Structure and transport properties of triple-conducting BaxSr1−xTi1−yFeyO3−δ oxides

In this work, Ba_xSr_1−xTi_1−yFe_yO_3−δ perovskite-based mixed conducting ceramics (for x = 0, 0.2, 0.5 and y = 0.1, 0.8) were synthesized and studied. The structural analysis based on the X-ray diffraction results showed significant changes in the unit cell volume and Fe(Ti)–O distance as a function of Ba content. The morphology of the synthesized samples studied by means of scanning electron microscopy has shown different microstructures for different contents of barium and iron. Electrochemical impedance spectroscopy studies of transport properties in a wide temperature range in the dry- and wet air confirmed the influence of barium cations on charge transport in the studied samples. The total conductivity values were in the range of 10⁻³ to 10⁰ S cm⁻¹ at 600 °C. Depending on the barium and iron content, the observed change of conductivity either increases or decreases in humidified air. Thermogravimetric measurements have shown the existence of proton defects in some of the analysed materials. The highest observed molar proton concentration, equal to 5.0 × 10⁻² mol mol⁻¹ at 300 °C, was obtained for Ba_0.2Sr_0.8Ti_0.9Fe_0.1O_2.95. The relations between the structure, morphology and electrical conductivity were discussed.

Ba_xSr_1−xTi_1−yFe_yO_3−δ-based perovskite materials with different barium and iron contents are reported as triple conducting oxides (TCOs), which may conduct three charge carriers: oxygen ions, protons and electrons/holes.     

Chemical stability of Ca3Co4−xO9+δ/CaMnO3−δ p–n junction for oxide-based thermoelectric generators

An all-oxide thermoelectric generator for high-temperature operation depends on a low electrical resistance of the direct p–n junction. Ca₃Co_4−xO_9+δ and CaMnO_3−δ exhibit p-type and n-type electronic conductivity, respectively, and the interface between these compounds is the material system investigated here. The effect of heat treatment (at 900 °C for 10 h in air) on the phase and element distribution within this p–n junction was characterized using advanced transmission electron microscopy combined with X-ray diffraction. The heat treatment resulted in counter diffusion of Ca, Mn and Co cations across the junction, and subsequent formation of a Ca₃Co_1+yMn_1−yO₆ interlayer, in addition to precipitation of Co-oxide, and accompanying diffusion and redistribution of Ca across the junction. The Co/Mn ratio in Ca₃Co_1+yMn_1−yO₆ varies and is close to 1 (y = 0) at the Ca₃Co_1+yMn_1−yO₆–CaMnO_3−δ boundary. The existence of a wide homogeneity range of 0 ≤ y ≤ 1 for Ca₃Co_1+yMn_1−yO₆ is corroborated with density functional theory (DFT) calculations showing a small negative mixing energy in the whole range.

The heat treatment beneficially affects the performance of an all-oxide thermoelectric generator through phase and element distribution within this p–n junction.     

Photoreduction properties of novel Z-scheme structured Sr0.8La0.2(Ti1−δ4+Tiδ3+)O3/Bi2MoO6 composites for the removal of Cr(vi)

Novel Z-scheme structured Sr_0.8La_0.2(Ti_1−δ⁴⁺Ti_δ³⁺)O₃/Bi₂MoO₆ (LSTBM) composites were prepared via a facile two-step solvothermal method. Several characterization techniques were employed to investigate the phases, microstructures, compositions, valence states, oxygen vacancies, surface oxygen absorption, energy band structures and lifetime of photoproduced carriers. It was found that the lifetime and transfer of the photoproduced carriers of LSTBM were better than those of Bi₂MoO₆ (BMO) and Sr_0.8La_0.2(Ti_1−δ⁴⁺Ti_δ³⁺)O₃ (LSTO). The LSTBM with a molar ratio of BMO/(LSTO + BMO) = 0.07 (denoted as LSTBM7) showed 1.9 and 3.1 times removal rates than those for BMO and LSTO, respectively. Importantly, the built-in electric field in the heterojunction of LSTBM and O_v-s, especially in O_v-s on the higher-Fermi-level side of the heterojunction, had co-played roles in prolonging the lifetime and improving the transfer of photogenerated carriers. The photoproduced e⁻ played a dominant role in reducing Cr(vi) to Cr(iii) and the produced Cr(iii) tends to form Cr(OH)₃ and adsorb onto the surface of the photocatalyst to decrease the nucleation energy. The possible reduction route for Cr(vi) to Cr(iii) over LSTBM7 was figured out. This study implies that inducing O_v-s on the higher-Fermi-level side of the Z-scheme heterojunction is a more effective route for separating the photogenerated electrons and holes and improving the transfer of photogenerated carriers.

