Insights into mechanism of peroxymonosufate activation by Mo single-atom catalysts: Singlet oxygen evolution and role of Mo-N coordination.

Recently, the Fenton-like reaction using peroxymonosulfate (PMS) has been acknowledged as a potential method for breaking down organic pollutants. In this study, we successfully synthesized a highly efficient and stable single atom molybdenum (Mo) catalyst dispersed on nitrogen-doped carbon (Mo-NC-0.1). This catalyst was then utilized for the first time to activate PMS and degrade bisphenol A (BPA). The Mo-NC-0.1/PMS system demonstrated the ability to completely degrade BPA within just 20 min. Scavenging tests and density functional theory (DFT) calculations have demonstrated that the primary reactive oxygen species was singlet oxygen (1O2) produced by Mo-N4 sites. The self-cycling of Mo facilitated PMS activation and the transition from a free radical activation pathway to a non-radical pathway mediated by 1O2. Simultaneously, the nearby pyridinic N served as adsorption sites to immobilize BPA and PMS molecules. The exceptionally high catalytic activity of Mo-NC-0.1 derived from its unique Mo-N coordination, which markedly reduced the distance for 1O2 to migrate to the BPA molecules. The Mo-NC-0.1/PMS system effectively reduced the acute toxicity of BPA and exhibited excellent cycling stability with minimal leaching. This study presented a new catalyst with high selectivity for 1O2 generation and provided valuable insights for the application of single atom catalysts in PMS-based AOPs.

Self-Organized Spatiotemporal Mineralization of Hydrogel: A Simulant of Osteon.

Nature creates fascinating self-organized spatiotemporal patterns through the delicate control of reaction-diffusion dynamics. As the primary unit of cortical bone, osteon has concentric lamellar architecture, which plays a crucial role in the mechanical and physiological functions of bone. However, it remains a great challenge to fabricate the osteon-like structure in a natural self-organization way. Taking advantage of the nonequilibrium reaction in hydrogels, a simple mineralization strategy to closely mimic the formation of osteon in a mild physiological condition is developed. By constructing two reverse concentration gradients of ions from periphery to interior of cylindrical hydrogel, spatiotemporal self-organization of calcium phosphate in concentric rings is generated. It is noteworthy that minerals in different layers possess diverse contents and crystalline phases, which further guide the adhesion and spread of osteoblasts on these patterns, resembling the architecture and cytological behavior of osteon. Besides, theoretical data indicates the predominate role of ion concentrations and pH values of solution, in good accordance with experimental results. Independent of precise instruments, this lifelike method is easily obtained, cost-efficient, and effectively imitates the mineral deposition in osteon from a physiochemical view. The strategy may be expanded to develop other functional material patterns via spatiotemporal self-organization.

Development and validation of a clinical prediction model for glioma grade using machine learning.

BACKGROUND: Histopathological evaluation is currently the gold standard for grading gliomas; however, this technique is invasive. OBJECTIVE: This study aimed to develop and validate a diagnostic prediction model for glioma by employing multiple machine learning algorithms to identify risk factors associated with high-grade glioma, facilitating the prediction of glioma grading. METHODS: Data from 1114 eligible glioma patients were obtained from The Cancer Genome Atlas (TCGA) database, which was divided into a training set (n= 781) and a test set (n= 333). Fifty machine learning algorithms were employed, and the optimal algorithm was selected to construct a prediction model. The performance of the machine learning prediction model was compared to the clinical prediction model in terms of discrimination, calibration, and clinical validity to assess the performance of the prediction model. RESULTS: The area under the curve (AUC) values of the machine learning prediction models (training set: 0.870 vs. 0.740, test set: 0.863 vs. 0.718) were significantly improved from the clinical prediction models. Furthermore, significant improvement in discrimination was observed for the Integrated Discrimination Improvement (IDI) (training set: 0.230, test set: 0.270) and Net Reclassification Index (NRI) (training set: 0.170, test set: 0.170) from the clinical prognostic model. Both models showed a high goodness of fit and an increased net benefit. CONCLUSION: A strong prediction accuracy model can be developed using machine learning algorithms to screen for high-grade glioma risk predictors, which can serve as a non-invasive prediction tool for preoperative diagnostic grading of glioma.

Preparation of biochar derived from waste cotton woven by low-dosage Fe(NO3)3 activation: characterization, pore development, and adsorption.

