Similar Ionic Radii Research Articles

The first principle calculations of band offsets among Cs2(Ti, Zr, Hf)X6 double halide perovskites

This study investigates the band offsets among Cs2(Ti, Zr, Hf)X6 double halide perovskites. Valence band offsets (VBO) and conduction band offsets (CBO) were calculated using density functional theory (DFT) with the Perdew–Burke-Ernzerhof (PBE) functional and the hybrid Heyd–Scuseria–Ernzerhof (HSE) functional, employing the supercell technique. This technique offers greater accuracy and reliability by explicitly calculating the potential differences at the interface. A critical factor influencing the results is the contribution of the dipole potential (VD), which induces shifts in the VBO and CBO by approximately 0.2 to 0.6 eV relative to values predicted by the electron affinity rule. This discrepancy arises from the inclusion of interface-specific effects, such as charge redistribution and polarization. Additionally, the findings indicate that the energy band alignments among these compounds are type-I within the same group of halides, with nearly identical lattice constants for Zr- and Hf-based compounds due to their similar ionic radii. These results provide valuable insights for the design of heterostructures in electronic applications and highlight the potential of Cs2(Ti, Zr, Hf)X6 compounds as efficient materials for solar cells, light-emitting diodes, and photodetectors.

Robustly Boosting Thermoelectric Performance of N-Type PbSe via Lattice Plainification and Dynamic Doping.

Ideal thermoelectrics shall possess a high average ZT, which relies on high carrier mobility and appropriate carrier density at operating temperature. However, conventional doping usually results in a temperature-independent carrier concentration, making performance optimization over a wide temperature range be challenging. This work demonstrates the combination of lattice plainification and dynamic doping strategies is an effective route to boost the average ZT of N-type PbSe. Because Sn and Pb have similar ionic radii and electronegativity, this allows Sn to fill the intrinsic Pb vacancies and effectively improves the carrier mobility of PbSe to 1300 cm2 V-1 s-1. Furthermore, a trace amount of Cu is introduced into the Sn-filled PbSe to optimize the carrier concentration. The extra Cu is situated in the interstitial sides of the lattice, which undergoes a dissolution-precipitation process with temperature, leading to a strongly temperature-dependent carrier density in the material. This dynamic doping effectively improves the electrical transport properties and is also valid to suppress the lattice thermal conductivity. Ultimately, the resulting PbSn0.004Se+3‰Cu obtains a maximum ZT of ≈1.7 at 800 K and an average ZT of ≈1.0, with a 7.7% power generation efficiency in a single-arm device, showing significant potential for commercial application.

Conformation and Photodissociation Process of Benzo-15-Crown-5 and Benzo-18-Crown-6 Complexes with Ammonium Ions Investigated by Cold UV and IR Spectroscopy in the Gas Phase.

We examined the conformation of benzo-15-crown-5 (B15C5) and benzo-18-crown-6 (B18C6) complexes with ammonium ions, NH4+, CH3NH3+ (MeNH3+), CH3CH2NH3+ (EtNH3+), and CH3CH2CH2NH3+ (PrNH3+), using cold UV and IR spectroscopy in the gas phase. We measured the UV photodissociation (UVPD) spectra of the ammonium complexes and compared them with those of the K+(B15C5) and K+(B18C6) complexes in order to identify the conformation on the basis of the band position. The number of possible conformations for the ammonium complexes of B15C5 is limited compared with alkali metal ions with similar ionic radii. The NH4+(B15C5), MeNH3+(B15C5), and EtNH3+(B15C5) complexes show two conformers, whereas the K+(B15C5) complex has three stable conformers. In the case of the PrNH3+(B15C5) complex, one conformer was found predominantly in the UVPD spectrum. The ammonium complexes of B15C5 prefer to adopt crown conformations with large dihedral angles on the C-O-C-C atoms around the benzene moiety. In the case of the ammonium complexes of B18C6, two or three conformers were found in the UVPD spectra. One conformation of the B18C6 complexes is similar to that of the K+(B18C6) complex, which has a planar form on the C-O-C-C atoms around the benzene moiety. The other but dominant conformations of the ammonium complexes could be attributed to those with large C-O-C-C dihedral angles. These conformational findings for the ammonium complexes suggest that the benzo-crown ethers tend to adopt nonplanar conformations around the benzene moiety to encapsulate the ammonium ions. The IR-UV double-resonance (DR) spectra of the B15C5 and B18C6 complexes were compared to those of benzo-12-crown-4 (B12C4) and dibenzo-18-crown-6 (DB18C6) complexes. The N-H···O hydrogen bond (H-bond) is weaker with increasing ring size from B12C4 to B18C6, although the calculated binding energy is smaller for B12C4 than for B18C6. This result indicates that cooperative H-bonds with three N-H groups can strengthen the intermolecular bond between the ammonium ions and B18C6. The difference in the conformational preference between the ammonium and K+ complexes is attributed to directed N-H···O H-bonds in the ammonium complexes. Proton transfer and dissociation of the crown ring were also observed for the photoexcitation of the NH4+(B15C5) and NH4+(B18C6) complexes.

