稀土-1,10-菲啰啉配合物的热分解动力学研究

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稀土席夫碱邻菲咯啉三元配合物的合成及其生物活性研究

文章编号：０４１５（０８０一１８０１０ —６６２０）９ｊ３－５
稀土席夫碱邻菲咯啉三元配合物的合成及其生物活性研究
马树芝，何其庄，自芳，杨许东芳，孙大志
（海师范大学生命与环境科学学院，海上上２０３）０２４
摘要：以稀土氯化物、席夫碱水杨醛缩苯丙氨酸和邻菲咯啉为配体，在无水乙醇溶液中反应，制备了一类新型稀土三元配合物，通过元素分析、摩尔电导、核磁共振、红外光谱、拉曼光谱，定了该配合物的化学组成：Ｅ确Ｒ（）ｈｎ１（）Ｒ＝Ｃ “ ，ｍ，ｕ， ¨ ，ｄ；Ｌ（Ｐｅ）ＣＨ０（Ｅｅｓ ¨ Ｅ ¨ ＹＧ ¨ Ｌ＝席夫碱水杨醛缩苯丙氨酸；ｈｎ＝邻菲咯Ｐｅ
邻菲咯啉三元配合物的研究并不多见，我们期望利用这三种具有生物活性的配体的协同作用合成出一种生物活性更好的物质，文首次合成了一本种新型稀土席夫碱邻菲咯啉三元配合物，讨了探这类配合物的光谱学性质，究了其与微生物（研细菌与真菌）以及与癌细胞的作用方式与机制，为该
维普资讯
第２０卷第９期２００８年９月
化学研究与应用
ＣｅｃｌＲｓａｃｎｐｉａｉｎｈｍｉａｅｅｒｈａｄＡｐｌｔｃｏ
Ｖｏ．０．ｏ９１２Ｎ．Ｓｐ２０ｅ．，０８
１实验部分
栅１０８０和６０的光谱仪，０４× ５０１２２６液氮冷却型ＣＤ检测器，ｅｅ气体激光器）得，辨率ＣＨ— Ｎ采分２ｍ～美国ＶｒｎＶＲ３０ｃ；ａｉＸ０ＭＨｚＮａＭＲ型核磁共振

稀土水杨酸邻菲罗啉三元固体配合物的研究_王则民

第29卷第1期上海师范大学学报(自然科学版)Vol .29,No .12000年3月 J .of Shanghai Teachers Univ .(Natural Sciences )Mar .2000稀土水杨酸邻菲罗啉三元固体配合物的研究王则民,何其庄,俞膺浩,罗衍庆,曹锦荣(上海师范大学生命与环境科学学院,上海200234)摘　要:合成了4种稀土水杨酸邻菲罗啉三元固体配合物,其通式为RE (Hsal )3phen (RE =La ,Nd ,Eu ,Er ;Hsal =水杨酸根;phen =邻菲罗啉)。

通过元素分析,摩尔电导,IR ,UV ,XPS 和TG -DTA 分析,研究了配合物的组成和性质。

关键词:稀土;水杨酸;邻菲罗啉;配合物中图分类号:0164.33 文献标识码:A 文章编号:1000-5137(2000)01-0070-05 收稿日期:1999-09-16作者简介:王则民(1942-),男,上海师范大学生命与环境科学学院教授。

稀土水杨酸固体配合物的研究已有报道[1],某些稀土水杨酸邻菲罗啉配合物的光谱研究也有过报道[2],但关于稀土水杨酸邻菲罗啉三元固体配合物的合成和性质研究至今未见系统报道。

鉴于稀土离子、水杨酸和邻菲罗啉分别具有抑菌作用,预料它们形成的三元固体配合物具有抑菌增效作用[3]。

本文介绍4种新的稀土水杨酸邻菲罗啉三元配合物的合成、组成、性质及成键特征。

1　实验部分1.1　试　剂RE 2O 3(RE =La ,Nd ,Eu ,Er ),纯度均大于99.95%以上,上海跃龙有色金属有限公司出品;水杨酸(H 2sal ),分析纯,天津化学试剂一厂;邻菲罗啉(phen ·H 2O ),分析纯,上海试剂三厂出品。

其余试剂均为分析纯。

1.2　仪　器意大利1106型自动元素分析仪;美国Mattson 公司PK 60000-First 傅立叶红外光谱仪;美国P .E .公司PHI 5000C 型X 射线光电子能谱仪;上海分析仪器三厂756MC 型紫外可见光谱仪;上海天平仪器厂CDR -I 型差动热分析仪和JRT -I 型热重分析仪;国产DDS -11A 型电导率仪。