Found an effective way to improve the lifetime and transfer of photogenerated carriers: extrinsic O_v-s in the higher-Fermi-level side of the heterojunction. Z-scheme mechanism and O_v-s have synergistic effect on improving photocatalytic performance.     

Optical and dielectric properties of NaCoPO4 in the three phases α, β and γ

In this work, we are interested in the synthesis of monophosphate α-NaCoPO₄, β-NaCoPO₄ and γ-NaCoPO₄ compounds by mechanochemical method and their characterization by X-ray powder diffraction patterns. These compounds are crystallized in the orthorhombic, hexagonal and monoclinic system, in Pnma, P6₅ and P2₁/n space groups, respectively. The optical properties were measured by means of the UV-vis absorption spectrometry in order to deduce the absorption coefficient α and optical band gap E_g. The calculated values of the indirect band gaps (E_gi) for three samples were estimated at 4.71 eV, 4.63 eV and 3.8 for compounds α, β and γ, respectively. The Tauc model was used to determine the optical gap energy of the synthesized compounds. Then, the results of the dielectric proprieties measured by varying the frequency are described.

In this work, we are interested in the synthesis of monophosphate α-NaCoPO₄, β-NaCoPO₄ and γ-NaCoPO₄ compounds by mechanochemical method and their characterization by X-ray powder diffraction patterns.     

Additive effects of alkali metals on Cu-modified CH3NH3PbI3−δClδ photovoltaic devices

We investigated the addition of alkali metal elements (namely Na⁺, K⁺, Rb⁺, and Cs⁺) to Cu-modified CH₃NH₃PbI_3−δCl_δ photovoltaic devices and their effects on the photovoltaic properties and electronic structure. The open-circuit voltage was increased by CuBr₂ addition to the CH₃NH₃PbI_3−δCl_δ precursor solution. The series resistance was decreased by simultaneous addition of CuBr₂ and RbI, which increased the external quantum efficiencies in the range of 300–500 nm, and the short-circuit current density. The energy gap of the perovskite crystal increased through CuBr₂ addition, which we also confirmed by first-principles calculations. Charge carrier generation was observed in the range of 300–500 nm as an increase of the external quantum efficiency, owing to the partial density of states contributed by alkali metal elements. Calculations suggested that the Gibbs energies were decreased by incorporation of alkali metal elements into the perovskite crystals. The conversion efficiency was maintained for 7 weeks for devices with added CuBr₂ and RbI.

Addition of alkali metal elements (Na⁺, K⁺, Rb⁺, and Cs⁺) to Cu-modified CH₃NH₃PbI_3−δCl_δ devices improved the photovoltaic properties.     

Electronic and optical properties of perovskite compounds MA1−αFAαPbI3−βXβ (X = Cl,Br) explored for photovoltaic applications

As outstanding light harvesters, solution-processable organic–inorganic hybrid perovskites (OIHPs) have been drawing considerable attention thanks to their higher power conversion efficiency (PCE) and cost-effective synthesis relative to other photovoltaic materials. Nevertheless, their further development is severely hindered by the drawbacks of poor stability and rapid degradation in particular. First-principles calculations based on density functional theory (DFT) are hence performed towards the perovskite compounds MA_1−αFA_αPbI_3−βX_β (X = Cl, Br), with the aim of exploring more efficient and stable OIHPs. In addition to that, a hybrid density functional is adopted for exact electronic properties, and their band structures indicate that the doped series are all direct band-gap semiconductors. Moreover, the defect formation energies indicate that the stability of perovskite compounds can be significantly enhanced via ion doping. Meanwhile, it is unveiled that the optical performance of the doped perovskite series is also effectively improved through ion doping. Therefore, the investigated perovskite compounds MA_1−αFA_αPbI_3−βX_β (X = Cl, Br) are promising candidates for enhancing solar-energy conversion efficiency. Our results pave a way in deeper understanding of the inherent characteristics of OIHPs, which is useful for designing new-type perovskite-based photovoltaic devices.

