Metal element-fusion peptide heterostructured nanocoatings endow polyetheretherketone implants with robust anti-bacterial activities and in vivo osseointegration.

Polyetheretherketone (PEEK), renowned for its exceptional mechanical properties and bio-stability, is considered a promising alternative to traditional metal-based implants. However, the inferior bactericidal activity and the limited angiogenic and osteogenic properties of PEEK remain the three major obstacles to osseointegration in vivo. To overcome these obstacles, in this work, a versatile heterostructured nanocoating was conceived and equipped on PEEK. This nanocoating was designed to endow PEEK with the ability of photo-activated pathogen disinfection, along with enhanced angiogenesis and osteogenesis, effectively addressing the triple-barrier challenge towards osseointegration. The crafted nanocoating, encompassing diverse nutritional metal elements (Fe3+, Mg2+, and Sr2+) and a fusion peptide adept at promoting angiogenesis and osteogenesis, was seamlessly decorated onto PEEK. The engineered implant exhibited an antibacterial activity of over 94% upon near-infrared illumination by virtue of the photothermal conversion of the polyphenol nanocoating. Simultaneously, the decorated hierarchical nanocoatings synergistically promoted cellular adhesion and proliferation and up-regulated angiogenesis-/osteogenesis-associated cytokine expression in endothelial/osteoblast cells, resulting in superior angiogenic differentiation and osteoinductive capability in vitro. Moreover, an in vivo assay in a rabbit femoral defect model revealed that the decorated implant can achieve ameliorative osseointegrative fixation. Collectively, this work offers a practical and instructive clinical strategy to address the triple-barrier challenge associated with PEEK-based implants.

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.

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.

Aqueous Self-Assembly of Y-Shaped Amphiphilic Block Copolymers into Giant Vesicles.

The preparation and aqueous self-assembly of newly Y-shaped amphiphilic block polyurethane (PUG) copolymers are reported here. These amphiphilic copolymers, designed to have two hydrophilic poly(ethylene oxide) (PEO) tails and one hydrophobic alkyl tail via a two-step coupling reaction, can self-assemble into giant unilamellar vesicles (GUVs) (diameter ≥ 1000 nm) with a direct dissolution method in aqueous solution, depending on their Y-shaped structures and initial concentrations. More interesting, the copolymers can self-assemble into various distinct nano-/microstructures, such as spherical micelles, small vesicles, and GUVs, with the increase of their concentrations. The traditional preparation methods of GUVs generally need conventional amphiphilic molecules and additional complicated conditions, such as alternating electrical field, buffer solution, or organic solvent. Therefore, the self-assembly of Y-shaped PUGs with a direct dissolution method in aqueous solution demonstrated in this study supplies a new clue to fabricate GUVs based on the geometric design of amphiphilic polymers.