High Metal Ion Research Articles

The effect of inoculum source of different pollution levels on the performances of microbial fuel cell biosensors

Selection of inoculum sources is a key factor in constructing microbial fuel cells (MFCs), and the property of inoculum sources is greatly affected by the degree of environmental pollution. However, limited attention has been paid to how these differences affect the response of MFC biosensors. Here the effects of inoculum sources with varying pollution levels on the performances of constructed MFCs were evaluated, and the microbial communities were analyzed before and after inoculation. The results showed significant differences in the detection of biochemical oxygen demand (BOD) and toxicity (Cu2+) among the five groups of MFC biosensors. Combined with the data of the microbial community, the results indicated that the increase rate of the initial start-up voltage is related to the abundance of original electroactive bacteria (EAB) in the inoculum source. The higher the abundance of EAB, the faster increase rate in the initial start-up voltage and the shorter start-up time. The difference in the detection range of the BOD should be related to the ability of the microbial communities to withstand the organic shock loads. The microbial community's tolerance to Cu2+ was affected by the original water quality of the inoculum source. The high metal ion content leads to low sensitivity of MFC biosensor to Cu2+ ion. Enterobacteriaceae were abundant in all the five groups of MFCs, indicating that the dominant bacteria can be enriched in MFC anode biofilms with the inoculum sources of different pollution levels. The microbial community compositions of the anode biofilms were affected by the inoculum sources of different pollution levels, which in turn resulted in the differences in MFCs performances.

Pollutant degradation and hydrogen production of landfill leachate membrane concentrates via aqueous phase reforming

Membrane filtration is a mainstream method for landfill leachate treatment, leaving the landfill leachate membrane concentrates (LLMCs) a high-toxicity residue. Conventional LLMCs disposal technology shows specific challenges due to the low biodegradability, high inorganic salts, and high heavy metal ions content of LLMCs. Therefore, it is necessary to degrade LLMCs with a more suitable technology. In this study, a special method was proposed to convert some organic chemicals into valuable compounds by aqueous phase reforming (APR). Ni-based catalysts (Ni//La2O3, Ni/CeO2, Ni/MgO, and Ni/Al2O3) were prepared to investigate the effect of different supports on the APR of LLMCs. APR performed outstanding characteristics in the decrease of chemical oxygen demand (COD) and total organic carbon (TOC), the degradation of macromolecules, and the removal of heavy metal ions in the aqueous phase. In addition, H2 was generated which is beneficial for energy compensating during the APR process. The best-performing catalyst (Ni/Al2O3) was selected to investigate the effects of reaction temperature, reaction time, and catalyst addition on product distribution. The optimal H2 selectivity (44.71%) and H2 production (11.63 mmol/g COD) were obtained at 250 °C with 2 g Ni/Al2O3 usage for 1 h. This paper provided a new perspective on the disposal of LLMCs, which will degrade pollutants efficiently.

Dioxomolybdenum(VI) and oxovanadium(IV) organo-complexes of tartrato-dihydrazone ligand as reactive antitumor and antimicrobial agents. ctDNA interactive nature

Form the condensed > C = O of salicyldehyde with -NH2 of tartric dihydrazide, a new chelating bis-tridentate tartrato-dihydrazone ligand (HTL) was constructed. Due to the high applicability of metal aryl/aroyl-hydrazone complexes, its ligational behavior versus two high valent dioxo/oxo-metal ions of MoO22+ and VO2+ ions was explored to build up two new organo-dimetallic complexes (MoO2TL and VOTL, respectively). Chemical structure elucidation of HTL, MoO2TL, and VOTL was formulated through the analyses of different spectroscopic tools, along with the thermogravimetric and micro-elemental analyses, the conductance and magnetic measurements.The inhibition strength of the current compounds against the growth of various entitled microorganisms and tumor cell lines of humans was evaluated regarding the role action of the high valent metal ions (MoO22+ and VO2+ ions in their metallodrug candidates). Both MoO2TL and VOTL displayed a significant inhibition action more than that of HTL based on the inhibition zone areas in mm for the microbial series and the half inhibitory concentration in µM (IC50) for the tumor cell lines of their cells’ growth.Also, the interactive and binding nature of HTL, MoO2TL, and VOTL with calf thymus DNA (ctDNA) was evaluated viscometric and spectrophotometric titrations. The interactive modes of HTL, MoO2TL, and VOTL was estimated within the chromism type, the Gibb’s free energy, and binding constant values (ΔGb≠ and Kb, respectively), with reported magnitudes ΔGb≠ (Gibb’s free energy) = -42.06, −48.11 and −47.67 kJ mol−1, and Kb (binding constant) = 14.09, 17.11 and 16.89 × 107 mol−1 dm3, respectively. The bio-reactivity of both MoO2TL and VOTL complexes was modified compared to that of HTL towards ctDNA with covalent/non-covalent and replacement binding interaction.

