Biomimetic hydrogels with spatial- and temporal-controlled chemical cues for tissue engineering.

Biomimetic hydrogels have emerged as the most useful tissue engineering scaffold materials. Their versatile chemistry can recapitulate multiple physical and chemical features to integrate cells, scaffolds, and signaling molecules for tissue regeneration. Due to their highly hydrophilic nature hydrogels can recreate nutrient-rich aqueous environments for cells. Soluble regulatory molecules can be incorporated to guide cell proliferation and differentiation. Importantly, the controlled dynamic parameters and spatial distribution of chemical cues in hydrogel scaffolds are critical for cell-cell communication, cell-scaffold interaction, and morphogenesis. Herein, we review biomimetic hydrogels that provide cells with spatiotemporally controlled chemical cues as tissue engineering scaffolds. Specifically, hydrogels with temporally controlled growth factor-release abilities, spatially controlled conjugated bioactive molecules/motifs, and targeting delivery and reload properties for tissue engineering applications are discussed in detail. Examples of hydrogels that possess clinically favorable properties, such as injectability, self-healing ability, stimulus-responsiveness, and pro-remodeling features, are also covered.

In Situ Deactivation of Catechol-Containing Adhesive Using Electrochemistry.

Marine mussels secret catechol-containing adhesive proteins that enable these organisms to bind to various surfaces underwater. Synthetic mimics of these proteins have been created to function as adhesives and coatings for a wide range of applications. Here, we demonstrated the use of in situ electrical field stimulation to deactivate the adhesive property of catechol-containing adhesive that is in direct contact with a surface. Johnson-Kendall-Roberts (JKR) contact mechanics test was performed using a titanium (Ti) sphere in the presence of a pH 7.5 aqueous buffer. The Ti sphere also served as a conductive electrode for applying electricity to the adhesive, while a platinum (Pt) wire served as the counter electrode. Work of adhesion (Wadh) decreased with increased levels of applied voltage and current, exposure time to the applied electricity, and salt concentration of the interfacial buffer. Application of 9 V for 1 min completely deactivated the adhesive. UV-vis diffuse reflectance spectra and tracking of catechol oxidation byproduct, hydrogen peroxide, confirmed that catechol was oxidized as a result of applied electricity. Contact mechanics testing further confirmed that the Young's modulus of the adhesive increased by nearly 4 folds at the interface as a result of oxidative cross-linking, even though the modulus of the bulk of the adhesive was unaffected by applied electricity. The accumulation of hydroxyl ions near the cathode increased the local solution pH, which promoted oxidation-induced cross-linking of catechol and subsequently decreased its adhesive property. Tuning adhesive properties through in situ electrochemical oxidation provides on-demand control over the adhesive, which will potentially add another dimension in designing synthetic mimics of mussel adhesive proteins.

Iron Magnetic Nanoparticle-Induced ROS Generation from Catechol-Containing Microgel for Environmental and Biomedical Applications.

Reactive oxygen species (ROS) can degrade organic compounds and function as a broad-spectrum disinfectant. Here, dopamine methacrylamide (DMA) was used to prepare catechol-containing microgels, which can release ROS via metal-catechol interaction. A combination of the microgel and iron magnetic nanoparticle (FeMNP) significantly reduced the concentration of four organic dyes (Alizarin Red S, Rhodamine B, Crystal Violet, and Malachite Green) and an antibiotic drug, ciprofloxacin, dissolved in solution. Degradation of dye occurred across a wide range of pH levels (pH 3-9). This simple combination was also antimicrobial against both Escherichia coli and Staphylococcus aureus. Electron paramagnetic resonance spectroscopy (EPR) results indicate that singlet oxygen was generated during the reaction between catechol and FeMNP at both pH 3 and 7.4, which was responsible for the degradation of organic compounds and bactericidal features of the microgel. Unlike autoxidation that only occurs at a neutral to basic pH, FeMNP-induced catechol oxidation generated singlet oxygen over a wide range of pH level. Additionally, catechol chelates heavy metal ions, resulting in their removal from solution and repurposed these metal ions for dye degradation. This multifunctional microgel can potentially be used for environmental applications for the removal of organic pollutants and heavy metal ions from wastewater, as well as reducing bacterial infection in biomedical applications.