Single Crystal Sn-Based Halide Perovskites.

Sn-based halide perovskites are expected to be the best replacement for toxic lead-based counterparts, owing to their similar ionic radii and the optimal band gap for use in solar cells, as well as their versatile use in light-emitting diodes and photodetection applications. Concerns, however, exist about their stability under ambient conditions, an issue that is exacerbated in polycrystalline films because grain boundaries present large concentrations of defects and act as entrance points for oxygen and water, causing Sn oxidation. A current thriving research area in perovskite materials is the fabrication of perovskite single crystals, promising improved optoelectronic properties due to excellent uniformity, reduced defects, and the absence of grain boundaries. This review summarizes the most recent advances in the fabrication of single crystal Sn-based halide perovskites, with emphasis on synthesis methods, compositional engineering, and formation mechanisms, followed by a discussion of various challenges and appropriate strategies for improving their performance in optoelectronic applications.

The dynamic roles of intracellular vacuoles in heavy metal detoxification by Rhodotorula mucilaginosa.

Rhodotorula mucilaginosa (Rho) can develop a range of strategies to resist the toxicity of heavy metals. This study aimed to investigate the physiological responses and transcriptomic regulation of the fungus under different heavy metal stresses. This study applied transmission electron microscopy and RNA-seq to investigate the fungal resistance to Pb, Cd, and Cu stresses. Under Pb stress, the activated autophagy-related genes, vesicle-fusing ATPase, and vacuolar ATP synthase improved vacuolar sequestration. This offsets the loss of lipids. However, the metal sequestration by vacuoles was not improved under Cd stress. Vacuolar fusion was also inhibited following the interference of intravacuolar Ca2+ due to their similar ionic radii. Cu2+ showed the maximum toxic effects due to its lowest cellular sorption (as low as 7%) with respect to Pb2+ and Cd2+, although the efflux pumps and divalent metal ion transporters partially contributed to the detoxification. Divalent cation transporters and vacuolar sequestration are the critical strategies for Rho to resist Pb stress. Superoxide dismutase (SOD) is the main strategy for Cd resistance in Rho. The intracellular Cu level was decreased by efflux pump and divalent metal ion transporters.

Sr and Fe-Substituted LaMnO3 Perovskite for High-Rate Asymmetric Hybrid Supercapacitors

Perovskite has been getting significant attention in solar cells, photocatalysts, and hybrid supercapacitors. The symmetry or structural stability of ABO3-type perovskite oxides depends mainly on the size of ‘A’ and ‘B’ cations, which determines the material properties. The partial substitution of these cations may be used to tune these properties. The ionic sizes and valence states of the cations play an important role in improving the properties of perovskite. In this study, the substitution of La3+ with Sr2+ with a larger ionic radius and Mn3+ with Fe3+ with a similar ionic radius favored both the crystal symmetry and the mixed ionic-electronic conductivity of the perovskite. Electrodes based on La0.7Sr0.3Mn0.5Fe0.5O3 (LSMFO55) exhibited a faradaic behavior with a specific capacity of 330 C g-1 (92 mAh g-1) at a 12C rate, while this electrode maintained a capacity of 259 C g-1 at 240C (charge or discharge in 15s). Additionally, exohedral carbon nano-onions (CNO) were introduced as a negative electrode to design an asymmetric hybrid supercapacitor (AHS) with a widened cell voltage. The use of CNO as a negative electrode in the AHS improved the rate capability drastically compared to rGO. This device maintained a good energy density even at an extra-high charging rate (600C), owing to its outstanding rate capability. The high-rate performance of the LSMFO55//CNO AHS can be elucidated by successful fabrication with a mixed ionic-electronic conductive positive electrode and a CNO negative electrode. Tuning the electronic and ionic conductivities by cationic substitution and introducing CNO negative electrodes can provide a practical high-rate hybrid device using various perovskites.

