Auswahl der wissenschaftlichen Literatur zum Thema „Ultra-Soft Hydrogels“

As an ultra-soft material (elastic modulus in magnitude of kPa), polyvinyl alcohol (PVA) hydrogels have the potential to substitute articular cartilage, but the measurement of the dynamic stress–strain relations of ultra-soft materials is still challenging. In this paper, a double-striker electromagnetic driving split-Hopkinson pressure bar (SHPB) system was developed, in which all the bars were made of polycarbonate, and the polycarbonate striker was pushed by a metal striker driven electromagnetically to ensure the precise control of impact velocity. With the new SHPB system, well design of the size of hydrogel specimen and rational processing of the signal data, the stress–strain relations of hydrogels with varied PVA contents at different strain rates were measured successfully. Experimental results indicate that PVA hydrogels are a positive strain rate sensitive material with different strain-rate effects at low and high strain rates. Finally, based on the latest quasi-static constitution of the PVA hydrogel, a rate-dependent constitutive equation was recommended, which may well depict the mechanical behaviors of hydrogels with different fiber contents at varied strain rates. It also derives that the contributions of strain rate and fiber content on the mechanical behaviors of the hydrogel are relatively independent.

Millions of years’ evolution has imparted life on earth with excellent environment adaptability. Of particular interest to scientists are some plants capable of macroscopically and reversibly altering their morphological and mechanical properties in response to external stimuli from the surrounding environment. These intriguing natural phenomena and underlying actuation mechanisms have provided important design guidance and principles for man-made soft robotic systems. Constructing bio-inspired soft robotic systems with effective actuation requires the efficient supply of mechanical energy generated from external inputs, such as temperature, light, and electricity. By combining bio-inspired designs with stimuli-responsive materials, various intelligent soft robotic systems that demonstrate promising and exciting results have been developed. As one of the building materials for soft robotics, hydrogels are gaining increasing attention owing to their advantageous properties, such as ultra-tunable modulus, high compliance, varying stimuli-responsiveness, good biocompatibility, and high transparency. In this review article, we summarize the recent progress on plant-inspired soft robotics assembled by stimuli-responsive hydrogels with a particular focus on their actuation mechanisms, fabrication, and application. Meanwhile, some critical challenges and problems associated with current hydrogel-based soft robotics are briefly introduced, and possible solutions are proposed. We expect that this review would provide elementary tutorial guidelines to audiences who are interested in the study on nature-inspired soft robotics, especially hydrogel-based intelligent soft robotic systems.

Exceptionally fast temperature-responsive, mechanically strong, tough and extensible monolithic non-porous hydrogels were synthesized. They are based on divinyl-crosslinked poly(N-isopropyl-acrylamide) (PNIPAm) intercalated by hydroxypropyl methylcellulose (HPMC). HPMC was largely extracted after polymerization, thus yielding a ‘template-modified’ PNIPAm network intercalated with a modest residue of HPMC. High contents of divinyl crosslinker and of HPMC caused a varying degree of micro-phase-separation in some products, but without detriment to mechanical or tensile properties. After extraction of non-fixed HPMC, the micro-phase-separated products combine superior mechanical properties with ultra-fast T-response (in 30 s). Their PNIPAm network was highly regular and extensible (intercalation effect), toughened by hydrogen bonds to HPMC, and interpenetrated by a network of nano-channels (left behind by extracted HPMC), which ensured the water transport rates needed for ultra-fast deswelling. Moreover, the T-response rate could be widely tuned by the degree of heterogeneity during synthesis. The fastest-responsive among our hydrogels could be of practical interest as soft actuators with very good mechanical properties (soft robotics), while the slower ones offer applications in drug delivery systems (as tested on the example of Theophylline), or in related biomedical engineering applications.