The absorption performance of perovskite CH₃NH₃PbI₃ can be significantly improved via mono-, or co-doping of organic cations and halide ions.     

Evaluation of BaCo0.4Fe0.4Zr0.2−xNixO3−δ perovskite cathode using nickel as a sintering aid for IT-SOFC

In this research work, BaCo₀.₄Fe₀.₄Zr_0.2−xNi_xO_3−δ (x = 0, 0.01, 0.02, 0.03, 0.04) perovskite cathode material for IT-SOFC is synthesized successfully using a combustion method and sintered at low temperature. The effects of nickel as a sintering aid on the properties of BaCo₀.₄Fe₀.₄Zr₀.₂O_3−δ are investigated through different characterization methods. The addition of nickel increased the densification and grain growth at a lower sintering temperature 1200 °C. XRD analysis confirms a single phase of BaCo₀.₄Fe₀.₄Zr₀.₂O_3−δ, and an increase in crystalline size is observed. SEM micrographs show formation of dense microstructure with increased nickel concentration. TGA analysis revealed that BaCo₀.₄Fe₀.₄Zr_0.2−xNi_x cathode materials are thermally stable within the SOFC temperature range, and negligible weight loss of 2.3% is observed. The bonds of hydroxyl groups and metal oxides are confirmed for all samples through FTIR analysis. The highest electrical properties are observed for BaCo₀.₄Fe₀.₄Zr_0.2−xNi_x (x = 0.04) due to increased densification and electronic defects compared to other compositions. The maximum power density of 0.47 W cm⁻² is obtained for a cell having cathode material BaCo₀.₄Fe₀.₄Zr_0.2−xNi_x (x = 0.02) owing to its permeable and well-connected structure compared to others.

Electrochemical performance of BaCo₀.₄Fe₀.₄Zr_0.2−xNi_xO_3−δ at 600 °C.     

Cold sintering of YBa2Cu3O7−δ

Cold sintering is a sintering technique which enables ceramic powders to be densified at greatly reduced temperatures compared to traditional solid state techniques, which often require temperatures in excess of 1000 °C. These temperatures often preclude the exploitation of size or orientational effects in ceramics as these are lost during heating. One such effect is the orientation of the crystallographic c axis in YBa₂Cu₃O_7−δ (YBCO) which can be controlled through applied pressure. This effect is of interest for increasing critical current density which is highly dependent on the orientation of the a–b (CuO₂) planes within the ceramic. Using cold sintering, we demonstrate that dense YBCO can be created at 180 °C (vs. 1000 °C using solid state) and demonstrate that the likely sintering mechanism is mediated by the cracking which occurs in YBCO when exposed to water. In addition, the ceramics produced show and retain the orientational effect, representing a unique opportunity to study the effect on critical current density. We show that the intergranular critical current when the a–b planes are parallel to the applied field is around 15% higher than when perpendicular.

Cold sintered superconducting YBa₂Cu₃O_7−δ densified at 180 °C shows enhanced critical current densities by exploiting grain alignment created during pressing.     

A-site deficient semiconductor electrolyte Sr1−xCoxFeO3−δ for low-temperature (450–550 °C) solid oxide fuel cells

Fast ionic conduction at low operating temperatures is a key factor for the high electrochemical performance of solid oxide fuel cells (SOFCs). Here an A-site deficient semiconductor electrolyte Sr_1−xCo_xFeO_3−δ is proposed for low-temperature solid oxide fuel cells (LT-SOFCs). A fuel cell with a structure of Ni/NCAL-Sr_0.7Co_0.3FeO_3−δ–NCAL/Ni reached a promising performance of 771 mW cm⁻² at 550 °C. Moreover, appropriate doping of cobalt at the A-site resulted in enhanced charge carrier transportation yielding an ionic conductivity of >0.1 S cm⁻¹ at 550 °C. A high OCV of 1.05 V confirmed that neither short-circuiting nor power loss occurred during the operation of the prepared SOFC device. A modified composition of Sr_0.5Co_0.5FeO_3−δ and Sr_0.3Co_0.7FeO_3−δ also reached good fuel cell performance of 542 and 345 mW cm⁻², respectively. The energy bandgap analysis confirmed optimal cobalt doping into the A-site of the prepared perovskite structure improved the charge transportation effect. Moreover, XPS spectra showed how the Co-doping into the A-site enhanced O-vacancies, which improve the transport of oxide ions. The present work shows that Sr_0.7Co_0.3FeO_3−δ is a promising electrolyte for LT-SOFCs. Its performance can be boosted with Co-doping to tune the energy band structure.

