Evaluation of enamel surface integrity after orthodontic bracket debonding: comparison of three different system.

OBJECTIVE: This study aimed to evaluate enamel surface integrity and time consumed during residual cement removal after bracket debonding using different adhesive removal burs with and without a dental loupe. MATERIAL AND METHODS: Sixty human-extracted premolars were collected, cleaned, mounted, and prepared for orthodontic bracket bonding. Teeth were randomly divided into three main groups (n = 20) based on the adhesive removal method: tungsten carbide system (TC), sof-lex discs system (SD), and diamond system (DB) groups. Then, each group was subdivided into two subgroups (naked eye and magnifying loupe subgroups). The brackets were bonded and then debonded after 24 h, and the Adhesive Remnant Index (ARI) was assessed. The adhesive remnants were removed by different systems, and the final polishing was performed by Silicone OneGloss. The enamel surface roughness was evaluated before bracketing (T0), after residual cement removal (T1), and finally after polishing (T2) using surface Mitutoyo SJ-210 profilometry and Scanning Electron Microscopy (SEM) to determine the Enamel Damage Index (EDI) score. The time consumed for adhesive removal was recorded in seconds. RESULTS: The Kruskal Wallis test showed a statistically significant difference in roughness values at T1 compared to T2 between subgroups (p < 0.001). When comparing EDI at T1 and T2, the Kruskal-Wallis H-test showed statistically significant differences in all subgroups. The pairwise comparisons revealed that EDI scores showed a statistically significant difference at T1 and T2 between DB vs. TC and SD (p = 0.015) but not between TC vs. SD (p = 1.000), indicating the highest roughness value observed in the DB group. The time for cement removal was significantly shorter in the magnifying loupe group than in the naked eye group and was shortest with the TC group, whereas the time was the longest with the DB group (p < 0.05). CONCLUSION: All three systems were clinically satisfactory for residual orthodontic adhesive removal. However, TC system produced the lowest enamel roughness, while the DB system created the greatest. The polishing step created smoother surfaces regardless of the systems used for resin removal.

Adsorption behavior of Mo(VI) from aqueous solutions using tungstate-modified magnetic nanoparticle.

A new magnetic nanoparticle modified with sodium tungstate (Mnp-Si-W) was synthesized and employed for the sorption of molybdenum from aqueous solutions. The prepared nanoparticles (Mnp-Si-W) were characterized by different advanced techniques. Different parameters that influenced the adsorption percent of Mo(VI) were investigated using a batch process. Based on a systematic investigation of the adsorption isotherms and kinetics models, Mo(VI) adsorption follows the Langmuir model and pseudo-second-order kinetics. According to the Langmuir isotherm model, the Mnp-Si-W nanoparticles exhibited a maximum adsorption capacity of 182.03 mg g-1 for Mo(VI) at pH 2.0. The effect of competing ions showed that the prepared nanoparticles have a high selectivity for the sorption of molybdenum. Moreover, the effect of some interfering anions on Mo(VI) ion sorption is found in the following order: phosphate < sulfate < chromate. Finally, the nanoparticle (Mnp-Si-W) can be successfully reused five times.

Role of tungsten disulfide quantum dots in specific protein-protein interactions at air-water interface.

The intriguing network of antibody-antigen (Ab-Ag) interactions is highly governed by environmental perturbations and the nature of biomolecular interaction. Protein-protein interactions (PPIs) have potential applications in developing protein-adsorption-based sensors and nano-scale materials. Therefore, characterizing PPIs in the presence of a nanomaterial at the molecular level becomes imperative. The present work involves the investigation of antiferritin-ferritin (Ab-Ag) protein interactions under the influence of tungsten disulfide quantum dots (WS2 QDs). Isothermal calorimetry and contact angle measurements validated the strong influence of WS2 QDs on Ab-Ag interactions. The interfacial signatures of nano-bio-interactions were evaluated using sum frequency generation vibration spectroscopy (SFG-VS) at the air-water interface. Our SFG results reveal a variation in the tilt angle of methyl groups by ∼12° ± 2° for the Ab-Ag system in the presence of WS2 QDs. The results illustrated an enhanced ordering of water molecules in the presence of QDs, which underpins the active role of interfacial water molecules during nano-bio-interactions. We have also witnessed a differential impact of QDs on Ab-Ag by raising the concentration of the Ab-Ag combination, which showcased an increased inter-molecular interaction among the Ab and Ag molecules and a minimal influence on the methyl tilt angle. These findings suggest the formation of stronger and ordered Ab-Ag complexes upon introducing WS2 QDs in the aqueous medium and signify the potentiality of WS2 QDs relevant to protein-based sensing assays.

