Abstract  The aims of this study were to investigate the occurrence and distribution of total mercury (Hg) and other trace elements of environmental concern, such as arsenic (As), copper (Cu), chromium (Cr), manganese (Mn), nickel (Ni), lead (Pb), zinc (Zn) and vanadium (V), in soils from the abandoned Merník cinnabar mine in eastern Slovakia. For this purpose, thirty soil samples from two depth intervals within the mine area (n = 60 soil samples) and additional sixteen soil samples from adjacent areas (n = 25 soil samples) were collected. Total Hg was measured by atomic absorption spectrometry, while As and other metals were analyzed using inductively coupled plasma atomic emission spectrometry. High mercury concentrations (> 100 mg/kg with a maximum of 951 mg/kg) were observed only in surface soils close to mine waste heaps and adits. Otherwise, Hg concentrations in the majority of surface soils were lower (0.14-19.7 mg/kg), however, higher than Hg in soils collected from sites outside the mine area (0.19-6.92 mg/kg) and even considerably higher than Hg in soils at sites not influenced by the Merník mine. Elevated Cr and Ni concentrations in soils regardless of their sampling sites (mean of 276 mg/kg and median of 132 mg/kg for Cr and 168 mg/kg and 81 mg/kg for Ni, respectively) were attributed to the lithology of the area; the soils are underlain by the sediments of the Central Carpathian Palaeogene, containing a detritus of ultrabasic rocks. As our geochemical data are compositional in nature, they were further treated by compositional data analysis (CoDA). Robust principal component analysis (RPCA) applied on centred (clr) log-ratio-transformed data and correlation analysis of compositional parts based on symmetric balances distinguished very well different sources of origin for the chemical elements. The following three element associations were identified: Hg association with the main source in mining/roasting, Cr-Ni association derived from bedrock and As-Cu-Mn-Pb-Zn-V association (natural background and minor sulphides/sulfosalts in mineralized rocks). The values of geoaccumulation index and enrichment factor suggested that concentrations of Hg in the soils were influenced by human industrial activities.

Abstract  The evaluation of plants occurring naturally at contaminated environments are essential for applying this species in remediation techniques. In this context, the Sagittaria montevidensis with potential for phytoremediation was studied at an anthropogenic polluted stream in southern Brazil. The nutrients and heavy metal content were determined in the phytomass. The phytoremediation indexes were evaluated such as bioconcentration factor (BCF), translocation factor (TF), plant effective number (PEN), and potential phytoremoval (mg m-2). The S. montevidensis was then detected as presenting natural phytoextraction ability for potassium and calcium elements and also demonstrated rhizofiltration potential for phosphorus, manganese, aluminum, vanadium, sulfur, iron, arsenic, copper, magnesium, zinc, sodium, lead, cadmium, nickel, chromium, considering its ability of bioaccumulating these contaminants and retain high levels in the roots. The highest potential for bioremoval (mg m-2) of the S. montevidensis was detected for potassium and calcium (recommending thus the use for phytoextraction) and for aluminum, phosphorus, iron, magnesium, sulfur, and sodium, along with heavy metals (recommended for rhizofiltration). The S. montevidensis decontamination ability, along with its biomass production and its adaptability represents a great advance in order to the recovery of this degraded area and possible application in other contaminated watercourses in Brazil.

Abstract  This study aimed to determine the effect of exposure to heavy metals in pregnant women in Beijing, China. We also evaluated the association of these heavy metals with birth weight and length of newborns. We measured the levels of 10 heavy metals, including lead (Pb), titanium (Ti), manganese (Mn), nickel (Ni), cadmium (Cd), chromium (Cr), antimony (Sb), stannum (Sn), vanadium (V), and arsenic (As), in 156 maternal and cord blood pairs. An inductively coupled plasma mass spectrometry method was used for measurement. Pb, As, Ti, Mn, and Sb showed high detection rates (>50%) in both maternal and cord blood. Fourteen (9%) mothers had blood Pb levels greater than the United States Center for Disease Control allowable threshold limit for children (50 μg/L). In prenatal exposure to these heavy metals, there was no significant association between any heavy metal and birth weight/length. Moreover, we estimated the placental transfer efficiency of each heavy metal, and the median placental transfer efficiency ranged from 49.6% (Ni) to 194% (Mn) (except for Cd and Sn). The level and detection rate of Cd in maternal blood were much higher than that in cord blood, which suggested that Cd had difficulty in passing the placental barrier. Prospective research should focus on the source and risk of heavy metals in non-occupationally exposed pregnant women in Beijing.