Currently, researchers are looking for efficient and sustainable methods to synthesize biochar for the adsorption of pollutants. In this study, biochar with high specific surface area, tunable pore structure, and abundant functional groups were prepared from waste cotton woven (WCW) using low-dosage Fe(NO3)3 activation at 400-900 °C. The biochar obtained at 800 °C possessed the excellent specific surface area of 1167.37 m2/g with a unique micro-mesoporous structure. XRD analysis showed that the Fe species changed from Fe2O3 to Fe3O4 and then Fe0 with the increase of pyrolysis temperature. TEM images further confirmed the template effect of iron oxides for mesoporous formation. The effect of Fe(NO3)3 on the pyrolysis pathway of waste cotton woven was systematically investigated by TG and XPS analyses to explore the pore development of biochar. The results indicated that Fe(NO3)3 could enhance the dehydration, decarbonylation and dehydroxylation of WCW components, thereby reducing the temperature required for WCW pyrolysis. Moreover, the synergistic effect of Fe and N species improved the development of microporous and mesoporous structure through carbon structure corrosion and reorganization, and volatile release. Additionally, satisfactory adsorption capacity for Eriochrome Black T (456.01 mg/g) of the prepared biochar was obtained at 25 °C. This study demonstrated that low-dosage Fe(NO3)3 activation of waste cotton woven could be used as a facile method to prepare promising inexpensive biochar for contaminants removal.

A hydrogel gripper enabling fine movement based on spatiotemporal mineralization.

Fine tailoring of the subtle movements of a hydrogel actuator through simple methods has widespread application prospects in wearable electronics, bionic robots and biomedical engineering. However, to the best of our knowledge, this challenge is not yet completed. Inspired by the diffusion-reaction process in nature, a hydrogel gripper with the capability of fine movement was successfully prepared based on the spatiotemporal fabrication of the polypyrrole (PPY) pattern in a poly (N-isopropylacrylamide) (PNIPAM) hydrogel. The hydrogel was given gradient porous structures using a one-step UV irradiation method. Moreover, photothermal PPY patterns on the hydrogel were obtained through spatiotemporal mineralization of ferric hydroxide followed by the polymerization of pyrrole in a controllable manner. Taking advantage of the unique structures, the hydrogel gripper can not only achieve reversible grasping-releasing of substrates with the tuning of temperature (similar to that of hands), but also generate delicate movement under the irradiation of light (resembling that of finger joints). The strategy reported here is easily accessible and there is no need for sophisticated templates, therefore making it superior to other existing methods. We believe this work will provide references for the design and application of more advanced soft actuators.

Mild-temperature photothermal assisted CuSi nanowires for promoting infected wound healing.

In clinical practice, the utilization of antibiotics is still the main approach for the treatment of wound contamination, which lacks the ability to accelerate wound healing and arises the global concern of antimicrobial resistance. Plenty of alternative methods have been explored in recent years due to the fast development of material science. Here, CuO/SiO2 nanowires (CuSi NWs) with good near-infrared (NIR) photothermal conversion ability are synthesized by a one-step hydrothermal method. The as-prepared CuSi NWs possess excellent antibacterial ability against both Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), which could be enhanced by the assistance of mild photothermal therapy (PTT). Moreover, CuSi NWs at suitable concentrations can promote proliferation, migration, and angiogenic gene expression of human umbilical vein endothelial cells (HUVECs), exhibiting a remarkable pro-vascularization ability. The in vivo mouse infect model further proves that the CuSi NWs might be a good candidate for the treatment of infected wounds as the high antibacterial efficiency and accelerated wound healing is obtained.

Chitosan based photothermal scaffold fighting against bone tumor-related complications: Recurrence, infection, and defects.

After bone tumor resection, the severe complications including cancer recurrence, infection and extensive bone loss are still a challenge. To address this problem, a chitosan/hydroxypropyltrimethyl ammonium chloride chitosan/hydroxyapatite/black phosphorus (CS/HC/HA/BP) hybrid photothermal scaffold with a multistage photothermal strategy was developed. HC-stabilized BP endowed the scaffold with simultaneous antitumor/antibacterial properties under photothermal stimulation of <50 °C. Subsequently, excellent osteogenesis could be achieved with mild hyperthermia stimulation (∼42 °C) through up-regulating the expressions of heat shock proteins. Under NIR irradiation, the scaffold could eliminate 95 % of osteosarcoma cells as well as 97 % of E. coli and 92 % of S. aureus. The osteogenic gene expressions of ALP, COL 1A1, and OCN in photothermal group were 1.64, 1.31 and 1.27 folds higher than that of non-photothermal group in vivo, respectively. Therefore, the obtained scaffold synergized with multistage photothermal strategy was effective and a reference for the treatment of other complex diseases.