A Novel Label-Free Electrochemical Immunosensor for the Detection of Thyroid Transcription Factor 1 Using Ribbon-like Tungsten Disulfide-Reduced Graphene Oxide Nanohybrids and Gold Nanoparticles.

Thyroid transcription factor 1 (TTF1) is an important cancer-related biomarker for clinical diagnosis, especially for carcinomas of lung and thyroid origin. Herein, a novel label-free electrochemical immunosensor was prepared for TTF1 detection based on nanohybrids of ribbon-like tungsten disulfide-reduced graphene oxide (WS2-rGO) and gold nanoparticles (AuNPs). The proposed immunosensor employed H2O2 as the electrochemical probe because of the excellent peroxidase-like activity of ribbon-like WS2-rGO. The introduction of AuNPs not only enhanced the electrocatalytic activity of the immunosensor, but also provided immobilization sites for binding TTF1 antibodies. The electrochemical signals can be greatly amplified due to their excellent electrochemical performance, which realized the sensitive determination of TTF1 with a wide linear range of 0.025-50 ng mL-1 and a lower detection limit of 0.016 ng mL-1 (S/N = 3). Moreover, the immunosensor exhibited high selectivity, good reproducibility, and robust stability, as well as the ability to detect TTF1 in human serum with satisfactory results. These observed properties of the immunosensor enhance its potential practicability in clinical applications. This method can also be used for the detection of other tumor biomarkers by using the corresponding antigen-antibody complex.

Luminescence and dosimetry approach in terbium(III)-activated tungstate double perovskite.

A series of tungstate double perovskite Ca3 WO6 doped with Tb3+ was prepared by a combustion process using urea as a flux. The crystal structure identification of Ca3 WO6 :Tb3+ phosphors was done using X-ray diffraction patterns, and a monoclinic structure was discovered. The Fourier transform infrared spectrum of Ca3 WO6 :Tb3+ displayed characteristic vibrations of tungstate bonds. Under 278 nm excitation, Ca3 WO6 :Tb3+ exhibited intense downconversion green emission, which corresponded to the 5 D4 -7 FJ (J = 4,5) transitions of Tb3+ . The phosphor exhibited the highest photoluminescence (PL) intensity when it was doped with 1 mol% of Tb3+ ; later intensity quenching appeared to be due to the multipolar interaction at higher dopant concentrations. Moreover, high-quality thermoluminescence (TL) was detected when phosphors were irradiated using beta rays. The effects of Tb3+ concentration and beta dose on TL intensity were the two major aspects studied in detail. The TL intensity demonstrated excellent linear response to the applied range of beta dose. The trap parameters of the studied phosphors were computed by the peak shape approach and glow curve deconvolution. The fading effect on TL intensity was studied by recording the TL glow curves after 1 month of beta irradiation. Obtained results from the PL and TL characterizations showed that the phosphors under study have the potential to be used in lighting displays and in thermoluminescence dosimetry.

The Effect of Water Coolant and Bur Type on Pulp Temperature When Removing Tooth Structure and Restorative Dental Materials.

