2-噻吩乙酸邻菲啰啉铕、铽配合物的合成表征及荧光性能研究

合成了以Eu3 ,Tb3 及Eu3 ,Tb3 掺杂RE3 (La3 ,Gd3 ,Y3 )为中心,以2-噻吩乙酸和1,10-邻菲啰啉为配体的两个系列8种同核与掺杂稀土固体配合物.对其进行了稀土及C、H和N元素分析、摩尔电导、热谱、红外光谱、核磁共振氢谱的测定及荧光性能研究.确定了配合物的组成为REL3L′和RE0.5Ln0.5L3L′(RE=Eu,Tb;Ln=La,Gd,Y;L=2-噻吩乙酸;L′=1,10-邻菲啰啉,在常温下测定了它们的固态粉末荧光光谱,发现掺杂离子(La3 ,Gd3 ,T3 )使稀土Eu3 离子发光明显增强,讨论了掺杂稀土离子对铕、铽配合物的发光影响.     

低温固相反应合成苯羟乙酸稀土配合物及其性质研究

利用低温固相反应合成了4种苯羟乙酸稀土配合物:RE(L)3·4H2O[RE＝La,Nd,Eu,Tb; L= C6H5CH(OH)COO-],并通过元素分析、稀土络合滴定、摩尔电导及热重分析确定了配合物的组成.红外光谱、核磁共振氢谱表明,苯羟乙酸稀土配合物中配体通过羧基以羧基氧负离子和醇羟基同时参与稀土离子(Ⅲ)配位,两分子水也参与稀土的配位.铕(Ⅲ)、铽(Ⅲ)配合物的荧光光谱和配体的磷光光谱表明,配体对铕(Ⅲ)、铽(Ⅲ)的荧光具有一定的敏化作用.     

掺杂卤代苯甲酸、含氮杂环铕配合物的合成、表征及荧光性能研究

分别以对溴苯甲酸和对碘苯甲酸为第一配体、含氮杂环(TPTZ和phen)为第二配体,以单一稀土Eu3+和Eu3+掺杂Gd3+、y3+为中心合成了12种配合物.对其进行了元素分析、紫外光谱、红外光谱、荧光激发和发射光谱的测定.推测化合物的组成分别为:(1)Eu(P- BrBA)3(TPTZ)·2H2 O; (2) Eu(P - IBA)3 (TPIZ)·2H2O;(3)Eu0.5Gd0.5 (P - BrBA)3 (TPTZ)·2H2O; (4) Eu0.5 Gd0.5(P- IBA)3(TPTZ)· 2H2O; (5) Eu0.5Y0.5(P - BrBA)3(TPTZ)· 2H2O;(6)Eu0.5Y0.5(P-IBA)3(TPTZ) · 2H2O;(7)Eu(P-BrBA)3(phen)· 2C2H5OH;(8)Eu(P- IBA)3(phen)· 2C2 H5 OH; (9) Eu0.5 Gd0.5(P- BrBA)3(phen)·2C2H5OH; (10) Eu0.5Gd0.5(P- IBA)3( phen).2C2H5OH;(11)Eu0.5Y0.5(P- BrBA)3(phen)·2C2H5OH和(12) Eu0.5Y0.5(P- IBA)3 (phen)·2C2H5 OH.卤代苯甲酸的羧基氧和稀土离子配位,TPTZ和phen的氮原子与稀土离子成键;配合物的形成对配体的共轭π-π*跃迁影响不大;几种不同的卤代苯甲酸铕配合物的发光强度有所差别,对溴苯甲酸配合物较强,中性配体TPTZ强于phen;掺钆、钇的铕配合物的荧光强度大于纯铕配合物,表明掺杂配合物并非简单配合物的混合,而是有一定混配配合物形成.     

铕、铽-2-噻吩甲酸-1,10-菲咯啉三元配合物的合成及荧光性质的研究

同时合成了高氯酸铕、铽与2-噻吩甲酸、1,10-菲咯啉(phen)的三元配合物和高氯酸铕、铽与2-噻吩甲酸的二元配合物,对配合物进行了元素分析、稀土络合滴定、红外光谱、摩尔电导测定,确定了配合物组成分别为REL3·2H2O及REL3L'·C2H5OH(RE=Eu,Tb;L=2-噻吩甲酸,L'=1,10-菲咯啉).摩尔电导数据表明,此类配合物为非电解质.红外光谱测定表明,配体2-噻吩甲酸羧基氧与稀土离子配位,配体1,10-菲咯啉两个氮原子与稀土离子配位.荧光光谱实验表明,1,10-菲咯啉加入到铕-2-噻吩甲酸二元配合物和铽-2-噻吩甲酸二元配合物中形成三元配合物后它们的荧光明显增强.     

