Toward Ultrahigh-Rate Energy Storage of 3000 mV s-1 in Hollow Carbon: From Methodology to Surface-to-Bulk Synergy Insights.

Despite great efforts on economical and functionalized carbon materials, their scalable applications are still restricted by the unsatisfying energy storage capability under high-rate conditions. Herein, theoretical and methodological insights for surface-to-bulk engineering of multi-heteroatom-doped hollow porous carbon (HDPC), with subtly designed Zn(OH)F nanoarrays as the template are presented. This fine-tuned HDPC delivers an ultrahigh-rate energy storage capability even at a scan rate of 3000 mV s-1 (fully charged within 0.34 s). It preserves a superior capacitance of 234 F g-1 at a super-large current density of 100 A g-1 and showcases an ultralong cycling life without capacitance decay after 50 000 cycles. Through dynamic and theoretical analysis, the key role of in situ surface-modified heteroatoms and defects in decreasing the K+-adsorption/diffusion energy barrier is clarified, which cooperates with the porous conductive highways toward enhanced surface-to-bulk activity and kinetics. In situ Raman aids in visualizing the reversibly dynamic adsorption/releasing of the electrolyte ions on the tailored carbon structure during the charge/discharge process. The potential of the design concept is further evidenced by the enhanced performances in water-in-salt electrolytes. This surface-to-bulk nanotechnology opens the path for developing high-performance energy materials to better meet the practical requirements in the future.

New Insight into the Electronic Effect for Cu Porphyrin Catalysts in Electrocatalytic of CO2 into CH4.

Perturbation of the copper (Cu) active site by electron manipulation is a crucial factor in determining the activity and selectivity of electrochemical carbon dioxide (CO2 ) reduction reaction (e-CO2 RR) in Cu-based molecular catalysts. However, much ambiguity is present concerning their electronic structure-function relationships. Here, three molecular Cu-based porphyrin catalysts with different electron densities at the Cu active site, Cu tetrakis(4-methoxyphenyl)porphyrin (Cu─T(OMe)PP), Cu tetraphenylporphyrin (Cu─THPP), and Cu tetrakis(4-bromophenyl)porphyrin (Cu─TBrPP), are prepared. Although all three catalysts exhibit e-CO2 RR activity and the same reaction pathway, their performance is significantly affected by the electronic structure of the Cu site. Theoretical and experimental investigations verify that the conjugated effect of ─OCH3 and ─Br groups lowers the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbitals (LUMO) gap of Cu─T(OMe)PP and Cu─TBrPP, promoting faster electron transfer between Cu and CO2 , thereby improving their e-CO2 RR activity. Moreover, the high inductive effect of ─Br group reduces the electron density of Cu active site of Cu─TBrPP, facilitating the hydrolysis of the bound H2 O and thus creating a preferable local microenvironment, further enhancing the catalytic performance. This work provides new insights into the relationships between the substituent group characteristics with e-CO2 RR performance and is highly instructive for the design of efficient Cu-based e-CO2 RR electrocatalysts.

Toward Ultrahigh-Rate Energy Storage of 3000 mV s-1 in Hollow Carbon: From Methodology to Surface-to-Bulk Synergy Insights.

Despite great efforts on economical and functionalized carbon materials, their scalable applications are still restricted by the unsatisfying energy storage capability under high-rate conditions. Herein, theoretical and methodological insights for surface-to-bulk engineering of multi-heteroatom-doped hollow porous carbon (HDPC) is presented, with subtly designed Zn(OH)F nanoarrays as the template. This fine-tuned HDPC delivers an ultrahigh-rate energy storage capability even at a scan rate of 3000 mV s-1 (fully charged within 0.34 s). It preserves a superior capacitance of 234 F g-1 at a super-large current density of 100 A g-1 and showcases an ultralong cycling life without capacitance decay after 50 000 cycles. Through dynamic and theoretical analysis, the key role of in situ surface-modified heteroatoms and defects in decreasing the K+ -adsorption/diffusion energy barrier is clarified, which cooperates with the porous conductive highways toward enhanced surface-to-bulk activity and kinetics. In situ Raman further aids in visualizing the reversibly dynamic adsorption/releasing of the electrolyte ions on the tailored carbon structure during the charge/discharge process. The potential of the design concept is further evidenced by the enhanced performances in water-in-salt electrolytes. This surface-to-bulk nanotechnology opens the path for developing high-performance energy materials to better meet the practical requirements in future.