Abstract  The discoveries of intrinsic ferromagnetism in atomically thin van der Waals crystals have opened a new research field enabling fundamental studies on magnetism at two-dimensional (2D) limit as well as development of magnetic van der Waals heterostructures. Currently, a variety of 2D ferromagnetism has been explored mainly by mechanically exfoliating "originally ferromagnetic (FM)" van der Waals crystals, while a bottom-up approach by thin-film growth technique has demonstrated emergent 2D ferromagnetism in a variety of "originally non-FM" van der Waals materials. Here we demonstrate that V5Se8 epitaxial thin films grown by molecular-beam epitaxy exhibit emergent 2D ferromagnetism with intrinsic spin polarization of the V 3d electrons despite that the bulk counterpart is "originally antiferromagnetic". Moreover, thickness-dependence measurements reveal that this newly developed 2D ferromagnet could be classified as an itinerant 2D Heisenberg ferromagnet with weak magnetic anisotropy, broadening a lineup of 2D magnets to those potentially beneficial for future spintronics applications.

Abstract  Controlling the surface is necessary to adjust the essential properties and desired functions of nanomaterials and devices. For nanostructured multivalent vanadium oxides, unwanted surface oxidation occurs at ambient atmosphere generally and needs to be suppressed or avoided. We describe the suppressed surface oxidation of VO2 nanostructures through blocking oxygen adsorption. During an enhanced photoinduced surface oxidation process, the increased oxidation states of vanadium in VO2 nanostructures are suppressed by the use of an inert atmosphere or coating. Intermediate oxidation states are observed, and an ALD-TiO2 coating has a good antioxidant capacity for preventing the formation of oxygen-enriched components. Such oxidation suppression is beneficial to improving the stability of VO2 nanostructures. Controllable surface oxidation helps us to understand the physical essentials of surface chemical reactions and achieve better control of surface functions and performances on correlated vanadium oxide nanostructures.

Abstract  Nutrient limitation of primary producers is a fundamental principle in biogeochemical oceanography and has been used with great success in prescribing understanding to patterns of marine primary productivity. In recent years the paradigm of nutrient limitation has expanded from single nutrient limitation towards concepts of co-limitation by multiple resources. Interactive effects between multiple limiting resources are now thought commonplace in marine microbial communities. Here we investigate the response exhibited by phosphate-limited Thalassiosira oceanica to elevated concentrations of the phosphate analogs vanadate, arsenate and molybdate. Enrichments in external arsenate and vanadate to phosphate-limited cultures act to suppress growth rates entirely, an effect not seen in phosphate replete conditions. Retardation of growth rates is attributed to mistaken uptake through ion promiscuity as evidenced by observations of significant intracellular accumulation of both arsenic and vanadium under phosphate limited conditions. We describe this novel co-limitation scenario as dependent antagonistic co-limitation (DAC), and suggest that this phenomenon of non-deliberate intracellular accumulation could be used as both a proxy of phosphate stress in the modern ocean and a possible marker of phosphate depletion limiting the duration of oceanic anoxic events.

Abstract  Vanadium is a metal whose toxicity towards terrestrial and aquatic species has been under-reported to date.. The biochemical responses of vanadium in amphibian species have not been determined. To establish the effects of vanadium (V) on exposed adult Xenopus laevis, acute and chronic exposures were conducted, and biomarker analyses were performed on liver and muscle tissues from exposed frogs. Biomarkers of exposure, such as acetylcholinesterase (AChE) and metallothioneins (MT), were analysed. Biomarkers of effect were also analysed to determine possible increases in reactive oxygen species (ROS), and the effect of the exposure on the energy balance in the organisms. These included superoxide dismutase (SOD), catalase (CAT), reduced glutathione (GSH), protein carbonyls (PC), malondialdehyde (MDA), and cellular energy allocation (CEA) (energy available, energy consumption, lipids, proteins and glucose). In acute exposures, the energy balances in organisms were distinctly affected, possibly due to insulin mimetic properties of V. In chronic exposures, MT, AChE, SOD, CAT and GSH responses were more pronounced. Although AChE is generally inhibited by pollutant exposure, in this study, it was stimulated. There were significant inhibitions of SOD and CAT, previously observed in frog species. PC levels increased in the highest acute exposure concentration, indicating protein damage. The IBR.v2 revealed the biochemical responses of V more effectively than traditional statistical analysis.