OBJECTIVE: The aim was to compare intrapulp temperature (IPT) changes when flat-fissure diamond burs and pear-shaped tungsten carbide burs were used to cut tooth structure, amalgam, and composite resin with and without water coolant. METHODS: Thermocouples were inserted into the pulp chamber of extracted intact mandibular molars. The thermocouples were connected to an electronic thermometer that detects temperature every second to an accuracy of 0.1°C. IPT changes were recorded while using a high-speed handpiece during MOD cavity preparations (n=40), composite resin removal (n=40), and amalgam removal (n=40). A two-way ANOVA was used for each procedure to test for the effect of bur (pear-shaped tungsten carbide vs flat-fissured diamond) and water coolant (on vs off), with significant main effects (α=0.05) further analyzed using Tukey's multiple comparison test. RESULTS: During MOD cavity preparation, water coolant reduced changes in IPT (0.03±0.27°C) compared to no water coolant (1.27±0.29°C) when tungsten carbide burs were used (p<0.05) but not when diamond burs were used. During composite resin removal, tungsten carbide burs had less changes in IPT (0.55±0.18°C) compared to diamond burs (1.66±0.50°C) with no water coolant (p<0.05). Water coolant also reduced changes in IPT (0.09±0.14°C) compared to no water coolant (1.66±0.50°C) when diamond burs were used (p<0.01). Water coolant did not significantly affect IPT when tungsten carbide burs were used. During amalgam removal, tungsten carbide burs had lower changes in IPT (0.56±0.15°C) compared to diamond burs (1.88±0.43°C) with no water coolant (p<0.05). Water coolant also significantly reduced changes in IPT (0.71±0.2°C) compared to no water coolant (1.88±0.43°C) when diamond burs were used (p<0.05) but not when tungsten carbide burs were used. CONCLUSIONS: Water coolant reduced IPT changes when drilling tooth structure with tungsten carbide burs, but not when removing amalgam or composite. Conversely, water coolant reduced IPT changes when drilling with flat fissure diamond burs to remove amalgam and composite, but not when removing tooth structure. When amalgam and composite were removed without water coolant, the tungsten carbide burs resulted in lower IPT changes than when flat fissure diamond burs were used in the same way.

Combined Experimental and Computational Study of V-Substituted Lindqvist Polyoxotungstate: Screening by Docking for Potential Antidiabetic Activity.

In the current work, a novel vanadotungstate compound, (C6H9N2)4[V2W4O19]·2H2O (1), is isolated by a simple stepwise synthesis method and characterized by a combined experimental and computational study. Molecular docking is conducted for the first time for this kind of substituted Lindqvist polyoxometalates to elucidate for potential antidiabetic activity. Hence, the modeling results revealed a significant docking score of the reported compound to bind to the active sites of α-glucosidase with the lowest binding energy of -5.7 kcal/mol, where the standard drug acarbose (ACB) had -4.6 kcal/mol binding energy. The stability of binding was enhanced by strong H-bonding, van der Waals, and electrostatic interactions occurring in the three-dimensional (3D) supramolecular network of polyanionic vanadotungstate subunits templated with organic moieties as shown by X-ray diffraction and Hirshfeld analyses. Furthermore, density functional theory (DFT) calculations supported with photophysical measurements are also discussed to predict the most chemical and biological reactivity. In this view, the complete description of electronic and biological features of (1) is enhanced by determination of the highest occupied molecular orbital (HOMO)/least unoccupied molecular orbital (LUMO) energy, electronic density, ionization potential, electron affinity, etc. These chemical descriptors, intermolecular interactions, docking score, and binding free energy estimation are essential in understanding the reactivity of this bioactive compound offering potential inhibition of the α-glucosidase enzyme.

Decoupling of catalysis and transition state analog binding from mutations throughout a phosphatase revealed by high-throughput enzymology.

Using high-throughput microfluidic enzyme kinetics (HT-MEK), we measured over 9,000 inhibition curves detailing impacts of 1,004 single-site mutations throughout the alkaline phosphatase PafA on binding affinity for two transition state analogs (TSAs), vanadate and tungstate. As predicted by catalytic models invoking transition state complementary, mutations to active site and active-site-contacting residues had highly similar impacts on catalysis and TSA binding. Unexpectedly, most mutations to more distal residues that reduced catalysis had little or no impact on TSA binding and many even increased tungstate affinity. These disparate effects can be accounted for by a model in which distal mutations alter the enzyme's conformational landscape, increasing the occupancy of microstates that are catalytically less effective but better able to accommodate larger transition state analogs. In support of this ensemble model, glycine substitutions (rather than valine) were more likely to increase tungstate affinity (but not more likely to impact catalysis), presumably due to increased conformational flexibility that allows previously disfavored microstates to increase in occupancy. These results indicate that residues throughout an enzyme provide specificity for the transition state and discriminate against analogs that are larger only by tenths of an Ångström. Thus, engineering enzymes that rival the most powerful natural enzymes will likely require consideration of distal residues that shape the enzyme's conformational landscape and fine-tune active-site residues. Biologically, the evolution of extensive communication between the active site and remote residues to aid catalysis may have provided the foundation for allostery to make it a highly evolvable trait.