Fast ionic conduction at low operating temperatures is a key factor for the high electrochemical performance of solid oxide fuel cells (SOFCs).     

Interactions between β-cyclodextrin and tea catechins,and potential anti-osteoclastogenesis activity of the (−)-epigallocatechin-3-gallate–β-cyclodextrin complex

Galloylated catechins, the most important secondary metabolites in green tea including (−)-epigallocatechin-3-gallate (EGCG) and (−)-epicatechin-3-gallate, constitute nearly 75% of all tea catechins and have stronger health effects than non-galloylated catechins such as (−)-epigallocatechin and (−)-epicatechin. EGCG is the most abundant, active, and thoroughly investigated compound in green tea, and its bioactivity might be improved by complexing with β-cyclodextrin (β-CD). We investigated interactions between four catechins and β-CD in a PBS buffer solution of pH 6.5 at 25 °C using biolayer interferometry and isothermal titration calorimetry, and to determine whether β-CD could enhance the anti-osteoclastogenesis effect of EGCG. β-CD could directly bind galloylated catechins at a stoichiometric ratio close to 1 : 1, with high specificities and affinities, and these inclusion interactions were primarily enthalpy-driven processes. We synthesized the EGCG–β-CD complex and identified it using infrared radiation and nuclear magnetic resonance spectra. Interestingly, we revealed that the EGCG–β-CD complex could inhibit osteoclastogenesis significantly more than EGCG.

The EGCG–β-CD complex inhibited osteoclastogenesis significantly more than EGCG, and the molecular mechanism was closely associated with the downregulation of NFATc1.     

High capacity rock salt type Li2MnO3−δ thin film battery electrodes

Recent investigations of layered, rock salt and spinel-type manganese oxides in composite powder electrodes revealed the mutual stabilization of the Li–Mn–O compounds during electrochemical cycling. A novel approach of depositing such complex compounds as an active cathode material in thin-film battery electrodes is demonstrated in this work. It shows the maximum capacity of 226 mA h g⁻¹ which is superior in comparison to that of commercial LiMn₂O₄ powder as well as thin films. Reactive ion beam sputtering is used to deposit films of a Li₂MnO_3−δ composition. The method allows for tailoring of the active layer''s crystal structure by controlling the oxygen partial pressure during deposition. Electron diffractometry reveals the presence of layered monoclinic and defect rock salt structures, the former transforms during cycling and results in thin films with extraordinary electrochemical properties. X-ray photoelectron spectroscopy shows that a large amount of disorder on the cation sub-lattices has been incorporated in the structure, which is beneficial for lithium migration and cycle stability.

The work demonstrates a novel route to synthesize disorder rich rock salt-type Li₂MnO_3−δ electrodes flaunting remarkably high capacity due to dynamic phase transformation during cycling.     

Transferable Anergy: Superantigen Treatment Induces CD4+ T Cell Tolerance That Is Reversible and Requires CD4−CD8− Cells and Interferon γ

Bacterial superantigens induce peripheral unresponsiveness in CD4⁺ T cell populations that express appropriate Vβ chains. We have used Vβ3/Vα11 T cell receptor transgenic (Tg) mice and the Vβ3-specific superantigen staphylococcal enterotoxin A (SEA) to further investigate the mechanisms that contribute to such unresponsiveness. As in other models, in vivo exposure to SEA rendered the Tg CD4⁺ cells unresponsive to subsequent restimulation in vitro with antigen or mitogens. However, when the SEA-treated CD4⁺ cells were completely purified away from all other contaminating cells, they regained the ability to proliferate and secrete cytokines. Moreover, enriched CD4⁻CD8⁻ cells from the SEA-treated mice suppressed the responses of fresh control CD4⁺ cells in mixed cultures indicating that the apparent “anergy” was both transferable and reversible. Further analysis demonstrated that interferon γ, but not the Fas receptor, played a critical role in the suppression.     