稀土2-噻吩甲酸系列配合物的合成及其Eu3+的发光

合成了6种稀土2-噻吩甲酸(L)配合物.通过元素分析、摩尔电导及差热-热重分析确定其化学组成为REL3·2H2O(RE= Y,La,Pr,Nd,Sm,Eu;L=C4H3SCOOH),测定了配体及配合物的红外光谱、紫外光谱及铕配合物荧光激发和发射光谱.红外光谱测定表明,配体通过羧基以鏊合双齿的方式与稀土离子(Ⅲ)配位成键.荧光光谱数据表明, 铕配合物具有良好的荧光性能.     

邻氨基苯甲酸-联吡啶-混合稀土(Eu、Tb)配合物的荧光研究

:研究用邻氨基苯甲酸铵、2 ,2’-联吡啶与氯化铕、氯化铽在水 -乙醇溶液中反应合成了邻氨基苯甲酸- 2 ,2’-联吡啶 -铕铽异核稀土配合物 ,并测定了配合物的红外光谱。红外光谱数据表明 :邻氨基苯甲酸中的羧基和氨基均与稀土离子配位 ,联吡啶中的氮也与稀土离子配位 ;由元素分析数据推测 ,配合物的化学组成式为(Eux Tb1 - x) L3L′(其中 L 为邻氨基苯甲酸 ,L′为 2 ,2’-联吡啶 ) ;在 35 1nm紫外光激发下 ,研究了配合物的荧光光谱 ,结果表明 ,Eu3 的荧光发射被 Tb3 强烈敏化 ,而 Tb3 的荧光发射被 Eu3 离子强烈猝灭     

2-羟基-6-甲基尼古丁酸-1,10-菲咯啉三元稀土配合物的合成、表征及谱学性质

合成了四种新型的2-羟基-6-甲基尼古丁酸(HA)-1,10-菲咯啉(Phen)三元稀土配合物,通过元素分析、红外光谱法确定其组成为LnA3phen·3H2O(Ln=La、Eu、Gd、Tb),配体的羧基与稀土离子以螯合双齿配位。另重点研究了铕和铽的配合物的荧光性能,两种配合物均具有比较优异的荧光性能,Eu3+和Tb3+均不处于反演中心。EuA3phen·3H2O和TbA3phen·3H2O的荧光寿命分别为1.56 ms和0.32 ms。     

二苯基亚砜、苯甲酸与重稀土高氯酸四元配合物的合成及Tb3+、Dy3+光致发光

合成并表征了高氯酸稀土与二苯基亚砜、苯甲酸的六种四元配合物.经元素分析、差热-热重分析,表明四元配合物组成为[REL5L′(ClO4)](ClO4)(RE=Tb,Dy,Ho,Er,Tm,Yb;L=C6H5SOC6H5,L′=C6H5COO-).IR、1 HNMR表明,第一配体二苯基亚砜通过一个亚砜基氧原子、第二配体苯甲酸脱质子以阴离子形式通过一个羧基氧原子单齿与稀土离子配位.摩尔电导率表明配合物为1:1型,两个 ClO4-无机抗衡阴离子,其中一个在内界,一个在外界;配合物的荧光光谱表明,Tb3+、Dy3+四元配合物的荧光强度分别比二苯基亚砜与高氯酸稀土二元配合物的荧光强度提高226%和422%.磷光光谱表明第二配体的加入提高了配体的三重态能级与稀土离子激发态能级的匹配程度.铽配合物的电子顺磁共振谱在g=1.9920处出现一个单峰,表明该配合物具有成单电子,是顺磁性物质.     

[RE(pic)L](pic)_2·6H_2O的合成、荧光性质及与DNA作用方式初探

合成了四种N,N’-二(2-氨基吡啶)-1,1’-联萘-2,2’-二(氧杂乙酰胺)(L)稀土配合物。通过元素分析、红外光谱、紫外光谱、热重分析和摩尔电导率的分析,确定配合物的组成为[RE(pic)L](pic)2.6H2O[RE=La(Ⅲ)、Eu(Ⅲ)、Tb(Ⅲ)、Sm(Ⅲ),pic为苦味酸根],稀土离子的配位数为8,在CH3OH溶液中属于2∶1型电解质,该系列配合物的荧光光谱表明,Eu(Ⅲ)配合物的荧光强度远大于Tb(Ⅲ)配合物,说明配体L的三重态能级与Eu3+的激发态能级匹配较好。通过电子吸收光谱、荧光光谱和粘度法对配合物和DNA之间的作用方式进行了初步研究,结果表明,配合物与DNA之间存在着插入作用。     