P-Morpholinomethylcalix[4]arene incorporated polyacrylonitrile nanofibers as selective adsorbent for removal of Cu+2 from aqueous environment

ABSTRACT In this study, p-morpholinomethylcalix[4]arene (p-MC4) was synthesized using Mannich reaction and utilized for the fabrication of polyacrylonitrile nanofibers impregnated with p-morpholinomethylcalix[4]arene (PAN/p-MC4) using electrospinning. The nanofibers were prepared by blending 12% solution of PAN with 20% solution of p-MC4. The PAN/p-MC4 NFs were thoroughly evaluated for their removal efficiency of Cu2+ from the aqueous media. The selectivity of PAN/-p-MC4 nanofibers was also examined by adsorbing a set of metal ions with same charge and similar ionic radius. The results of distribution ratio showed that PAN/p-MC4 nanofibers have superior selectivity for Cu2+ as compared to other heavy metal ions. The relative selectivity coefficients of PAN/p-MC4 nanofibers were found to be 25.2, 14.1, 8.9, and 4.03 for Cu2+/Ni2+, Cu2+/Co2+, Cu2+/Cd2+ and Cu2+/Pb2+, respectively. This indicates that PAN/p-MC4 nanofibers have a higher selectivity for Cu2+ ions. Numerous parameters such as pH, time, adsorbent dosage and analyte concentration were optimized to evaluate the maximum adsorption capacity of nanofibers for Cu2+. Adsorption isotherm models showed that the adsorption is promising and follows Langmuir adsorption isotherm. Whereas, PAN/p-MC4 nanofibers followed pseudo- second order kinetics during adsorption experiments. The PAN/p-MC4 nanofibers showed excellent adsorption capacity (q o ) of 65.35 mg/g for Cu2+ at pH 5 in 60 min under shaking speed of 120 rpm. Moreover, PAN/p-MC4 nanofibers had been used to remove Cu2+ from real surface water samples. According to the results, PAN/p-MC4 nanofibers are more effective adsorbent for removing Cu2+ from contaminated water.

Rare Earth Element Binding and Recovery by a Beta Roll-Forming RTX Domain.

The Block V of the RTX domain of the adenylate cyclase protein from Bordetella pertussis is disordered, and upon binding eight calcium ions, it folds into a beta roll domain with a C-terminal capping group. Due to their similar ionic radii and coordination geometries, trivalent lanthanide ions have been used to probe and identify calcium-binding sites in many proteins. Here, we report using a FRET-based assay that the RTX domain can bind rare earth elements (REEs) with higher affinities than calcium. The apparent disassociation constants for lanthanide ions ranged from 20 to 75 μM, which are an order of magnitude higher than the affinity for calcium, with a higher selectivity toward heavy REEs over light REEs. Most proteins release bound ions at mildly acidic conditions (pH 5-6), and the high affinity REE-binding lanmodulin protein can bind 3-4 REE ions at pH as low as ∼2.5. Circular dichroism (CD) spectra of the RTX domain demonstrate pH-induced folding of the beta roll domain in the absence of ions, indicating that protonation of key amino acids enables structure formation in low pH solutions. The beta roll domain coordinates up to four ions in extreme pH conditions (pH < 1), as determined by equilibrium ultrafiltration experiments. Finally, to demonstrate a potential application of the RTX domain, REE ions (Nd3+ and Dy3+) were recovered from other non-REEs (Fe2+ and Co2+) in a NdFeB magnet simulant solution (at pH 6).