Abstract  Disordered rock-salt compounds are becoming increasingly important due to their potential as high-capacity positive electrode materials for lithium-ion batteries. Thereby, a significant number of studies have focused on increasing the accessible Li capacity, but studies to manipulate the electrochemical potential are limited. This work explores the effect of transition-metal substitution on the electrochemistry of ternary disordered rock-salt-type compounds with LiM2+0.5V0.54+O2 stoichiometry (M = Mn, Fe, Co) directly synthesized through mechanochemistry. Rietveld refinements of synchrotron X-ray diffraction patterns confirm the disordered rock-salt structures. First-principles density functional theory study is used to predict the impact of the cation substitution on the expected average voltage and the electronic structures of these materials are used to analyze the underlying redox processes. For LiM2+0.5V4+0.5O2 (M = Mn, Fe, Co), discharge voltages increase in the order of Mn < Fe < Co with 2.28, 2.41, and 2.51 V, exhibiting discharge capacities of 219, 207, and 234 mAh g-1, respectively. In comparison, for the disordered rock-salt Li2VO3, an average discharge voltage of ∼2.2 V with V5+/4+ redox couple has been reported. However, detrimental electrode-electrolyte interactions manifested as transition-metal dissolution has been found to result in severe capacity fading. Thereto, the use of a concentrated 5.5 M LiFSI increased the cycling stability significantly, effectively reducing transition-metal dissolution. The underlying reasons for the capacity fading of disordered rock salts are yet unclear. We stress the importance of cathode-electrolyte interactions, thus opening new directions for the improvement of cation-disordered materials.

Abstract  The 2D materials of ultrathin nanosheets possess plentiful active sites, effectively enhancing the electrochemical kinetics of various electrode materials. However, 2D materials usually suffer from the aggregation issue due to the strong van der Waals force of the individual nanosheets, leading to irreversible stacking and decreasing capacity. In this work, we develop a universal method to in-situ space the nanosheet cathodes for the electrodes of ZIBs. As a proof of concept, the V2O5 nanosheets with in-situ AB spacer were obtained, which were used as the cathode of aqueous ZIBs. Owing to plentiful active sites usable for electrolyte/electrode interfaces of the spaced V2O5, the ion diffusion kinetics of the electrodes would be enhanced. In contrast with the stacked V2O5, the spaced V2O5 delivers an exceptional specific capacity (452 mAh g-1), superior rate capability, and stable cycle life (the capacity retention of 92% after 5000 cycles). Moreover, the resultant ZIBs assembled with spaced V2O5 show an impressive energy/power density (158 Wh kg-1 at 19.3 kW kg-1). These superior electrochemical properties make the method of in-situ adding AB spacer hold promising potential to obtain advanced nanosheet electrodes for energy storage systems.

Abstract  The reaction of [Cp'''Co(η4 -P4 )] (1) (Cp'''=1,2,4-tBu3 C5 H2 ) with Me NHC (Me NHC=1,3,4,5-tetramethylimidazol-2-ylidene) leads through NHC-induced phosphorus cation abstraction to the ring contraction product [(Me NHC)2 P][Cp'''Co(η3 -P3 )] (2), which represents the first example of an anionic CoP3 complex. Such NHC-induced ring contraction reactions are also applicable for triple-decker sandwich complexes. The complexes [(Cp*Mo)2 (μ,η6:6 -E6 )] (3 a, 3 b) (Cp*=C5 Me5 ; E=P, As) can be transformed to the complexes [(Me NHC)2 E][(Cp*M)2 (μ,η3:3 -E3 )(μ,η2:2 -E2 )] (4 a, 4 b), with 4 b representing the first structurally characterized example of an NHC-substituted AsI cation. Further, the reaction of the vanadium complex [(Cp*V)2 (μ,η6:6 -P6 )] (5) with Me NHC results in the formation of the unprecedented complexes [(Me NHC)2 P][(Cp*V)2 (μ,η6:6 -P6 )] (6), [(Me NHC)2 P][(Cp*V)2 (μ,η5:5 -P5 )] (7) and [(Cp*V)2 (μ,η3:3 -P3 )(μ,η1:1 -P{Me NHC})] (8).