Construction of Low-Coordination Cu-C2 Single-Atoms Electrocatalyst Facilitating the Efficient Electrochemical CO2 Reduction to Methane.

Constructing Cu single-atoms (SAs) catalysts is considered as one of the most effective strategies to enhance the performance of electrochemical reduction of CO2 (e-CO2 RR) towards CH4 , however there are challenges with activity, selectivity, and a cumbersome fabrication process. Herein, by virtue of the meta-position structure of alkynyl in 1,3,5-triethynylbenzene and the interaction between Cu and -C≡C-, a Cu SAs electrocatalyst (Cu-SAs/HGDY), containing low-coordination Cu-C2 active sites, was synthesized through a simple and efficient one-step method. Notably, this represents the first achievement of preparing Cu SAs catalysts with Cu-C2 coordination structure, which exhibited high CO2 -to-CH4 selectivity (72.1 %) with a high CH4 partial current density of 230.7 mA cm-2 , and a turnover frequency as high as 2756 h-1 , dramatically outperforming currently reported catalysts. Comprehensive experiments and calculations verified the low-coordination Cu-C2 structure not only endowed the Cu SAs center more positive electricity but also promoted the formation of H•, which contributed to the outstanding e-CO2 RR to CH4 electrocatalytic performance of Cu-SAs/HGDY. Our work provides a novel H⋅-transferring mechanism for e-CO2 RR to CH4 and offers a protocol for the preparation of two-coordinated Cu SAs catalysts.

Construction of Synergistic Ni3 S2 -MoS2 Nanoheterojunctions on Ni Foam as Bifunctional Electrocatalyst for Hydrogen Evolution Integrated with Biomass Valorization.

The intrinsic sluggish kinetics of the oxygen evolution reaction (OER) limit the improvement of hydrogen evolution reaction (HER) performance, and substituting the anodic oxidation of biomass materials is an alternative approach, given its lower oxidation potential and higher added value compared to those of OER. In this study, a Ni3 S2 -MoS2 nanoheterojunction catalyst with strong electronic interactions is prepared. It exhibits high efficiency for both the HER and the electrooxidation of 5-hydroxymethylfurfural (HMF). In a two-electrode cell with Ni3 S2 -MoS2 serving as both the anode and cathode, the potential is only 1.44 V at a current density of 10 mA cm-2 , which is much lower than that of pure water splitting. Density functional theory calculations confirm that the strong chemisorption of H and HMF at the interface leads to outstanding electrocatalytic activity. The findings not only provide a strategy for developing efficient electrocatalysts, but also provide an approach for the continuous production of high value-added products and H2 .

All-Organic Superhydrophobic Coating Comprising Raspberry-Like Particles and Fluorinated Polyurethane Prepared via Thiol-Click Reaction.

Mechanically robust superhydrophobic coatings have been extensively reported using chemically susceptible inorganic fillers like slica, titanium dioxide, and zinc oxide for constructing micro-nano structures. Organic particles are good candidates for improving chemical resistance, whereas the synthesis of organic particles with well-defined and stable micro-nano structures remains exclusive. Here, an all-organic, cross-linked superhydrophobic coating comprising raspberry-like fluorinated micro particles (RLFMP) and fluorinated polyurethane (FPU) is prepared via thiol-click reaction. Benefiting from the robust micro-nano structure of RLFMP and the excellent flexibility of FPU, the coating can maintain superhydrophobicity after severe alkali corrosion or mechanical damage, while the superhydrophobicity can be repaired readily by the fast recovery of micro-nano roughness and migration of branched fluoroalkyl chains to the coating surface. This design strategy is expected to provide a good application of thiol-click chemistry.

Recombinant Plasminogen Activator Modified Nanoparticles for Targeting Thrombolysis in Branch Retinal Vein Occlusion.