间硝基苯甲酸稀土配合物与大肠杆菌作用的热动力学研究

微生物耐药性在世界范围内的泛滥已成为当今公众健康所面临的最大挑战之一，菌药物的开发已远远抗
落后于现实需要．的抗菌药物研究以及新的抗菌活性筛选试验方法已成为现实需要．稀土及其配合物的新对生物化学效应、药理作用的深入研究的结果表明：土和许多生物分子有亲合力，与重要的生命过程… ，稀参对多种酶或酶原具有激活或抑制作用，具有明显的抗菌消炎作用和抗肿瘤作用４．土与有机物形成配合物ＩＪ当稀后，不但能显著增强抗菌消炎效果，而且比许多有机合成药物或过渡金属配合物的毒性低，过口服或外用稀通土配合物未发现在其体内积累Ｊ我国有丰富的稀土资源，速其应用研究具有格外重要的意义．．加
匀，编号，盖上瓶盖并用专用钳压紧．然后将安瓿瓶依次吊入仪器的通道，行数据采集，进连续记录在３．０Ｃ７０ｃ大肠杆菌生长的产热功率（）Ｐ— 曲线．
３结果与讨论
３１大肠杆菌的生长产热曲线．
如图１所示．
２２实验材料．
稀土配合物［ｍ（Ｓｍ—ＮＡ）ｐｅ￣・ＩＯ由河北师范大学实验中心提供随．Ｂｈｎ：２／－２］大肠杆菌（ＴＣ７９，ＡＣ８３）由广东省微生物研究所微生物菌种保藏中心提供．培养基为ＬＢ培养基：ＮＣ５０，白胨１．ｇ酵母粉５０，取ａ１．ｇ蛋００，．ｇ溶

用DSC法研究配合物[Sm(m-BrBA)3phen]2·2H2O脱水反应的动力学

脱水反应的动力学
柴兴泉，任宁
（郸学院化学系，河北邯郸０６０）邯５０５
摘要：合成了稀土配合物［ｍｍＢＢ）ｈｎ２２２（．ｒＡ间溴苯甲酸；ｈｎ邻菲罗啉）用差示扫描量热（ｓ）ｓ（・ｒＡａｅ］・Ｈ０ｍＢＢ，ｐｐｅ，。Ｄｃ技术研究了该配合物脱水反应的动力学方程和动力学参数。验数据用双等双步法处理，到脱水反应的动力学方程为ｄ／ｔｅｐ一Ｅ尺）（．）一Ｉ实得ａｄ＝Ａｘ（，１［ｎａ
一
和分解反应动力学研究的重要手段，其研究方法也很多，如微分法与积分法相结合的方法］等，温法与非等温法相结合的方法，］动力学模式函数法［等。８本文新合成配合物［ｍ（ — ｒＡ，ｈｎＳｍＢＢ）ｅ］・ｐ
２利用ＤＣ技术，采取一种较新的处理动力ＨＯ，Ｓ
Ｋｒ片，测量范围为４０Ｂ压００—４０ｃ０ｍ～。紫外吸收光谱在ｕ一５１Ｖ２０分光光度计（日本，岛津）测定。上
ＦｙｎＷａ — ｚｗｌｎ — ｌＯａａ方程【ｌ “
ｌ＝ｌｇｇｌｆ（
）２３５．４６＿．１．．５７Ｅ０
５３卷１
这里，Ｇ（）积分形式的机制函数，Ａ为指前因ａ为子，Ｒ为气体常数，Ｅ为活化能，为绝对温度。将几条Ｔ曲线上同一温度处的ａ值和不同的机Ａ

丙烯酸稀土与邻菲罗啉配合物的合成与表征_王学智

第11卷第1期安　徽　机　电　学　院Vol.11No.1 1996年9月Jou rnal of Anhui Ins titute of M ech anical and ElectricalEngineering Sep.1996丙烯酸稀土与邻菲罗啉配合物的合成与表征王学智(安徽机电学院芜湖　241000)摘　要　本文合成了8种由稀土离子(La3+～T b3+)与丙烯酸(C2H3CO2H)和邻菲罗啉(Phen)形成的三元固态配合物。

经元素分析确定其组成式为RE(C2H3CO2)3(Phen)。

研究了它们的红外吸收光谱、紫外吸收光谱、核磁共振谱及荧光光谱。

探讨了中性配体对Eu(Ⅲ)配合物荧光性能的影响。

关键词　稀土;丙烯酸;邻菲罗啉;三元配合物;光谱性质中图法分类号　O61.4;O6141.331　引　言丙烯酸是一不饱和酸,有C=C及C=O双键共轭,丙烯酸根离子内存在着π65大π键,这有利于能量转移型荧光产生。

邻菲罗啉为一中性含氮芳香体系,分子内亦具有较大的共轭体系,它与三氟醋酸钕的配合物已用作激光材料[1],它与Sm(Ⅲ)、Eu(Ⅲ)、Tb(Ⅲ)的配合物常具有荧光[2]。

但丙烯酸稀土与邻菲罗啉的三元配合物未见报导。

为研究该三元体系的荧光性质,探索新型固体发光材料,本文用氯化稀土作为底物,合成出了8个稀土元素与丙烯酸和邻菲罗啉的三元固态配合物,并对其多种光谱性质进行了研究。

2　实验部分2.1　仪器及试剂Carlo Erba1106型元素分析仪;Nico let170SX型FT—IR光谱仪;岛津UV—240型紫外可见分光光度计;日立850型荧光光谱仪;FT—80A型核磁共振仪;Dupo nt1190型热谱分析仪;DDS—11A型电导率仪。

