Mechanochromic Fluorescent Polymers Enabled by AIE Processes.

Polymeric materials are susceptible to the chain re-conformation, reorientation, slippage, and bond cleavage upon mechanical stimuli, which are likely to further grow into macro-damages and eventually lead to the compromise or loss of materials performance. Therefore, it is of great academic importance and practical significance to sensitively detect the local mechanical states in polymers and monitor the dynamic variations in polymer structures and properties under external forces. Mechanochromic fluorescent polymers (MFP) are a class of smart materials by utilizing sensitive fluorescent motifs to detect polymer chain events upon mechanical stimuli. Taking advantage of the unique aggregation-induced emission (AIE) effect, a variety of MFP systems that can self-report their mechanical states and mechano-induced structural and property changes through fluorescence signals have been developed. In this feature article, an overview of the recent progress on MFP systems enabled by AIE process is presented. The main design principles, including physically doping dispersed or microencapsulated AIE luminogens (AIEgens) into polymer matrix, chemically linking AIEgens in polymer backbones, and utilizing the clusterization-triggered emission of polymers containing nonconventional luminogens, are discussed with representative examples. Perspectives on the existing challenges and problems in this field are also discussed to guide future development.

Reversible hydrogel-solution system of silk with high beta-sheet content.

Silkworm silk has been widely used as a textile fiber, as biomaterials and in optically functional materials due to its extraordinary properties. The ß-sheet-rich natural nanofiber units of about 10-50 nm in diameter are often considered the origin of these properties, yet it remains unclear how silk self-assembles into these hierarchical structures. A new system composed of ß-sheet-rich silk nanofibers about 10-20 nm in diameter is reported here, where these nanofibers formed into "flowing hydrogels" at 0.5-2% solutions and could be transformed back into the solution state at lower concentrations, even with a high ß-sheet content. This is in contrast with other silk processed materials, where significant ß-sheet content negates reversibility between solution and solid states. These fibers are formed by regulating the self-assembly process of silk in aqueous solution, which changes the distribution of negative charges while still supporting ß-sheet formation in the structures. Mechanistically, there appears to be a shift toward negative charges along the outside of the silk nanofibers in our present study, resulting in a higher zeta potential (above -50 mV) than previous silk materials which tend to be below -30 mV. The higher negative charge on silk nanofibers resulted in electrostatic repulsion strong enough to negate further assembly of the nanofibers. Changing silk concentration changed the balance between hydrophobic interactions and electrostatic repulsion of ß-sheet-rich silk nanofibers, resulting in reversible hydrogel-solution transitions. Furthermore, the silk nanofibers could be disassembled into shorter fibers and even nanoparticles upon ultrasonic treatment following the transition from hydrogel to solution due to the increased dispersion of hydrophobic smaller particles, without the loss of ß-sheet content, and with retention of the ability to transition between hydrogel and solution states through reversion to longer nanofibers during self-assembly. These reversible solution-hydrogel transitions were tunable with ultrasonic intensity, time, or temperature.

Highly efficient extraction of uranium from seawater by polyamide and amidoxime co-functionalized MXene.

Uranium mainly exists in the form of uranyl carbonate in seawater. [UO2(CO3)3]4- has strong stability, which increases the difficulty of uranium extraction from seawater. Meanwhile, the complex marine environment, a large number of coexisting competing ions and biological pollution are all non-negligible disturbing factors. Herein, we introduced amidoxime (AO) groups into the surface of Ti3C2 and grafted polyamides (PA) by a simple one-step hydrothermal method to produce an efficient seawater uranium extraction adsorbent Ti3C2-AO-PA. Owing to the amidoxime groups, the material was highly selective for uranium. And the large number of amino groups in the polyamides gave it ideal resistance to biofouling. The possibility of Ti3C2-AO-PA as an adsorbent for uranium extraction from seawater was confirmed by various characterization techniques, numerous adsorption batch experiments, simulated seawater experiments and antibacterial performance tests. It was demonstrated that the uptake of [UO2(CO3)3]4- by Ti3C2-AO-PA showed fast reaction kinetics (about 120 min), brilliant absorption capacity (81.1 mg·g-1 at pH 8.3), significant high selectivity (32.8 mg-U/g-Ads) and outstanding anti-biological contamination performance (92.9% antibacterial rate). XPS and DFT further indicated that the high extraction ability of Ti3C2-AO-PA for uranium was mainly attributed to the strong complexation of AO and -NH2 with [UO2(CO3)3]4-. These conclusions showed that Ti3C2-AO-PA not only had an ideal application prospect for uranium extraction from seawater, but also provided an available strategy for rapid and selective uranium adsorption from real seawater.

Biomineralization of stable and monodisperse vaterite microspheres using silk nanoparticles.