Abstract  In this study, the waste V2O5-WO3/TiO2 denitrification catalysts from the coal-fired power plant were washed with water or nitric acid, followed by impregnating different contents of V2O5. The effects of the HNO3 concentration and the additional amount of vanadium on the low-temperature selective catalytic reduction denitrification activity were investigated under the condition of high concentration of SO2 and H2O. The catalysts were characterized by inductively coupled plasma optical emission spectrometry, X-ray powder diffraction , N2 adsorption/desorption, H2-temperature-programmed reduction, NH3-temperature-programmed desorption , Fourier transform infrared spectroscopy , and Raman spectroscopy. The evaluation results revealed that optimum activity was achieved by using 0.8 mol/L HNO3 solution and loading 1.60 wt % V2O5 to make the total V2O5 reach 2.3 wt %. The characterization results showed that nitric washing can remove most of the ammonium salts deposited on the surface of the waste catalyst and produce crystalline WO3, which can effectively inhibit the agglomeration of vanadium species in the process of impregnation. Furthermore, it can also increase the amount of oligomeric VO x , which can improve the denitration activity.

Abstract  A biomaterials surface enabling the induction of tumor cell death is particularly desirable for implantable biomedical devices that directly contact tumor tissues. However, this specific antitumor feature is rarely found. Consequently, an antitumor-cell nanocoating comprised of vanadium dioxide (VO2) prepared by customized reactive magnetron sputtering has been proposed, and its antitumor-growth capability has been demonstrated using human cholangiocarcinoma cells. The results reveal that the VO2 nanocoating is able to interrupt the mitochondrial electron transport chain and then elevate the intracellular reactive oxygen species levels, leading to the collapse of the mitochondrial membrane potential and the destruction of cell redox homeostasis. Indeed, this chain reaction can effectively trigger oxidative damage in the cholangiocarcinoma cells. Additionally, this study has provided new insights into designing a tumor-cell-inhibited biomaterial surface, which is modulated by the mechanism of mitochondria-targeting tumor cell death.

Abstract  A series of mono-, double-, and tri-doped LiNbO3 crystals with vanadium were grown by Czochralski method, and their photorefractive properties were investigated. The response time for 0.1 mol% vanadium, 4.0 mol% zirconium, and 0.03 wt.% iron co-doped lithium niobate crystal at 488 nm was shortened to 0.53 s, which is three orders of magnitude shorter than the mono-iron-doped lithium niobate, with a maintained high diffraction efficiency of 57% and an excellent sensitivity of 9.2 cm/J. The Ultraviolet-visible (UV-Vis) and OH- absorption spectra were studied for all crystals tested. The defect structure is discussed, and a defect energy level diagram is proposed. The results show that vanadium, zirconium, and iron co-doped lithium niobate crystals with fast response and a moderately large diffraction efficiency can become another good candidate material for 3D-holographic storage and dynamic holography applications.

Abstract  Our purpose was to examine the effect of model, puffing topography (voltage, air-flow, puff interval), and method of collection on 19 elements/metals in aerosols from six tank-style electronic cigarettes (EC). Aerosols were collected from six brands using a cold trap or impinger and various puffing topographies. 19 elements were quantified using inductively coupled plasma optical emission spectroscopy. 16 elements/metals were present and quantified in the aerosols. The total concentrations of elements/metals ranged from 43 to 3,138 µg/L with the impinger method of collection and 226 to 6,767 µg/L with the cold trap method. The concentrations of individual elements were often similar across brands and across topographies. Some elements (e.g., zinc) were present in most aerosols, while others (e.g., cadmium, titanium, vanadium) were rarely found. Concentrations of some elements (e.g., lead) increased in aerosols as voltage/power increased. The model with fewest metal parts in the atomizer had the fewest metals in its aerosols. Most elements/metals in the aerosols have been found previously in the atomizers of EC. All tank-style aerosols had elements/metals that appeared to originate in the atomizers, and concentrations increased with increasing power. Concentrations of some elements were high enough to be a health concern.