Density functional theory (DFT) investigation on the structure and photocatalysis properties of double-perovskite Gd1−xCaxBaCo2O5+δ (0 ≤ x ≤ 0.4)

GdBaCo₂O_5+δ (GCBC) has been widely used in various applications because of its unique structural characteristics. However, calcium-doped GCBC materials have not been comprehensively studied in terms of their structure and catalytic properties. Based on the first-principles density functional theory, the structure and electronic density of states were revealed by experiments and simulations. Ca-doping has a great influence on the materials'' crystal structure, optical absorption, and catalytic performance. Furthermore, Gd_0.8Ca_0.2BaCo₂O_5+δ show the best efficiency in the photocatalytic degradation of congo red (C₃₂H₂₂N₆Na₂O₆S₂). The presented Ca-doping method affects the overall band structure, electron cloud distribution, and electronic density of states to strengthen the charge-transfer between O-2p and Co-3d orbitals, and Co may be an active site. Our results provide a deep and systematic study on Gd_1−xCa_xBaCo₂O_5+δ based on theoretical calculations and experiments, including analysis of crystal structure, electron distribution, and catalytic performance.

Ca-doping affects the overall catalytic efficiency by adjusting the distribution of Co valence states and oxygen vacancies due to the strengthening of the charge transfer between O-2p and Co-3d orbitals upon substitution of Gd by Ca.     

Critical current density improvement in CSD-grown high-entropy REBa2Cu3O7−δ films

High-entropy oxide (HEO) superconductors have been developed since very recently. Different superconductors can be produced in the form of a high-entropy compound, including REBa₂Cu₃O_7−δ (REBCO). However, until now, mainly bulk samples (mostly in polycrystalline form) have been reported. In this work, the first CSD-grown high-entropy (HE) REBCO nanocomposite films were successfully synthesized. In particular, high-quality Gd_0.2Dy_0.2Y_0.2Ho_0.2Er_0.2Ba₂Cu₃O_7−δ nanocomposite films with 12 mol% BaHfO₃ nanoparticles were grown on SrTiO₃ substrates. The X-ray diffraction patterns show a near-perfect c-axis oriented grain growth. Both T_c and 77 K J^sf_c, 91.9 K and 3.5 MA cm⁻², respectively, are comparable with the values of the single-RE REBCO films. Moreover, at low temperatures, specifically at 30 K, the J_c values are larger than those of the single-RE samples. A transmission electron microscopy (TEM) study, including energy-dispersive X-ray spectroscopy (EDXS) measurements, reveals that the different RE³⁺ ions are distributed homogeneously in the matrix without forming clusters. This distribution causes point-like pinning centres that explain the superior performances of these samples at low temperatures. Although still seen as a proof-of-concept for the feasibility of preparing such films, these results demonstrate that the HE REBCO films are a promising option for the future fabrication of high-performance coated conductors. In the investigated B–T range, however, their J_c values are still lower than those of other, medium-entropy REBCO films, which shows that an optimization of the composition of the HE REBCO films is needed to maximize their performance.

High-resolution STEM-EDXS chemical analysis of (a) medium-entropy and (b) high-entropy REBCO films grown on SrTiO₃. The RE signals are homogeneously distributed in the films.     

Influence of defect on the electrical and optical properties of A-site non-stoichiometry Ca0.67La0.22□0.11Ti(1−x)CrxO3−δ perovskite