Mo4+-Doped CuS Nanosheet-Assembled Hollow Spheres for CO2 Electroreduction to Ethanol in a Flow Cell.

Electrocatalytic CO2 reduction reaction (CO2RR) to ethanol has been widely researched for potential commercial application. However, it still faces limited selectivity at a large current density. Herein, Mo4+-doped CuS nanosheet-assembled hollow spheres are constructed to address this issue. Mo4+ ion doping modifies the local electronic environments and diversifies the binding sites of CuS, which increases the coverage of linear *COL and produces bridge *COB for subsequent *COL-*COH coupling toward ethanol production. The optimal Mo9.0%-CuS can electrocatalyze CO2 to ethanol with a faradaic efficiency of 67.5% and a partial current density of 186.5 mA cm-2 at -0.6 V in a flow cell. This work clarifies that doping high valence transition metal ions into Cu-based sulfides can regulate the coverage and configuration of related intermediates for ethanol production during the CO2RR in a flow cell.

Oxidation state regulation of iron-based bimetallic nanoparticles for efficient and simultaneous electrochemical detection of Pb2+ and Cu2+

In this work, bimetallic nanocomposites were synthesized by an emulsion hydrothermal method, and the electronic structure of the nanocomposite’s surface was adjusted to make it optimal by introducing different transition metal salts, providing more active adsorption sites for detecting heavy metal ions (HMIs). The results showed that different transition metal cations underwent redox reactions with Fe3+ at high temperature, resulting in generation of more Fe2+ as well as high valence transition metal ions. And this process formed more oxygen vacancies (OVs) on the material surface, enhancing the adsorption properties of HMIs. Among these nanocomposites, CoFe2O4 produced the most Fe2+ (Fe2+/Fe3+ = 1.29) and Co3+ (Co3+ = 44.0%) at a high temperature, suggesting the generation of the most active sites on the material surface. The corresponding modified electrode CoFe2O4 (CoFe2O4/GCE) also exhibited good electrochemical performance for simultaneously detecting Pb2+ and Cu2+, with the limit of detections of 3.94 and 8.27 nM, respectively. Compared with other nanocomposites, adsorption experiments showed that the CoFe2O4/GCE had the largest adsorption capacity of Pb2+ and Cu2+ (QPb2+=49.82 μC, QCu2+=48.88 μC). Therefore, this work showed that the interaction between metal ions in bimetallic nanomaterials can regulate the electronic structures of the material surface at high-temperature treatment, improve the adsorption capacity of nanomaterials, and lead to good electrochemical detection performance of HMIs.

Flexible nanofiber composite solar evaporator for simultaneous interfacial evaporation and heavy metal ion adsorption

Solar driven interfacial evaporation (SDIE) is promising in harvesting fresh water because of its low cost, environmental friendless and sustainability; however, it is desirable but still difficult to achieve high efficiency heavy metal ion removal during SDIE. Here, we develop a superhydrophilic and stretchable nanofiber composite solar evaporator via carbon nanofiber (CNF) assembly on polymer fiber surface and then polydopamine (PDA) modification. The evaporation rate reaches as high as 1.456 kg m−2 h−1 with the evaporation efficiency of 91.40 %. The functional groups of PDA endow the nanofiber composite with good heavy metal ion adsorption performance that is proved to be an endothermic process, and SDIE can induce the increase of interface temperature and localized ion concentration and hence promote the Cr (VI) adsorption. One the other hand, NaCl ions are able to diffuse into body water without salt precipitation by virtue of powerful water transportation capability of the evaporation device. The dual Cr (VI) adsorption and NaCl ion diffusion channels ensure simultaneous and high efficiency Cr (VI) removal and seawater interface evaporation. SDIE accelerated heavy metal ion adsorption and the dual ion channel model provide inspiration to design multifunctional solar evaporator materials for waste water purification.