轻稀土高氯酸盐甲基苯甲酰甲基亚砜配合物的合成及表征

合成了5种甲基苯甲酰甲基亚砜与轻稀土高氯酸盐配合物RE(ClO4)3·L5·C2H5OH(RE=La,n,Nd,Sm,Eu;L=C6H5COCH2SOCH3),经元素分析、稀土络合滴定、摩尔电导及热重分析确定了配合物的组成,测定了配体及配合物的的IR谱、1HNMR及铕配合物的磷光光谱、荧光激发和发射光谱,根据磷光发射光谱数据计算了配体的三重态能级值.荧光发射光谱表明,配体可有效的向Eu3+离子传能使其发射较强荧光.     

Synthesis and Fluorescence Properties of Europium,Terbium Doped Zn^2＋, Cd^2＋, and Cr^3＋ Complexes

Europium and terbium complexes with strong fluorescence intensity and long fluorescence lifetime were prepared. By replacing half of the europium or terbium ion with M （M = Zn^2＋, Cd^2＋, and Cr^3＋） using the doped method, and then incorporating it with 18-crown-6 ether and terephthalic acid, six heteronuclear samples EuZnLL＇Cl3·3H2O（1）, EuCdLL2＇Cl3·5H2O（2）, EuCrLL＇Cl4· 4H2O（3）, TbZnLL＇Cl3·4H2O（4）, TbCdLL＇2Cl3·4H2O（5）, and TbCrLL＇2Cl4 ·4H2O（6） （L = terephthalic acid, L＇= 18-Crown-6 ether） were obtained. The elemental analysis, molar conductivities, rare earth complexometry, Fourier Transform Infrared Spectroscopy （FT-IR）, ultraviolet （UV）, TGA, fluorescence intensity, and fluorescence lifetime of the samples were measured. The results showed that there were good luminescence properties for heteronuclear complexes （1）, （2）, （4）, and （5）, which were even stronger than those of the homonuclear complexes Eu2LL＇2Cl4·4H2O and Tb2LL＇2Cl4 ·4H2O, but the luminescence properties of EuCrLL＇Cl4·4H2O, TbCrLL＇Cl4·4H2O were very weak. A possible luminescence mechanism was suggested by the organic-inorganic doped mechanism and the law of intramolecular energy transfer.     

Synthesis, Characterization and Fluorescence Properties of Europium, Terbium Complexes with Biphenyl-4-Carboxylic Acid and o-Phenanthroline

Two series of solid complexes of europium and terbium with biphenyl 4-carboxylic acid and phen were synthesized and characterized in this report. Their elemental analysis, molar conductivities and TG-DTA studies indicate that the complexes have the composition of Eu(phen)L3·1/2H2O, Eu0.5RE0.5(phen)L3·1/2H2O; Tb(phen)L3·H2O and Tb0.5RE0.5(Phen)L3·1/2H2O. (RE=Y3 , La3 and Gd3 ; L=biphenyl 4-carboxylic acid; phen=o-Phenanthroline). The studies of their IR, UV 1H NMR and molar conductivities demonstrate that biphenyl 4-carboylic acid is bounded with RE(Ⅲ) ion. Rare earth ions coordinate with two nitrogen atoms of phen molecules directly in these rare earth complexes. The fluorescence spectra and fluorescence lifetimes of the rare earth complexes show that the fluorescent intensity and lifetime of a series of europium complexes are longer than those of the series of terbium complexes as having the some ligands. There are better fluorescent intensity and lifetime of hetero-nuclear rare earth complexes than homo-nuclear rare earth complexes for europium complexes. The fluorescence emission intensity of Eu3 is raised by inert fluorescent rare earth ions (Y3 , Gd3 and La3 ), but in Tb3 hetero-nuclear rare earth complexes the intensity of Tb3 ions are quenched by the inert fluorescent rare earth ions.     

电动铲运机在会泽铅锌矿麒麟坑的综合应用

总结分析了电动铲运机在我矿麒麟坑采矿、工程掘进等方面的综合应用 ,提出了“设备进口与国产相结合 ,核心部件进口化 ,一般部件国产化 ,坚持国产化改代和运检相结合”的设备应用思路     

Complex Trauma, Complex Reactions: Assessment and Treatment.

