Mesomorphism of Lanthanide(Ⅲ) 4-Hexyloxybenzoates

The 4-alkoxybenzoic acids are well-known liquid crystals showing several mesophases(nematic,smectic C phase or both)depending on the alkoxy chain length and whereby the rigid core of the mesogen is formed by intermolecular hydrogen bonds.In this paper it is shown that the thermal behaviour of lanthanide salts of 4-hexyloxybenzoic acids depends on the lanthanide ion(Ln=La,Pr,Nd,Sm,Eu).The lanthanum(Ⅲ)and praseodymium(Ⅲ)4-hexyloxybenzoates exhibit a smectic A mesophase.No mesophase is found for the corresponding compounds of heavier lanthanides.The thermal properties of the lanthanide(Ⅲ)4-hexyloxybenzoates were investigated by differential scanning calorimetry(DSC),polarising thermo-optical microscopy and synchrotron X-ray radiation.     

超临界流体络合萃取镧系和锕系元素的研究进展

超临界流体络合萃取是1种可用于萃取金属离子的新型分离技术，它应用于乏燃料后处理和核废物处理中的最大优点是能大幅减少二次废物的产生。文章主要介绍超临界流体的特点、超临界流体络合萃取的基本原理及其影响因素，并对超临界流体络合萃取镧系和锕系元素的研究进展及其在乏燃料后处理工艺研究中的应用进行综述。     

Lanthanide-binding tags as versatile protein coexpression probes

Comprehensive proteomic analyses require new methodologies to accelerate the correlation of gene sequence with protein function. Key tools for such efforts include biophysical probes that integrate into the covalent architecture of proteins. Lanthanide-binding tags (LBTs) are expressible, multitasking fusion partners that are optimized to bind lanthanide ions and have several desirable attributes, which include long-lived luminescence, excellent X-ray scattering power for phase determination, and magnetic properties to facilitate NMR spectroscopic structure elucidation. Herein, we present peptide sequences with a 40-fold higher affinity for Tb(3+) ions and significantly brighter luminescence intensity compared with existing peptides. Incorporation of an LBT onto ubiquitin as a prototype fusion protein allows the use of powerful protein-visualization techniques, which include rapid luminescence detection of LBT-tagged proteins in SDS-PAGE gels, as well as determination of protein concentrations in complex mixtures. The LBT strategy is a new alternative for expressing fluorescent fusion proteins by routine molecular biological techniques.     

Activatable NIR-II Lanthanides-Polymetallic Oxomolybdate Hybrid Nanosensors for Monitoring Chemotherapy Induced Enteritis

Chemotherapy-induced enteritis is one of the side effects associated with cancer therapy, which significantly affects the treatment effect, but there is no effective clinical detection method that can early diagnose its occurrence and progression. Here, a series of second near-infrared window (NIR-II) hybrid nanosensors are designed that consisted of lanthanide nanoparticles and β-Mo2C-derived polymetallic oxomolybdate nanoclusters (Ln@POM). Based on the high sensitivity of POM to reactive oxygen species (ROS) closely related to chemotherapy-induced enteritis, the NIR-II luminescence intensity and lifetime of Ln@POM (Ln: Yb³⁺, Nd³⁺, Ho³⁺, Tm³⁺, Er³⁺) show excellent responsiveness to H₂O₂ and HClO with the detection limit down to 0.15 and 0.14 µm , respectively. Utilizing Nd@POM as a ROS-activated NIR-II nanosensor, the chemotherapeutic enteritis is successfully detected within 7 h after induction of chemotherapy drugs, which is significantly earlier than the gold standard method (immunohistochemistry, 24 h). These results demonstrate that the designed hybrid nanosensors are promising optical tools for the early diagnosis of ROS-related diseases.     

Bis(Diphenylcarbamoylmethylphosphine Oxide) Ligand Containing 4, 7, 10 – Trioxatridecane Spacer: Novel Effective Extractant for Actinides and Lanthanides

A novel polydentate neutral organophosphorus ligand 1 containing two Ph₂P(O)CH₂C(O)NH- bidentate moieties connected by a 4, 7, 10 - trioxatridecane spacer through amide nitrogen atoms was synthesized and studied as an extractant for U(VI), Th(IV), and lanthanides(III) ions from HNO₃ solutions. The influence of aqueous and organic phases on the extraction efficiency was elucidated and stoichiometry of the complexes extracted was determined. Bis-CMPO ligand 1 was found to possess a higher extraction efficiency towards U(VI), Th(IV), and lanthanides(III) ions than its mono analog diphenylphosphorylacetic acid N-nonylamide 5 and bis-CMPO ligands containing a di- and a triethylene glycol spacers. The values of D_U, D_Th, and D_Ln for compound 1 are more than two orders of magnitude higher than those for its mono-CMPO analog 5.     

Relationship Between Structure and Coordination Strength of N and N,O-Hybrid Donor Ligands with Trivalent Lanthanides

ABSTRACT

To effectively separate lanthanides (Ln(III)) from actinides (An(III)), symmetrical 2,2′-bipyridyl (Bpy), 1,10-phenanthroline (Phen), and unsymmetrical N-methyl-N-tolyl-1,10-phenanthroline-2-carboxamide (MeTol-PTA) were investigated. According to the crystal structures and EXAFS experiments, the decreasing ionic radius from light to heavy Ln led to decreases in the Ln–N (Bpy) and Ln–N (Phen) distances, while log β simply increased due to the electrostatic interaction and the order of Ln–O (MeTol-PTA) < Ln–N (Bpy, Phen) < Ln–N (MeTol-PTA) was obtained. This indicated that the bulky phenanthroline moiety of MeTol-PTA may not allow N (MeTol-PTA) to come close to Ln. Consequently, the log β of MeTol-PTA exhibited a local maximum (around Nd).     

镧系元素性质递变的双峰现象

本文从镧系的电子结构和化学键参数分析了镧系元素性质遂变的双峰现象的本质。并探讨了它在稀土分离提取工艺方面应用的可能性。     

Recent Progress on Spectroscopy of Lanthanide Ions Incorporated in Semiconductor Nanocry stals

Doping luminescent lanthanide ions into semiconductor nanocrystals is an ideal approach for developing nanodevices for various applications. Quantum confinement effects are expected for lanthanide ions doped in small semiconductor nanocrystals. The most recent progress on the synthesis and spectroscopy of lanthanide ions in various semiconductor nanocrystals such as Ⅱ -Ⅵ, Ⅲ-Ⅴ and Ⅳ-Ⅵ families were systematically reviewed, focusing on our recent findings on the optical spectroscopy of Eu^3 ＋ doped in ZnO and TiO2 nanocrystals by wet chemical synthesis. The energy transfer from the band-gap excitation to lanthanides further confirmed that lanthanide ions could be successfully incorporated into the lattice sites in spite of the mismatch in ionic radii.