Preparation and properties of cordierite-based multi-phase composite far-infrared emission ceramics by fine-grained tailings

In this paper, cordierite ceramics with high far-infrared emission properties are synthesized by a high-temperature solid-phase method using molybdenum tailings and vanadium-titanium magnetite tailings. The microstructure, physical properties and far-infrared emission mechanism of ceramics are investigated. The results show that the ceramics synthesized with 10 wt% molybdenum tailings and 30 wt% vanadium-titanium magnetite tailings have a flexural strength of 67 MPa, a bulk density of 2.531 g/cm3 and a maximum far-infrared emissivity of 0.958 when the sintering temperature is 1200 °C. The crystal phase of the ceramic are 21.4 % cordierite and 58.7 % magnesia-alumina spinel. In the sintering process, the Fe3+ in vanadium-titanium magnetite tailings doped into the cordierite to substitute the Mg2+, which has the similar ionic radius with Fe3+, to form a substitutional solute. Ionic substitution causes the lattice parameters of cordierite larger, reducing the symmetry of the lattice vibrations and leading to lattice distortion. In addition, the composition of a large amount of magnesia-aluminum spinel is attributed to the far-infrared emission properties of ceramics.

Unraveling Parent Rock and Mineral Influences in Tropical Weathering Profiles: REE, Nd and Sr Isotopic Geochemistry

This study aims to investigate the effects of parent rock and minerals on lateritic weathering. The study presents X-ray diffraction (XRD), whole-rock geochemistry, and Nd-Sr isotopic data for examining two profiles, 10 and 12 m thick, respectively, that illustrate the regional tropical weathering status in the Midwest of Brazil. The profiles, developed from metasedimentary and sedimentary rocks, are constituted by saprolite, mottled horizon, lateritic duricrust, and oxisol. Across the profiles, the minerals controlling the weathering geochemistry are muscovite, microcline, quartz, kaolinite, hematite, goethite, and gibbsite. Red and yellow zones in the saprolite and mottled horizon as well as the lateritic duricrust with breccia/fragmental, pisolitic, and oolitic textures make profile 1 more complex. In contrast, profile 2 has an oxisol that mantles the homogeneous vermiform lateritic duricrust. Fe2O3, accumulated during surface weathering, is a potent element in the geochemical profile control since it forms the harder goethite to hematite lateritic duricrust, bearing most of the trace elements (As, Cu, Cs, Pb, Sc, Sr, Th, U, V, and Zn) with similar ionic radii and electrovalence. The LREE have affinity for the elements of the Fe2O3 group of the lateritic duricrust. On the other hand, the K2O group together with Zr and TiO2 e in the phyllite, saprolite, and mottled horizon of profile 1, are associated with the HREE. Additionally, in profile 2, the HREE are mostly associated with the Al2O3 group and the residual minerals in the oxisol. The indication that REE is associated with phosphates, zircon, rutile/anatase, cereanite, and muscovite/illite, which have variable weathering behavior, caused the REE fractionation to occur across and between the profiles. Despite the REE fractionation, the ƐNd(0) values along the profiles consistently maintain the signature of the parent rock. Muscovite and microcline weathering, in profiles 1 and 2, respectively, control the decrease in 87Sr/86Sr signatures of both profiles and the distinct radiogenic ratios. The development of lateritic duricrust in both profiles indicates a similar weathering intensity, although the gibbsite–kaolinite predominance in the oxisol of profile 2 highlights a geochemical reorganization under humid conditions, as well as near-intense soluble silica leaching.

Structure and activity relationships of AMn2O4 (A = Mg and Zn) spinels in selective catalytic reduction of NOx with NH3

Mn-based spinel as a catalyst for low-temperature selective catalytic reduction with ammonia (NH3-SCR) has been widely studied. However, most researchers have focused on double transition metal Mn-based spinel and the reports about doping with non-transition metal are not common. Herein, Mg2+ and Zn2+ with similar ionic radii were used to prepare high purity MgMn2O4 and ZnMn2O4 (named MMO and ZMO) to study their structure and activity relationships in NH3-SCR. It was found that the denitration performance of the two showed significant differences at low temperature despite have a very similar crystal structure. A series of characterization methods and first-principles calculations demonstrates that the relatively weak bonding strength and basic adsorption sites of MMO catalyst are the key factors contributing to its superior reactivity at low temperatures. This work provides novel insights and ideas in comprehending the catalytic function of non-transition metal-doped Mn-based spinels in NH3-SCR reactions.