Chloroplast-inspired Scaffold for Infected Bone Defect Therapy: Towards Stable Photothermal Properties and Self-Defensive Functionality.

Bone implant-associated infections induced by bacteria frequently result in repair failure and threaten the health of patients. Although black phosphorus (BP) material with superior photothermal conversion ability is booming in the treatment of bone disease, the development of BP-based bone scaffolds with excellent photothermal stability and antibacterial properties simultaneously remains a challenge. In nature, chloroplasts cannot only convert light into chemical energy, but also hold a protective and defensive envelope membrane. Inspired by this, a self-defensive bone scaffold with stable photothermal property is developed for infected bone defect therapy. Similar to thylakoid and stroma lamella in chloroplasts, BP is integrated with chitosan and polycaprolactone fiber networks. The mussel-inspired polydopamine multifunctional "envelope membrane" wrapped above not only strengthens the photothermal stability of BP-based scaffolds, but also realizes the in situ anchoring of silver nanoparticles. Bacteria-triggered infection of femur defects in vivo can be commendably inhibited at the early stage via these chloroplast-inspired implants, which then effectively promotes endogenous repair of the defect area under mild hyperthermia induced by near-infrared irradiation. This chloroplast-inspired strategy shows outstanding performance for infected bone defect therapy and provides a reference for the functionality of other biomedical materials.

Direct Current Stimulation for Improved Osteogenesis of MC3T3 Cells Using Mineralized Conductive Polyaniline.

Hydroxyapatites (HAPs) are usually coated on the surface of an implant to improve the osseointegration with defect bone tissue. Besides, conducting polymers have the advantages of good conductivity, reasonable biocompatibility, and easy of modification, which endow them applicable to electrical stimulation therapy. However, it still remains a great challenge to fabricate hybrid coating combing HAP with conducting polymer on implant surface efficiently. In this work, phytic acid-doped polyaniline (PANI) were successfully synthesized on medical titanium (Ti) sheets. By virtue of the abundant anodic phosphoric groups of phytic acid, HAP nanocrystals were biomineralized on PANI. The PANI-HAP hybrid layer exhibits good cell compatibility with MC3T3 cells. More importantly, HAP nanocrystals and PANI operate synergistically on cell proliferation and osteogenesis through electrical stimulation. Alkaline phosphatase activity and extracellular calcium contents of cells on PANI-HAP display 3-fold and 2.6-fold increases, compared with bare Ti sheets, respectively. The valid integration of mineralization and electrical stimulation in this work renders an efficient strategy for implant coating, which might have potential applications in bone-related defects.

Heterogenous hydrogel mimicking the osteochondral ECM applied to tissue regeneration.

Inspired by the intricate extracellular matrix (ECM) of natural cartilage and subchondral bone, a heterogenous bilayer hydrogel scaffold is fabricated. Gelatin methacrylate (GelMA) and acryloyl glucosamine (AGA) serve as the main components in the upper layer, mimicking the chondral ECM. Meanwhile, vinylphosphonic acid (VPA) as a non-collagen protein analogue is incorporated into the bottom layer to induce the in situ biomineralization of calcium phosphate. The two heterogenous layers are effectively sutured together by the inter-diffusion between the upper and bottom layer hydrogels, together with chelation between the calcium ions and alginate added to separate layers. The interfacial bonding between the two different layers was thoroughly investigated via rheological measurements. The incorporation of AGA promotes chondrocytes to produce collagen type II and glycosaminoglycans and upregulates the expression of chondrogenesis-related genes. In addition, the minerals induced by VPA facilitate the osteogenesis of bone marrow mesenchymal stem cells (BMSCs). In vivo evaluation confirms the biocompatibility of the scaffold with minor inflammation and confirms the best repair ability of the bilayer hydrogel. This cell-free, cost-effective and efficient hydrogel shows great potential for osteochondral repair and inspires the design of other tissue-engineering scaffolds.

Template-Directing Coupled with Chemical Activation Methodology-Derived Hexagon-like Porous Carbon Electrode with Outstanding Compatibility to Electrolytes and Low-Temperature Performance.

