MMgF_4(M=Ca,Sr,Ba)体系中Eu和Tb的电荷迁移

于不同气流中,合成了MMgF_4:xEU,yTb复合氟化物燐光体.该体系中Eu~(3+)和Eu~(2+)共存.Tb的存在影响Eu的价态存在形式.ESR测试表明,随Tb的掺入浓度增加,Eu~(2+)的浓度呈规律性变化.随Eu的掺入,样品的XPS谱中出现了四价铽的Tb_3d(5/2)特征伴峰.认为Eu~(3+)和Tb~(3+)之间存在电荷迁移平衡.即Eu~(3+)+Tb~(3+)(?)Eu~(2+)+Tb~(4+).通过半定量手段研究了SrMgF_4中这一平衡的平衡常数.

BaLiF_3：Eu~（2＋）一种新型X射线存贮材料

ＢａＬｉＦ３微晶经Ｘ射线辐照所产生的热释光，在日光下照射１５分钟或在室温条件下放置２～３天都会消失，表明Ｘ射线对ＢａＬｉＦ３微晶的辐照损伤是轻微的，易擦除的。实验还发现ＢａＬｉＦ３：Ｅｕ（２＋）具有光激励发光特性，因此可以认为ＢａＬｉＦ３：Ｅｕ（２＋）是一种具有潜在应用价值的新型Ｘ射线存贮材料。

INTERACTION OF LANTHANUM AND CALCIUM WITH HUMAN ERYTHROCYTE-MEMBRANES

The effect of lanthanum and calcium on the structure and function of human erythrocyte membranes was investigated by fluorescence polarization, spin- labeled electron spin resonance (ESR) and laser Raman spectroscopy. The results showed that low concentration of La3+ (0.5 mu mol/L) activated a Little (Na++K+)-ATPase and Mg2+-ATPase activities, and it inhibited obvi ously the ATPase activities with increasing its concentrations. La3+ lowered the lipid fluidity of human erythrocyte membranes and decreased the vibration intensity of alpha-helix of the protein in the Amide I '. The effect of Ca2+ on the lipid fluidity and alpha-helix of the protein in the Amide I ' was smaller than that of La3+.

PREPARATION AND MICROSTRUCTURAL CHARACTERIZATION OF SURFACE-MODIFIED NANOSIZED SNO2 PARTICLES

Nanosized stannic oxide particles modified with a layer of DBS were successfully prepared through the colloidal chemical method and their microstructures were characterized. FTIR and XPS were used for the determination of the main components. It can be proved that the nanosized SnO2 particles were capped by DBS. The sizes of particle were determined by TEM and XRD. By the investigation of XPS, we can conclude that there are a lot of oxygen vacancies in the surface of the nanoparticulates. Based on this conclusion, the ESR signal of the sample can be explained.

INTERACTIONS OF RARE-EARTH LENS WITH BOVINE BLOOD CU(ZN)-SUPEROXIDE DISMUTASE

The interactions of lanthanium trichloride and terbium trichloride with bovine blood Cu (Zn)-superoxide dismutase [Cu(Zn)-SOD] in the aqueous solution of hexamethylenetetrarnine buffer (pH = 6.3) have been studied by using fluorescece, CD and ESR spectra. The results indicated that rare earth ions were coordinated to the carboxyl groups of acidic amino acid residues which were far from active center of the Cu(Zn)-SOD molecule and only lightly disturbed the secondary structure of the enzyme protien, and made the coordination structure of enzyme-bound CU2+ come from the rhombchedron to the axial shape at 77 K and the activity of Cu(Zn)-SOD enzyme was not nearly changed at room temperature.

Electron transfer between Eu3+ and Ce3+ in SrM-F-4 matrix

Emissions of europium (II) and europium (III) have been observed in SrMgF4:Eu and SrMgF4:Eu,Ce phosphors which are synthesized in Ar flow, It is notable that the intensity of the ESR peaks corresponding to Eu2+ is increased when cerium ion is incorporated which can be explained by electron transfer mechanism.

Electron Transfer and its Equilibrium between Eu and Tb in SrMgF4 System

Emission of europium(II) and europium(III) have been observed in SrMgF4 xEu, yTb phosphors winch are synthesized in Ar flow. The valence state of En is influenced by terbium, It is noted that the intensities of the ESR peaks corresponding to Eu2+ are increased when terbium ion is codopech this can be explained by electron transfer mechanism which is Eu3++Tb3+-->Eu2++Tb4+. And its equilibrium constant is calculated.