Band Gap Narrowing by Suppressed Lone-Pair Activity of Bi3.

Post-transition metal cations with a lone pair (ns2np0) electronic configuration such as Pb2+ and Bi3+ are important components of materials for solar-to-energy conversion. As in molecules like NH3, the lone pair is often stereochemically active in crystals, associated with distorted coordination environments of these cations. In the present study, we demonstrate that suppressed lone pair stereochemical activity can be used as a tool to enhance visible light absorption. Based on an orbital interaction model, we predict that a centrosymmetric environment of the cations limits the orbital interactions with anions, deactivates the lone pair, and narrows the band gap. A high-symmetry Bi3+ site is realized by isovalent substitutions with Y3+ by considering its similar ionic radius and absence of a lone pair. The quaternary photocatalyst Bi2YO4X is singled out as a candidate for Bi substitution from a survey of the coordination environments in Y-O compounds. The introduction of Bi3+ to the undistorted Y3+ site in Bi2YO4X results in a narrowed band gap, as predicted theoretically and confirmed experimentally. The orbital interaction controlled by site symmetry engineering offers a pathway for the further development of post-transition metal compounds for optoelectronic applications.

Promoting Na-ion storage in P2-Na0.67Ni0.33Mn0.67O2 cathode via synergetic Ti and Zn Co-incorporation

P2-Na0.67Ni0.33Mn0.67O2 (NNMO) is regarded as a promising cathode candidate for sodium-ion batteries due to its high energy density. However, the electrochemical performance is hindered by Na+/vacancy order, irreversible P2–O2 phase transition at high voltage (&amp;gt;4.2 V), and harmful oxygen evolution. Herein, a synergetic Zn and Ti co-incorporation tactic is proposed for designing a Na0.67Ni0.29Zn0.04Mn0.63Ti0.04O2 (NNZMTO) cathode to overcome the above-mentioned challenges. First, the incorporated Ti heteroatom could break down Na+/vacancy order of NNMO by taking advantage of a similar ionic radius and substantially different Fermi levels with host Mn atom. Subsequently, the introduced Zn heteroatom could induce local Na–O–Zn configurations, buffer interlayer O2−–O2− electrostatic repulsion, as well as inhibit unfavorable phase transition. Moreover, the d10 band of Zn is lower than the oxygen states, and the Zn behaves like an s/p metal with oxygen, thus avoiding O2 release. Notably, in comparison with highly oxidized (Ni4+/Mn4+O6)δ− octahedron, the partial Na+ for charge neutrality in alkali metal layers could be well maintained in the as-designed (Zn2+/Ti4+O6)δ′−, which could be served as “pillars” to avoid layer gliding and structural collapse in the c-direction. As a result, an excellent electrochemical performance with high specific capacity of 90.9 mA h g−1 at 7 C could be retained for NNZMTO thanks to the synergetic effect from Ti and Zn incorporation. This study provides deep insights for designing superior layered cathode via conducting a rational cations co-incorporation strategy.

Carbene Complexes of Plutonium: Structure, Bonding, and Divergent Reactivity to Lanthanide Analogs.

