Rapid Fabrication of Large-Grain Opal Films and Photonic Crystal Hydrogel Sensors by a Filter Paper-Enhanced Evaporation Chip.

Developing a rapid fabrication method for crack-free opal films is a significant challenge with broad applications. We developed a microfluidic platform known as the "filter paper-enhanced evaporation microfluidic chip" (FPEE-chip) for the fabrication of photonic crystal and inverse opal hydrogel (IOPH) films. The chip featured a thin channel formed by bonding double-sided adhesive poly(ethylene terephthalate) with a polymethyl methacrylate cover and a glass substrate. This channel was then filled with nanosphere colloids. The water was guided to evaporate rapidly at the surface of the filter paper, allowing the nanospheres to self-assemble and accumulate within the channel under capillary forces. Experimental results confirmed that the self-assembly method based on the FPEE-chip was a rapid platform for producing high-quality opal, with centimeter-sized opal films achievable in less than an hour. Furthermore, the filter paper altered the stress release mechanism of the opal films during drying, resulting in fewer cracks. This platform was proven capable of producing large-grain, crack-free opal films of up to 30 mm2 in size. We also fabricated crack-free IOPH pH sensors that exhibited color and size responsiveness to pH changes. The coefficient of variation of the gray color distribution for crack-free IOPH ranged from 0.03 to 0.07, which was lower than that of cracked IOPH (ranging from 0.07 to 0.14). Additionally, the grayscale peak value in 1 mm2 of the crack-free IOPH was more than twice that of the cracked IOPH at the same pH. The FPEE-chip demonstrated potential as a candidate for developing vision sensors.

A novel array-type microdroplet parallel-generation device.

In this study, the innovative design of a new array microdroplet parallel-generation device is proposed based on the principle of fluid inertial force using a capillary glass needle. The entire device used an electromagnetic actuator as the power source. It was designed as a 9-channel parallel array of glass needles. All glass needles feed independently, allowing different solutions to be sprayed simultaneously while effectively avoiding cross-contamination. We achieved non-contact parallel precision dispensing of nanoliter-sized microdroplet arrays using a relatively simple method. In this study, we first investigated the homogeneity of the generated droplet arrays and the stability of the device over long periods of operation. Then, the influence of the driving-voltage amplitude of the electromagnet and nozzle diameter on microdroplet generation was analyzed. Finally, a prediction model for the droplet size was developed using regression analysis to investigate the on-demand generation of droplets. In summary, the device designed in this study had a novel design, low cost, and modular assembly. It has excellent potential for applications in high precision and low-volume microdroplet-array generation.

Adaptable Fast Relaxing Boronate-Based Hydrogels for Probing Cell-Matrix Interactions.

Hydrogels with tunable viscoelasticity hold promise as materials that can recapitulate many dynamic mechanical properties found in native tissues. Here, covalent adaptable boronate bonds are exploited to prepare hydrogels that exhibit fast relaxation, with relaxation time constants on the order of seconds or less, but are stable for long-term cell culture and are cytocompatible for 3D cell encapsulation. Using human mesenchymal stem cells (hMSC) as a model, the fast relaxation matrix mechanics are found to promote cell-matrix interactions, leading to spreading and an increase in nuclear volume, and induce yes-associated protein/PDZ binding domain nuclear localization at longer times. All of these effects are exclusively based on the hMSCs' ability to physically remodel their surrounding microenvironment. Given the increasingly recognized importance of viscoelasticity in controlling cell function and fate, it is expected that the synthetic strategies and material platform presented should provide a useful system to study mechanotransduction on and within viscoelastic environments and explore many questions related to matrix biology.

High-velocity micro-particle impact on gelatin and synthetic hydrogel.

The high-velocity impact response of gelatin and synthetic hydrogel samples is investigated using a laser-based microballistic platform for launching and imaging supersonic micro-particles. The micro-particles are monitored during impact and penetration into the gels using a high-speed multi-frame camera that can record up to 16 images with nanosecond time resolution. The trajectories are compared with a Poncelet model for particle penetration, demonstrating good agreement between experiments and the model for impact in gelatin. The model is further validated on a synthetic hydrogel and the applicability of the results is discussed. We find the strength resistance parameter in the Poncelet model to be two orders of magnitude higher than in macroscopic experiments at comparable impact velocities. The results open prospects for testing high-rate behavior of soft materials on the microscale and for guiding the design of drug delivery methods using accelerated microparticles.

Antiviral Agents from Multivalent Presentation of Sialyl Oligosaccharides on Brush Polymers.

Bioinspired brush polymers containing α-2,6-linked sialic acids at the side chain termini were synthesized by protection-group-free, ring-opening metathesis polymerization. Polymers showed strain-selective antiviral activity through multivalent presentation of the sialosides. The multivalent effect was further controlled by independently varying the degree of polymerization, the number density of sialic acids, and the length of side chains in the brush polymers. Optimizing the three-dimensional sialoside spacing for better binding to hemagglutinin trimers was of critical importance to enhance the multivalent effect and the antiviral activity determined by hemagglutination inhibition assays and in vitro infection assays. By taking advantage of their structural similarities with native mucins, these brush polymers can be used as model systems to dissect the intricate design principles in natural mucins.

