Bavarian Polymer Institute

The development and formulation of printable inks for extrusion-based 3D bioprinting has been a major challenge in the field of biofabrication. Inks, often polymer solutions with the addition of crosslinking to form hydrogels, must not only display adequate mechanical properties for the chosen application but also show high biocompatibility as well as printability. Here we describe a reproducible two-step method for the assessment of the printability of inks for bioprinting, focussing firstly on screening ink formulations to assess fibre formation and the ability to form 3D constructs before presenting a method for the rheological evaluation of inks to characterise the yield point, shear thinning and recovery behaviour. In conjunction, a mathematical model was formulated to provide a theoretical understanding of the pressure-driven, shear thinning extrusion of inks through needles in a bioprinter. The assessment methods were trialled with a commercially available crème, poloxamer 407, alginate-based inks and an alginate-gelatine composite material. Yield stress was investigated by applying a stress ramp to a number of inks, which demonstrated the necessity of high yield for printable materials. The shear thinning behaviour of the inks was then characterised by quantifying the degree of shear thinning and using the mathematical model to predict the window of printer operating parameters in which the materials could be printed. Furthermore, the model predicted high shear conditions and high residence times for cells at the walls of the needle and effects on cytocompatibility at different printing conditions. Finally, the ability of the materials to recover to their original viscosity after extrusion was examined using rotational recovery rheological measurements. Taken together, these assessment techniques revealed significant insights into the requirements for printable inks and shear conditions present during the extrusion process and allow the rapid and reproducible characterisation of a wide variety of inks for bioprinting.

Biofabrication aims to fabricate biologically functional products through bioprinting or bioassembly (Groll et al 2016 Biofabrication 8 013001). In biofabrication processes, cells are positioned at defined coordinates in three-dimensional space using automated and computer controlled techniques (Moroni et al 2018 Trends Biotechnol. 36 384-402), usually with the aid of biomaterials that are either (i) directly processed with the cells as suspensions/dispersions, (ii) deposited simultaneously in a separate printing process, or (iii) used as a transient support material. Materials that are suited for biofabrication are often referred to as bioinks and have become an important area of research within the field. In view of this special issue on bioinks, we aim herein to briefly summarize the historic evolution of this term within the field of biofabrication. Furthermore, we propose a simple but general definition of bioinks, and clarify its distinction from biomaterial inks.

BACKGROUND: Aminosalicylates are used as standard treatment for maintaining remission in ulcerative colitis. As yet, there is no other existing alternative with proven efficacy. In light of the hypothesis that the intestinal environment may contribute to the pathophysiology of ulcerative colitis, a trial was conducted to test the effects of probiotic treatment with an oral preparation of non-pathogenic E. coli. METHODS: A total of 120 patients with inactive ulcerative colitis were included in a double-blind, double-dummy study comparing mesalazine 500 mg t.d.s. to an oral preparation of viable E. coli strain Nissle (Serotype 06: K5: H1) for 12 weeks with regard to their efficacy in preventing a relapse of the disease. Study objectives were to assess the equivalence of the clinical activity index (CAI) under the two treatment modalities and to compare relapse rates, relapse-free times and global assessment. RESULTS: The start and end scores of the CAI demonstrated no significant difference (P = 0.12) between the two treatment groups. Relapse rates were 11.3% under mesalazine and 16.0% under E. coli Nissle 1917 (N.S.). Life table analysis showed a relapse-free time of 103 +/- 4 days for mesalazine and 106 +/- 5 days for E. coli Nissle 1917 (N.S.). Global assessment was similar for both groups. Tolerability to the treatment was excellent and did not differ. No serious adverse events were reported. CONCLUSIONS: From the results of this preliminary study, probiotic treatment appears to offer another option for maintenance therapy of ulcerative colitis. Additional support is provided for the hypothesis of a pathophysiological role for the intestinal environment in ulcerative colitis.

Porous organic materials are an emerging class of functional nanostructures with unprecedented properties. Dynamic covalent assembly of small organic building blocks under thermodynamic control is utilized for the intriguingly simple formation of complex molecular architectures in one-pot procedures. In this Review, we aim to analyze the basic design principles that govern the formation of either covalent organic frameworks as crystalline porous polymers or covalent organic cage compounds as shape-persistent molecular objects. Common synthetic procedures and characterization techniques will be discussed as well as more advanced strategies such as postsynthetic modification or self-sorting. When appropriate, comparisons are drawn between polymeric frameworks and discrete organic cages in terms of their underlying properties. Furthermore, we highlight the potential of these materials for applications ranging from gas storage to catalysis and organic electronics.