MMgF_4：Eu（M＝Ca，Sr，Ba）体系中铕离子的发光中心及价态

合成了铕离子激活的ＭＭｇＦ４．磷光体，研究了Ｅｕ３＋离子的光谱特征与基质化合物的关系，存在三类发光中心，讨论了基质组成对铕离子价态的影响。

［Cu（IO_5OH））_2］~（5－）离子配合物中~（127）I超超精细相互作

用ＥＳＲ方法研究了［Ｃｕ（ＩＯ５ＯＨ）２］５－离子配合物中１２７Ｉ核的超超精细相互作用，旨在证实在碘离子上存在未成对电子自旋和找到一种解释Ｃｕ２＋离子中电子离域的机制。根据ＥＳＲ参数的计算指出碘离子上自旋密度为０．７７％。

稀土离子与牛血Cu(Zn)-SOD的作用

采用ESR、CD谱和荧光光谱研究了pH=6.3时六次甲基四胺-HCl缓冲溶液中LaCl_3和TbCl_3与Cu(Zn)-SOD的配位作用和结构。Cu(Zn)-SOD可增强Tb~(3+)的荧光发射,Tb~(3+)与Cu(Zn)-SOD有多个配位位置,其中有2个强结合位点,La~(3+)与Tb~(3+)可竞争Cu(Zn)…SOD上相同结合位点,77K下La~(3+)与Tb~(3+)使Cu(Zn)-SOD的Cu~(2+)活性中心的配位环境由菱形对称结构向轴对称结构转变,使Cu(Zn)-SOD的局部结构变松散,但对SOD酶活性基本无影响,表明稀土离子主要与酶蛋白分子中的酸性氨基酸羧基配位,对酶蛋白二级结构仅产生微弱扰动,对活性中心空间结构影响较小,基本不影响Cu(Zn)-SOD酶活性。

SrF_2:Eu,Tb中稀土离子的价态变化

我们曾提出,电子组态具有共轭性的一对三价稀土离子,在一定条件下,会实现电子转移而产生价态变化.价态变化会明显改变材料的功能特性,因此,研究稀土元素价态变化,对新型功能材料设计具有重要意义.本工作研究了SrF_2:xEu,yTb磷光体中Eu-Tb的价态变化,发现SrF_2中,电子组态共轭的Eu~(3+)与Tb~(3+)在本实验条件下,可以实现电子转移.这一现象的发现有助于了解团相反应中稀土离子价态变化的规律.为寻找共轭稀土离子对之间实现电子转移条件提供了实验依据.

MF_2:Eu,Ce(M=Ca,Sr,Ba)中稀土离子的价态变化

我们已经实验证明并报道了Eu-Tb之间、Ce-Yb之间的电荷转移.本文首次实验证实了Ce~(3+)离子和Eu~(3+)离子之间电荷转移现象的存在,进一步阐述了稀土价态与其电子组态共轭特征的相关性.1 实验部分1.1 试剂CaF_2,SrF_2,BaF_2,NH_4HF_2、氢氟酸、盐酸均为分析纯,EuF_3和CeF_3分别由高纯Eu_2O_3(99.95%)及CeO_2(99.99%)自制.1.2 MF_2:Eu,Ce体系的合成按化学计量比(MF_2:X%CeF_2,y%EuF_3;X=1,y=0,0.1,0.3,0.5,1;X=0,0.05,0.1,0.3,0.5,y=1)准确称取原料,放人玛瑙研钵中充分研混后装入刚玉柑涡中,置于管状炉内(用氢气

用快速低温冷冻和ESK方法分析兔脂肪栓塞脑组织中自由基

用快速低温冷冻－ＥＳＲ实验方法研究兔脂肪栓塞模型脑组织自由基的变化，实验发现脂肪栓塞实验组自由基相对浓度是正常对照组的２－３倍。ＥＳＲ检测到脂类过氧化自由基和以碳为中心的烷基类自由基的事实表明脂肪栓塞病变存在活性氧自由基作用过程。文中对快速冷冻法可行性进行评估。

氟化镁锶中铕和铽的电荷迁移及其平衡解析

在氩气氛中，合成了SrMgF4：xEu，yTb复合组化物磷光体．该体系中Eu3+和Eu2+共存．随共掺入Tb浓度的增加，Eu3+的荧光发射强度降低，Eu2+的发光增强；并且Eu2+的ESR信号增强．认为Eu3+和Tb3+之间存在电荷迁移．即Eu3+＋Tb3+→Eu2+＋Tb4+.通过半定量手段研究了这一电荷迁移反应的平衡常数

CoTPP电化学催化还原溴代环己烷的机理

以电化学循环伏安、现场ＥＳＲ电化学以及现场薄层电化学方法研究了电生Ｃｏ（Ⅰ）ＴＰＰ与溴代环己烷的反应机制。在ＤＭＦ中，Ｃｏ（Ⅱ）／Ｃｏ（Ⅰ）的氧化还原有明显的催化溴代环己烷还原的特征，反应现场有自由基生成。反应产物之一是Ｃｏ—Ｃ键化合物，可以在－１．３０Ｖ（ＳＣＥ）一电子还原。当存在ＣＨ＿２＝ＣＨＣＮ时，生成另一种Ｃｏ—Ｃ键化合物，该化合物在—１．１０Ｖ（ＳＣＥ）处一电子还原。证明溴代环己烷与Ｃｏ（Ⅰ）ＴＰＰ反应主要是经过形成烷基自由基的机制进行的。