Enhancing the photothermal efficiency of MoS2 through ultraviolet-ozone exposure for improved solar evaporation

MoS2 has been explored as a photothermal layer for solar-driven water evaporators to produce clean water. However, there have been no reports studying the effects of ultraviolet-ozone (UVO) exposure on the photothermal properties of MoS2. This study investigates the impact of UVO exposure (10, 20, and 30 minutes) on bulk 2H-MoS2 synthesized via a hydrothermal method at 200°C for 16 hours. The freshly prepared MoS2 contained high concentrations of molybdenum oxide phases, which significantly diminished after 10 minutes of UVO exposure, indicating improved purity of MoS2. The increased purity of UVO-exposed MoS2 led to a rise in layer temperature to 47.37°C, surpassing the 43.40°C temperature of MoS2 without UVO exposure. Extending the UVO exposure to 30 minutes further increased the number of surface edge sites, thereby enhancing the wettability of MoS2 due to the increased binding sites for polar water molecules. Consequently, MoS2 exposed to UVO for 30 minutes demonstrated the highest evaporation rate of 1.83 kg m−2 h−1, achieving a photothermal efficiency of 94%, a high salt rejection rate of 99.98%, and a high heavy metal ion rejection rate of 91.84%. Therefore, the application of UVO-exposed MoS2 serves as an effective photothermal layer for sustainable and eco-friendly clean water production technologies.

Identification and Characterization of a Novel Thermostable GDSL Lipase LipGt6 from Geobacillus thermoleovorans H9

Lipases are versatile biocatalysts for various biological reactions. In the detergent industry, lipases must exhibit high activity in environments with high temperature, high pH values, metal ions, and organic solvents. Therefore, researchers are intensively searching for more stable and efficient lipases. A new thermophilic lipase, LipGt6, was identified in Geobacillus thermoleovorans H9, a new thermophilic strain isolated from ultrahigh-temperature compost. A structural model of LipGt6 was constructed using an esterase from Geobacillus thermodenitrificans as a template, and site-directed mutagenesis confirmed the predicted active site residues. LipGt6 exhibited the highest activity towards medium- and long-chain fatty acids (C8–C14), and the optimum temperature and pH were 50 °C and 9.0, respectively. LipGt6 was found to be thermostable up to 70 °C. In the presence of 1% H2O2 and sodium deoxycholate, LipGt6 retained 70 to 75% relative activity. These findings reveal that LipGt6 is potentially useful for the industrial production of detergent. Based on comparison of the amino acid sequences, the enzyme belongs to a new subfamily called lipolytic enzyme family II. The catalytic residues Ser and His were more critical than Asp, and the Asp221 catalytic residue is not likely critical for the lipolytic reaction of LipGt6.

Two-dimensional copper vanadate intercalated vanadium carbide MXene nanoplates as a high-performance cathode for aqueous Zn-ion batteries