Branch Retinal Vein Occlusion (BRVO) is the second chronic branch retinal vascular disease that causes abnormal vision loss after acute branch retinal disease in type 2 diabetes. There is no scientific conclusion about its specific pathogenic mechanism at present. Most clinical scholars generally support the theory that the partial human anatomical structure and various systemic risk psychological factors cause insufficient oxygen supply and hemostasis in the local branch retinal arteries. The research results of this article aim to reconstruct a non-nanocell-targeted thrombolytic drug delivery system without modification of rtPA without polyethylene glycol-methyl polycaprolactone and to re-evaluate its thrombus targeting and dissolution. The effect and safety of thrombus provide a new strategy for realizing combined treatment of thrombus. It is a study on the targeting of rtPA-NP to thrombus and its thrombolytic properties. HPLC method was used to detect the binding of fibrin clot prepared in vitro with coumarin-6 labeled NP and rtPA-NP; immunofluorescence technique was used to observe the location of nanomedicine and fibrin clot in branch retinal vein occlusion model Condition. The rtPA-NP drug delivery system constructed in this study not only retains the activity of rtPA and good thrombus targeting but also significantly prolongs its half-life and simplifies the way of administration. The therapeutic efficiency of rtPA-NP thrombus targeted administration on branch retinal vein occlusion reached 85.64%. The successful construction of the rtPA-NP thrombus targeted drug delivery system provides a new way for thrombosis treatment and lays the foundation for the future combination of anticoagulants and vascular protection drugs to achieve the combined treatment of thrombosis and the development of safe and efficient thrombolytic drugs.

A clean process for selective recovery of copper from industrial wastewater by extraction-precipitation with p-tert-octyl phenoxy acetic acid.

A novel method for the selective removal and recovery of copper ion from copper-containing wastewater by extraction-precipitation with p-tert-octyl phenoxy acetic acid as a precipitant is presented. The morphology, thermal stability and solubility of POAA were synthesized and characterized. Then the application of POAA to precipitate copper from simulated copper-containing wastewater was studied. The effects of some factors (i.e., time, pH, temperature, dosage of precipitant) on copper precipitation efficiency (P%) and water solubility of POAA were discussed. The extraction-precipitation mechanism of POAA and Cu2+ was investigated by slope analysis combined with SEM, EDS, XPS and IR spectra. The concentration and purity of copper from industrial wastewater increased from 100.2 mg/L to 27,916 mg/L and 13.71%-93.01% respectively, treating by the proposed extraction-precipitation. Moreover, POAA revealed good stability in the recycling processes. Extraction-precipitation strategy is simple, efficient and sustainable, which can effectively reduce the volume of sludge in the process of wastewater treatment and produce copper concentrated solution with industrial value, which has revealed application potential for the clean production of copper smelting enterprises.

The enrichment of rare earth from magnesium salt leaching solution of ion-adsorbed type deposit: A waste-free process for removing impurities.

Due to the complex composition of ion-adsorbed type rare earth ore leaching solution, there are challenges in the process of rare earth (RE) separation, such as large RE loss rate, low product purity, radioactive residue and so on. In this article, 8-hydroxyquinoline modified silica gel (HQ-SiO2) and 2,2'-(1,4-phenylenebis(oxy)) dioctanoic acid (PPBOA) were used to form an efficient process for impurities removal and RE enrichment. Solid phase extraction successfully intercepted 96.7% of the radioactive element thorium. The concentration of aluminium was reduced to 2.14 ppm by frank chromatography. Rare earth elements were enriched from 336.35 mg/L to 237.75 g/L by extraction-precipitation, that is, the enrichment multiple reached more than 700 and the proportion of RE was increased from 21.85% to 96.62%. The loss rate of RE was controlled below 1.59%. Moreover, the magnesium salt leaching solution could be recycled for the leaching of RE ores. Although some liquid waste need to be treated in the processes of HQ-SiO2 production and regeneration, the integrated process helps to decrease volatile organic solvent, acid-base consumption, wastewater and waste residue. It is an environment-friendly RE enrichment and impurity removal process, which shows application potential in the production field of ion-adsorbed type rare earth mineral products.

Nanoenzyme-Reinforced Injectable Hydrogel for Healing Diabetic Wounds Infected with Multidrug Resistant Bacteria.

