Fluorescence Sensing Mechanisms of Versatile Graphene Quantum Dots toward Commonly Encountered Heavy Metal Ions.

Graphene quantum dots (GQDs) have received tremendous attention as fluorescent probes for detection of diverse heavy metal ions (HMIs). Nevertheless, the fluorescence sensing mechanisms of versatile GQDs with respect to different HMIs remain elusive. Herein, the fluorescence sensing behaviors and mechanisms of GQDs with amino and carboxyl groups toward commonly encountered Cr6+, Fe3+, Cu2+, Cr3+, Mn2+, Co2+, Ni2+, Zn2+, Cd2+, and Hg2+ under different pH conditions are systemically explored. The results show that the fluorescence of GQDs can be enhanced by Zn2+/Cd2+ and quenched by other HMIs at pH 5.8, while it can be enhanced by HMIs except Cr6+/Fe3+/Cu2+ at pH 2.0. Systematic studies verify that the fluorescence quenching/enhancing is mediated by the synergistic effect of the inner filter effect (IFE) and the photoinduced electron transfer (PET) or metal orbital-controlled chelation-quenched/enhanced fluorescence (CHQF/CHEF) effect. The strong and weak IFEs of Cr6+/Fe3+ and Cr3+/Cu2+, respectively, are one of the reasons for the fluorescence quenching, while other HMIs have no IFE. Moreover, the PET effect caused by the interaction of GQDs with Hg2+ at pH 5.8 and the CHQF/CHEF effect caused by the interaction of GQDs with other HMIs are also crucial for fluorescence quenching/enhancing. The findings suggest that the pH condition, the existing forms of functional groups on GQDs, and the complexation states of HMIs in aqueous systems dominate the PET and CHQF/CHEF effects. The elucidating of the fluorescence sensing mechanisms of GQDs toward different HMIs paves the way for developing versatile sensing platforms for monitoring of HMI contamination.

Programmable Multifunctional Gels with On-Demand Patterning Capability toward Hierarchical and Multi-Dimensional Encryption and Anti-Counterfeiting.

Hydrogels capable of optical switching have recently become one of the most celebrated materials for information encryption and anti-counterfeiting. However, challenges still remain for developing versatile gel-based platforms with on-demand multistage patterning and multi-dimensional encryption capacities as well as long-term stability. Herein, elaborately designed programmable and multifunctional gels with fascinating anti-swelling (swelling ratios < 0.1%), anti-freezing (below -70 °C), and anti-dehydration (over 3 months) abilities, solvent-induced reversible transparence variations, adjustable fluorescence, self-healing (86% in stress and 94% in strain), Fe3+-ethylenediaminetetraacetic acid disodium (EDTA·2Na)-induced reversible shape memory, and fluorescence off/on switch capabilities are facilely fabricated based on glycidyl methacrylate functionalized graphene quantum dots and Al3+ cross-linked gelatin and polyacrylic acid. Employing a simple mask photopolymerization or welding technique, various patterns can be readily and hierarchically encrypted on-demand into a single gel label, which can be further fixed into complex multi-dimensional architectures while quenching fluorescence after the treatment with Fe3+ to achieve high-security-level information encryption originating from the synergistic effects of the above multifunctions. The encrypted multi-level information can only be stepwise decrypted by an authorized individual who has mastered all decryption keys. Therefore, the creative design strategy for programing multifunctional gels opens up the possibility for hierarchical and multi-dimensional information encryption and anti-counterfeiting.

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.

Liquid-Free Ion-Conducting Elastomer with Environmental Stability for Soft Sensing and Thermoelectric Generating.

Ionic conductors are promising candidates for fabricating soft electronics, but currently applied ionic hydrogels and organogels suffer from liquid leakage and evaporation issues. Herein, we fabricated a free-liquid ionic conducting elastomer (LFICE) with dry lithium bis(trifluoromethane sulfonimide) and elastomeric waterborne polyurethane. The resultant versatile LFICE exhibits superior tensile strength (∼4.5 MPa), satisfactory stretchability (>900%), excellent ionic conductivity (8.32 × 10-4 S m-1 at 25 °C), and sensitive strain (3.21) and temperature (2.22% °C-1) response. The LFICE also presents durable environmental stability due to the all-solid-state feature. In the exploration of application prospects, the as-assembled LFICE sensor can precisely and repeatedly detect human motion and temperature changes, demonstrating its potentials in digital medical diagnosis and monitoring; the as-assembled LFICE thermoelectric generator (TEG) shows a high ionic thermovoltage of 4.41 mV K-1, paving a bright path for the advent of self-powered soft electronics. It is believed that this research boosts the facile fabrication of environmental stable stretchable ionic conductors holding great promise in next-generation soft electronics integrated with dual thermo- and strain-response and energy harvesting.

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.

Achieving Fast Self-Healing and Reprocessing of Supertough Water-Dispersed "Living" Supramolecular Polymers Containing Dynamic Ditelluride Bonds under Visible Light.

It is very challenging to achieve polymers that are mechanically robust and fast self-healable at ambient conditions, which are highly desirable for smart materials of the next-generation. Herein, combining dynamic ditelluride bonds and 2-ureido-4[1H]-pyrimidinone (UPy) moieties in the main chains, a novel type of visible-light-induced self-healing water-dispersed supramolecular polymers (DTe-WSPs) with outstanding healing properties were developed. The prepared DTe-WSPs emulsions showed excellent emulsion stability, and highly transparent DTe-WSPs films obtained from these emulsions exhibited much improved mechanical properties and fast recoverability after the incorporation of UPy groups, owing to the physical cross-links formed by quadruple hydrogen-bonded UPy moieties. Supertoughness (105.2 MJ m-3) and fast self-healability under visible light (healing efficiency of 85.6% within 10 min) could be achieved simultaneously with the adjustment of the ditelluride content and the UPy content, and the toughness of our polymers is higher than those of the reported ambient temperature self-healable polymers. The visible-light-induced ditelluride metathesis is a predominant factor in the healing process of DTe-WSPs, and the ditelluride metathesis triggered by photothermy and hydrogen bonding could also afford the ultimate healing result. Meanwhile, DTe-WSPs can be reprocessed using visible light, providing a facile way to process polymers at mild conditions. To our surprise, the "living" DTe-WSPs exhibited the ability to initiate the polymerization of vinyl monomers under visible light, which is first reported for water-dispersed self-healing polymers. We considered the elaborated design philosophy, based on the readily available, clean, safe, and easily manipulated visible light, which can not only provide inspiration for preparing fast ambient temperature self-healing and reprocessing polymer materials with robust mechanical properties but also develop a new macroinitiator to initiate the ambient temperature polymerization of vinyl monomers.