Cathode materials play a crucial role in the energy-storage performances of zinc ion battery (ZIB). In this paper, the two-dimensional vanadium carbide MXene (V2C-MXene) nanoplates intercalated by Cu3V2O7(OH)2·2 H2O (CuVO) are synthesized. The intercalation of CuVO in the interlayers of V2C-MXene overcomes self-aggregation of CuVO and improves its structural stability. Meanwhile, the enlarged interlayer spacing of highly conductive V2C-MXene upgrades the electron transfer within the composite. As the cathode electrode of ZIB, the CuVO intercalated V2C-MXene (CuVO@V2C-MXene) battery shows capacity as high as 551.8 mAh g−1 when discharged at 0.5 A g−1. The capacity retention rate reaches 91.8% after 3000 cycles at high current density of 6.0 A g−1. As a comparison, the CuVO//Zn battery has capacity only 193.3 mAh g−1 at 0.5 A g−1, with the capacity retention of just 43.1% after 3000 cycles at 6.0 A g−1. Simultaneously, the CuVO@V2C-MXene//Zn illustrates greatly improved rate capability compared with CuVO//Zn. The CuVO@V2C-MXene composite nanoplates in this work show promise in fabrication of high capacity metal ion batteries.

Morphology, Development, and Pigment Production of Talaromyces marneffei are Diversely Modulated Under Physiologically Relevant Growth Conditions.

Talaromyces marneffei is an opportunistic pathogenic fungus that mainly affects HIV-positive individuals endemic to Southeast Asia and China. Increasing efforts have been made in the pathogenic mechanism and host interactions understanding of this pathogen in the last two decades; however, there are still no conclusions on how T. marneffei was transmitted from the donor bamboo rats to humans. A perception that the failure of fungus isolation from soil was attributed to the low salt tolerance of T. marneffei. Therefore, the effect of environmental fluctuations in fungal growth and development is fundamental for the characterization of its origin and fungal biology understanding. Herein, we characterized high osmolarity, pH, metal ions, nutrients, and oxidative stress have versatile effects on T. marneffei hyphal or yeast growth, conidia generation, and pigment production. Among these, high pH, low glucose amounts, and the inorganic nitrogen ammonium tartrate stimulated the red pigment production, whereas high osmolarity, high pH, and the inorganic nitrogen sodium nitrate could significantly accelerate the conidia generation. Specifically, zinc starvation repressed conidia generation and prevented the wrinkled yeast colony formation, indicating the function of zinc regulators in pathogenicity regulation. Since conidia are recognized as the infectious propagules, the effects characterization of different environmental factors in T. marneffei morphology in this work will not only expand the growth and pathogenic biology understanding of the fungus but also provide more clues for the T. marneffei infection transmission origin investigation.

Current Status of Zero Liquid Discharge Technology for Desulfurization Wastewater

Desulfurization wastewater is industrial wastewater with a high salt content, high metal ions, and high hardness produced by flue gas desulfurization of the limestone-gypsum method in coal-fired power plants. This paper summarizes the source of desulfurization wastewater, water quality characteristics, water quality impacts, and other factors, combined with the current status of research worldwide to introduce the advantages and shortcomings of the existing desulfurization wastewater treatment technology. In addition, zero liquid discharge technology as a novel method to treat desulfurization wastewater is also summarized. It mainly includes evaporation and crystallization, flue gas evaporation, membrane distillation removal, etc. Finally, this manuscript looks forward to the future development direction of desulfurization wastewater based on its existing technology and emission standards.

Characterization and Eco-Friendly Synthesis of Silver and Iron Nanoparticles Using Microalgae Extracts: Implications for Nanobiotechnology.

<b>Background and Objective:</b> The remarkable surface-to-volume ratio and efficient particle interaction capabilities of nanoparticles have garnered significant attention among researchers. Microalgal synthesis presents a sustainable and cost-effective approach to nanoparticle production, particularly noteworthy for its high metal uptake and ion reduction capabilities. This study focuses on the eco-friendly and straightforward synthesis of Silver (AgNPs) and Iron (FeNPs) nanoparticles by utilizing Spirulina (<i>Arthrospira platensis</i>) and <i>Chlorella pyrenoidosa</i> extract, devoid of any chemical reducing or capping agents. <b>Materials and Methods:</b> Following the mixing of 1 mM AgNO<sub>3</sub> and 1 mM iron oxide solution with the algal extract, the resulting filtrated solution underwent comprehensive characterization, including UV-visible absorption spectra analysis, observation of particle morphology, Zetasizer measurements and Scanning Electron Microscope-Energy Dispersive X-Ray (SEM-EDX) analysis. <b>Results:</b> The UV-visible spectroscopy revealed a maximum absorbance peak at 430-440 nm, confirming the successful green synthesis of AgNPs and FeNPs, as indicated by the distinct color change from transparent to dark reddish-yellow and brown to reddish-brown, respectively. The SEM-EDX analysis further elucidated the spherical morphology of the nanoparticles, with an average diameter of 93.71 nm for AgNPs and 6198 nm for FeNPs. The Zeta potential measurements indicated average values of -56.68 mV for AgNPs and 29.73 mV for FeNPs, with conductivities of 0.1764 and 0.6786 mS/cm, respectively. <b>Conclusion:</b> The observed bioaccumulation of silver and iron nanoparticles within the algal extract underscores its potential as an environmentally friendly and cost-effective method for nanoparticle synthesis. These findings suggested a promising avenues for the application of silver and iron nanoparticles in the field of nanobiotechnology. Future research endeavors could focus on optimizing preparation conditions and controlling nanoparticle size to further enhance their utility and effectiveness.

