On the Hydration of Heavy Rare Earth Ions: Ho3+, Er3+, Tm3+, Yb3+ and Lu3+-A Raman Study.

Raman spectra of aqueous Ho3+, Er3+, Tm3+, Yb3+, and Lu3+-perchlorate solutions were measured over a large wavenumber range from 50-4180 cm-1. In the low wavenumber range (terahertz region), strongly polarized Raman bands were detected at 387 cm-1, 389 cm-1, 391 cm-1, 394 cm-1, and 396 cm-1, respectively, which are fairly broad (full widths at half height at ~52 cm-1). These isotropic Raman bands were assigned to the breathing modes, ν1 Ln-O of the heavy rare earth (HRE) octaaqua ions, [Ln(H2O)8]3+. The strong polarization of these bands (depolarization degree ~0) reveals their totally symmetric character. The vibrational isotope effect was measured in Yb(ClO4)3 solutions in H2O and D2O and the shift of the ν1 mode in changing from H2O to D2O further supports the character of the band. The Ln-O bond distances of these HRE ions (Ho3+, Er3+, Tm3+, Yb3+, and Lu3+) follow the order of Ho-O > Er-O > Tm-O > Yb-O > Lu-O which correlates inversely with the band positions of the breathing modes of their corresponding octaaqua ions [Ln(OH2)8]3+. Furthermore, the force constants, kLn-O, were calculated for these symmetric stretching modes. Ytterbium perchlorate solutions were measured over a broad concentration range, from 0.240 mol·L-1 to 2.423 mol·L-1, and it was shown that with increasing solute concentration outer-sphere ion pairs and contact ion pairs were formed. At the dilute solution state (~0.3 mol·L-1), the fully hydrated ions [Yb(H2O)8]3+ exist, while at higher concentrations (CT > 2 mol·L-1), ion pairs are formed. The concentration behavior of Yb(ClO4)3 (aq) shows similar behavior to the one observed for La(ClO4)3(aq), Ce(ClO4)3(aq) and Lu(ClO4)3(aq) solutions. In ytterbium chloride solutions in water and heavy water, representative for the behavior of the other HRE ions, 1:1 chloro-complex formation was detected over the concentration range from 0.422-3.224 mol·L-1. The 1:1 chloro-complex in YbCl3(aq) is very weak, diminishing rapidly with dilution and vanishing at a concentration < 0.4 mol·L-1.

There and Back Again-The Journey of LiNiO2 as a Cathode Active Material.

This Review provides a comprehensive overview of LiNiO2 (LNO), almost 30 years after its introduction as a cathode active material. We aim to highlight the physicochemical peculiarities that make LNO a complex material in every aspect. We specifically stress the effect of the Li off-stoichiometry (Li1-z Ni1+z O2 ) on every property of LNO, especially the electrochemical ones. The key instability issues that plague the compound and the strategies that have been implemented so far to overcome them are discussed in detail. Finally, the open questions that remain to be addressed by the scientific community are summarized, and the research directions that seem the most promising to enable LNO to be fully exploited are elucidated.

Electrochemically Assisted Construction of a La2NiO4+δ@Pt Core-Shell Structure for Enhancing the Performance and Durability of La2NiO4+δ Cathodes.

Ruddlesden-Popper oxide La2NiO4+δ (LNO) has a high ionic conductivity and good thermal match with the electrolyte of solid oxide fuel cells (SOFCs); however, LNO suffers from performance decay owing to the La surface segregation under the operation conditions of SOFCs. Herein, we report an in situ electrochemical decoration strategy to improve the electrocatalytic activity and durability of LNO cathodes. We show that the electrochemical polarization leads to in situ construction of the LNO@Pt core-shell structure, significantly suppressing the detrimental effect of La surface segregation on the LNO cathode. The initial peak power density of a single cell with the LNO cathode is 0.71 W cm-2 at 750 °C, increasing to 1.39 W cm-2 by the in situ construction of the LNO@Pt core-shell structure after polarization at 0.5 A cm-2 for 20 h. The LNO@Pt core-shell structure is also highly durable without noticeable performance degradation over the duration of the test for 180 h. The findings shed light on the design and fabrication of highly active and durable LNO-based cathodes for SOFCs.

On the Sensitivity of the Ni-rich Layered Cathode Materials for Li-ion Batteries to the Different Calcination Conditions.

Ni-rich layered oxides, i.e., LiNi0.6Mn0.2Co0.2O2 (NMC622) and LiNiO2 (LNO), were prepared using the two-step calcination procedure. The samples obtained at different calcination temperatures (750-950 °C for the NMC622 and 650-850 °C for the LNO cathode materials) were characterized using nitrogen physisorption, PXRD, SEM and DLS methods. The correlation of the calcination temperature, structural properties and electrochemical performance of the studied Ni-rich layered cathode materials was thoroughly investigated and discussed. It was determined that the optimal calcination temperature is dependent on the chemical composition of the cathode materials. With increasing nickel content, the optimal calcination temperature shifts towards lower temperatures. The NMC-900 calcined at 900 °C and the LNO-700 calcined at 700 °C showed the most favorable electrochemical performances. Despite their well-ordered structure, the materials calcined at higher temperatures were characterized by a stronger sintering effect, adverse particle growth, and higher Ni2+/Li+ cation mixing, thus deteriorating their electrochemical properties. The importance of a careful selection of the heat treatment (calcination) temperature for each individual cathode material was emphasized.

Exchange Bias Effect and Orbital Reconstruction in (001)-Oriented LaMnO3/LaNiO3 Superlattices.

