X-Ray Absorption and Diffraction Studies of Pr3+, Tb3+ and Er3+-Activated Silica Gels

Rare-earth (Pr³⁺, Tb³⁺, Er³⁺) doped silica xerogels were studied by x-ray absorption spectroscopy and x-ray diffraction. A change of the local environment around rare-earth ions upon xerogel densification at 900–950°C and co-doping with aluminum ions was determined from the rare-earths L₃-edge EXAFS signals. The densification process induces a decrease of the coordination number and a compression and deformation of the first coordination shell, composed of oxygen atoms. The second coordination shell, composed of silicon and/or aluminum ions, also experiences some modification, which is attributed mainly to a shortening of the shell radius. No evidence of clustering of rare-earth ions upon densification was observed. X-ray diffraction data on Tb-doped gels confirm the EXAFS results.     

Simultaneous Chain‐Growth and Step‐Growth Polymerization of Methoxystyrenes by Rare‐Earth Catalysts

The simultaneous chain‐growth and step‐growth polymerization of a monomer is of great interest and importance because it can produce unique macromolecules which are difficult to prepare by other means. However, such a transformation is usually difficult to achieve in one polymerization system because chain‐growth polymerization and step‐growth polymerization proceed by different reaction mechanisms. Reported here is the simultaneous chain‐growth and step‐growth polymerization of para‐ and meta‐methoxystyrenes catalyzed by half‐sandwich rare‐earth alkyl complexes, and the step‐growth polymerization proceeds by the C?H polyaddition of anisyl units to vinyl groups. This unprecedented transformation affords a new family of macromolecules containing unique alternating anisole‐ethylene sequences. In contrast to para‐ and meta‐methoxystyrenes, ortho‐methoxystyrene exclusively undergo syndiospecific, living chain‐growth polymerization by continuous C=C bond insertion to give perfect syndiotactic poly(ortho‐methoxystyrene) with high molecular weight and narrow polydispersity (rrrr >99 %, M_n up to 280 kg mol^?1, M_w/M_n <1.10).     

钾位铈掺杂黄钾铁矾的磷吸附特性及机理研究※

黄钾铁矾是一种自然界常见的含铁矿物, 它对砷酸根有一定吸附作用, 但几乎不吸附同样构型的磷酸根. 为了改善黄钾铁矾的磷吸附性质, 本研究制备了铈掺杂的黄钾铁矾, 并采用X射线衍射(XRD)、电感耦合等离子发射光谱(ICP-OES)等表征手段, 构建了铈离子占据钾离子位的结构模型. 磷吸附实验结果表明, 少量铈的掺杂可将黄钾铁矾的磷吸附容量(pH=7, 24 h)从1.69 mg/g显著提升至29.33 mg/g. 同时, 初始pH和共存阴离子对其除磷效果影响较小, 说明含铈黄钾铁矾对磷酸盐的吸附具备高选择性. 进一步分析表明, 该吸附过程符合准二级动力学模型, 吸附等温线符合Freundlich等温吸附模型, 分析结果表明吸附过程可能是易进行的化学吸附. 利用XRD及阴离子交换色谱, 证实了相比于纯黄钾铁矾, 铈的掺杂提高了黄钾铁矾的反应活性, 大幅提升了吸附过程中磷酸根与硫酸根的置换. 通过X射线光电子能谱与红外光谱表征, 推测吸附过程形成稳定的Ce—O—P化学键, 实现特异性化学吸附. 这些研究结果为含磷废水的吸附治理提供了一种新的吸附材料, 并有望为黄钾铁矾的改性和资源化利用提供参考.     

近红外二区发光稀土纳米材料的设计及生物成像应用

近年来,近红外二区(NIR-II,1000~1700 nm)荧光成像因其较高的空间分辨率、较深的组织穿透能力,在分子影像领域引起了广泛的关注。常见的NIR-II发光材料(如有机小分子、共轭聚合物、量子点等)通常具有光稳定性差、荧光量子产率低、斯托克斯位移小、荧光峰宽等问题,限制了这一新型成像技术的进一步发展与应用。稀土纳米材料由于其独特的发光特性,能够较好地克服这些不足,近年来不同结构的稀土纳米材料也逐渐被设计开发并应用于近红外二区荧光成像与检测,展示出了巨大的应用潜力。本综述首先介绍了稀土纳米材料的光学特性,然后按敏化离子的不同(Yb³⁺、Nd³⁺、Er³⁺、Tm³⁺)详细介绍了近红外二区稀土纳米材料的设计方法及相关应用,最后对稀土纳米材料在近红外二区成像领域的进一步发展进行了展望。     

Synthesis,Spectroscopic Properties and Redox Behavior Kinetics of Rare-Earth Bistetrakis-4-[3-(3,4-dicyanophenoxy)phenoxy]phthalocyaninato Metal Complexes with Er,Lu and Yb