Magnetically engineering enhanced EMA property through high entropy transition metal ions within all-inorganic perovskite

Addressing challenges such as signal interference and crosstalk requires the development of new materials capable of electromagnetic absorption (EMA). In this study, we explored magnetically high-entropy engineering by incorporating transition metal ions into the B sites of all-inorganic CsPbBr3 perovskite. This approach yielded excellent EMA properties, including a minimum reflection loss of 75 dB at 10.2 GHz with a thickness of 2.5 mm and an effective bandwidth of 8.8 GHz. Fe, Co, Ni, and Mn ions were successfully introduced into the CsPbBr3 lattice using high-energy ball milling and the combustion method. Through rigorous characterization techniques such as Rietveld refinement of X-ray diffraction and Grazing-Incidence Wide-Angle Scattering patterns, we confirmed the presence of high-entropy phases. Additionally, we conducted comprehensive studies using Vibrating-sample magnetometer, L2,3 edge XANES, and Mossbauer spectra to investigate the magnetic polarization, spin states, and dipolar exchanges of the transition metal ions. The observed synergistic effects among the magnetic permeability, polarization, and magnetic loss of these ions underscored their role in enhancing the EMA performance of CsPbBr3.

Achieving Less Than 100 ppb Total Metal Ion Concentration in ESCAP Resins Synthesized by Atom Transfer Radical Polymerization

AbstractIn the photolithography process of integrated circuits （IC） manufacturing, it is desired that the photoresist resins have both smaller polydispersity index (PDI) and lower trace metal ion concentrations. The commercial environmentally stable chemical amplified photoresist (ESCAP) resins for 248 nm lithography are synthesized by free radical polymerization with PDI >1.5. Although using atom transfer radical polymerization (ATRP) can result in lower PDI, the potential of high metal ion contamination is a major concern, as the reaction initiators usually are copper‐containing compounds. In this study, copolymer of p‐acetoxy styrene and tert‐butyl acrylate [poly(AOST‐co‐TBA)] is synthesized via ATRP achieving PDI as low as 1.25. It is then purified by ion exchange with two different resins, IRC747 and A15, which are effective at removing Cu and other metal ions. This reduces the total metal ion concentration in the copolymer powder to <30 ppb with individual metal ion <6 ppb. This is the first reported ATRP synthesized ESCAP resin having both low PDI and metal ion concentrations suitable for 248 nm photoresist application.

Supramolecular Engineering of Ti3C2Tx MXene -Perylene Diimide Hybrid Electrodes for the Pseudocapacitive Electrochemical Storage of Calcium Ions.