An investigation of the dielectric dispersion, electrical properties, scaling behavior and optical defects of Ca_0.67La_0.22□_0.11Ti_(1−x)Cr_xO_3−δ (CLT_(1−x)Cr_x) with x = 0 and x = 0.1 compositions is presented. The square in the formula is attributed to a vacancy in A-site. Relaxation phenomena were studied with dielectric and modulus formalism, while, the conductivity mechanism was investigated using electrical conductivity. A high permittivity of around 10⁴, low dielectric loss and low electrical conductivity of around 10⁻³ S cm⁻¹ for Ca_0.67La_0.22TiO₃ (CLT) was observed. These values make this composition interesting for microelectric applications. A comparison between the Z′′ and M′′ indicated that the short-range carrier motion dominates at low temperature and becomes less localized at high temperature. The optical defects of CLT and Ca_0.67La_0.22Ti_0.9Cr_0.1O₃ (CLT_0.9Cr_0.1) were studied by electron paramagnetic resonance (EPR) spectroscopy. The results suggest the formation of a [TiO₆]⁹⁻ center, a (Ti³⁺–V_O) center, and dipole defect for CLT compound and Cr³⁺–V_O center defect for CLT_0.9Cr_0.1 compound. These defects are the source of the in-gap electron traps, which improve the optical properties of CLT_(1−x)Cr_x and hence make it an interesting optical material for different applications.

An investigation of the real part of permittivity for the compositions (a) x = 0 and (b) x = 0.1 solid solution Ca_0.67La_0.22□_0.11Ti_(1−x)Cr_xO_3−δ ceramics.     

Phosphine-catalyzed [3 + 2] annulation of β-sulfonamido-substituted enones with trans-α-cyano-α,β-unsaturated ketones for the synthesis of highly substituted pyrrolidines

To synthesize highly substituted pyrrolidines, we developed a phosphine-catalyzed [3 + 2] annulation of β-sulfonamido-substituted enones with trans-α-cyano-α,β-unsaturated ketones. We prepared a series of pyrrolidines under mild conditions with high yields and moderate-to-good diastereoselectivities. A catalytic mechanism for this reaction is suggested.

To synthesize highly substituted pyrrolidines, we developed a phosphine-catalyzed [3 + 2] annulation of β-sulfonamido-substituted enones with trans-α-cyano-α,β-unsaturated ketones.

Nucleophilic phosphine catalysis is a practical and powerful synthetic approach to obtain heterocyclic compounds using various annulation reactions, the advantages of which are it being mild and metal-free, ecologically friendly, and inexpensive.¹ Phosphine-catalyzed intermolecular [3 + 2],² [4 + 1],³ [2 + 2 + 1]⁴ and intramolecular annulations are often used to obtain pyrrole derivatives. Intermolecular [3 + 2] annulations of imines and phosphorus ylides formed in situ from allenoates, alkynes, or Morita–Baylis–Hillman carbonates under the presence of phosphine catalysts are especially the most widely used approach to synthesize pyrrolidine derivates. In these reactions, phosphorus ylides act as C–C–C synthons for the [3 + 2] annulations with a C N bond converting to a pyrrolidine ring (Scheme 1). However, literature reports on exploring new activation modes, namely, phosphorus ylides acting as C–C–N synthons for the [3 + 2] annulations, are rare.Open in a separate windowScheme 1Pyrrolidine ring formation through reaction of phosphorus ylides act as C–C–C and C–C–N synthons.β-Sulfonamido-substituted enones could be used as C–C–N synthons to form various N-based heterocycles. Catalytically activated (by amines) β-sulfonamido-substituted enones act as nucleophiles towards electron-deficient olefins or imines during [3 + 2] annulation reactions. Du''s⁵ and Pan''s groups⁶ have made outstanding contributions to this field.⁷ In 2018, Guo''s group developed a Bu₃P-catalyzed [5 + 1] annulation of γ-sulfonamido-substituted enones with N-sulfonyl-imines to obtain chiral 2,4-di-substituted imidazolidines. They also synthesized γ-sulfonamido-substituted enones attacked by phosphine catalyst and acting as C–C–C–C–N synthon (see Scheme 2).⁸ Recently, Guo et al.⁹ used β-sulfonamido-substituted enone as a phosphine acceptor as well as a C–C–N synthon for the [3 + 2] annulation with sulfamate-derived cyclic imines (see Scheme 2). Using of β-sulfonamido-substituted enone as a novel phosphine acceptor is very promising for phosphine-catalyzed reactions. Inspired by Guo''s work, we further extended the substrate scope of this reaction from sulfamate-derived cyclic imines to unsaturated ketones for the construction of pyrrolidine rings. Therefore, in this work, we report phosphine-catalyzed [3 + 2] annulation of β-sulfonamido-substituted enones and trans-α-cyano-α,β-unsaturated ketones, to synthesize highly substituted pyrrolidines (see Scheme 2), which are among the primary building blocks and the core structures of natural and bioactive compounds.¹⁰Open in a separate windowScheme 2Phosphine-catalyzed annulation of γ-sulfonamido-substituted enones and β-sulfonamido-substituted enones.We first used trans-α-cyano-α,β-unsaturated ketone 1a and β-sulfonamido-substituted enone 2a as model substrates to obtain optimum reaction conditions. Tertiary phosphine catalysts were screened with 1,2-dichloroethane (DCE) as solvent at room temperature (see † Thus, the optimum reaction conditions were determined as follows: using 20 mol% of PMe₃ as catalyst, CHCl₃ as solvent at room temperature.Optimization of reaction conditions^a