In 2013, the "biofabrication window" was introduced to reflect the processing challenge for the fields of biofabrication and bioprinting. At that time, the lack of printable materials that could serve as cell-laden bioinks, as well as the limitations of printing and assembly methods, presented a major constraint. However, recent developments have now resulted in the availability of a plethora of bioinks, new printing approaches, and the technological advancement of established techniques. Nevertheless, it remains largely unknown which materials and technical parameters are essential for the fabrication of intrinsically hierarchical cell-material constructs that truly mimic biologically functional tissue. In order to achieve this, it is urged that the field now shift its focus from materials and technologies toward the biological development of the resulting constructs. Therefore, herein, the recent material and technological advances since the introduction of the biofabrication window are briefly summarized, i.e., approaches how to generate shape, to then focus the discussion on how to acquire the biological function within this context. In particular, a vision of how biological function can evolve from the possibility to determine shape is outlined.

The transport of excitation energy in molecular aggregates is of crucial importance for the function of organic optoelectronic devices and next‐generation solar cells. First, this review summarizes the theoretical background of the nature of the electronically excited states of molecular aggregates. For these systems, the electronic interaction between the monomers leads to the formation of exciton states. This goes along with a shift of the excitation energies and a redistribution of the oscillator strength with respect to the monomers. Next, a brief overview is provided over experimental techniques that allow to study the properties of excitons in molecular aggregates. This includes single‐molecule spectroscopy, coherent two‐dimensional (2D) spectroscopy, and single‐molecule coherent spectroscopy. Finally, examples of molecular aggregates spanning the range from natural systems that act in photosynthesis as light‐harvesting antennas to artificial aggregates built from synthetic chromophores are illustrated.

Microplastic particles ubiquitously found in the environment are ingested by a huge variety of organisms. Subsequently, microplastic particles can translocate from the gastrointestinal tract into the tissues likely by cellular internalization. The reason for cellular internalization is unknown, since this has only been shown for specifically surface-functionalized particles. We show that environmentally exposed microplastic particles were internalized significantly more often than pristine microplastic particles into macrophages. We identified biomolecules forming an eco-corona on the surface of microplastic particles, suggesting that environmental exposure promotes the cellular internalization of microplastics. Our findings further indicate that cellular internalization is a key route by which microplastic particles translocate into tissues, where they may cause toxicological effects that have implications for the environment and human health.

In contrast to conventional hard actuators, soft actuators offer many vivid advantages, such as improved flexibility, adaptability, and reconfigurability, which are intrinsic to living systems. These properties make them particularly promising for different applications, including soft electronics, surgery, drug delivery, artificial organs, or prosthesis. The additional degree of freedom for soft actuatoric devices can be provided through the use of intelligent materials, which are able to change their structure, macroscopic properties, and shape under the influence of external signals. The use of such intelligent materials allows a substantial reduction of a device's size, which enables a number of applications that cannot be realized by externally powered systems. This review aims to provide an overview of the properties of intelligent synthetic and living/natural materials used for the fabrication of soft robotic devices. We discuss basic physical/chemical properties of the main kinds of materials (elastomers, gels, shape memory polymers and gels, liquid crystalline elastomers, semicrystalline ferroelectric polymers, gels and hydrogels, other swelling polymers, materials with volume change during melting/crystallization, materials with tunable mechanical properties, and living and naturally derived materials), how they are related to actuation and soft robotic application, and effects of micro/macro structures on shape transformation, fabrication methods, and we highlight selected applications.