Paramagnetic LaNiO3 (LNO)-based heterostructures have been attracting the attention of researches, especially since the interesting exchange bias (EB) effect has been observed in (111)-oriented LaMnO3 (LMO)/LNO superlattices (SLs). However, this effect is not expected to occur in the (001) direction SLs. In this paper, we report the observation of an unexpected EB effect in (001)-oriented (LMO)3/(LNO)t SLs. The orbits of interfacial Mn/Ni ions preferentially occupy the strain-stabilized x2 - y2 in ultrathin LNO layers [t ≤ 4 unit cells (u.c.)]. Conversely, as the LNO layer becomes thicker (t ≥ 6 u.c.), the EB effect is absent, and the orbits are reconstructed to form the 3z2 - r2 preferential occupancy. The absence of the EB in thicker LNO-based SLs is attributed to the interfacial charge transfer suppressed by orbital reconstruction as a consequence of the increasing LNO thickness. In the thinner LNO-based SLs, the larger charge transfer results in stronger localized magnetic moments for the cause of the EB effect. These results provide a useful interpretation of the relationship between macroscopic magnetic properties and the microscopic electronic structure in oxide-based heterostructures.

Robust Interfacial Exchange Bias and Metal-Insulator Transition Influenced by the LaNiO3 Layer Thickness in La0.7Sr0.3MnO3/LaNiO3 Superlattices.

Artificial heterostructures based on LaNiO3 (LNO) have been widely investigated with the aim to realize the insulating antiferromagnetic state of LNO. In this work, we grew [(La0.7Sr0.3MnO3)5-(LaNiO3)n]12 superlattices on (001)-oriented SrTiO3 substrates by pulsed laser deposition and observed an unexpected exchange bias effect in field-cooled hysteresis loops. Through X-ray absorption spectroscopy and magnetic circular dichroism experiments, we found that the charge transfer at the interfacial Mn and Ni ions can induce a localized magnetic moment. A remarkable increase of exchange bias field and a transition from metal to insulator were simultaneously observed upon decreasing the thickness of the LNO layer, indicating the antiferromagnetic insulator state in 2 unit cells LNO ultrathin layers. The robust exchange bias of 745 Oe in the superlattice is caused by an interfacial localized magnetic moment and an antiferromagnetic state in the ultrathin LNO layer, pinning the ferromagnetic La0.7Sr0.3MnO3 layers together. Our results demonstrate that artificial interface engineering is a useful method to realize novel magnetic and transport properties.

Mitochondrially targeted nitro-linoleate: a new tool for the study of cardioprotection.

BACKGROUND AND PURPOSE: Cardiac ischaemia-reperfusion (IR) injury remains a significant clinical problem with limited treatment options available. We previously showed that cardioprotection against IR injury by nitro-fatty acids, such as nitro-linoleate (LNO2 ), involves covalent modification of mitochondrial adenine nucleotide translocase 1 (ANT1). Thus, it was hypothesized that conjugation of LNO2 to the mitochondriotropic triphenylphosphonium (TPP(+) ) moiety would enhance its protective properties. EXPERIMENTAL APPROACH: TPP(+) -LNO2 was synthesized from aminopropyl-TPP(+) and LNO2 , and characterized by direct infusion MS/MS. Its effects were assayed in primary cultures of cardiomyocytes from adult C57BL/6 mice and in mitochondria from these cells, exposed to simulated IR (SIR) conditions (oxygen and metabolite deprivation for 1h followed by normal conditions for 1h) by measuring viability by LDH release and exclusion of Trypan blue. Nitro-alkylated mitochondrial proteins were also measured by Western blots, using antibodies to TPP(+) . KEY RESULTS: TPP(+) -LNO2 protected cardiomyocytes from SIR injury more potently than the parent compound LNO2 . In addition, TPP(+) -LNO2 modified mitochondrial proteins, including ANT1, in a manner sensitive to the mitochondrial uncoupler carbonylcyanide-p-trifluoromethoxyphenylhydrazone (FCCP) and the ANT1 inhibitor carboxyatractyloside. Similar protein nitro-alkylation was obtained in cells and in isolated mitochondria, indicating the cell membrane was not a significant barrier to TPP(+) -LNO2 . CONCLUSIONS AND IMPLICATIONS: Together, these results emphasize the importance of ANT1 as a target for the protective effects of LNO2 , and suggest that TPP(+) -conjugated electrophilic lipid compounds may yield novel tools for the investigation of cardioprotection.

Identification and analysis of LNO1-like and AtGLE1-like nucleoporins in plants.

Nucleoporins (Nups) are building blocks of the nuclear pore complex (NPC) that mediate cargo trafficking between the nucleus and the cytoplasm. Although the physical structure of the NPC is well studied in yeast and vertebrates, little is known about the structure of NPCs or the function of most Nups in plants. Recently we demonstrated two Nups in Arabidopsis: LONO1 (LNO1), homolog of human NUP214 and yeast Nup159, and AtGLE1, homolog of yeast Gle1, are required for early embryogenesis and seed development. To identify LNO1 and AtGLE1 homologs in other plant species, we searched the protein databases and identified 30 LNO1-like and 35 AtGLE1-like proteins from lower plant species to higher plants. Furthermore, phylogenetic analyses indicate that the evolutionary trees of these proteins follow expected plant phylogenies. High sequence homology and conserved domain structure of these nucleoporins suggest important functions of these proteins in nucleocytoplasmic transport, growth and development in plants.