Conductive hydrogel-based materials are attracting considerable interest for bioelectronic applications due to their ability to act as more compatible soft interfaces between biological and electrical systems. Despite significant advances that are being achieved in the manufacture of hydrogels, precise control over the topographies and architectures remains challenging. In this work, we present for the first time a strategy to manufacture structures with resolutions in the micro-/nanoscale based on hydrogels with enhanced electrical properties. Gelatine methacrylate (GelMa)-based inks were formulated for two-photon polymerisation (2PP). The electrical properties of this material were improved, compared to pristine GelMa, by dispersion of multi-walled carbon nanotubes (MWCNTs) acting as conductive nanofillers, which was confirmed by electrochemical impedance spectroscopy and cyclic voltammetry. This material was also confirmed to support human induced pluripotent stem cell-derived cardiomyocyte (hPSC-CMs) viability and growth. Ultra-thin film structures of 10 µm thickness and scaffolds were manufactured by 2PP, demonstrating the potential of this method in areas spanning tissue engineering and bioelectronics. Though further developments in the instrumentation are required to manufacture more complex structures, this work presents an innovative approach to the manufacture of conductive hydrogels in extremely low resolution.

Intraneural electrodes can be harnessed to control neural prosthetic devices in human amputees. However, in chronic implants we witness a gradual loss of device functionality and electrode isolation due to a nonspecific inflammatory response to the implanted material, called foreign body reaction (FBR). FBR may eventually lead to a fibrous encapsulation of the electrode surface. Poly(ethylene glycol) (PEG) is one of the most common low-fouling materials used to coat and protect electrode surfaces. Yet, PEG can easily undergo encapsulation and oxidative damage in long-term in vivo applications. Poly(sulfobetaine methacrylate) - poly(SBMA) - zwitterionic hydrogels may represent more promising alternatives to minimize the FBR due to their ultra-low fouling features. Here, we tested and compared the poly(SBMA) zwitterionic hydrogel coating with the PEG coating in reducing adhesion and activation of pro-inflammatory and pro-fibrotic cells to polyimide surfaces, which are early hallmarks of FBR. We aimed to coat polyimide surfaces with a hydrogel thin film and analysed the release of a model drug from the hydrogel.We performed hydrogel synthesis, mechanical characterization and biocompatibility analysis. Cell adhesion, viability and morphology of human myofibroblasts cultured on PEG- and hydrogel-coated surfaces were evaluated through confocal microscopy-based high-content analysis (HCA). Reduced activation of pro-inflammatory human macrophages cultured on hydrogels was assessed as well as the hydrogel drug release profile.Because of its high hydration, biocompatibility, low stiffness and ultra-low fouling characteristics the hydrogel enabled lower adhesion and activation of pro-inflammatory and pro-fibrotic cells vs. polystyrene controls, and showed a long-term release of the anti-fibrotic drug Everolimus. Furthermore, a polyimide surface was successfully coated with a hydrogel thin film.Our soft zwitterionic hydrogel could outperform PEG as more suitable coating material of neural electrodes for mitigating the FBR. Such poly(SBMA)-based biomaterial could also be envisioned as long-term delivery system for a sustained release of anti-inflammatory and anti-fibrotic drugs in vivo.

A self-healing hydrogel ionic conductor has been developed by combining dynamic covalent chemistry with nanofiller reinforcement and micelle crosslinking, and used for sensing of diverse human activities.

Three-dimensional hydrogels are ideal for tissue engineering applications due to their structural integrity and similarity to native soft tissues; however, they can lack mechanical stability. Our objective was to develop a bioactive and mechanically stable hydrogel for clinical application. Auricular cartilage was decellularised using a combination of hypertonic and hypotonic solutions with and without enzymes to produce acellular tissue. Methacryloyl groups were crosslinked with alginate and PVA main chains via 2-aminoethylmathacrylate and the entire macromonomer further crosslinked with the acellular tissue. The resultant hydrogels were characterised for its physicochemical properties (using NMR), in vitro degradation (via GPC analysis), mechanical stability (compression tests) and in vitro biocompatibility (co-culture with bone marrow-derived mesenchymal stem cells). Following decellularisation, the cartilage tissue showed to be acellular at a significant level (DNA content 25.33 ng/mg vs. 351.46 ng/mg control tissue), with good structural and molecular integrity of the retained extra cellular matrix (s-GAG= 0.19 μg/mg vs. 0.65 μg/mg ±0.001 control tissue). Proteomic analysis showed that collagen subtypes and proteoglycans were retained, and SEM and TEM showed preserved matrix ultra-structure. The hybrid hydrogel was successfully cross-linked with biological and polymer components, and it was stable for 30 days in simulated body fluid (poly dispersal index for alginate with tissue was stable at 1.08 and for PVA with tissue was stable at 1.16). It was also mechanically stable (Young’s modulus of 0.46 ± 0.31 KPa) and biocompatible, as it was able to support the development of a multi-cellular feature with active cellular proliferation in vitro. We have shown that it is possible to successfully combine biological tissue with both a synthetic and natural polymer and create a hybrid bioactive hydrogel for clinical application.