Diabetic wound healing remains a critical challenge due to its vulnerability to multidrug-resistant (MDR) bacterial infection, as well as the hyperglycemic and oxidative wound microenvironment. Herein, an injectable multifunctional hydrogel (FEMI) was developed to simultaneously overcome these hurdles. The FEMI hydrogel was fabricated through a Schiff-based reaction between ε-polylysine (EPL)-coated MnO2 nanosheets (EM) and insulin-loaded self-assembled aldehyde Pluronic F127 (FCHO) micelles. Through a synergistic combination of EPL and "nanoknife-like" MnO2 nanosheets, the FEMI hydrogel exhibited extraordinary antimicrobial capacities against MDR bacteria. The MnO2 nanoenzyme reshaped the hostile oxidative wound microenvironment by decomposing the endogenous H2O2 into O2. Meanwhile, the pH/redox dual-responsive FEMI hydrogel achieved a sustained and spatiotemporal controlled release of insulin to regulate the blood glucose. Our FEMI hydrogel demonstrated an accelerated MDR bacteria-infected diabetic wound healing in vivo and represents a versatile strategy for healing a broad range of tissue damages caused by diabetes.

Surface Microstructure Regulation of Porous Polymer Microspheres by Volume Contraction of Phase Separation Process in Traditional Suspension Polymerization System.

In the present work, the suspension polymerization method is used for the preparation of porous polymer microspheres with different surface morphology, and the preparation mechanism is systematically expounded. The morphology results show that the smooth, convex, and wrinkled microspheres could be controlled by adjusting the ratio of monomer to porogens. The micelles forming the framework support the "Eggshell," and its size and shape directly affect the morphology of "Eggshell." The addition of monomers (GMA), whose polymer has low glass transition temperature (Tg ), is important for the formation of wrinkled morphology. The amount of toluene and polydimethylsiloxane also affects the surface morphology of microspheres. In addition, the effect of polydimethylsiloxane is also more significant. The preparation process of the wrinkled P(GMA-St-EGDA) microspheres with abundant epoxy groups can be amplified. The morphology of the material prepared in the 100 L reactor is well maintained, and the yield in the size range of 80-160 µm is more than 80%. The surface wrinkled porous polymer microspheres have potential applications in the fields of enzyme carrier, separation and purification, and light scattering.

Retraction: Yang, C., et al. miR-126 Functions as a Tumor Suppressor in Osteosarcoma by Targeting Sox2. Int. J. Mol. Sci. 2014, 15, 423-437, doi:10.3390/ijms15010423.

Experimental results from [...].

MicroRNA-224 promotes the sensitivity of osteosarcoma cells to cisplatin by targeting Rac1.

Osteosarcoma is the most common primary bone tumour in children and adolescents. Accumulating evidence has shown that microRNAs (miRNAs) participate in the development of almost all types of cancer. Here, we investigated the role of miR-224 in the development and progression of osteosarcoma. We demonstrated that miR-224 was down-regulated in osteosarcoma cell lines and tissues. Lower miR-224 levels were correlated with shorter survivalin osteosarcoma patients. Furthermore, overexpression of miR-224 suppressed osteosarcoma cell proliferation, migration and invasion and contributed to the increased sensitivity of MG-63 cells to cisplatin. We identified Rac1 as a direct target gene of miR-224 in osteosarcoma. Rac1 expression was up-regulated in the osteosarcoma cell lines and tissues, and there was an inverse correlation between Rac1 and miR-224 expression in osteosarcoma tissues. Furthermore, rescuing Rac1 expression decreased the sensitivity of miR-224-overexpressing MG-63 cells to cisplatin. We also demonstrated that ectopic expression of Rac1 promoted the proliferation, migration and invasion of miR-224-overexpressing MG-63 cells. These data suggest that miR-224 plays a tumour suppressor role in the development of osteosarcoma and is related to the sensitivity of osteosarcoma to cisplatin.

Large-Scale Fabrication of Polymer Microcavities with Adjustable Openings and Surface Roughness Regulated by the Polarity of both Seed Surface and Monomers.