Abstract  Biological effects of titanium (Ti) alloys were analyzed on biofilms of Candida albicans, Enterococcus faecalis, Pseudomonas aeruginosa, Staphylococcus aureus, Streptococcus mutans, and Streptococcus sanguinis, as well as on osteoblast-like cells (MG63) and murine macrophages (RAW 264.7). Standard samples composed of aluminum and vanadium (Ti-6Al-4V), and sample containing niobium (Ti-35Nb) and zirconium (Ti-13Nb-13Zr) were analyzed. Monomicrobial biofilms were formed on the Ti alloys. MG63 cells were grown with the alloys and the biocompatibility (MTT), total protein (TP) level, alkaline phosphatase (ALP) activity, and mineralization nodules (MN) formation were verified. Levels of interleukins (IL-1β and IL-17), tumor necrosis factor alpha (TNF-α), and oxide nitric (NO) were checked, from RAW 264.7 cells supernatants. Data were statically analyzed by one-way analysis of variance (ANOVA) and Tukey's test, or T-test (P ≤ 0.05). Concerning the biofilm formation, Ti-13Nb-13Zr alloy showed the best inhibitory effect on E. faecalis, P. aeruginosa, and S. aureus. And, it also acted similarly to the Ti-6Al-4V alloy on C. albicans and Streptococcus spp. Both alloys were biocompatible and similar to the Ti-6Al-4V alloy. Additionally, Ti-13Nb-13Zr alloy was more effective for cell differentiation, as observed in the assays of ALP and MN. Regarding the stimulation for release of IL-1β and TNF-α, Ti-35Nb and Ti-13Nb-13Zr alloys inhibited similarly the synthesis of these molecules. However, both alloys stimulated the production of IL-17. Additionally, all Ti alloys showed the same effect for NO generation. Thus, Ti-13Nb-13Zr alloy was the most effective for inhibition of biofilm formation, cell differentiation, and stimulation for release of immune mediators.

Abstract  OBJECTIVES: Due to bone loss, endosseous implants often require addition of a bone graft to support adequate primary fixation, bone regeneration, and osseointegration. The aim of this study was to compare effectiveness of autogenic and allogenic bone grafts when used during simultaneous insertion of the implant.

MATERIALS AND METHODS: 4-mm-diameter rabbit diaphyseal bone autografts or allografts (n = 16/group) with a 3.2-mm pre-drilled hole in the center were placed into a 4 mm defect in the proximal femur of 3.5 kg male New Zealand White rabbits. Machined 3.2 × 10 mm grit-blasted, acid-etched titanium-aluminum-vanadium (Ti6Al4V) implants were placed. Control implants were placed into progressively drilled 3.2-mm holes in the contralateral limbs. Post-insertion day 70, samples were analyzed by micro-CT and calcified histology, or by mechanical torque and push-out testing followed by decalcified histology.

RESULTS: Both grafts were integrated with the native bone. Micro-CT showed less bone volume (BV) and bone volume/total volume (BV/TV) in the allograft group, but histology showed no differences in BV or BV/TV between groups. Allograft lacked living cells, whereas autograft was cellularized. No difference was found in maximum removal torque between groups. Compressive loading at the graft-to-bone interface was significantly lower in allograft compared with autograft groups.

CONCLUSIONS: There was less bone in contact with the implant and significantly less maximum compressive load in the allograft group compared with autograft. The allograft remained acellular as demonstrated by empty lacunae. Taken together, block allograft implanted simultaneously with an implant produces a poorer quality bone compared with autograft.

Abstract  Temporal and spatial atmospheric deposition trends of elements to the boreal forest surrounding bitumen production operations in the Athabasca Oil Sands Region (AOSR), Alberta, Canada were investigated as part of a long-term lichen bioindicator study. The study focused on eight elements (sulfur, nitrogen, aluminum, calcium, iron, nickel, strontium, vanadium) that were previously identified as tracers for the major oil sand production sources. Samples of the in situ epiphytic lichen Hypogymnia physodes were collected in 2002, 2004, 2008, 2011, 2014, and 2017 within a ~150 km radius from the center of surface oil sand production operations in the AOSR. Site-specific time series analysis conducted at eight jack pine upland sites that were repeatedly sampled generally showed significant trends of increasing lichen concentrations for fugitive dust linked elements, particularly at near-field (<25 km from a major oil sands production operation) sample locations. Multiple regional scale geostatistical models were developed and evaluated to characterize broad-scale changes in atmospheric deposition based on changes in H. physodes elemental concentrations between 2008 and 2014. Empirical Bayesian kriging and cokriging lichen element concentrations with oil sands mining, bitumen upgrading, coke materials handling, and limestone quarry/crushing influence variables produced spatial interpolation estimates with the lowest validation errors. Gridded zonal mean lichen element concentrations were calculated for the two comprehensive sampling years (2008, 2014) and evaluated for spatial and temporal change. Lichen sulfur concentrations significantly increased in every grid cell within the domain with the largest increases (44-88%) in the central valley in close proximity to the major surface oil sand production operations, while a minor nitrogen concentration decrease (-20%) in a single grid cell was observed. The areal extent of fugitive dust element deposition generally increased with significantly higher deposition to lichens restricted to the outer grids of the enhanced deposition field, reflecting new and expanding surface mining activity.