The rare combination of metallic conductivity and surface redox activity enables 2D MXenes as versatile charge storage hosts for the design of high-rate electrochemical energy storage devices. However, high charge density metal ions including but not limited to Ca+2 and Mg+2 pose challenges such as sluggish solid-state diffusion and also inhibiting the charge transfer across electrode-electrolyte interfaces. In this work, free-standing hybrid electrode architectures based on 2D titanium carbide-cationic perylene diimide (Ti3C2Tx@cPDI) via supramolecular self-assembly are developed. Secondary bonding interactions such as dipole-dipole and hydrogen bonding between Ti3C2Tx and cPDI are investigated by zeta potential and Fourier-transformed infrared (FTIR) spectroscopy . Ti3C2Tx@cPDI free-standing electrodes show typical volumetric capacitance up to 260 F cm-3 in Mg2+ and Ca2+ aqueous electrolytes at charging times scales from 3minutes to a few seconds. Three-dimensional (3D) Bode maps are constructed to understand the charge storage dynamics of Ti3C2Tx@cPDI hybrid electrode in an aqueous Ca-ion electrolyte. ,Pseudocapacitance is solely contributed by the nanoscale distribution of redox-active cPDI supramolecular polymers across 2D Ti3C2Tx. This study opens avenues for the design of a wide variety of MXene@redox active organic charge hosts for high-rate pseudocapacitive energy storage devices.

Influence of Physical Activity and Cup Orientation on Metal Ion Release and Oxidative Stress in Metal-on-Metal and Ceramic-on-Metal Total Hip Arthroplasty.

Metal-on-metal (M-M) total hip arthroplasty (THA) has shown adverse reactions to metal debris, abnormal soft-tissue reactions, and high blood metal ion levels. This study aims to: (1) assess whether the toxicity of high levels of ions is related to altered oxidative stress and (2) evaluate tribological factors related to increased blood levels of chromium (Cr) and cobalt (Co) ions. A cross-sectional analytical descriptive study was conducted on 75 patients. A total of 25 underwent M-M THA, 25 ceramic-on-metal (C-M) THA, and 25 were on the THA waiting list. Ion metallic levels in blood, oxidative stress, physical activity, and implant position were compared. In the M-M group, Co and Cr levels were significantly higher than those found in the C-M group and the control group (p < 0.01). We found no differences in terms of oxidative stress between the groups. Also, we did not find a correlation between metal blood levels and oxidative stress indicators, the physical activity of the patients or the position of the implants between groups. The use of M-M bearing surfaces in THA raises the levels of metals in the blood without modifying oxidative stress regardless of the physical activity levels of the patients. Therefore, although patients with M-M bearings require close monitoring, it does not seem necessary to recommend the restriction of physical activity in patients with M-M or C-M arthroplasties.

The photocatalyst with a strong internal electric field grown in situ on the surface of copper foam collaborates with peroxymonosulfate to enhance directional charge transfer and achieve ultra-fast Mn+/M(n+1)+ cycling

To address three pressing problems that limit the application of photocatalytic synergic peroxymonosulfate (PMS) technology, namely difficult reuse, low photogenerated carrier separation efficiency, and sluggish metallic ions redox cycle, we utilized an in-situ growth method to construct a vertical nanosheet heterojunction on the surface of copper foam (CF). This heterojunction is characterized by a strong internal electric field (IEF) that serves as both a “pump” for the rapid and efficient migration of electrons and a driving force for the activation of PMS by these electrons. In the CF@CCS@CO-3/7/Vis/PMS system, the photoelectrons generated by photocatalysis quickly replenish the high valence metals activated by PMS, allowing for highly efficient cycling of differently valenced metal ions and reducing the dissolution of high valence metal ions produced by PMS. As a result, close to 100 % of ciprofloxacin (CIP) was degraded within 60 min in the CF@CCS@CO-3/7/Vis/PMS system with a reaction rate constant k of 0.0621 min−1, which is about 3.22 times higher than that of the CF@CCS@CO-3/7/Vis system and 2.65 times higher than that of the CF@CCS@CO-3/7/PMS system. Moreover, the in-situ growth of active ingredients with vertical nanosheet structure on the CF surface can well maintain structure and reactivity in complex environments, allowing more than 10 cycles to be realized. The results of the free radical burst assay and EPR analysis indicated that SO4∙−, ∙O2− and h+ were the main reactive species involved in the catalytic process. Building upon CF@CCS@CO-3/7, we assembled a fixed-bed continuous treatment device that enables high mineralization flow treatment of pharmaceutical wastewater (after Secondary biological treatment).