Polymer microcavities with adjustable openings and surface roughness are fabricated on a large scale via single-hole poly(glycidyl methacrylate) (PGMA) swelling seed particles. The size of openings of these microcavities can be adjusted by changing the amount of hydrophilic monomer, and the degree of surface roughness is easily regulated relying on the adjustment of the polarity of monomer. Furthermore, the morphology of PGMA/poly(styrene-methacrylic acid) (PGMA/P(S-MAA)) microparticles from microcavity to erythrocyte shape is controlled by the polarity of seed surface. From transmission electron microscopy images of PGMA/P(S-MAA) microparticles, a fresh polymer particle appears in the cavity. To confirm this phenomenon, thermal annealing process in dioxane/water solution is carried out. Considering the flexibility of polymers, the openings and closing of the prepared microparticles are regulated following the increase in volume ratio of dioxane/water. Ball-in-bowl-shaped PGMA/P(S-MAA) microparticles are further presented, which proves secondary nucleation of monomer in the polymerization stage.

Bovine serum albumin surface imprinted polymer fabricated by surface grafting copolymerization on zinc oxide rods and its application for protein recognition.

A novel bovine serum albumin (BSA) surface imprinted polymer based on ZnO rods was synthesized by surface grafting copolymerization. It exhibited an excellent recognition performance to bovine serum albumin. The adsorption capacity and imprinting factor of bovine serum albumin could reach 89.27 mg/g and 2.35, respectively. Furthermore, the fluorescence property of ZnO was used for tracing the process of protein imprinting and it implied the excellent optical sensing property of this material. More importantly, the hypothesis that the surface charge of carrier could affect the imprinting process was confirmed. That is, ZnO with positive surface charge could not only improve the recognition specificity of binding sites to template proteins (pI < 7), but also deteriorate the bindings between sites and non-template proteins (pI > 7). It was also important that the reusability of ZnO@BSA molecularly imprinted polymers was satisfactory. This implied that the poor mechanical/chemical stability of traditional zinc oxide sensors could be solved by the introduction of surface grafting copolymerization. These results revealed that the ZnO@BSA molecularly imprinted polymers are a promising optical/electrochemical sensor element.

Steroid receptor co-activator-3 promotes osteosarcoma progression through up-regulation of FoxM1.

Increasing evidence suggests that the three homologous members of steroid receptor co-activator (SRC) family (SRC-1, SRC-2, and SRC-3) play key roles in enhancing cell proliferation in various human cancers, such as breast, prostate, and hepatocellular carcinoma. However, the function of SRC-3 in osteosarcoma remains largely unexplored. In the current study, we found that SRC-3, but not SRC-1 and SRC-2, was dramatically up-regulated in human osteosarcoma tissues, compared with adjacent normal tissues. To explore the functions of SRC-3 in osteosarcoma, in vitro studies were performed in MG63 and U2OS cells. SRC-3 overexpression promoted osteosarcoma cell proliferation, whereas knockdown of SRC-3 inhibits its proliferation. In support of these findings, we further demonstrated that SRC-3 up-regulated FoxM1 expression through co-activation of C/EBPγ. Together our results show that SRC-3 drives osteosarcoma progression and imply it as a therapeutic target to abrogate osteosarcoma.

An eco-friendly and high-yield extraction of rare earth from the leaching solution of ion adsorbed minerals.

Ion-adsorbed rare earth minerals are rich in medium and heavy rare earth (RE), which are important strategic resources. In this article, a novel approach for the extraction of RE from ion adsorbed minerals was developed. Through a comprehensive assessment of their extraction and separation performance, the hydrophobic deep eutectic solvents (HDES) with a composition of trioctylphosphine oxide (TOPO): dodecanol (LA): 2-thiophenoyltrifluoroacetone (HTTA) = 1:1:1 was determined as the optimal configuration. Under optimized conditions, only RE were extracted by the HDES, while Al, Ca, Mg were not extracted at all. The HDES based extraction obviated the need for diluent such as kerosene, eliminating the generation of impurity removal residues. The RE in the stripping solution could be successfully enriched by saponified lauric acid, achieving an impressive precipitation rate of 99.7%. The RE precipitate underwent further enrichment, resulting in a RE concentration of 176 g/L (REO = 210 g/L). Unlike industrial precipitants such as oxalic acid and ammonium bicarbonate, lauric acid can be effectively recycled, thereby avoiding a large amount of wastewater and carbon dioxide emissions. The obtained RE solution product exhibits high yield and purity, this study provides an eco-friendly and high-yield approach for extracting RE.

