Ultrahigh-Ionic-Conductivity, Antifreezing Poly(amidoxime)-Grafted Polyzwitterion Hydrogel for Facile Integrated into High-Performance Stretchable Flexible Supercapacitor.

Developing wearable supercapacitors (SCs) with high stretchability, arbitrary deformability, and antifreezing ability is still a challenge. In the present work, an ultrahigh-ionic-conductivity, antifreezing poly(amidoxime)-graft-polyzwitterion (PAO-g-PSBMA) hydrogel electrolyte is fabricated by grafting PSBMA in PAO. Owing to the abundant hydrophilic and high ionic adsorption capacity of amidoxime groups in PAO and zwitterion groups in PSBMA, the as-prepared PAO-g-PSBMA hydrogel can facilitate the dissociation of lithium salt and exhibit an ultrahigh ionic conductivity of 29.8 S m-1 at 25 °C and 3.4 S m-1 even at -30 °C. Employing mATi3C2Tx and mSTi3C2Tx, which contain small amounts of PAO-AGE and PAO-g-PSBMA dispersions, respectively, coated onto both sides of the PAO-g-PSBMA hydrogel, we followed a thermal treatment to facilely form integrated stretchable flexible SCs. The as-prepared SCs show an outstanding recoverable tensile stain of 80% and an excellent electrochemical stability under many types and times of arbitrary deformation. More importantly, as-prepared mATi3C2Tx- and mSTi3C2Tx-based SCs present fantastic antifreezing ability and excellent stability with 74.6 and 78.3% retention of the initial capacitance, respectively, even after 1000 times of stretching to 60% at -30 °C. This work offers a new strategy of using PAO-grafted polyzwitterion for obtaining an antifreezing stretchable SC, which shows a high potential for application in next-generation integrated stretchable devices in various fields.

Redox-responsive carrier based on fluorinated gemini amphiphilic polymer for combinational cancer therapy.

Polymeric micelle has emerged as an efficient implement to overcome the shortcomings of conventional cancer chemotherapy due to its superior solubility of hydrophobic drugs and less side effects of drugs. However, insufficient dilution resistance and ordinary therapeutic effect severely restrict the further translation of current drug-loaded polymeric micelles. Here, we showed that well-defined G-Fn (n = 5, 9, 13) polymeric micelles possessed excellent capabilities as a drug carrier in light of high drug loading content, high stability and precise drug release combined with wonderful endocytosis efficiency to tumors. The representative G-F13 exhibited an excellent dilution resistance, outstanding high drug loading content (22 wt%) and drug loading efficiency (82%), which might be attributed to the extremely low critical micelle concentration conferred by its special Gemini structure and the superhydrophobicity of the fluorocarbon chain. Furthermore, the "cross-linked" internal fluoride membrane consisted of the two chains of the Gemini structure made G-F13 stable even after 24 h of incubation in 10% fetal bovine serum (FBS). The camptothecin (CPT) release was selectively triggered by glutathione (GSH) and H2O2, reaching 75% and 85% after 24 h respectively, in which only 15% of drugs leak under physiological conditions. The CCK-8 assays of Hela cells showed that CPT-loaded G-F13 micelles had high cell compatibility (200 µg/mL, 93% cell viability, 48 h) and high cancer cytotoxicity (IC50 0.1 µg/mL). Notably, a tenfold lower dosage of loaded CPT had an higher tumor growth inhibition than the free CPT. This result was attributed to the combined treatment of fluorinated drug carriers were more likely to penetrate the cell membrane to enter tumor cells, the cytotoxicity of selenic acid generated after the oxidation of G-F13 and the large amounts of CPT after redox release. Excellent physical and chemical properties as well as good therapeutic effects reveal that G-F13 can act as a promising drug carrier to widely use in cancer chemotherapy.

Mechanisms behind excitation- and concentration-dependent multicolor photoluminescence in graphene quantum dots.

Despite numerous efforts, the mechanism behind multicolor photoluminescence (PL) in graphene quantum dots (GQDs) is still controversial. A deep insight into the origin of the multicolor emissions in GQDs is quite necessary for modulating their luminescence to facilitate the better use of this fluorescent material. Herein, GQDs with amino, carboxyl, and ammonium carboxylate groups were synthesized. The as-prepared GQDs exhibited intriguing excitation- and concentration-dependent multicolor PL characteristics. By regulating the excitation wavelength or concentration of GQDs, specific luminescence colors including blue, cyan, green, yellow, and even orange can be obtained. Systematic structural and optical studies indicated that the graphene basal plane and different functional groups dominantly exhibited nN 2P-σ*, π-π*, nO 2p-π* (-COOH), nO 2p-π* (-COO-) and nN 2p-π* electronic transitions, which appeared as multi-fluorescent centers that gave rise to the excitation-dependent multicolor PL. The occurrence of different types of electronic transitions and their color emissions were proved by pH-dependent PL measurements. In addition, systematic optical and morphology analyses revealed that GQDs could self-assemble into J-type aggregates with different morphologies and sizes as the concentration increased, and the observed concentration-dependent multicolor PL can be ascribed to aggregation-mediated energy level reconstruction in GQDs. Our findings further suggest that the competition among various fluorescent centers and self-aggregation processes dominated the luminescent properties of GQDs. This work will contribute to understand the origins of excitation- and concentration-dependent multicolor emissions in GQDs, which is also highly instructive for broadening the application fields of GQDs.