Broadband Vibration-Based Energy Harvesting for Wireless Sensor Applications Using Frequency Upconversion.

Silicon-based kinetic energy converters employing variable capacitors, also known as electrostatic vibration energy harvesters, hold promise as power sources for Internet of Things devices. However, for most wireless applications, such as wearable technology or environmental and structural monitoring, the ambient vibration is often at relatively low frequencies (1-100 Hz). Since the power output of electrostatic harvesters is positively correlated to the frequency of capacitance oscillation, typical electrostatic energy harvesters, designed to match the natural frequency of ambient vibrations, do not produce sufficient power output. Moreover, energy conversion is limited to a narrow range of input frequencies. To address these shortcomings, an impacted-based electrostatic energy harvester is explored experimentally. The impact refers to electrode collision and it triggers frequency upconversion, namely a secondary high-frequency free oscillation of the electrodes overlapping with primary device oscillation tuned to input vibration frequency. The main purpose of high-frequency oscillation is to enable additional energy conversion cycles since this will increase the energy output. The devices investigated were fabricated using a commercial microfabrication foundry process and were experimentally studied. These devices exhibit non-uniform cross-section electrodes and a springless mass. The non-uniform width electrodes were used to prevent pull-in following electrode collision. Springless masses from different materials and sizes, such as 0.5 mm diameter Tungsten carbide, 0.8 mm diameter Tungsten carbide, zirconium dioxide, and silicon nitride, were added in an attempt to force collisions over a range of applied frequencies that would not otherwise result in collisions. The results show that the system operates over a relatively wide frequency range (up to 700 Hz frequency range), with the lower limit far below the natural frequency of the device. The addition of the springless mass successfully increased the device bandwidth. For example, at a low peak-to-peak vibration acceleration of 0.5 g (peak-to-peak), the addition of a zirconium dioxide ball doubled the device's bandwidth. Testing with different balls indicates that the different sizes and material properties have different effects on the device's performance, altering its mechanical and electrical damping.

Adaptive Responses of a Peroxidase-like Polyoxometalate-Based Tri-Assembly to Bacterial Microenvironment (BME) Significantly Improved the Anti-Bacterial Effects.

The present study presents the tertiary assembly of a POM, peptide, and biogenic amine, which is a concept to construct new hybrid bio-inorganic materials for antibacterial applications and will help to promote the development of antivirus agents in the future. To achieve this, a Eu-containing polyoxometalate (EuW10) was first co-assembled with a biogenic amine of spermine (Spm), which improved both the luminescence and antibacterial effect of EuW10. Further introduction of a basic peptide from HPV E6, GL-22, induced more extensive enhancements, both of them being attributed to the cooperation and synergistic effects between the constituents, particularly the adaptive responses of assembly to the bacterial microenvironment (BME). Further intrinsic mechanism investigations revealed in detail that the encapsulation of EuW10 in Spm and further GL-22 enhanced the uptake abilities of EuW10 in bacteria, which further improved the ROS generation in BME via the abundant H2O2 involved there and significantly promoted the antibacterial effects.

Reactivity of a Dithiocarbamate-Ligated [WVI≡S] Complex with Hydride Donors: Toward a Synthetic Mimic of Formate Dehydrogenase.