Organoplutonium chemistry was established in 1965, yet structurally authenticated plutonium-carbon bonds remain rare being limited to π-bonded carbocycle and σ-bonded isonitrile and hydrocarbyl derivatives. Thus, plutonium-carbenes, including alkylidenes and N-heterocyclic carbenes (NHCs), are unknown. Here, we report the preparation and characterization of the diphosphoniomethanide-plutonium complex [Pu(BIPMTMSH)(I)(μ-I)]2 (1Pu, BIPMTMSH = (Me3SiNPPh2)2CH) and the diphosphonioalkylidene-plutonium complexes [Pu(BIPMTMS)(I)(DME)] (2Pu, BIPMTMS = (Me3SiNPPh2)2C) and [Pu(BIPMTMS)(I)(IMe4)2] (3Pu, IMe4 = C(NMeCMe)2), thus disclosing non-actinyl transneptunium multiple bonds and transneptunium NHC complexes. These Pu-C double and dative bonds, along with cerium, praseodymium, samarium, uranium, and neptunium congeners, enable lanthanide-actinide and actinide-actinide comparisons between metals with similar ionic radii and isoelectronic 4f5 vs 5f5 electron-counts within conserved ligand fields over 12 complexes. Quantum chemical calculations reveal that the orbital-energy and spatial-overlap terms increase from uranium to neptunium; however, on moving to plutonium the orbital-energy matching improves but the spatial overlap decreases. The bonding picture that emerges is more complex than the traditional picture of the bonding of lanthanides being ionic and early actinides being more covalent but becoming more ionic left to right. Multiconfigurational calculations on 2M and 3M (M = Pu, Sm) account for the considerably more complex UV/vis/NIR spectra for 5f5 2Pu and 3Pu compared to 4f5 2Sm and 3Sm. Supporting the presence of Pu═C double bonds in 2Pu and 3Pu, 2Pu exhibits metallo-Wittig bond metathesis involving the highest atomic number element to date, reacting with benzaldehyde to produce the alkene PhC(H)═C(PPh2NSiMe3)2 (4) and "PuOI". In contrast, 2Ce and 2Pr do not react with benzaldehyde to produce 4.

Mechanism insight into enhanced oxygen reduction reaction over heterovalent ion incorporated pyrochlore Pr2Zr2O7 for direct ammonia solid oxide fuel cells

An effective B-site doping strategy through heterovalent ions was developed to synthesize a series of pyrochlore Pr2Zr1.95X0.05O7+δ (PZX, X = Mn, Sc, Sn, Nb, Mo, Al, Ga, In) for the direct ammonia solid oxide fuel cell (DA-SOFC) cathode. To guide the design of efficient cathodes for DA-SOFC, we explore the relationships between the ionic radius/valence of dopant and electrochemical performance. In view of the energy matching and interaction between the dopant and the host lattice, the substitution of trivalent Sc3+ with similar ionic radius for tetravalent Zr4+ can greatly improve the oxygen reduction reaction activity of Pr2Zr2O7 due to the reduced bond energy of 48f-oxygen ions in octahedral [ZrO6] units. As a result, the anode-supported single cell Ni-YSZ|YSZ|PZSc-60YSZ yields an output power density of 0.44 and 1.45 W·cm−2 at 600 and 800 °C with ammonia fuel, outperforming PZX (X = Mn, Sn, Nb, Mo, Al, Ga, In) and common La0.8Sr0.2MnO3 (LSM)-based DA-SOFC. The detailed characterizations are employed to gain insight into the structure-activity relationship and reaction mechanism.

