Bridge-rich and loop-less hydrogel networks through suppressed micellization of multiblock polyelectrolytes.

Most triblock copolymer-based physical hydrogels form three-dimensional networks through micellar packing, and formation of polymer loops represents a topological defect that diminishes hydrogel elasticity. This effect can be mitigated by maximizing the fraction of elastically effective bridges in the hydrogel network. Herein, we report hydrogels constructed by complexing oppositely charged multiblock copolymers designed with a sequence pattern that maximizes the entropic and enthalpic penalty of micellization. These copolymers self-assemble into branched and bridge-rich network units (netmers), instead of forming sparsely interlinked micelles. We find that the storage modulus of the netmer-based hydrogel is 11.5 times higher than that of the micelle-based hydrogel. Complementary coarse grained molecular dynamics simulations reveal that in the netmer-based hydrogels, the numbers of charge-complexed nodes and mechanically reinforcing bridges increase substantially relative to micelle-based hydrogels.

Plasma-Activated Media Produced by a Microwave-Excited Atmospheric Pressure Plasma Jet Is Effective against Cisplatin-Resistant Human Bladder Cancer Cells In Vitro.

Media exposed to atmospheric pressure plasma (APP) produce reactive oxygen and nitrogen species (RONS), with hydrogen peroxide (H2O2), nitrite (NO2-), and nitrate (NO3-) being among the most detected species due to their relatively long lifetime. In this study, a standardized microwave-excited (ME) APP jet (APPJ) source was employed to produce gaseous RONS to treat liquid samples. The source was a commercially available plasma jet, which generated argon plasma utilizing a coaxial transmission line resonator at the operating frequency of 2.45 GHz. An ultraviolet-visible spectrophotometer was used to measure the concentrations of H2O2 and NO3- in plasma-activated media (PAM). Three different types of media (deionized water, Hank's balanced salt solution, and cell culture solution Dulbecco's modified eagles medium [DMEM]) were utilized as liquid samples. Among these media, the plasma-treated DMEM was observed to have the highest levels of H2O2 and NO3-. Subsequently, the feasibility of using argon ME-APPJ-activated DMEM (PAM) as an adjuvant to enhance the therapeutic effects of cisplatin on human bladder cancer cells (T-24) was investigated. Various cancer cell lines, including T-24 cells, treated with PAM were observed in vitro for changes in cell viability using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay. A viability reduction was detected in the various cancer cells after incubation in PAM. Furthermore, the study's results revealed that PAM was effective against cisplatin-resistant T-24 cells in vitro. In addition, a possible connection between HER expression and cell viability was sketched.

Promoting Homogeneous Zinc-Ion Transfer Through Preferential Ion Coordination Effect in Gel Electrolyte for Stable Zinc Metal Batteries.

Aqueous zinc metal batteries (AZMBs) are emerging energy storage systems that are poised to replace conventional lithium-ion batteries owing to their intrinsic safety, facile manufacturing process, economic benefits, and superior ionic conductivity. However, the issues of inferior anode reversibility and dendritic plating during operation remain challenging for the practical use of AZMBs. Herein, a gel electrolyte based on zwitterionic poly(sulfobetaine methacrylate) (poly(SBMA)) dissolved with different concentrations of ZnSO4 is proposed. Two-dimensional correlation spectroscopy based on Raman analysis reveals an enhanced interaction priority between the polar groups in SBMA and the dissolved ions as electrolyte concentration increases, which establishes a robust interaction and renders homogeneous ion distribution. Attributable to the modified coordination, zwitterionic gel polymer electrolyte with 5 mol kg-1 of ZnSO4 (ZGPE-5) facilitates stable zinc deposition and improves anode reversibility. By taking advantage of preferential coordination, a symmetrical cell evaluation employing ZGPE-5 demonstrates a cycle life over 3600 h, where ZGPE-5 also exerts a beneficial effect on the full cell cycling when assembled with Zn0.25 V2 O5 cathode. This study elucidates changes in the internal ion behavior that are dependent on electrolyte concentrations and pave the way for durable AZMBs.

Electroconductive, Adhesive, Non-Swelling, and Viscoelastic Hydrogels for Bioelectronics.