Improvement of O2 adsorption for α-MnO2 as an oxygen reduction catalyst by Zr4+ doping

Zr⁴⁺ doped α-MnO₂ nanowires were successfully synthesized by a hydrothermal method. XRD, SEM, TEM and XPS analyses indicated that Mn³⁺ ions, Mn⁴⁺ ions, Mn^4+δ ions and Zr⁴⁺ ions co-existed in the crystal structure of synthesized Zr⁴⁺ doped α-MnO₂ nanowires. Zr⁴⁺ ions occupied the positions originally belonging to elemental manganese in the crystal structure and resulted in a mutual action between Zr⁴⁺ ions and Mn³⁺ ions. The mutual action made Mn³⁺ ions tend to lose their electrons and Zr⁴⁺ ions tend to get electrons. Cathodic polarization analyses showed that the electrocatalytic activity of α-MnO₂ for oxygen reduction reaction (ORR) was remarkably improved by Zr⁴⁺ doping and the Zr/Mn molar ratio notably affected the ORR performance of the air electrodes prepared by Zr⁴⁺ doped α-MnO₂ nanowires. The highest ORR current density of the air electrodes prepared by Zr⁴⁺ doped α-MnO₂ nanowires in alkaline solution appeared at Zr/Mn molar ratio of 1 : 110, which was 23% higher than those prepared by α-MnO₂ nanowires. EIS analyses indicated that the adsorption process of O₂ molecules on the surface of the air electrodes prepared by Zr⁴⁺ doped α-MnO₂ nanowires was the rate-controlling step for ORR. The DFT calculations revealed that the mutual action between Zr⁴⁺ and Mn³⁺ in Zr⁴⁺ doped α-MnO₂ nanowires enhanced the adsorption process of O₂ molecules.

O₂ adsorption was enhanced after doping Zr⁴⁺ into MnO₂ nanowires subsequently led to the improvement of ORR catalytic performance.     

Pharmacodynamics of (−)-β-2′,3′-Dideoxy-3′-Thiacytidine in Chronically Virus-Infected Woodchucks Compared to Its Pharmacodynamics in Humans

The pharmacodynamics of (−)-β-2′,3′-dideoxy-3′-thiacytidine (3TC) was studied in chronically woodchuck hepatitis virus-infected woodchucks and compared to that in previous studies in hepatitis B virus (HBV)-infected humans. Net depletion rates of serum virus DNA in woodchucks receiving 3TC were modeled as a sum of an exponentially declining virus input and a first-order elimination. Preceding shoulders and pseudo-first-order virus half-lives in serum ranged from 1 to 7 days and were dose dependent. Higher plasma 3TC concentrations were needed in woodchucks for virus depletion similar to that attained in humans. Human HBV depletion curves from a previous clinical study with 3TC (≥100 mg per day) were described by a biexponential relationship. The average half-life value in humans, normalized to fraction of area under the serum virus load-time curve, was similar to the average half-life value observed in woodchucks given the highest 3TC dose (2.4 and 2.0 days, respectively). On cessation of therapy, virus load rebounds in woodchucks were dose dependent and resembled posttherapy virus “flares” reported to occur in humans. The estimates of drug exposures that could lead to optimal antiviral effects presented indicate that 3TC should not be underdosed and compliance should be monitored. The study of chronically infected woodchucks may prove useful for optimizing drug regimens for hepadnavirus infections.