Non-Aqueous Rechargeable Rb-O2 Batteries

Li-O2 batteries have attracted increasing attention because their theoretical energy density exceeds that of current lithium-ion batteries.[1] Generally, the positive electrode reaction in nonaqueous alkali metal-O2 batteries proceeds through oxygen reduction and corresponding reoxidation, forming alkali metal superoxide (MO2) as the discharge product. It is known that the stability of the superoxide (MO2) depends on the relationship between the ionic radius of the alkali metal ion (M+) and the superoxide ion (O2 −).[2] For example, LiO2 consists of small Li+ (ionic radius in octahedral coordination: 0.76 Å) and relatively large O2 − (1.49 Å), resulting in its short lifetime and rapid disproportionation reaction; 2LiO2 → Li2O2+O2. As the two-electron reduction product, Li2O2, exhibits a large overpotential to re-oxidize it, Li-O2 cells are known to have low reversibility.[1] On the other hand, NaO2 is relatively stable because the ionic radius of Na+ (1.02 Å) is relatively large compared to that of Li+. Thus, Na-O2 battery is also promising due to the low charge overpotential of the one-electron reduction product, NaO2. However, NaO2 is highly reactive with a trace amount of moisture, CO2, and electrolyte components, partially forming Na2O2 and/or its hydrates.[3] Further stabilization was observed by using K+ (1.38 Å) to form KO2, thus K-O2 cell is known to have high stability and reversibility as well as low overpotential.[4] Following these trends, in this study, we focused on Rb+ (1.52 Å), which has a similar ionic radius to O2 − (1.49 Å), and investigated the electrochemistry of oxygen reduction and evolution reaction in Rb-containing non-aqueous electrolytes.The working electrode is prepared by mixing Ketjen black (KB) and polytetrafluoroethylene (PTFE) in a weight ratio of 80:20, followed by coating it on carbon paper. The counter electrode consists of activated carbon, KB, and PTFE mixed with an 80:10:10 weight ratio. Ag+/Ag reference electrode and rubidium bis(trifluoromethanesulfonyl)amide (RbTFSA)/ triglyme (G3) electrolytes were also used to fabricate three-electrode O2-cell. The cells were first assembled in an Ar-filled glove box, followed by purging dry-O2 gas to supply an adequate amount of O2 in the cell. Note that Rb metal was not used for safety reasons.Figure (a) presents the charge-discharge curves obtained with 1 mol/dm3 RbTFSA/G3 electrolyte under a dry-O2 and dry-Ar atmosphere. While no capacity was observed under the Ar atmosphere, distinct plateaus appeared at 2.57 and 2.67 V (vs. Rb+/Rb) at discharge and charge sequence, respectively, under the O2 atmosphere. A discharge capacity of ~0.6 mAh cm−2 and a relatively small overpotential of 100 mV were achieved, as well as high Coulombic efficiency at the initial cycle of 71 %. Figure (b) shows XRD patterns of pristine and fully discharged electrodes, where all of the new peaks that appeared through discharge reaction can be assignable to RbO2. Therefore, the discharge product of the Rb-O2 cell is confirmed to be RbO2, similar to Na-O2 and K-O2 cells. The reaction mechanism, reversibility, and stability of the O2/RbO2 electrode will be presented and discussed.Reference:[1] P. Bruce, J-M. Tarascon, et al., Nat. Mater., 11, 19-29 (2012).[2] L. Qin, Y. Wu, et al., J. Am. Chem Soc., 142, 11629 (2020).[3] P. Hartmann, P. Adelhelm, et al., Nat. Mater., 12, 228 (2013).[4] X. Ren, Y. Wu, J. Am. Chem. Soc., 2, 2923 (2013). Figure 1

Calcium Activation of the Androgen Receptor in Prostate Cells.

Although prostate cancer patients initially respond to androgen deprivation therapy, most patients progress to a resistant phenotype. Castration resistance is due, in part, to intratumoral and/or adrenal synthesis of androgens, overexpression or mutation of the androgen receptor (AR), stabilization of AR by chaperones, and ligand-independent activation of AR. Increasing evidence also links disruption of calcium homeostasis to progression of prostate cancer. Our previous study shows that heavy metal cadmium activates the AR through a ligand-independent mechanism. Cadmium mimics calcium in biological systems due to their similar ionic charge and radius. This study determines whether calcium activates AR and whether first- and second-generation antiandrogens block the ability of calcium to activate the receptor. The expression of androgen-responsive genes and calcium channels was measured in prostate cells using a quantitative real-time polymerase chain reaction assay. Cell growth was measured. To ask whether calcium activates AR, prostate cells were treated with calcium in the absence and presence of the first-generation antiandrogens hydroxyflutamide and bicalutamide and the second-generation antiandrogen enzalutamide, and the expression of androgen-responsive genes and cell growth was measured. In the normal PWR-1E cells and HEK293T cells transiently expressing AR, treatment with calcium increased the expression of androgen-responsive genes by approximately 3-fold. The increase was blocked by enzalutamide but was not consistently blocked by the first-generation antiandrogens. In LNCaP cells which contain a mutant AR, treatment with calcium also increased the expression of androgen-responsive genes by approximately 3-fold, and the increase was more effectively blocked by enzalutamide than by hydroxyflutamide or bicalutamide. Treatment with calcium also increased cell growth that was blocked by enzalutamide. To ask whether dysregulation of calcium channels is associated with castration resistance, calcium channels were measured in the normal PWR-1E prostate cells, the hormone-responsive LNCaP cells, and the castration-resistant VCaP and 22RV1 cells. Compared to normal prostate cells, the hormone-responsive and hormone-resistant cells overexpressed several calcium channels. The results of this study show that calcium activates AR and increases cell growth and that calcium channels are overexpressed in hormone-responsive and hormone-resistant prostate cancer cells. Taken together, the results suggest a novel role of calcium in the castration-resistant phenotype.