Novel bistetrakis-4-[3-(3,4-dicyanophenoxy)phenoxy]phthalocyaninato of complexes erbium, lutetium and ytterbium were synthesized using a template fusion method to prevent any polymerization process. The complexes were separated from the reaction mixtures and characterized by NMR, IR and electron absorption spectroscopy. The spectroscopic properties of the metal phthalocyaninates in chloroform, acetone and tetrahydrofuran were studied. The regular bathochromic shift in the Er–Yb–Lu series was determined. In acetone medium all the complexes obtained were found to exist in an equilibrium state between neutral and reduced forms. The linearity of Lambert-Bouger-Beer curves makes it possible to study the kinetics of redox processes in the presence of phenylhydrazine and bromine. The lutetium complex showed better reducing properties and turned fully into the reduced form, while the erbium and ytterbium ones changed only partially. Upon oxidizing all the phthalocyaninates transformed into a mixture of oxidized and neutral-radical forms. The extinction coefficients and effective redox constants were calculated.     

Spectral properties of Eu(III) compound with antibacterial agent ciprofloxacin (cfqH). Crystal structure of [Eu(cfqH)(cfq)(H2O)4]Cl2 · 4.55H2O

A novel europium complex of fluoroquinolone ciprofloxacin (cfqH) with formula [Eu(cfqH)(cfq)(H₂O)₄]Cl₂ · 4.55H₂O (1) was synthesized and its crystal structure determined by X-ray crystallography. The coordination number of europium is eight and in this structure two bidentate, O,O-bonded quinolone molecules and four aqua ligands are coordinated to the metal. One molecule of quinolone is anionic whereas the other is zwitterionic. Additionally, two chloride ions are also present in the structure to compensate the charge of the europium(III) whilst disordered solvent water molecules too are present. The spectral properties (IR, Raman, luminescence) of compound 1 were studied. Analysis of the Stark structure of the luminescence spectra was carried out and the scheme of the electronically excited states and photophysical processes of compound 1 was arranged. The spectral properties show that europium–ciprofloxacin complexes could be suitable for various applications based on their solution-state stability as measured by ¹H and ¹⁹F NMR.     

Sc3+ Chloro and Alkyl Complexes Coordinated by Pincer NHC-Tethered Bis(phenolate) Ligands

Bis(phenolate) ligands with benzimidazole-2-ylidene ( L¹) and tetrahydropyrimidine-2-ylidene ( L² ) linkers proved to be suitable coordination environments for the synthesis of isolable Sc³⁺ chloro and alkyl complexes. The treatment of Sc(CH₂SiMe₃)₃(THF)₂ with equimolar amounts of [ L^1,2H₃ ] Cl afforded chloro complexes L^1,2ScCl ( solv ) ₂ (solv=THF, Py) in 76–85 % yields. L^1,2ScCl ( THF ) ₂ were also prepared by the salt metathesis reactions of ScCl₃ with [ L^1,2 ] Na₂ generated from [ L^1,2H₃ ] Cl and 3 equiv. of NaN(SiMe₃)₂ (−40 °C, THF) and isolated in somewhat lower yields (68–73 %). L²ScCl ( THF ) ₂ was subjected to the alkylation reaction with LiCH₂SiMe₃ affording alkyl derivative [ L²Sc ( CH₂SiMe₃ )] ₂ . This compound can be alternatively prepared by the subsequent reactions of [ L²H₃ ] Cl with equimolar amount of NaN(SiMe₃)₂ and Sc(CH₂SiMe₃)₃(THF)₂. In the dimeric alkyl compound [ L²Sc ( CH₂SiMe₃ )] ₂ , one of the phenoxide groups of the dianionic ligand is coordinated to one scandium center, while the second one features μ-bridging coordination with two metal centers.     

糠醛甘氨酸Schiff碱及其稀土La(Ⅲ)配合物的合成与表征

糠醛甘氨酸Schiff碱稀土配合物具有生理活性。本文采用分步法制得Schill碱配合物：     

电感耦合等离子体原子发射光谱(ICP-OES)法测定铝合金中微量的钆、镧、钕、镨、钐

研究了电感耦合等离子体发射光谱(ICP-OES)法测定6系铝合金中微量的钆、镧、钕、镨、钐的方法,优化了ICP-OES工作条件,用标准加入法和标准曲线法做了比较,测定微量含量时,标准加入法比标准曲线法准确,在定量限和检出限之间约5倍空白标准偏差(5σ)含量时,标准加入法的加标回收率在80%~112%,检测结果具有参考价值.     

金属间化合物RMn_2Ge_2(R=La,Pr,Nd,Sm,Gd,Tb和Y)中的自发磁相变及相变时的磁弹性异常

在 10— 80 0K的温度范围内用X射线衍射方法测量了RMn2 Ge2 (R =La ,Pr,Nd ,Sm ,Gd ,Tb和Y)的晶格常数与温度的变化关系 .在各种类型的自发磁相变观察到晶格常数的磁弹性异常现象 .实验得出 ,自发磁相变时的磁弹性异常主要由Mn次晶格引起 ,并且Mn Mn交换相互作用能不仅与晶格常数a有关 ,而且与晶格常数c有关 .用Kittle的交换反转模型讨论了低温时的铁磁—反铁磁一阶相变 .