Complex trauma occurs repeatedly and escalates over its duration. In families, it is exemplified by domestic violence and child abuse and in other situations by war, prisoner of war or refugee status, and human trafficking. Complex trauma also refers to situations such as acute/chronic illness that requires intensive medical intervention or a single traumatic event that is calamitous. Complex trauma generates complex reactions, in addition to those currently included in the DSM-IV (American Psychiatric Association, 1994) diagnosis of posttraumatic stress disorder (PTSD). This article examines the criteria contained in the diagnostic conceptualization of complex PTSD (CPTSD). It reviews newly available assessment tools and outlines a sequenced treatment based on accumulated clinical observation and emerging empirical substantiation. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Men, machines, and models.

"Models are analogies." Among the values of models are: they describe and help us to understand complex systems or events, they help us learn complex skills, they provide the framework within which experiments are done, they help us see new relationships, they help us predict when experiments are impossible, and they assist in engineering design. Some dangers in the use of models include: they invite overgeneralization, they entice us into committing a logical fallacy, the relationships between the variables may be incorrect, the constants used in the model may be incorrect, models are too often not validated, and model building diverts useful energy into nonproductive activity. From Psyc Abstracts 36:02:2LJ13C. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Eu3+、Tb3+、Dy3+与L-脯氨酸、甘氨酸、L-丙氨酸四元固态配合物的荧光光谱研究

对在水中合成的稀土元素(Eu 、Tb 、Dy)与L-脯氨酸(L-Pro)、甘氨酸 (Gly)、L-丙氨酸(L-Ala)四元固态配合物的荧光光谱进行了研究.结果表明铕、铽配合物的荧光强度均较其相应的盐高(铕高出4.5倍,铽高出9倍);四元配合物的荧光强度较三元配合物有不同程度的提高;四元配合物中,铽的荧光强度较铕的荧光强度高出近11倍.同时对上述实验结果进行了解释.     

PVAc-Sm(Ⅲ),Nd(Ⅲ) 配合物的合成、表征及荧光性质

以聚醋酸乙烯酯 (PVAc)为配体 ,分别与SmCl3,NdCl3在乙醇中进行反应 ,生成PVAc Sm(Ⅲ ) ,PVAc Nd(Ⅲ )的配合物。用电导率法确定PVAc Sm(Ⅲ ) ,PVAc Nd(Ⅲ )配合物中Sm3 ,Nd3 与PVAc链节单元 [-CH2 -CH (OCOCH3) -]的配比为 1∶6。IR和XPS测试表明 :PVAc的CH3COO中酯基氧共同提供电子与Sm3 ,Nd3 形成配位键 ,溶剂分子C2 H5OH参与配位 ;TG DTA分析表明 :配合物的热分解温度比PVAc的低 ;荧光光谱显示 :PVAc Sm(Ⅲ ) ,PVAc Nd(Ⅲ )配合物具有荧光特性 ,分别在 42 7,418nm产生荧光。     

Synthesis, structures,thermal and magnetic properties of a series of lanthanide [Ln=Sm, Gd, Er, Yb] complexes with 4-quinolineacarboxylate

A series of lanthanide binuclear complexes, [Ln2(L)6(H2O)4]·2H2O (Ln=Sm(III), Gd(III), Er(III), Yb(III), HL=4-quinolineacarboxylic acid, were synthesized by reactions of corresponding rare earth salts with 4-quinolineacarboxylic acid at room temperature and were characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. X-ray diffraction analyses showed that they exhibited the same binuclear architecture and crystallized in monoclinic system and P21/c space group. In four complexes, each metal center adopted nine-coordinated mode coordinated by nine O atoms from two H2O molecules and three carboxyls of three ligands, and HL showed three different coordination modes. The variable-temperature magnetic susceptibility showed that complex [Gd2(L)6(H2O)4]·2H2O performed very weak antiferromagnetic property at low temperature and exchange was almost paramagnetic at high temperature. Complexes [Er2(L)6(H2O)4]·2H2O and [Yb2(L)6(H2O)4]·2H2O performed dominating antiferromagnetic coupling.     

双鸭山七星河金矿矽卡岩中金矿化地质特征、成矿规律及矿床成因探讨

位于佳木斯地块中部的双鸭山金矿是一个典型的矽卡岩型金矿。勘探、开采过程中的地质调查结果表明,矿体分布强烈受矽卡岩化及NW向破碎带共同控制。岩石微金分析结果显示,金矿源自混合岩化、基性火山岩。携带金络合物的混合流体沿断裂带迁移,与碳酸盐岩地层反应,使地层矽卡岩化,矽卡岩化过程使流体酸度下降,金络合物分解,金元素沉淀形成金矿。矿石矿物分析结果表明,金矿的主要赋矿矿物为毒砂,次为其他硫化物。据此推测,成矿流体中的络阴离子可能为[AsS3]^3-。