As a new class of materials, implantable flexible electrical conductors have recently been developed and applied to bioelectronics. An ideal electrical conductor requires high conductivity, tissue-like mechanical properties, low toxicity, reliable adhesion to biological tissues, and the ability to maintain its shape in wet physiological environments. Despite significant advances, electrical conductors that satisfy all these requirements are insufficient. Herein, a facile method for manufacturing a new conductive hydrogels through the simultaneous exfoliation of graphite and polymerization of zwitterionic monomers triggered by microwave irradiation is introduced. The mechanical properties of the obtained conductive hydrogel are similar to those of living tissue, which is ideal as a bionic adhesive for minimizing contact damage due to mechanical mismatches between hard electronics and soft tissues. Furthermore, it exhibits excellent adhesion performance, electrical conductivity, non-swelling, and high conformability in water. Excellent biocompatibility of the hydrogel is confirmed through a cytotoxicity test using C2C12 cells, a biocompatibility test on rat tissues, and their histological analysis. The hydrogel is then implanted into the sciatic nerve of a rat and neuromodulation is demonstrated through low-current electrical stimulation. This hydrogel demonstrates a tissue-like extraneuronal electrode, which possesses high conformability to improve the tissue-electronics interfaces, promising next-generation bioelectronics applications.

Differential Sensitivity of Melanoma Cells and Their Non-Cancerous Counterpart to Cold Atmospheric Plasma-Induced Reactive Oxygen and Nitrogen Species.

Despite continuous progress in therapy, melanoma is one of the most aggressive and malignant human tumors, often relapsing and metastasizing to almost all organs. Cold atmospheric plasma (CAP) is a novel anticancer tool that utilizes abundant reactive oxygen and nitrogen species (RONS) being deposited on the target cells and tissues. CAP-induced differential effects between non-cancerous and cancer cells were comparatively examined. Melanoma and non-cancerous skin fibroblast cells (counterparts; both cell types were isolated from the same patient) were used for plasma-cell interactions. The production of intracellular RONS, such as nitric oxide (NO), hydroxyl radical (•OH), and hydrogen peroxide (H2O2), increased remarkably only in melanoma cancer cells. It was observed that cancer cells morphed from spread to round cell shapes after plasma exposure, suggesting that they were more affected than non-cancerous cells in the same plasma condition. Immediately after both cell types were treated with plasma, there were no differences in the amount of extracellular H2O2 production, while Hanks' balanced salt solution-containing cancer cells had lower concentrations of H2O2 than that of non-cancerous cells at 1 h after treatment. The melanoma cells seemed to respond to CAP treatment with a greater rise in RONS and a higher consumption rate of H2O2 than homologous non-cancerous cells. These results suggest that differential sensitivities of non-cancerous skin and melanoma cells to CAP-induced RONS can enable the applicability of CAP in anticancer therapy.

Fast and Large Shrinking of Thermoresponsive Hydrogels with Phase-Separated Structures.

Thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) hydrogels have been attracting attention in a variety of functional materials, such as biomaterials, because they exhibit a volume phase transition phenomenon near physiological temperatures. However, the slow kinetics and small volume shrinkage of bulk PNIPAAm hydrogels upon heating greatly limit their practical application. Here, we report PNIPAAm hydrogels with phase-separated structures that exhibited ultrafast shrinking upon heating. The phase separation into a PNIPAAm-rich phase and a water-rich phase was formed through aqueous polymerization in the presence of NaClO4 salt. Through structural analysis of the hydrogels, a topologically heterogeneous and porous structure was observed, which was highly dependent on the NaClO4 concentration in the polymerization step. Compared to conventional PNIPAAm hydrogels, the phase-separated hydrogels exhibited much faster and larger shrinkage upon heating. Simultaneously, the hydrogels quickly released a large amount of water owing to the effective water channels inside them. The present method can be widely applied to general hydrogels, and it can address the numerous limitations of hydrogels in terms of operating programmability and deformation efficiency.

Nanocomposite hydrogel actuators hybridized with various dimensional nanomaterials for stimuli responsiveness enhancement.

Hydrogel actuators, that convert external energy, such as pH, light, heat, magnetic field, and ion strength, into mechanical motion, have been utilized in sensors, artificial muscles, and soft robotics. For a practicality of the hydrogel actuators in a wide range of fields, an establishment of robust mechanical properties and rapid response are required. Several solutions have been proposed, for example, setting porous and anisotropy structures to hydrogels with nanocomposite materials to improve the response speed and deformation efficiency. In this review paper, we focused on hydrogel actuators including various nanocomposite by categorizing the dimensional aspects of additive materials. Moreover, we described the role of diverse additive materials in terms of the improvement of mechanical property and deformation efficiency of the hydrogel actuators. We assumed that this review will provide a beneficial guidance for strategies of developing nanocomposite hydrogel actuators and outlooks for the future research directions.