The conversion of asphalt into hexagon-like porous carbon (HPC) with a micro-mesoporous structure is realized by the coupling of template-directing and chemical activation methodologies. The specific surface area of HPC can reach up to 1356 m2 g-1 even at such a low-proportioned dosage of activator (0.5-fold) and is also larger than those of template-directed carbon and activation-derived carbon, as it benefited from the coupling merits of template-directing and chemical activation. Excellent capacitive-energy-storage behavior with respect to rate capability, capacitance retention, and durability are delivered by HPC//HPC symmetric supercapacitors assembled with aqueous and organic electrolytes. This great compatibility for different kinds of electrolytes and electrode properties is owed to the robust hexagon-like microarchitecture feature associated with hierarchical pore structure, which not only hinders the stacking between each other but also provides a buffer function for the volume variation and sufficient active sites for the storage of electrolyte ions. The drastic temperature variation has almost no influence on the diffusion and transfer rate of electrolyte ions, further evidencing the advanced feature of the hierarchical pore structure. Additionally, HPC//Li4Ti5O12 LIC assembled with the Li-based electrolyte also presents a superior Ragone performance. The coexistence of micro- and mesopores for the HPC makes it an attractive electrode material for various capacitive-energy-storage devices. This work provides a promising way to realize the plasticity of pore channels and mass production of high capacitive storage ability of electrode material via the combination of template-directing and chemical activation strategies.

The diagnostic value of quantitative analysis of ASL, DSC-MRI and DKI in the grading of cerebral gliomas: a meta-analysis.

OBJECTIVE: To perform quantitative analysis on the efficacy of using relative cerebral blood flow (rCBF) in arterial spin labeling (ASL), relative cerebral blood volume (rCBV) in dynamic magnetic sensitivity contrast-enhanced magnetic resonance imaging (DSC-MRI), and mean kurtosis (MK) in diffusion kurtosis imaging (DKI) to grade cerebral gliomas. METHODS: Literature regarding ASL, DSC-MRI, or DKI in cerebral gliomas grading in both English and Chinese were searched from PubMed, Embase, Web of Science, CBM, China National Knowledge Infrastructure (CNKI), and Wanfang Database as of 2019. A meta-analysis was performed to evaluate the efficacy of ASL, DSC-MRI, and DKI in the grading of cerebral gliomas. RESULT: A total of 54 articles (11 in Chinese and 43 in English) were included. Three quantitative parameters in the grading of cerebral gliomas, rCBF in ASL, rCBV in DSC-MRI, and MK in DKI had the pooled sensitivity of 0.88 [95% CI (0.83,0.92)], 0.92 [95% CI (0.83,0.96)], 0.88 [95% CI (0.82,0.92)], and the pooled specificity of 0.91 [95% CI (0.84,0.94)], 0.81 [95% CI (0.73,0.88)], 0.86 [95% CI (0.78,0.91)] respectively. The pooled area under the curve (AUC) were 0.95 [95% CI (0.93,0.97)], 0.91 [95% CI (0.89,0.94)], 0.93 [95% CI (0.91,0.95)] respectively. CONCLUSION: Quantitative parameters rCBF, rCBV and MK have high diagnostic accuracy for preoperative grading of cerebral gliomas.

Programmed antibacterial and mineralization therapy for dental caries based on zinc-substituted hydroxyapatite/ alendronate-grafted polyacrylic acid hybrid material.

The domination of cariogenic bacteria in dental plaque biofilms is the primary cause of dental caries. In view of this, for the purpose of an effective treatment of dental caries, it is of great importance to inhibit the activity of acidogenic bacteria and promote the remineralization of damaged teeth simultaneously. However, the expensive antibacterial agents and poor mineralization ability of materials limit the practical applications. Biomineralization regulated by non-collagenous proteins (NCPs) gives hints to combine the remineralization ability of NCPs with accessible antibacterial property effectively. In this work, we propose a programmed antibacterial and remineralization strategy for the therapy of dental caries based on zinc-substituted hydroxyapatite/ alendronate-grafted polyacrylic acid hybrid nanoneedles (ZHA@ALN-PAA). This hybrid material dissolves in the acidic caries environment and regulate the pH to nearly neutral (6.5). Abundant calcium/ phosphate ions are supplemented and the ALN-PAA embedded in it has also been released, which assists the biomineralization on tooth defect. It has been revealed that the inhibition ratio of ZHA@ALN-PAA against Streptococcus mutans is the highest (11.25 folds that of HA), which originates from the highest zinc ions released (132.9 mg/L). Besides, the interspace of etched enamel is fully filled with regenerated nanorods and the surface microhardness (SMH) is significantly improved (3.68 folds that of etched enamel) after only 3 days of mineralization in vitro. This strategy developed here is simple and cost-effective, which can be referred to design the effective anti-caries materials applied for clinic treatment and daily oral care.