Efficacy and safety of 0.01% atropine combined with orthokeratology lens in delaying juvenile myopia: An observational study.

It aims to study the efficacy and safety of low-concentration Atropine combined with orthokeratology (OK) lens in delaying juvenile myopia. This is a prospective study, 172 adolescents aged 8 to 12 years who were admitted to the diopter department of Hengshui People Hospital from April 2021 to May 2022 were selected. According to the equivalent spherical diopter measured at the time of initial diagnosis, myopic patients were randomly divided into low myopia group (group A) and moderate myopia group (group B). At the same time, according to the different treatment methods, the patients were divided into the group wearing frame glasses alone (group c), the group wearing frame glasses with low-concentration Atropine (group d), the group wearing corneal shaping glasses alone at night (group e), and the group wearing corneal shaping glasses at night with low-concentration Atropine (group f). The control effect of myopia development and axial elongation in group f was better than that in groups d and e (P < .05). The effect of controlling myopia development and axial elongation in group f is with P > .05. The probability of postoperative adverse reactions in group f was lower and lower than that in the other groups. Low-concentration atropine combined with OK lens could effectively delay the development of juvenile myopia, and had a high safety. Low-concentration of Atropine would not have a significant impact on the basic tear secretion and tear film stability. Nightwear of OK lens also had no significant impact, but it would significantly reduce the tear film rupture time in the first 3 months, and at the same time, the tear film rupture time would be the same after 6 months as before treatment.

Synthesis of raspberry-like poly(styrene-glycidyl methacrylate) particles via a one-step soap-free emulsion polymerization process accompanied by phase separation.

We herein report a facile method to prepare raspberry-like poly(styrene-glycidyl methacrylate) [P(S-GMA)] particles with controllable structure via a one-step soap-free emulsion polymerization process accompanied by phase separation. In this method, corona particles with a size of 10-20 nm were produced in situ in the later polymerization stage by the migrating of S-enriched polymers from GMA-enriched core particles. The size of the corona particles and the roughness of the raspberry-like particles can be easily controlled by adjusting the amount of styrene (S), glycidyl methacrylate (GMA), and divinylbenzene (DVB). The structure of raspberry-like P(S-GMA) particles was confirmed by transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. A possible mechanism of the formation of raspberry-like particles was proposed.

miR-126 functions as a tumor suppressor in osteosarcoma by targeting Sox2.

Osteosarcoma (OS) is the most common malignant bone tumor in children and young adults, the early symptoms and signs of which are non-specific. The discovery of microRNAs (miRNAs) provides a new avenue for the early diagnosis and treatment of OS. miR-126 has been reported to be highly expressed in vascularized tissues, and is recently widely studied in cancers. Herein, we explored the expression and significance of miR-126 in OS. Using TaqMan RT-PCR analysis, we analyzed the expression of miR-126 in 32 paired OS tumor tissues and 4 OS cell lines and found that miR-126 was consistently under-expressed in OS tissues and cell lines compared with normal bone tissues and normal osteoblast cells (NHOst), respectively. As miR-126 is significantly decreased in OS tissues and cell lines, we sought to compensate for its loss through exogenous transfection into MG-63 cells with a miR-126 mimic. Ectopic expression of miR-126 inhibited cell proliferation, migration and invasion, and induced apoptosis of MG-63 cells. Moreover, bioinformatic prediction suggested that the sex-determining region Y-box 2 (Sox2) is a target gene of miR-126. Using mRNA and protein expression analysis, luciferase assays and rescue assays, we demonstrate that restored expression of Sox2 dampened miR-126-mediated suppression of tumor progression, which suggests the important role of miR-126/Sox2 interaction in tumor progression. Taken together, our data indicate that miR-126 functions as a tumor suppressor in OS, which exerts its activity by suppressing the expression of Sox2.