Formate dehydrogenase (FDH) enzymes catalyze redox interconversion of CO2 and HCO2-, with a key mechanistic step being the transfer of H- from HCO2- to an oxidized active site featuring a [MVI≡S] group in a sulfur-rich environment (M = Mo or W). Here, we report reactivity studies with HCO2- and other reducing agents of a synthetic [WVI≡S] model complex ligated by dithiocarbamate (dtc) ligands. Reactions of [WVIS(dtc)3][BF4] (1) conducted in MeOH solvent generated [WVIS(S2)(dtc)2] (2) and [WVS(µ-S)(dtc)]2 (3) products by a solvolysis pathway that was accelerated by the presence of [Me4N][HCO2] but did not require it. Under MeOH-free conditions, the reaction of 1 with [Et4N][HCO2] produced some [WIV(µ-S)(µ-dtc)(dtc)]2 (4), but predominantly [WV(dtc)4]+ (5), along with stoichiometric CO2 detected by headspace gas chromatography (GC) analysis. Stronger hydride sources such as K-selectride generated the more reduced analogue, 4, exclusively. The reaction of 1 with the electron donor, CoCp2, also produced 4 and 5 in varying amounts depending on reaction conditions. These results indicate that formates and borohydrides act as electron donors rather than hydride donors toward 1, an outcome that diverges from the behavior of FDHs. The difference is ascribed to the more oxidizing potential of [WVI≡S] complex 1 when supported by monoanionic dtc ligands that allows electron transfer to outcompete hydride transfer, as compared to the more reduced [MVI≡S] active sites supported by dianionic pyranopterindithiolate ligands in FDHs.

Exploiting Interactions between Polyoxometalates and Proteins for Applications in (Bio)chemistry and Medicine.

The specific interactions of anionic metal-oxo clusters, known as polyoxometalates (POMs), with proteins can be leveraged for a wide range of analytical and biomedical applications. For example, POMs have been developed as selective catalysts that can induce protein modifications and have also been shown to facilitate protein crystallization, both of which are instrumental in the structural characterization of proteins. POMs can also be used for selective protein separation and enzyme inhibition, which makes them promising therapeutic agents. Hence, understanding POM-protein interactions is essential for the development of POM-based materials and their implementation in several fields. In this Review we summarize in detail the key insights that have been gained so far on POM-protein interactions. Emphasis is also given to hybrid POMs functionalized with organic ligands to prompt further research in this direction owing to the promising recent results on tuning POM-protein interactions through POM functionalization.

Performance and mechanism of a novel S-scheme heterojunction sonocatalyst CuS/BaWO4 for degradation of bisphenol A by ultrasonic activation.

A novel CuS/BaWO4 heterojunction catalyst was prepared and characterized. Taking bisphenol A as the target pollutant for catalytic degradation, the sonocatalytic activity of CuS/BaWO4 composite was evaluated, and the combination with persulfate improved the sonocatalytic degradation of bisphenol A. The results showed that CuS/BaWO4 composite had good sonocatalytic degradation activity for bisphenol A, and the degradation rate was 70.99% ± 1.46%. After combined with persulfate, the degradation rate was further increased to 95.34% ± 0.10%, and the reaction time was relatively shortened. The results of the trapping experiment and calculated energy band positions showed that the formation of S-scheme heterojunction and the formation of hydroxyl radicals and holes were the key to the catalytic degradation of bisphenol A by CuS/BaWO4 composite. In this study, a new CuS/BaWO4 heterojunction sonocatalyst was synthesized. The catalyst can efficiently remove bisphenol A from the water environment and can be used as a potential solution for endocrine disruptor pollution in the water environment.

A Cyclen-Functionalized Cobalt-Substituted Sandwich-Type Tungstoarsenate with Versatility in Removal of Methylene Blue and Anti-ROS-Sensitive Tumor Cells.