The influence of silk fibroin (SF) on calcium carbonate (CaCO3) biomineralization has been investigated; however, the formation of small, uniform SF-regulated vaterite microspheres has not been reported. In this work, spherical CaCO3 was synthesized via coprecipitation in the presence of SF. SF nanostructures were first tuned by self-assembly at 60 °C to provide better control of the nucleation of CaCO3. Subsequently, monodisperse vaterite microspheres about 1.1 µm were generated by controlling aggregation and growth of CaCO3 under appropriate concentrations of SF and Ca ions. In contrast to unstable vaterite, the microspheres generated in the present study have sufficient stability in aqueous solution for at least 8 days without transformation into calcite, due to the electrostatic interactions between the Ca ions and the preassembled SF nanostructures. The microspheres as drug carriers of doxorubicin (DOX) were assessed and found to have good encapsulation efficiency, sustained drug release without burst release, and pH sensitivity. These new SF/CaCO3 hybrids may provide new options for various biomedical applications.

[Finite element analysis of the stress distribution of two-piece post crown with different adhesives ].

OBJECTIVE: To establish three-dimensional finite element model of two-piece post crown to the mandibular first molar residual roots, and analyze the stress distribution characteristic to the residual roots with different adhesives, so as to get the best combination under different conditions. METHODS: The complete mandibular first molar in vitro was selected, the crown was removed along the cemento-enamel junction, then the residual roots were scanned by CT. CT images were imported into a reverse engineering software, and the three-dimensional finite element model of the mandibular first molar residual roots was reconstructed. Titanium two-piece post crown of the mandibular first molar residual roots was produced, then was scanned by CT. The model was reconstructed and assembled by MIMICS. The stress distribution of the root canal and root section under the vertical load and lateral load with different bonding systems were analyzed. RESULTS: Three-dimensional finite element model of two-piece post crown to the mandibular first molar residual roots was established. With the increasing of elastic modulus of the adhesives, the maximum stress within the root canal was also increasing. Elastic modulus of zinc phosphate was the biggest, so the stress within the root canal was the biggest; elastic modulus of Superbond C&B was the smallest, so the stress within the root canal was the smallest. Lateral loading stress was much larger than the vertical load. Under vertical load, the load on the root section was even with different bonding systems. Under lateral load, the maximum stress was much larger than the vertical load. The stress on the root section was minimum using zinc phosphate binder, and the stress on the root section was maximum using Superbond C&B. CONCLUSION: In two-piece post crown restorations, there is significant difference between different adhesives on tooth protection. When the tooth structure of the root canal orifices is weak, in order to avoid the occurrence of splitting, the larger elastic modulus bonding system is the first choice, such as zinc phosphate binder. When the resistance form of the root canal orifices is good enough but the root is too weak, it is suggested that the smaller elastic modulus bonding system is the first choice, such as Superbond C&B.

Biocompatibility of Fe3O4/DNR magnetic nanoparticles in the treatment of hematologic malignancies.

PURPOSE: The objectives of this research were to assess the biocompatibility of self-assembled Fe(3)O(4) magnetic nanoparticles (MNPs) loaded with daunorubicin (DNR), ie, (Fe(3)O(4)-MNPs/DNR), and to explore their potential application in the treatment of hematologic malignancies. METHODS: A hemolysis test was carried out to estimate the hematologic toxicity of Fe(3)O(4)- MNPs/DNR and a micronucleus assay was undertaken to identify its genotoxicity. Fe(3)O(4)-MNPs/ DNR were injected intraperitoneally into mice to calculate the median lethal dose (LD(50)). The general condition of the mice was recorded, along with testing for acute toxicity to the liver and kidneys. RESULTS: Hemolysis rates were 2.908%, 2.530%, and 2.415% after treatment with different concentrations of Fe(3)O(4)-MNPs/DNR. In the micronucleus assay, there was no significant difference in micronucleus formation rate between the experimental Fe(3)O(4)-MNPs/DNR groups and negative controls (P > 0.05), but there was a significant difference between the experimental groups and the positive controls (P < 0.05). The LD(50) of the Fe(3)O(4)-MNPs/DNR was 1009.71 mg/kg and the 95% confidence interval (CI) was 769.11-1262.40 mg/kg, while that of the DNR groups was 8.51 mg/kg (95% CI: 6.48-10.37 mg/kg), suggesting that these nanoparticles have a wide safety margin. Acute toxicity testing showed no significant difference in body weight between the treatment groups at 24, 48, and 72 hours after intraperitoneal injection. The mice were all in good condition, with normal consumption of water and food, and their stools were formed and yellowish-brown. Interestingly, no toxic reactions, including instability of gait, convulsion, paralysis, and respiratory depression, were observed. Furthermore, alanine transaminase, blood urea nitrogen, and creatinine clearance in the experimental Fe(3)O(4)-MNPs/ DNR groups were 66.0 ± 28.55 U/L, 9.06 ± 1.05 mmol/L, and 18.03 ± 1.84 µmol/L, respectively, which was not significantly different compared with the control and isodose DNR groups. CONCLUSION: Self-assembled Fe(3)O(4)-MNPs/DNR appear to be highly biocompatible and safe nanoparticles, and may be suitable for further application in the treatment of hematologic malignancies.