基于NMR的稀土生物效应代谢组学研究

近年来，随着高场傅里叶变换核磁共振波谱仪灵敏度的提高、分辨率的增加、化学位移的扩展、多脉冲实验技术的发展以及计算机技术的不断进步，使NMR技术在生物和医学领域的应用有了飞速的发展。而基于NMR技术结合模式识别方法的代谢组学方法更是在医学临床诊断、化合物生物效应、环境毒物学等领域得到广泛应用。稀土由于其特殊的电子层结构在光学、磁学领域应用非常广泛，同时因为其对农作物生长具有明显的促进作用，因此也被大量使用于农业中。本论文工作围绕农用稀土微肥常乐中两种主要成分斓、饰以及重稀土噜的急性生物效应，采用基于核磁共振技术的代谢组学方法，结合生化指标和组织切片显微照片，对给药稀土大鼠的体液（尿液、血清）和组织（肝、肾）进行了系统的研究。运用高分辨IHNMR技术，检测分析了大鼠腹腔注射不同剂量硝酸悯（2．0，10，50mg／kg体重）、硝酸饰（2．0，10，50mg瓜g体重）和灌胃给药硝酸噜（0．01，0．05，0．2，2，10，100mg／kg体重）48小时内尿液及48小时后血清及肝肾组织中的代谢物如柠檬酸、酮体、肌酸配、二甲胺、二甲基甘氨酸、TMAO、氨基酸、乳酸、唬拍酸、牛磺酸、甘油三脂、糖元等的浓度、物种的变化。结合模式识别方法，并根据血中生化指标和组织光镜图，对稀土在体内与细胞、组织和器官的作用机理及急性毒性进行了有意义的探讨。结果表明，各剂量硝酸悯主要导致大鼠肝脏受损，且损害程度与剂量成正比关系；而高剂量硝酸饰（10，50mg／kg体重）不仅在48小时内造成大鼠肝脏的能量代谢（糖代谢、脂肪代谢）紊乱，并导致肾小管炎症和肾乳头坏疽；重稀土噜在低剂量（0．2，2．0mg／kg体重）时主要导致肾小管重吸收能力下降，而高剂量（10，100mg众g体重）时主要表型为肝毒。该方法可用于其它药物的毒理研究。

多元氨基酸、肽体系中稀土存在形态及配位作用特点研究

本文研究了稀土在多元氨基酸小分子生物配体体系存在形态及其作用特点，探索了稀土元素在生物体内的分布、代谢及其生物效应的机理，同时研究了稀土与复杂的生物大分子作用及稀土氨基酸固体配合物。

Preparation and Characterization of BaLiF3:Er3+ Nanoparticles by the Hydrothermal Microemulsion Synthesized Method

Nanoparticles of BaLiF3:Er3+ were prepared from the quaternary microemulsions of Cetyltrim-Enthyl Ammonium Bromide (CTAB), n-butanol, n-octane, and water, using the hydrothermal-microemulsion technique. The complex fluorides were characterized by means of X-ray power diffraction, Environmental Scanning Electron Microscopy (ESEM), and fluorescence spectra.

Upconversion luminescence of Y2O3 : Er3+, Yb3+ nanoparticles prepared by a homogeneous precipitation method

Y2O3: Er3+, Yb3+ nanoparticles were synthesized by a homogeneous precipitation method without and with different concentrations of EDTA 2Na. Upconversion luminescence spectra of the samples were studied under 980 nm laser excitation. The results of XRD showed that the obtained Y2O3:Er3+,Yb3+ nanoparticles were of a cubic structure. The average crystallite sizes calculated were in the range of 28-40 nm. Green and red upconversion emission were observed, and attributed to H-2(11/2), S-4(3/2) -> I-4(15/2) and F-4(9/2) -> I-4(15/2) transitions of the Er3+ ion, respectively.

Synergistic extraction and recovery of Cerium(IV) and Fluorin from sulfuric solutions with Cyanex 923 and di-2-ethylhexyl phosphoric acid

Synergistic extraction and recovery of Cerium(IV) (Ce(IV)) and Fluorin (F) from sulfuric solutions using mixture of Cyanex 923 and di-2-ethylhexyl phosphoric acid (D2EHPA) in n-heptane have been carried out. in order to investigate the synergistic extraction of Cyanex 923 + D2EHPA, extraction Ce(IV), F, Ce(III) and Ce-F mixture solution using D2EHPA or Cyanex 923 as extractant alone were studied firstly, and then Synergistic extraction of Ce(IV), F and Ce(IV)-F mixture solution with D2EHPA + Cyanex 923 were carried out. The largest synergistic coefficient of Ce(IV) is obtained at the mole fraction X-Cyanex (923) = 0.8. The synergistic enhancement coefficients (R-max) obtained for Ce(IV) are 23.12 in Ce(IV) solution, and in Ce-F mixed solution R-max for Ce(IV) and F are 2.24 and 3.25 respectively.

The separation of Cerium(IV) from nitric acid solutions containing Thorium(IV) and Lanthanides(III) using pure [C(8)mim]PF6 as extracting phase

The extraction behavior of Ce(IV) along with Th(IV) and Ln(III) (Ln = Ce, Gd, Yb) nitrate by pure ionic liquid, [C(8)mim]PF6, was investigated. [C(8)mim]PF6 alone showed good extraction ability for Ce(IV), while it was slight for Th(IV) and negligible for Ln(III). The extraction behavior of Ce(IV) by [C(8)mim]PF6 was particularly studied, and the most probable extraction mechanism proposed was the anion exchange mechanism. Moreover, the stripping of Ce(IV) from IL phase was also investigated. The Ce(IV) in IL phase can be quantitatively recovered by water.

