Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

桉树杂交种与其亲本的近红外光谱判别

研究桉树控制授粉后目标性状的基因作用方式是探索其基因重组规律的重要内容。常规的数量统计分析精度往往不高,而DNA分析的专业要求高,且费时费力。该研究利用近红外光谱(NIRs)研究不同基因型桉树杂交种、亲本及杂交种与亲本间近红外光谱信息的关系,探索NIRs用于桉树杂交种与其亲本判别的可行性和准确性。以控制授粉的桉树亲本及其杂交F1代材料为对象,每种基因型从各自田间试验分别选取10个单株,采集树冠中上部新鲜健康叶片。用手持式近红外仪Phazir Rx(1624)采集桉树杂交种与其亲本叶片的NIRs信息。每单株选10片完全生理成熟的健康叶片,避开叶脉扫描其正面光谱5次,以50条NIRs信息的均值代表单个叶片的NIRs信息,最终每个基因型获得10条NIRs信息。对原始NIRs采用二阶多项式S.G一阶导数预处理。预处理后的NIRs用于多元统计分析,首先对桉树杂交亲本和子代样本进行主成分分析(PCA),直观展示不同基因型的分类情况。然后运用簇类独立软模式(SIMCA)和偏最小二乘判别分析(PLS-DA)两种有监督的判别模式验证NIRs用于桉树杂交种与其亲本树种的分类判别效果。PCA结果显示,不同的亲本间、杂交种间及杂交种与亲本间样本的主因子得分可以清晰地将各基因型分开。SIMCA模式判别分析中,桉树杂交种样本到亲本PCA模型的样本距离显示,待判别样本能够形成单独的聚类,且能直观反映两者的遗传相似。PLS-DA判别结果显示,桉树杂交亲本的PLS模型能通过预测其杂交子代的响应变量将其与亲本准确分开。结果表明,桉树叶片的NIRs信息可以准确地反映桉树杂交子代遗传信息的传递规律,NIRs判别模型可以准确地将各种基因型予以区分。因此,NIRs信息不仅可用于桉树杂交种和纯种的定性判别,还可以分析桉树基因重组过程中加性遗传效应的大小,从而为桉树遗传基础分析及其育种改良研究提供理论支撑。     

Setting local rank constraints by orthogonal projections for image resolution analysis: Application to the determination of a low dose pharmaceutical compound

Raman chemical imaging provides chemical and spatial information about pharmaceutical drug product. By using resolution methods on acquired spectra, the objective is to calculate pure spectra and distribution maps of image compounds. With multivariate curve resolution-alternating least squares, constraints are used to improve the performance of the resolution and to decrease the ambiguity linked to the final solution. Non negativity and spatial local rank constraints have been identified as the most powerful constraints to be used.     

The Effect of the Spacer of Bis(biurea) Ligands on the Structure of A2L3‐type (A=anion) Phosphate Complexes

By tuning the length and rigidity of the spacer of bis(biurea) ligands L, three structural motifs of the A₂L₃ complexes (A represents anion, here orthophosphate PO₄^3?), namely helicate, mesocate, and mono‐bridged motif, have been assembled by coordination of the ligand to phosphate anion. Crystal structure analysis indicated that in the three complexes, each of the phosphate ions is coordinated by twelve hydrogen bonds from six surrounding urea groups. The anion coordination properties in solution have also been studied. The results further demonstrate the coordination behavior of phosphate ion, which shows strong tendency for coordination saturation and geometrical preference, thus allowing for the assembly of novel anion coordination‐based structures as in transition‐metal complexes.     

Immobilizing redox enzymes at mesoporous and nanostructured electrodes

Three key challenges are stimulating intensive research in the development of productive direct electron transfer mode enzyme electrodes: proper enzyme orientation, high enzyme loading, and full retention of enzyme activity. In this review, we summarize some significant advances that have been reported in the last years on the design of mesoporous and nanostructured electrodes as enzyme scaffolds and of innovative methodologies for wiring enzymes to electrodes. Particular attention is given to investigations on physical factors that determine a favorable enzyme immobilization, to provide rational guidelines for the design of productive enzymatic electrodes. Finally, some emerging trends focused on the spatial organization of either single enzymes or enzyme cascades are also briefly addressed.     

Selective Catalytic Isomerization of β-Pinene Oxide to Perillyl Alcohol Enhanced by Protic Tetraimidazolium Nitrate

A series of tetraimidazolium salts with different anions was prepared and applied in the isomerization of β-pinene oxide. After examining the activity of different catalysts, a remarkable enhancement of the selectivity of perillyl alcohol (47 %) was obtained over [PEimi][HNO₃]₄ under mild reaction conditions and using DMSO as the solvent. Furthermore, noncovalent interactions between solvent molecules and the catalyst were found by FT-IR spectroscopy and confirmed by computational chemistry. The homogeneous catalyst showed excellent stability and was reused up to six times without significant loss.