Oxidative degradation by using reactive oxygen species (ROS) is an effective method to treat pollutants. The synthesis of artificial oxidase for the degradation of dyes is a hot spot in molecular science. In this study, a nanoscale sandwich-type polyoxometalate (POM) on the basis of a tetra-nuclear cobalt cluster and trivacant B-α-Keggin-type tungstoarsenate {[Co(C8H20N4)]4}{Co4(H2O)2[HAsW9O34]2}∙4H2O (abbreviated as CAW, C8H20N4 = cyclen) has been synthesized and structurally examined by infrared (IR) spectrum, ultraviolet-visible (UV-Vis) spectrum, X-ray photoelectron spectrum (XPS), single-crystal X-ray diffraction (SXRD), and bond valence sum (Σs) calculation. According to the structural analysis, the principal element of the CAW is derived from modifying sandwich-type polyanion {Co4(H2O)2 [HAsW9O34]2}8- with four [Co(Cyclen)]2+, in which 1,4,7,10-tetraazacyclododecane (cyclen) is firstly applied to modify POM. It is also demonstrated that CAW is capable of efficiently catalyzing the production of ROS by the synergistic effects of POM fragments and Co-cyclen complexes. Moreover, CAW can interfere with the morphology and proliferation of sensitive cells by producing ROS and exhibits ability in specifically eliminating methylene blue (MB) dyes from the solution system by both adsorption and catalytic oxidation.

Self-assembly of a novel multicomponent polyoxometalate-based tetrahedral supercluster with high catalytic activity for thioether oxidation.

A glamorous polyoxometalate (POM)-based macromolecule containing a tetrahedral supercluster (Hbiz)12[(P2Co2MoV4O8)2(P2MoV2O8)4(Pb⊂P6Co2MoV2MoVI14O73)4]·ca.129H2O (1) was in situ self-assembled from three novel components, [Pb⊂P6Co2Mo16O73]8- (P6Co2Mo16), [P2MoV2O8]4+ (P2Mo2) and [P2Co2MoV4O8]18+ (P2Co2Mo4), respectively. To our knowledge, 1 represents the first tetrahedral supercluster containing the basket-like POM structure. Besides, macromolecule 1 exhibits high catalytic activity and reusability for the oxidation of thioethers to sulfoxides.

Involvement of NO and Ca2+ in the enhancement of cold tolerance induced by melatonin in winter turnip rape (Brassica rapa L.).

As a multifunctional phytohormone, melatonin (Mel) plays pivotal roles in plant responses to multiple stresses. However, its mechanism of action remains elusive. In the present study, we evaluated the role of NO and Ca2+ signaling in Mel enhanced cold tolerance in winter turnip rape. The results showed that the NO content and concentration of intracellular free Ca2+ ([Ca2+]cyt) increased by 35.42% and 30.87%, respectively, in the leaves of rape seedlings exposed to cold stress. Compared with those of the seedlings in cold stress alone, the NO content and concentration of [Ca2+]cyt in rape seedlings pretreated with Mel increased further. In addition, the Mel-mediated improvement of cold tolerance was inhibited by L-NAME (a NO synthase inhibitor), tungstate (a nitrate reductase inhibitor), LaCl3 (a Ca2+ channel blocker), and EGTA (a Ca2+ chelator), and this finding was mainly reflected in the increase in ROS content and the decrease in osmoregulatory capacity, photosynthetic efficiency and antioxidant enzyme activities, and expression levels of antioxidant enzyme genes. These findings suggest that NO and Ca2+ are necessary for Mel to improve cold tolerance and function synergistically downstream of Mel. Notably, the co-treatment of Mel with L-NAME, tungstate, LaCl3, or EGTA also inhibited the Mel-induced expression of MAPK3/6 under cold stress. In conclusion, NO and Ca2+ are involved in the enhancement of cold tolerance induced by Mel through activating the MAPK cascades in rape seedlings, and a crosstalk may exist between NO and Ca2+ signaling.

Two Polyoxometalate-Encapsulated Two-Fold Interpenetrating dia Metal-Organic Frameworks for the Detection, Discrimination, and Degradation of Phenolic Pollutants.