In recently years, high-performance wearable strain sensors have attracted great attention in academic and industrial. Herein, a conductive polymer composite of electrospun thermoplastic polyurethane (TPU) fibrous film matrix-embedded carbon black (CB) particles with adjustable scaffold network was fabricated for high-sensitive strain sensor. This work indicated the influence of stereoscopic scaffold network structure built under various rotating speeds of collection device in electrospinning process on the electrical response of TPU/CB strain sensor. This structure makes the sensor exhibit combined characters of high sensitivity under stretching strain (gauge factor of 8962.7 at 155% strain), fast response time (60 ms), outstanding stability and durability (> 10,000 cycles) and a widely workable stretching range (0-160%). This high-performance, wearable, flexible strain sensor has a broad vision of application such as intelligent terminals, electrical skins, voice measurement and human motion monitoring. Moreover, a theoretical approach was used to analyze mechanical property and a model based on tunneling theory was modified to describe the relative change of resistance upon the applied strain. Meanwhile, two equations based from this model were first proposed and offered an effective but simple approach to analyze the change of number of conductive paths and distance of adjacent conductive particles.

Bioprinting can be defined as the art of combining materials and cells to fabricate designed, hierarchical 3D hybrid constructs. Suitable materials, so called bioinks, have to comply with challenging rheological processing demands and rapidly form a stable hydrogel postprinting in a cytocompatible manner. Gelatin is often adopted for this purpose, usually modified with (meth-)acryloyl functionalities for postfabrication curing by free radical photopolymerization, resulting in a hydrogel that is cross-linked via nondegradable polymer chains of uncontrolled length. The application of allylated gelatin (GelAGE) as a thiol-ene clickable bioink for distinct biofabrication applications is reported. Curing of this system occurs via dimerization and yields a network with flexible properties that offer a wider biofabrication window than (meth-)acryloyl chemistry, and without additional nondegradable components. An in-depth analysis of GelAGE synthesis is conducted, and standard UV-initiation is further compared with a recently described visible-light-initiator system for GelAGE hydrogel formation. It is demonstrated that GelAGE may serve as a platform bioink for several biofabrication technologies by fabricating constructs with high shape fidelity via lithography-based (digital light processing) 3D printing and extrusion-based 3D bioprinting, the latter supporting long-term viability postprinting of encapsulated chondrocytes.

Silk is mostly known as a luxurious textile, which originates from silkworms first cultivated in China. A deeper look into the variety of silk reveals that it can be used for much more, in nature and by humanity. For medical purposes, natural silks were recognized early as a potential biomaterial for surgical threads or wound dressings; however, as biomedical engineering advances, the demand for high-performance, naturally derived biomaterials becomes more pressing and stringent. A common problem of natural materials is their large batch-to-batch variation, the quantity available, their potentially high immunogenicity, and their fast biodegradation. Some of these common problems also apply to silk; therefore, recombinant approaches for producing silk proteins have been developed. There are several research groups which study and utilize various recombinantly produced silk proteins, and many of these have also investigated their products for biomedical applications. This review gives a critical overview over of the results for applications of recombinant silk proteins in biomedical engineering.

Controlling polymorphism in molecular solids is of great interest since the properties and performances of molecular materials depend on the molecules' mutual packing arrangements. Herein, we describe a perylene bisimide (PBI) organogelator molecule PBI-4 that self-assembles into three different one-dimensional supramolecular polymorphs (Agg 1-3) in the same solvent and at the same concentration at room temperature. The three supramolecular polymorphs were characterized by UV/vis, CD, fluorescence and IR spectroscopy, atomic force microscopy (AFM), and theoretical calculations, revealing that their packing arrangements are governed by distinct π-π-stacking modes and unique hydrogen-bonding patterns. Nudged elastic band (NEB) calculations for the nucleation processes toward Agg 2 and Agg 3 indicate that nucleation starts from a central kinetically trapped state Agg 1 and involves the reorganization of Agg 1 dimers. Time-, concentration-, and temperature-dependent UV/vis experiments provided insights into the thermodynamic stability of the supramolecular polymorphs of PBI-4 and the kinetics for their interconversion. On the basis of this information the production of a certain polymorph could be accomplished either physically by ultrasonication or chemically by seeding. This work contributes to the understanding of polymorphism at the lowest level of hierarchy that is the generation of self-assembled 1D aggregate structures.