Anomalous self-diffusion and sticky Rouse dynamics in associative protein hydrogels.

Natural and synthetic materials based on associating polymers possess diverse mechanical behavior, transport properties and responsiveness to external stimuli. Although much is known about their dynamics on the molecular and macroscopic level, knowledge of self-diffusive dynamics of the network-forming constituents remains limited. Using forced Rayleigh scattering, anomalous self-diffusion is observed in model associating protein hydrogels originating from the interconversion between species that diffuse in both the molecular and associated state. The diffusion can be quantitatively modeled using a two-state model for polymers in the gel, where diffusivity in the associated state is critical to the super diffusive behavior. The dissociation time from bulk rheology measurements was 2-3 orders of magnitude smaller than the one measured by diffusion, because the former characterizes submolecular dissociation dynamics, whereas the latter depicts single protein molecules completely disengaging from the network. Rheological data also show a sticky Rouse-like relaxation at long times due to collective relaxation of large groups of proteins, suggesting mobility of associated molecules. This study experimentally demonstrates a hierarchy of relaxation processes in associating polymer networks, and it is anticipated that the results can be generalized to other associative systems to better understand the relationship of dynamics among sticky bonds, single molecules, and the entire network.

Responsive block copolymer photonics triggered by protein-polyelectrolyte coacervation.

Ionic interactions between proteins and polyelectrolytes are demonstrated as a method to trigger responsive transitions in block copolymer (BCP) photonic gels containing one neutral hydrophobic block and one cationic hydrophilic block. Poly(2-vinylpyridine) (P2VP) blocks in lamellar poly(styrene-b-2-vinylpyridine) block copolymer thin films are quaternized with primary bromides to yield swollen gels that show strong reflectivity peaks in the visible range; exposure to aqueous solutions of various proteins alters the swelling ratios of the quaternized P2VP (QP2VP) gel layers in the PS-QP2VP materials due to the ionic interactions between proteins and the polyelectrolyte. Parameters such as charge density, hydrophobicity, and cross-link density of the QP2VP gel layers as well as the charge and size of the proteins play significant roles on the photonic responses of the BCP gels. Differences in the size and pH-dependent charge of proteins provide a basis for fingerprinting proteins based on their temporal and equilibrium photonic response. The results demonstrate that the BCP gels and their photonic effect provide a robust and visually interpretable method to differentiate different proteins.

Oxidatively Responsive Chain Extension to Entangle Engineered Protein Hydrogels.

Engineering artificial protein hydrogels for medical applications requires precise control over their mechanical properties, including stiffness, toughness, extensibility and stability in the physiological environment. Here we demonstrate topological entanglement as an effective strategy to robustly increase the mechanical tunability of a transient hydrogel network based on coiled-coil interactions. Chain extension and entanglement are achieved by coupling the cysteine residues near the N- and C- termini, and the resulting chain distribution is found to agree with the Jacobson-Stockmayer theory. By exploiting the reversible nature of the disulfide bonds, the entanglement effect can be switched on and off by redox stimuli. With the presence of entanglements, hydrogels exhibit a 7.2-fold enhanced creep resistance and a suppressed erosion rate by a factor of 5.8, making the gels more mechanically stable in a physiologically relevant open system. While hardly affecting material stiffness (only resulting in a 1.5-fold increase in the plateau modulus), the entanglements remarkably lead to hydrogels with a toughness of 65,000 J m-3 and extensibility to approximately 3,000% engineering strain, which enables the preparation of tough yet soft tissue simulants. This improvement in mechanical properties resembles that from double-network hydrogels, but is achieved with the use of a single associating network and topological entanglement. Therefore, redox-triggered chain entanglement offers an effective approach for constructing mechanically enhanced and responsive injectable hydrogels.

Controlling topological entanglement in engineered protein hydrogels with a variety of thiol coupling chemistries.

Topological entanglements between polymer chains are achieved in associating protein hydrogels through the synthesis of high molecular weight proteins via chain extension using a variety of thiol coupling chemistries, including disulfide formation, thiol-maleimide, thiol-bromomaleimide and thiol-ene. Coupling of cysteines via disulfide formation results in the most pronounced entanglement effect in hydrogels, while other chemistries provide versatile means of changing the extent of entanglement, achieving faster chain extension, and providing a facile method of controlling the network hierarchy and incorporating stimuli responsivities. The addition of trifunctional coupling agents causes incomplete crosslinking and introduces branching architecture to the protein molecules. The high-frequency plateau modulus and the entanglement plateau modulus can be tuned by changing the ratio of difunctional chain extender to the trifunctional branching unit. Therefore, these chain extension reactions show promise in delicately controlling the relaxation and mechanical properties of engineered protein hydrogels in ways that complement their design through genetic engineering.

Site-specific conjugation of RAFT polymers to proteins via expressed protein ligation.

Site-specific protein conjugates with RAFT polymers were synthesized using expressed protein ligation. Stable micelles were formed from both linear block copolymer and Y-shaped conjugates.