Phenols are widely used for commercial production, while they pose a hazard to the environment and human health. Thus, investigation of convenient and efficient methods for the detection, discrimination, and degradation of phenols becomes particularly important. Herein, two new polyoxometalate (POM)-based compounds, [Co2(btap)4(H2O)4][SiW12O40] (Co-POM) and [Ni2(btap)4(H2O)4][SiW12O40] (Ni-POM) (btap = 3,5-bis(triazol-1-yl)pyridine), are prepared via a hydrothermal synthesis method. The compounds show a fascinating structural feature of a POM-encapsulated twofold interpenetrating dia metal-organic framework. More importantly, besides the novel structures, the compound Co-POM realizes three functions, namely, the simultaneous detection, discrimination, and degradation of phenols. Specifically, Co-POM shows an excellent colorimetric detection performance toward phenol with a detection limit (LOD) ca. 1.32 µM, which is lower than most reported colorimetric detectors for phenol. Also, a new colorimetric sensor system based on Co-POM can discriminate phenol, 4-chlorophenol, and o-cresol with ease. Further, Co-POM exhibits a photocatalytic degradation property for 4-chlorophenol under irradiation of visible light with the highest degradation rate at 62% after irradiation for 5 h. Therefore, this work provides the first example of a POMs-based multifunctional material for achieving the detection, discrimination, and degradation of phenolic pollutants.

Mechano-Regulable and Healable Silk-Based Materials for Adaptive Applications.

Mechanically adaptive materials responsive to environmental stimuli through changing mechanical properties are highly attractive in intelligent devices. However, it is hard to regulate the mechanical properties of most mechanically adaptive materials in a facile way. Moreover, it remains a challenge to achieve mechano-regulable materials with mechanical properties ranging from high strength to extreme toughness. Here, inspired by the reversible nanofibril network structure of skeletal muscle to achieve muscle strength regulation, we present a mechano-regulable biopolymeric silk fibroin (SF) composite through regulating dynamic metal-ligand coordination bonds by using water molecules as competitive regulators. Efficient interfacial hydrogen bonds between tannic acid-tungsten disulfide nanohybrids and the SF matrix endow the composite with high mechanical strength and self-healing ability. The resulting composite exhibits 837-fold change in Young's modulus (5.77 ± 0.61 GPa to 6.89 ± 0.64 MPa) after water vapor triggering, high mechanical properties (72.5 ± 6.3 MPa), and excellent self-healing efficiency (nearly 100%). The proof-of-concept ultraconformable iontronic skin and smart actuators are demonstrated, thereby providing a direction for future self-adaptive smart device applications.

A Water-Soluble Antimony-Rich Polyoxometalate with Broad-Spectrum Antitumor Activities.

Herein, a giant Sb-rich polyoxometalate (POM) {Sb21 Tb7 W56 } is reported, which contains the largest number of Sb atoms in a POM so far. The Sb-rich POM has many interesting structural features and is a rare example of a soluble and water-stable giant POM. Biomedical studies indicate that the Sb-rich POM exhibits broad-spectrum antitumor activity against various cancer cell lines by reactivating the P53-dependent apoptotic processes and disrupting the mitochondrial membrane. In addition, this Sb-rich POM was capable of suppressing the growth and metastasis of a breast cancer in vivo. This work demonstrates that Sb-rich POMs are promising candidates for the development of new anticancer drugs.

Synthesis of Tin-Doped Three-Dimensional Flower-like Bismuth Tungstate with Enhanced Photocatalytic Activity.

Photocatalytic degradation of harmful organic matter is a feasible and environmentally friendly method. Bi2WO6 has become a hotspot of photocatalysts because of its unique layered structure and visible light response. In the present study, Sn doping was adopted to modified Bi2WO6 by hydrothermal method. The Sn-doped Bi2WO6 photocatalysts were characterized by XRD, SEM, TEM, BET, XPS, PL, and DRS, respectively. The results show that Sn-doped Bi2WO6 shows three-dimensional (3D) flower-like morphology, which is composed of two-dimensional (2D) nanosheets. Sn4+ ions enter into the Bi2WO6 lattice, producing a degree of Bi2WO6 lattice distortion, which is in favor of reducing the recombination of photogenerated electrons and holes. Moreover, the specific surface area of Bi2WO6 is significantly increased after doping, which is beneficial to providing more active sites. The photocatalytic results show that 2%Sn-Bi2WO6 exhibits the highest photocatalytic activity. After 60 min of irradiation, the photocatalytic degradation degree of methylene blue (MB) increases from 80.6% for pure Bi2WO6 to 92.0% for 2%Sn-Bi2WO6. The first-order reaction rate constant of 2%Sn-Bi2WO6 is 0.030 min-1, which is 1.7 times than that of pure Bi2WO6.