Abstract  Imaging of biological matter by using fluorescent nanoparticles (NPs) is becoming a widespread method for in vitro imaging. However, currently there is no fluorescent NP that satisfies all necessary criteria for short-term in vivo imaging: biocompatibility, biodegradability, photostability, suitable wavelengths of absorbance and fluorescence that differ from tissue auto-fluorescence, and near infrared (NIR) emission. In this paper, we report on the photoluminescent properties of magnesium oxide (MgO) NPs that meet all these criteria. The optical defects, attributed to vanadium and chromium ion substitutional defects, emitting in the NIR, are observed at room temperature in NPs of commercial and in-house ball-milled MgO nanoparticles, respectively. As such, the NPs have been successfully integrated into cultured cells and photostable bright in vitro emission from NPs was recorded and analyzed. We expect that numerous biotechnological and medical applications will emerge as this nanomaterial satisfies all criteria for short-term in vivo imaging.

Abstract  Alkali fusion method to extract vanadium and tungsten from spent SCR catalyst and to simultaneously prepare synthetic sodium titanate for the purpose of preparation of feedstock for TiO2 manufacturing by hydrometallurgical processing was investigated. Based on the Na2O-TiO2 phase diagram and experimentally obtained results, appropriate alkali-fusion temperature and molar ratio (MOx/Na2O + MOx) were determined to prepare soluble vanadium, tungsten salts, and sodium titanate. As results, the extraction efficiency of vanadium and tungsten was >99% and sodium titanate as feedstock for making TiO2 was obtained under the following alkali fusion conditions: Temperature, 950 °C; reaction time, 20 min; molar ratio, 0.5. When the molar ratio (MOx/Na2O + MOx) was less than 0.5, complete liquidized product (eutectic melt of the feedstock and Na2CO3) was obtained at the given conditions. This method, compared to conventional alkali roasting, is advantageous for rapid synthesis of water-soluble compounds for leaching of vanadium and tungsten, and for use as feedstock for the preparation of TiO2 by hydrometallurgical route.

Abstract  The recent surge of interest in brain-inspired computing and power-efficient electronics has dramatically bolstered development of computation and communication using neuron-like spiking signals. Devices that can produce rapid and energy-efficient spiking could significantly advance these applications. Here we demonstrate direct current or voltage-driven periodic spiking with sub-20 ns pulse widths from a single device composed of a thin VO2 film with a metallic carbon nanotube as a nanoscale heater, without using an external capacitor. Compared with VO2-only devices, adding the nanotube heater dramatically decreases the transient duration and pulse energy, and increases the spiking frequency, by up to 3 orders of magnitude. This is caused by heating and cooling of the VO2 across its insulator-metal transition being localized to a nanoscale conduction channel in an otherwise bulk medium. This result provides an important component of energy-efficient neuromorphic computing systems and a lithography-free technique for energy-scaling of electronic devices that operate via bulk mechanisms.

Abstract  The metallic phase (1T) of molybdenum sulfide is critical, pertaining to its exceptional interlayer structure and metastability, but forms up with low content. Herein, 1T-phase-prominent vanadium-incorporated MoS2 (MVS) nanoroses were synthesized through a hydrothermal process. A significant increase in 1T content (50 %) occurred with the addition of vanadium, enhancing the prompt diffusion of lithium ions by two orders. More exposed electroactive basal planes increased the number of redox active sites to 84 %, suggesting an excellent charge storage of 451 F g-1 at 1 A g-1 . On assembling MVS with MnO2 to form an asymmetric cell (MnO2 ∥MVS), a high energy density (62.7 Wh kg-1 at 428 W kg-1 ) with a threefold increment from the MVS‖MVS symmetric cell (21.8 Wh kg-1 at 255 Wkg-1 ) was achieved. The asymmetric cell also exhibited a superior cycling stability with 98 % retention of its capacitance after 10 000 cycles.

