venugopalan, Priyamvada; Kotlarek, Daria; Petri, Christian; Cencerrado, Alberto Moreno; Stanescu, Sorin; Herrera, Jose Luis Toca; Jonas, Ulrich; Möller, Martin; Mourran, Ahmed; Dostalek, JakubCollective (lattice) localized surface plasmons (cLSP) with actively tunable and extremely narrow spectral characteristics are reported. They are supported by periodic arrays of gold nanoparticles attached to a stimuli-responsive hydrogel membrane, which can on demand swell and collapse to reversibly modulate arrays period and surrounding refractive index. In addition, it features a refractive index-symmetrical geometry that promotes the generation of cLSPs and leads to strong suppression of radiative losses, narrowing the spectral width of the resonance, and increasing of the electromagnetic field intensity. Narrowing of the cLSP spectral band down to 13 nm and its reversible shifting by up to 151 nm is observed in the near infrared part of the spectrum by varying temperature and by solvent exchange for systems with a poly(N-isopropylacrylamide)-based hydrogel membrane that is allowed to reversibly swell and collapse in either one or in three dimensions. The reported structures with embedded periodic gold nanoparticle arrays are particularly attractive for biosensing applications as the open hydrogel structure can be efficiently post-modified with functional moieties, such as specific ligands, and since biomolecules can rapidly diffuse through swollen polymer networks. © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
- ItemIn-Gel Direct Laser Writing for 3D-Designed Hydrogel Composites That Undergo Complex Self-Shaping(Weinheim : Wiley-VCH, 2017) Nishiguchi, Akihiro; Mourran, Ahmed; Zhang, Hang; Möller, MartinSelf-shaping and actuating materials inspired by biological system have enormous potential for biosensor, microrobotics, and optics. However, the control of 3D-complex microactuation is still challenging due to the difficulty in design of nonuniform internal stress of micro/nanostructures. Here, we develop in-gel direct laser writing (in-gel DLW) procedure offering a high resolution inscription whereby the two materials, resin and hydrogel, are interpenetrated on a scale smaller than the wavelength of the light. The 3D position and mechanical properties of the inscribed structures could be tailored to a resolution better than 100 nm over a wide density range. These provide an unparalleled means of inscribing a freely suspended microstructures of a second material like a skeleton into the hydrogel body and also to direct isotropic volume changes to bending and distortion motions. In the combination with a thermosensitive hydrogel rather small temperature variations could actuate large amplitude motions. This generates complex modes of motion through the rational engineering of the stresses present in the multicomponent material. More sophisticated folding design would realize a multiple, programmable actuation of soft materials. This method inspired by biological system may offer the possibility for functional soft materials capable of biomimetic actuation and photonic crystal application.
- ItemDNA Nanotechnology Enters Cell Membranes(Weinheim : Wiley-VCH, 2019) Huo, Shuaidong; Li, Hongyan; Boersma, Arnold J.; Herrmann, AndreasDNA is more than a carrier of genetic information: It is a highly versatile structural motif for the assembly of nanostructures, giving rise to a wide range of functionalities. In this regard, the structure programmability is the main advantage of DNA over peptides, proteins, and small molecules. DNA amphiphiles, in which DNA is covalently bound to synthetic hydrophobic moieties, allow interactions of DNA nanostructures with artificial lipid bilayers and cell membranes. These structures have seen rapid growth with great potential for medical applications. In this Review, the current state of the art of the synthesis of DNA amphiphiles and their assembly into nanostructures are first summarized. Next, an overview on the interaction of these DNA amphiphiles with membranes is provided, detailing on the driving forces and the stability of the interaction. Moreover, the interaction with cell surfaces in respect to therapeutics, biological sensing, and cell membrane engineering is highlighted. Finally, the challenges and an outlook on this promising class of DNA hybrid materials are discussed.
- ItemQuantifying ligand-cell interactions and determination of the surface concentrations of ligands on hydrogel films: The measurement challenge(Melville, NY : AIP Publishing, 2015) Beer, Meike V.; Hahn, Kathrin; Diederichs, Sylvia; Fabry, Marlies; Singh, Smriti; Spencer, Steve J.; Salber, Jochen; Möller, Martin; Shard, Alexander G.; Groll, JürgenHydrogels are extensively studied for biomaterials application as they provide water swollen noninteracting matrices in which specific binding motifs and enzyme-sensitive degradation sites can be incorporated to tailor cell adhesion, proliferation, and migration. Hydrogels also serve as excellent basis for surface modification of biomaterials where interfacial characteristics are decisive for implant success or failure. However, the three-dimensional nature of hydrogels makes it hard to distinguish between the bioactive ligand density at the hydrogel-cell interface that is able to interact with cells and the ligands that are immobilized inside the hydrogel and not accessible for cells. Here, the authors compare x-ray photoelectron spectrometry (XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), enzyme linked immunosorbent assay (ELISA), and the correlation with quantitative cell adhesion using primary human dermal fibroblasts (HDF) to gain insight into ligand distribution. The authors show that although XPS provides the most useful quantitative analysis, it lacks the sensitivity to measure biologically meaningful concentrations of ligands. However, ToF-SIMS is able to access this range provided that there are clearly distinguishable secondary ions and a calibration method is found. Detection by ELISA appears to be sensitive to the ligand density on the surface that is necessary to mediate cell adhesion, but the upper limit of detection coincides closely with the minimal ligand spacing required to support cell proliferation. Radioactive measurements and ELISAs were performed on amine reactive well plates as true 2D surfaces to estimate the ligand density necessary to allow cell adhesion onto hydrogel films. Optimal ligand spacing for HDF adhesion and proliferation on ultrathin hydrogel films was determined as 6.5 ± 1.5 nm.
- ItemPolymer Brush-Functionalized Chitosan Hydrogels as Antifouling Implant Coatings(Columbus, Ohio : American Chemical Society, 2017) Buzzacchera, Irene; Vorobii, Mariia; Kostina, Nina Yu; de Los Santos Pereira, Andres; Riedel, Tomáš; Bruns, Michael; Ogieglo, Wojciech; Möller, Martin; Wilson, Christopher J.; Rodriguez-Emmenegger, CesarImplantable sensor devices require coatings that efficiently interface with the tissue environment to mediate biochemical analysis. In this regard, bioinspired polymer hydrogels offer an attractive and abundant source of coating materials. However, upon implantation these materials generally elicit inflammation and the foreign body reaction as a consequence of protein fouling on their surface and concomitant poor hemocompatibility. In this report we investigate a strategy to endow chitosan hydrogel coatings with antifouling properties by the grafting of polymer brushes in a "grafting-from" approach. Chitosan coatings were functionalized with polymer brushes of oligo(ethylene glycol) methyl ether methacrylate and 2-hydroxyethyl methacrylate using photoinduced single electron transfer living radical polymerization and the surfaces were thoroughly characterized by XPS, AFM, water contact angle goniometry, and in situ ellipsometry. The antifouling properties of these new bioinspired hydrogel-brush coatings were investigated by surface plasmon resonance. The influence of the modifications to the chitosan on hemocompatibility was assessed by contacting the surfaces with platelets and leukocytes. The coatings were hydrophilic and reached a thickness of up to 180 nm within 30 min of polymerization. The functionalization of the surface with polymer brushes significantly reduced the protein fouling and eliminated platelet activation and leukocyte adhesion. This methodology offers a facile route to functionalizing implantable sensor systems with antifouling coatings that improve hemocompatibility and pave the way for enhanced device integration in tissue.