Abstract The stability of polymers against environmental factors, chemicals, microorganisms, and hydrolysis has challenged society with the accumulation of plastic waste and its management worldwide. Large amounts of plastic litter accumulate in the environment and disintegrate into microplastics (small pieces less than 5 mm in size), a topic of real concern especially for products and applications where the plastics are used for a short time before becoming waste, and where they are difficult to recover after use and remain in the environment. Whether biodegradable polymers can be one of the solutions to the problem of plastic waste is a question very often raised in this context. Although the use of biodegradable polymers appears to be highly promising based on recent and past studies, several aspects need to be considered further regarding environmental sustainability, acceptability, and degradability in the complex natural environment. Intensive efforts need to be invested in developing new environmentally biodegradable polymers and smart mechanisms of degradation after use in the environment. The present viewpoint article discusses the present scenario of the environmental acceptability of biodegradable polymers and the opportunities and challenges they offer regarding solving the problem of microplastics and their impact on the environment.

Abstract In this contribution, the optical losses and gains attributed to periodic nanohole array electrodes in polymer solar cells are systematically studied. For this, thin gold nanomeshes with hexagonally ordered holes and periodicities ( P ) ranging from 202 nm to 2560 nm are prepared by colloidal lithography. In combination with two different active layer materials (P3HT:PC 61 BM and PTB7:PC 71 BM), the optical properties are correlated with the power conversion efficiency (PCE) of the solar cells. A cavity mode is identified at the absorption edge of the active layer material. The resonance wavelength of this cavity mode is hardly defined by the nanomesh periodicity but rather by the absorption of the photoactive layer. This constitutes a fundamental dilemma when using nanomeshes as ITO replacement. The highest plasmonic enhancement requires small periodicities. This is accompanied by an overall low transmittance and high parasitic absorption losses. Consequently, larger periodicities with a less efficient cavity mode, yet lower absorptive losses were found to yield the highest PCE. Nevertheless, ITO-free solar cells reaching ~77% PCE compared to ITO reference devices are fabricated. Concomitantly, the benefits and drawbacks of this transparent nanomesh electrode are identified, which is of high relevance for future ITO replacement strategies.

In materials science, there is an intrinsic conflict between high strength and high toughness, which can be resolved for different materials only through the use of innovative design principles. Advanced materials must be highly resistant to both deformation and fracture. We overcome this conflict in man-made polymer fibers and show multifibrillar polyacrylonitrile yarn with a toughness of 137 ± 21 joules per gram in combination with a tensile strength of 1236 ± 40 megapascals. The nearly perfect uniaxial orientation of the fibrils, annealing under tension in the presence of linking molecules, is essential for the yarn's notable mechanical properties. This underlying principle can be used to create similar strong and tough fibers from other commodity polymers in the future and can be used in a variety of applications in areas such as biomedicine, satellite technology, textiles, aircrafts, and automobiles.

ConspectusThe discovery of the self-assembly of cyanine dyes into J-aggregates had a major impact on the development of dye chemistry due to the emergence of new useful properties in the aggregated state. The unique optical features of these J-aggregates are narrowed, bathochromically shifted absorption bands with almost resonant fluorescence with an increased radiative rate that results from the coherently coupled molecular transition dipoles arranged in a slip-stacked fashion. Because of their desirable properties, J-aggregates gained popularity in the field of functional materials and enabled the efficient photosensitization of silver halide grains in color photography. However, despite a good theoretical understanding of structure–property relationships by the molecular exciton model, further examples of J-aggregates remained scarce for a long time as supramolecular designs to guide the formation of dye aggregates into the required slip-stacked arrangement were lacking.Drawing inspiration from the bacteriochlorophyll c self-organization found in the chlorosomal light-harvesting antennas of green sulfur bacteria, we envisioned the use of nature’s supramolecular blueprint to develop J-aggregates of perylene bisimides (PBIs). This class of materials is applied in high-performance color pigments and as n-type organic semiconductors in transistors and solar cells. Combining outstanding photochemical and thermal stability, high tinctorial strength and excellent fluorescence, PBIs are therefore an ideal model system for the preparation of J-aggregates with a wide range of potential applications.In this Account, we elucidate how a combination of steric constraints and hydrogen bonding receptor sites can guide the self-assembly of PBI dyes into slip-stacked packing motifs with J-type exciton coupling. We will discuss the supramolecular polymerization of multiple hydrogen-bonded PBI strands in organic and aqueous media and how minor structural modifications in monomeric PBI molecules can be used to obtain near-infrared absorbing J-aggregates, organogels, or thermoresponsive hydrogels. Pushing the boundaries of self-assembly into the bulk, engineering of the substituents’ steric requirements by a dendron-wedge approach afforded adjustable numbers of helical strands of PBI J-aggregates in the columnar liquid-crystalline state and the preparation of lamellar phases. To fully explore their potential, we have studied PBI J-aggregates in collaborative work with spectroscopists, physicists, and theoreticians. In this way, exciton migration over distances of up to 180 nm was shown, and insights into the influence of static disorder on the transport of excitation energy in PBI J-aggregates were derived. Furthermore, the application of PBI J-aggregates as functional materials was demonstrated in photonic microcavities, thin-film transistors, and organic solar cells.