Abstract  Vanadium oxide clusters with a mean diameter below 10 nm are investigated by high resolution Scanning Transmission Electron Microscopy (STEM), Electron Energy Loss Spectroscopy (EELS) and UV-vis absorption spectroscopy. The clusters are synthesised by sublimation from bulk vanadium(v) oxide, in combination with a pick-up by superfluid helium droplets. The latter act as reaction chambers which enable cluster growth under fully inert and solvent-free conditions. High-resolution STEM images of deposited vanadium oxide particles allowing for the determination of lattice constants, clearly indicate a dominating presence of V2O5. This finding is further supported by UV-vis absorption spectra of nanoparticles after deposition on fused silica substrates, which indicates that the oxidation state of the material is preserved over the entire process. From the results of the UV-vis measurement, the band gap of the nanosized V2O5 could be determined to be 3.3 eV. The synthesis approach provides a route to clean V2O5 clusters as it does not involve any surfactant or solvents, which is crucial for an unbiased measurement of intrinsic catalyst properties.

Abstract  Mine tailings contain toxic metals and can lead to serious pollution of soil environment. Phytoremediation using legumes has been regarded as an eco-friendly way for the rehabilitation of tailings-laden lands but little is known about the changes of microbial structure during the process. In the present study, we monitored the dynamic change of microbiota in the rhizosphere of Pongamia pinnata during a 2-year on-site remediation of vanadium-titanium magnetite tailings. After remediation, overall soil health conditions were significantly improved as increased available N and P contents and enzyme activities were discovered. There was also an increase of microbial carbon and nitrogen contents. The Illumina sequencing technique revealed that the abundance of taxa under Proteobacteria was increased and rhizobia-related OTUs were preferentially enriched. A significant difference was discovered for sample groups before and after remediation. Rhizobium and Nordella were identified as the keystone taxa at genus rank. The functional prediction indicated that nitrogen fixation was enhanced, corresponding well with qPCR results which showed a significant increase of nifH gene copy numbers by the 2nd year. Our findings for the first time elucidated that legume phytoremediation can effectively cause microbial communities to shift in favour of rhizobia in heavy metal contaminated soil.

Abstract  A switchable metamaterial with bifunctionality of absorption and electromagnetically induced transparency is proposed based on the phase-transition characteristic of phase change material-vanadium dioxide. When vanadium dioxide is in the metallic state, an isotropic narrow absorber is obtained in the terahertz region, which consists of a top metallic cross, a middle dielectric layer, and a bottom vanadium dioxide film. By adjusting structure parameters, perfect absorption is realized at the frequency of 0.498 THz. This designed narrow absorber is insensitive to polarization and incident angle. Absorptance can still reach 75% for transverse electric polarization and transverse magnetic polarization at the incident angle of 65∘. When vanadium dioxide is in the insulating state, the top metallic cross will interact with the bottom split ring resonator, and the interaction between them will lead to the appearance of electromagnetically induced transparency. The behavior of electromagnetically induced transparency works well for transverse electric polarization and transverse magnetic polarization at the small incident angle. The designed hybrid metamaterial opens possible avenues for achieving switchable functionalities in a single device.

Abstract  With their unprecedented flexibility in manipulating electromagnetic waves, metamaterials provide a pathway to structural materials that can fill the so-called "THz gap". It has been reported that vanadium dioxide (VO2) experiences a three orders of magnitude increase in THz electrical conductivity when it undergoes an insulator-to-metal transition. Here, we propose a VO2 based THz metamaterial absorber exhibiting broadband absorptivity that arises from the multiple resonances supported by a delicately balanced doubly periodic array of VO2 structures and numerically demonstrate that the corresponding absorption behavior is highly dependent on the VO2's THz electrical properties. Considering the phase transition induced dramatic change in VO2's material property, the proposed metamaterial absorbers have the potential for strong modulation and switching of broadband THz radiation.