Silica Materials Doped with Bifunctional Ionic Liquid Extractant for Yttrium Extraction

Two new silica-based organic-inorganic hybrid materials (B104SGs and O104SGs) doped with a binary mixture of imidazolium and phosphonium ionic liquids have been synthesized and used as sorbents in batch system for rare earths (RE) separation. Imidazolium ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate (C(4)mim(+)PF(6)(-)) or 1-octyl-3-methylimidazolium hexafluorophosphate (C(8)mim(+)PF(6)(-)) acted as porogens to prepare porous materials and additives to stabilize extractant within silica gel.

Photoluminescence properties of LaF3: Eu3+ nanoparticles prepared by refluxing method

The europium-doped LaF3 nanoparticles were prepared by refluxing method in glycerol/water mixture and characterized with X-ray diffraction(XRD), field emission scanning electron microscopy(FE-SEM), UV-vis diffuse reflectance spectrum, and photoluminescence spectra. The results of XRD indicated that the obtained LaF3: Eu3+ nanoparticles were well crystallized with a hexagonal structure. ne FE-SEM image illustrated that the LaF3: Eu3+ nanoparticles were spherical with an average size around 30 nm. Under irradiation of UV light, the emission spectrum of LaF3: Eu3+ nanoparticles exhibited the characteristic line emissions arising front the D-5(0)-> F-7(J), (J=1, 2, 3, 4) transitions of the Eu3+ ions, with the dominating emission centered at 590 nm. In addition, the emissions from the 51), level could be clearly observed due to the low phonon energies (-350 cm(-1)) of LaF3 matrix. The optimum doping concentration for LaF3: Eu3+ nanoparticles was determined to be 20mol.%.

Thermoluminescence characteristics of NaSr4(BO3)(3):Ce3+ under beta-ray irradiation

The thermoluminescence (TL) properties of Ce3+ doped NaSr4(BO3)(3) phosphor under the beta-ray irradiation were reported. The polycrystalline sample was synthesized by high temperature solid-state reaction. The TL glow curve of NaSr4(BO3)(3):Ce3+ phosphor was composed of only one peak. TL kinetic parameters of NaSr4(BO3)(3):Ce3+ were deduced by the peak shape method, the activation energy (E) was 0.590 eV and the frequency factor was 1.008x10(6) s(-1). TL dose response was linear in the range of measurement. The 3-dimensional (3D) TL emission spectrum was also recorded, the emission spectrum consisted of two bands located at 441 and 479 nm respectively, corresponding to the characteristic 4f(0)5d(1)-> F-2((5/2,7/2)) transitions of the Ce3+ ion. The fading behavior of the NaSr4(BO3)(3):Ce3+ phosphor over a period of 15 d was also studied.

Extraction and recovery of cerium(IV) along with fluorine(I) from bastnasite leaching liquor by DEHEHP in [C(8)mim]PF6

BACKGROUND: Ionic liquids (ILs) as environmentally benign solvents have been widely studied in the application of solvent extraction. However, few applications have been successfully industrialized because of the difficult stripping of metal ions or the loss of components of the ILs. More work needs to be done to investigate the extraction behaviour of IL-based extraction systems. In this work, the extraction behaviour of Ce(IV), Th(IV) and some trivalent rare earth (RE) nitrates by di(2-ethylhexyl) 2-ethylhexylphosphonate (DEHEHP) in the IL, 1-methyl-3-octylimidazolium hexafluorophosphate ([C(8)mim]PF6), was investigated and compared with that in the n-heptane system. In particular, the effect of F(I) on the extraction mechanism for Ce(IV) and its separation from Th(IV) was investigated. Otherwise, the recovery efficiency of Ce(IV) and F(I) from a practical bastnasite leach liquor was examined using IL based extraction.

Biochemical effects of gadolinium chloride in rats liver and kidney studied by H-1 NMR metabolomics

The biochemical effects of gadolinium chloride were studied using high-resolution H-1 nuclear magnetic resonance (NMR) spectroscopy to investigate the biochemical composition of tissue (liver and kidney) aqueous extracts obtained from control and gadolinium chloride (GdCl3) (10 and 50 mg/kg body weight, intraperitoneal injection. i.p.) treated rats. Tissue samples were collected at 48, 96 and 168 h p.d. after exposure to GdCl3, and extracted using methanol/chloroform solvent system. H-1 NMR spectra of tissue extracts were analyzed by pattern recognition using principal components analysis. The liver damages caused by GdCl3 were characterized by increased succinate and decreased glycogen level and elevated lactate, alanine and betaine concentration in liver. Furthermore, the increase of creatine and lactate, and decrease of glutamate, alanine, phosphocholine, glycophosphocholine (GPC), betaine, myo-inositol and trimethylamine N-oxide (TMAO) levels in kidney illustrated kidney disturbance induced by GdCl3.

Long lasting phosphorescence in Eu3+ and Ce3+ co-doped strontium borate glasses

Long lasting phosphorescence (LLP) was observed in Eu2+, Ce3+ co-doped strontium borate glasses prepared under the reducing atmosphere due to the emission of both Eu2+ and Ce3+. The methods of photoluminescence, thermoluminescence and phosphorescence were used to study the samples, and possible mechanism was suggested. The co-doping of Ce3+ ions poisoned the phosphorescence emission of Eu2+ because of the competition to obtain the trapped electron. The phosphorescence of Ce3+ in the sample decays more quickly than that of Eu2+, which is suggested for the reason that the emission energy of Ce3+ is higher or the distance between Ce3+ and electron traps of the glasses is longer.