Abstract There is a specialized niche for the electrohydrodynamic jetting of melts, from biomedical products to filtration and soft matter applications. The next frontier includes optics, microfluidics, flexible electronic devices, and soft network composites in biomaterial science and soft robotics. The recent emphasis on reproducibly direct‐writing continual molten jets has enabled a spectrum of contemporary microscale 3D objects to be fabricated. One strong suit of melt processing is the capacity for the jet to solidify rapidly into a fiber, thus fixing a particular structure into position. The ability to direct‐write complex and multiscaled architectures and structures has greatly contributed to a large number of recent studies, explicitly, toward fiber–hydrogel composites and fugitive inks, and has expanded into several biomedical applications such as cartilage, skin, periosteum, and cardiovascular tissue engineering. Following the footsteps of a publication that summarized melt electrowriting literature up to 2015, the most recent literature from then until now is reviewed to provide a continuous and comprehensive timeline that demonstrates the latest advances as well as new perspectives for this emerging technology.

Melt electrowriting (MEW) is an emerging high-resolution additive manufacturing technique based on the electrohydrodynamic processing of polymers. MEW is predominantly used to fabricate scaffolds for biomedical applications, where the microscale fiber positioning has substantial implications in its macroscopic mechanical properties. This review gives an update on the increasing number of polymers processed via MEW and different commercial sources of the gold standard poly(ε-caprolactone) (PCL). A description of MEW-processed polymers beyond PCL is introduced, including blends and coated fibers to provide specific advantages in biomedical applications. Furthermore, a perspective on printer designs and developments is highlighted, to keep expanding the variety of processable polymers for MEW.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTPeptoids and Polypeptoids at the Frontier of Supra- and Macromolecular EngineeringNiklas Gangloff†, Juliane Ulbricht†, Thomas Lorson†, Helmut Schlaad‡, and Robert Luxenhofer*†View Author Information† Functional Polymer Materials, Chair for Chemical Technology of Materials Synthesis, University of Würzburg, Röntgenring 11, 97070 Würzburg, Germany‡ Institute of Chemistry, University of Potsdam, Karl-Liebknecht-Str. 24-25, 14476 Potsdam, Germany*E-mail: [email protected]Cite this: Chem. Rev. 2016, 116, 4, 1753–1802Publication Date (Web):December 23, 2015Publication History Received1 May 2015Published online23 December 2015Published inissue 24 February 2016https://pubs.acs.org/doi/10.1021/acs.chemrev.5b00201https://doi.org/10.1021/acs.chemrev.5b00201review-articleACS PublicationsCopyright © 2015 American Chemical SocietyRequest reuse permissionsArticle Views8034Altmetric-Citations216LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Chemical structure,Monomers,Peptides and proteins,Polymers,Ring-opening polymerization Get e-Alerts

The additive manufacturing of highly ordered, micrometer-scale scaffolds is at the forefront of tissue engineering and regenerative medicine research. The fabrication of scaffolds for the regeneration of larger tissue volumes, in particular, remains a major challenge. A technology at the convergence of additive manufacturing and electrospinning-melt electrospinning writing (MEW)-is also limited in thickness/volume due to the accumulation of excess charge from the deposited material repelling and hence, distorting scaffold architectures. The underlying physical principles are studied that constrain MEW of thick, large volume scaffolds. Through computational modeling, numerical values variable working distances are established respectively, which maintain the electrostatic force at a constant level during the printing process. Based on the computational simulations, three voltage profiles are applied to determine the maximum height (exceeding 7 mm) of a highly ordered large volume scaffold. These thick MEW scaffolds have fully interconnected pores and allow cells to migrate and proliferate. To the best of the authors knowledge, this is the first study to report that z-axis adjustment and increasing the voltage during the MEW process allows for the fabrication of high-volume scaffolds with uniform morphologies and fiber diameters.