Genetic Modification of Acidithiobacillus ferrooxidans for Rare-Earth Element Recovery under Acidic Conditions.

As global demands for rare-earth elements (REEs) continue to grow, the biological recovery of REEs has been explored as a promising strategy, driven by potential economic and environmental benefits. It is known that calcium-binding domains, including helix-loop-helix EF hands and repeats-in-toxin (RTX) domains, can bind lanthanide ions due to their similar ionic radii and coordination preference to calcium. Recently, the lanmodulin protein from Methylorubrum extorquens was reported, which has evolved a high affinity for lanthanide ions over calcium. Acidithiobacillus ferrooxidans is a chemolithoautotrophic acidophile, which has been explored for use in bioleaching for metal recovery. In this report, A. ferrooxidans was engineered for the recombinant intracellular expression of lanmodulin. In addition, an RTX domain from the adenylate cyclase protein of Bordetella pertussis, which has previously been shown to bind Tb3+, was expressed periplasmically via fusion with the endogenous rusticyanin protein. The binding of lanthanides (Tb3+, Pr3+, Nd3+, and La3+) was improved by up to 4-fold for cells expressing lanmodulin and 13-fold for cells expressing the RTX domains in both pure and mixed metal solutions. Interestingly, the presence of lanthanides in the growth media enhanced protein expression, likely by influencing protein stability. Both engineered cell lines exhibited higher recoveries and selectivities for four tested lanthanides (Tb3+, Pr3+, Nd3+, and La3+) over non-REEs (Fe2+ and Co2+) in a synthetic magnet leachate, demonstrating the potential of these new strains for future REE reclamation and recycling applications.

Ultraviolet and visible persistent luminescence from Sr3MgSi2O8:Pr3+

In this paper, a low dose X-ray induced long afterglow luminescent phosphor Sr3MgSi2O8:Pr3+ has been reported. The structure analysis shows the as-prepared samples possess good crystallinity and the emitting center Pr3+ is more likely to occupy the lattice position of Sr2+ due to their similar ionic radius. And under 471.1 nm excitation, Sr3MgSi2O8:Pr3+ shows bright visible lights peaked at 545.5, 617.1 and 648.6 nm, respectively, corresponding to the transitions of 3P0→3H5, 3P0→3H6 and 3P0→3F2 of Pr3+. After the X-ray irradiation, this phosphor shows strong ultraviolet C (291.7 nm), blue (493.2 nm) and red lights (617.1 nm). More important, only 5 s X-ray irradiation X-ray irradiation can easily charge Sr3MgSi2O8:Pr3+ to produce 5400 s afterglow emission. Even after 5400 s, its afterglow emissions still remain strong, which is about 20 times of the background intensity. The thermoluminescent results indicate that Sr3MgSi2O8 possesses a high absorption rate for X-rays and thus X-ray irradiation can excite the host to produce large number of electrons, Secondary electron, which would rapidly fill up the traps and thus produce excellent long afterglow luminescence. In addition, the existing suitable traps with 0.76 eV trap depth are also favorable for persistent luminescence at room temperature. Thus, Sr3MgSi2O8:Pr3+ is confirmed to be a very efficient low dose X-ray induced long afterglow luminescent phosphor.

A theoretical–experimental study of KSr2Nb(3-x)TaxO10 (x = 0,1,2) systems as photocatalysts

Understanding the influence of structural changes arising from electronic characteristics is a significant challenge in novel material development. The Nb(V) and Ta(V) cations are pertinent due to their similar ionic radii across various coordinations. Layered perovskites (KSr2Nb(3-x)TaxO10, where x = 0,1, and 2) were synthesized using the solid-state method. These compounds were characterized employing experimental techniques and subjected to photocatalytic testing in a model reaction. Density Functional Theory simulations were conducted, confirming experimental data accuracy and prediction reliability. Evaluation of intra and inter-octahedral distortion and charge carrier effective masses were correlated with experimental outcomes. Remarkably, substituting Nb with Ta increased photocatalytic activity, suggesting a promising avenue for tailoring material properties.