We present experimental evidence of reusable, reliable cyclic olefin copolymer (COC) moulds in soft contact lens manufacturing. The moulds showed high performance surface roughness characteristics despite >20 kW exposure to 365 nm ultraviolet (UV) light from repeated use. Ultra-precision manufacturing techniques were used to fabricate transparent COC mould inserts and to produce soft contact lenses from liquid monomer compositions. Both polymer and silicone hydrogels were fabricated with more than 60 individual uses of the moulds. White light interferometry measured the surface roughness (Sa) of the COC moulds to be almost unchanged before and after repeated use (Sa 16.3 nm before vs. 16.6 nm after). The surface roughness of the prototyped lenses and that of commercially available soft contact lenses were then compared by white light interferometry. The surface roughness of the lenses was also nearly unchanged, despite undergoing more than 60 uses of the COC moulds (lens Sa 24.4 nm before vs. after Sa 26.5 nm). By comparison the roughness of the commercial lenses ranged from 9.3–28.5 nm, including conventional and silicone lenses, indicating that the reusable COC moulds produced competitive surface properties. In summary, COC moulds have potential as reusable and reliable mould inserts in the manufacturing of soft contact lenses, yet maintain high quality optical surfaces even after sustained exposure to UV light.

Generated by a hierarchical and multiscale self-assembling phenomenon, peptide-based hydrogels (HGs) are soft materials useful for a variety of applications. Short and ultra-short peptides are intriguing building blocks for hydrogel fabrication. These matrices can also be obtained by mixing low-molecular-weight peptides with other chemical entities (e.g., polymers, other peptides). The combination of two or more constituents opens the door to the development of hybrid systems with tunable mechanical properties and unexpected biofunctionalities or morphologies. For this scope, the formulation, the multiscale analysis, and the supramolecular characterization of novel hybrid peptide-polymer hydrogels are herein described. The proposed matrices contain the Fmoc-FF (Nα-fluorenylmethyloxycarbonyl diphenylalanine) hydrogelator at a concentration of 0.5 wt% (5.0 mg/mL) and a diacrylate α-/ω-substituted polyethylene-glycol derivative (PEGDA). Two PEGDA derivatives, PEGDA 1 and PEGDA2 (mean molecular weights of 575 and 250 Da, respectively), are mixed with Fmoc-FF at different ratios (Fmoc-FF/PEGDA at 1/1, 1/2, 1/5, 1/10 mol/mol). All the multicomponent hybrid peptide-polymer hydrogels are scrutinized with a large panel of analytical techniques (including proton relaxometry, FTIR, WAXS, rheometry, and scanning electronic microscopy). The matrices were found to be able to generate mechanical responses in the 2–8 kPa range, producing a panel of tunable materials with the same chemical composition. The release of a model drug (Naphthol Yellow S) is reported too. The tunable features, the different topologies, and the versatility of the proposed materials open the door to the development of tools for different applicative areas, including diagnostics, liquid biopsies and responsive materials. The incorporation of a diacrylate function also suggests the possible development of interpenetrating networks upon cross-linking reactions. All the collected data allow a mutual comparison between the different matrices, thus confirming the significance of the hybrid peptide/polymer-based methodology as a strategy for the design of innovative materials.