In Situ Fast Construction of Ni3S4/FeS Catalysts on 3D Foam Structure Achieving Stable Large-Current-Density Water Oxidation.

By increasing the content of Ni3+, the catalytic activity of nickel-based catalysts for the oxygen evolution reaction (OER), which is still problematic with current synthesis routes, can be increased. Herein, a Ni3+-rich of Ni3S4/FeS on FeNi Foam (Ni3S4/FeS@FNF) via anodic electrodeposition to direct obtain high valence metal ions for OER catalyst is presented. XPS showed that the introduction of Fe not only further increased the Ni3+ concentration in Ni3S4/FeS to 95.02%, but also inhibited the dissolution of NiOOH by up to seven times. Furthermore, the OER kinetics is enhanced by the combination of the inner Ni3S4/FeS heterostructures and the electrochemically induced surface layers of oxides/hydroxides. Ni3S4/FeS@FNF shows the most excellent OER activity with a low Tafel slope of 11.2mVdec-1 and overpotentials of 196 and 445mV at current densities of 10 and 1400mAcm-2, respectively. Furthermore, the Ni3S4/FeS@FNF catalyst can be operated stably at 1500mAcm-2 for 200h without significant performance degradation. In conclusion, this work has significantly increased the high activity Ni3+ content in nickel-based OER electrocatalysts through an anodic electrodeposition strategy. The preparation process is time-saving and mature, which is expected to be applied in large-scale industrialization.

Enhancement of performance and kinetics of layered Li2MnO3 by Fe doping

Layered Li2MnO3 exhibits great potential as a high-capacity cathode used in lithium-ion batteries, but materials synthesized by traditional solid-phase methods exhibit poor activity and poor cycling stability. In this work, Li2MnO3 nanoparticles were synthesized by solid state method combined with high-energy ball milling, in which Fe was doped at transition metal sites to obtain a Li-rich cathode material (Li1.32Fe0.034Mn0.64O2). We systematically studied the effects of Fe doping and calcination temperature on the crystal structure and electrochemical properties and conducted kinetic studies using the galvanostatic intermittent titration technique (GITT), electrical impedance spectroscopy (EIS) and density functional theory (DFT) calculations. Our results demonstrate that the performance was significantly improved, its discharge capacity is about 235 mAh g−1 after 10 cycles compared 138 mAh g−1 of the pristine sample. The GITT and EIS results show that the Fe-doped sample had smaller charge transfer impedance, larger lithium-ion diffusion coefficient and lower internal polarization than the pristine. The activation energy results show the Fe-doped sample has larger activation energy at the late discharging period due to the anion redox reaction activation, indicting its O activation is more active than Li2MnO3. Moreover, the DOS results showed that the Fe-doped sample had a narrow band-gap, indicating good electrical conductivity. The CI-NEB results showed that the Fe-doped sample had a high transition metal ion migration energy barrier, indicating that its structure was stable. In conclusion, Fe doping is helpful to active the anion redox reaction in Li2MnO3 and improve its electrochemical performance as a low cost and high-capacity cathode materials.

Simultaneous Localization of Two High Affinity Divalent Metal Ion Binding Sites in the Tetracycline RNA Aptamer with Mn2+-Based Pulsed Dipolar EPR Spectroscopy.

Mg2+ ions play an essential part in stabilizing the tertiary structure of nucleic acids. While the importance of these ions is well documented, their localization and elucidation of their role in the structure and dynamics of nucleic acids are often challenging. In this work, pulsed electron-electron double resonance spectroscopy (PELDOR, also known as DEER) was used to localize two high affinity divalent metal ion binding sites in the tetracycline RNA aptamer with high accuracy. For this purpose, the aptamer was labeled at different positions with a semirigid nitroxide spin label and diamagnetic Mg2+ was replaced with paramagnetic Mn2+, which did not alter the folding process or ligand binding. Out of the several divalent metal ion binding sites that are known from the crystal structure, two binding sites with high affinity were detected: one that is located at the ligand binding center and another at the J1/2 junction of the RNA.