Les matériaux ultra-mous présentent des caractéristiques de déformation et de fracture différentes de celles des matériaux mous ordinaires, en raison des effets anticipés de leur tension superficielle et de leur hétérogénéité de structure. Dans ce contexte, nous avons systématiquement étudié les propriétés de fracture d’hydrogels ultra-mous en utilisant des méthodes de ponction et de cavitation. Pour le polyacrylamide, le PDMS et le carraghénane, la résistance à la fracture est dominée par l'élasticité non linéaire au-dessus de l'échelle de longueur élasto-capillaire. En-dessous cette échelle spécifique, la résistance à la fracture augmente puisque la capillarité joue un rôle dans le début de la fracture. En synthétisant des hydrogels de poly(alcool vinylique) (PVA) à faible degré d'hydrolyse à partir de deux voies de percolation (percolation de liens et percolation de site), nous avons découvert que les gels formés par percolation de site, étudiés par diffusion dynamique de la lumière, possèdent une plus forte hétérogénéité de structure et entraînent une plus faible résistance à la fracture. Étonnamment, une cristallisation extrême induite par déformation pendant la ponction a été observée dans l'hydrogel de PVA avec un degré d'hydrolyse élevé. En effet, le réseau de cet hydrogel est renforcé localement autour de la pointe de l'aiguille et déplace le point d'initiation de la fissure de la pointe de l'aiguille vers le bord. Cette structure anisotrope donne lieu à une cavité sphérique irrégulière dans la méthode de cavitation et augmente significativement son énergie de fracture. En outre, nous avons constaté que l’augmentation de la masse moléculaire, l'ajout d'un tensioactif ou le dépôt d'une couche d'huile en surface augmentent chacun la résistance à la fracture de l’hydrogel. Enfin, nous avons mis au point une nouvelle technique optique : l'imagerie par corrélation de photons, qui permet de déterminer quantitativement la distribution des déformations en compression et en tension autour de l'aiguille. Ces nouvelles connaissances et avancées méthodologiques fourniront des informations utiles pour la conception de matériaux souples mais résistants aux fractures, et de robots assistant chirurgicaux dans les applications médicales
Ultra-soft material exhibits different deformation and fracture characteristics compared to common soft material due to anticipated surface tension effects and structural heterogeneity. To this end, we systematically investigated fracture properties of ultra-soft hydrogels using puncture and cavitation methods. For soft polyacrylamide, PDMS, and carrageenan, fracture resistance is dominated by the non-linear elasticity above the elasto-capillary length scale. Below this particular scale, fracture resistance is improved since capillarity must play a role in the onset of fracture. By synthesizing poly(vinyl alcohol) (PVA) hydrogels with low hydrolysis degree from two percolation paths (bond-percolation and site percolation), we discovered that gels formed by site-percolation possess stronger structural heterogeneity studied via dynamic light scattering and thus result in lower fracture resistance. Surprisingly, an extremely large strain-induced crystallization during puncture was discovered in PVA hydrogel with high hydrolysis degree, which locally reinforces the network around the needle tip and displaces the crack initiation point from the needle tip to the edge. This anisotropic structure results in an irregular spherical cavity in the cavitation experiment and largely improves its fracture energy. In addition, we found that increasing the molecular weight, adding surfactant, and placing an oil layer on hydrogel surfaces could each increase their fracture resistance. In the end, we developed a novel optical technique - photon correlation imaging - in which compression and tension strain distribution around the needle is quantitatively revealed. These new insights and methodological advances will provide useful information to design soft but fracture-resistant materials and surgical assistant robots in medical applications

Abstract Alginate hydrogels have properties that are similar to extra cellular matrix (ECM). Thus, their mechanical behavior approximates soft tissue, which makes them desirable for production of tissue-equivalent soft deformable structures. This study aims to determine the synthesis-structure-property relationship for alginate hydrogel with Young’s modulus in the range of 100∼101 kPa, equivalent to that of human lung tissue. Hydrogels are hydrophilic polymers with 3D network. Homogeneous alginate hydrogels are synthesized by direct mixture of sodium alginate and CaCO3, followed by the addition of D-glucono-δ-lactone to initiate in-situ Ca2+ release and gelation. The influence of alginate concentration and molar ratio of the constituent calcium ion to carboxyl group are evaluated while the Young’s modulus of the hydrogel is carefully controlled within the desired range. Elongation testing is performed to determine the initial-stage Young’s modulus of the material. FTIR is used to characterize the influence of synthesis parameters on the chemical bonds. Empirical relations are established between synthesis parameters and the mechanical property. The result of the study will be subsequently used to guide the additive manufacturing of soft deformable structures based on alginate hydrogels.