稀土氧化物,纯度为99.9%以上;丙烯酸,化学纯;邻菲罗啉,分析纯;其余试剂均为分析纯。

2.2　配合物的合成将稀土氧化物溶于1∶1盐酸,尔后蒸发近干,得稀土氯化物(RECl3·n H2O),干燥备用。

稀土-3-己烯二酸-1,10-邻菲咯啉兰元配合物的合成,表征和荧光性能研究

元素分析，ＤＴ配位滴定分析、外光谱确定了其组成，过荧光光谱，究了三元稀土配合物的荧ＥＡ红通研
光性能．
１实验部分
１１试剂．
稀土氧化物：度＞９．％，头稀土研究院；一纯，９包９３已烯二酸：国Ａｌｒｈ公司；，０邻菲咯啉美ｄｉｃ１１一
收稿日期：０７０ —８２０ —１０
・
基金项且内蒙古优秀学科带头人项目（０４０１和教育部春晖计划合作项目（２０ ——１０）２０１０）Ｚ０５２００１
作者简介：吉平，，士研究生．罗男硕通讯联系人：全伶，授， — ｉ：ｚｉｔｅｕｃ索教Ｅｍａｌｓｊｍｕ．ｄ．ｎ＠
稀土（ｍ” 、ｕ、 ” 、ｙ）ＳＥ ” ＴｂＤ。的三元配合物，过元素分析，Ｄ通ＥＴＡ配位滴定分
析、外光谱测定，定了其组成为ＲＥＩＰｅ红确２。ｈｎ・４Ｏ（Ｈ２ＲＥ—ＥｚＴｂ、ｍ” 、ｕ、 ” Ｓ
关键词：稀土；一３己烯二酸；，０邻菲咯啉；１１一三元稀土配合物；荧光性能；发光中图分类号：６４３文献标识码：Ｏ１．３Ａ
０引言
稀土光致发光配合物是一类具有独特性能的发光材料，由于其发光强度高、色性好，以在生物单所
１３稀土有机配合物的合成．稀土氧化物用１：１１ＨＣ加热溶解，发浓缩，出晶体．滤、蒸析过洗涤、燥后得稀土氯化物纯品．干

稀土邻菲罗啉硫代脯氨酸三元固体配合物的热化学研究

发浓缩至粘稠状物质，真空干燥，固体三元配合物．抽得红外光谱结果分析表明，配合物的化学组成与文献＿相符为［Ｅｔｈｎｃ］３ｔ０（Ｅ＝Ｌ，ｍ）ｌＲ（Ｈ）ｐｅ・ｋ・Ｉｃ－Ｒ２ａＳ．
长沙有机试剂厂）标定量热计用的基准物质Ｋ１，Ｃ为含量大于９．％的高纯试剂，９９９其他试剂均为分析纯，水为
三重蒸馏水．
１２稀土（Ｌ，ｍ）菲罗啉硫代脯氨酸三元固体配合物的合成与表征．ａＳ邻
收稿日期：１ —Ｃ —１；回日期：０１（一４０２ｌｌ２修５２１一）ｏ７
设计了合成固体配合物的热化学循环，并且在具有恒定温度环境的ＳＣ一１０溶解反应量热计中¨ Ｒ０测量了反
应物与配合物在相同溶剂中的溶解热，而利用Ｈｓ定理计算出配合物的标准摩尔生成焓，望为稀土邻菲从ｅｓ希
罗啉硫代脯氨酸配合物在生物医学方面的应用研究提供可靠的热力学数据．
基金项目：南省科技计划项目（００８）湖２１Ｆ０
作者简介：丽娟（９９，，南平江人，授，士，究方向：化学叶１６一）女湖教硕研热
・
６・４
叶丽娟李芬
李强国：稀土邻菲罗啉硫代脯氨酸三元固体配合物的热化学研究
物技术研究具有生物药用活性的稀土配合物的热力学、菌消炎等性质，化学与生命科学交叉的科学技术抗是领域［ —３．课题组在研究了稀土邻菲罗啉硫代脯氨酸固体配合物的合成与表征的基础上，据热力学原理１］本０根

两个新颖的1,10-菲罗啉衍生物的合成及其金属配合物在水溶液中热力学稳定性的研究

Much consideration has been given to interest in the func⁃tional polyamines and their complexes in coordination chem⁃istry have received considerable attention.The compound1,10⁃phenanthroline and its derivatives have received considerable interest because of their catalytic,redox and photoredox proper⁃ties,and also because of their biological activity,which are all exhibited when their compounds are in coordination with metal ions.1,10⁃phenanthroline has a peculiar structure;therefore,it is extensively used in the field of chemistry.It is rigid and the two nitrogen atoms occupy adjacent positions;therefore,it acts as a物理化学学报(Wuli Huaxue Xuebao)November Acta Phys.鄄Chim.Sin.,2006,22(11)：1377~1382新颖的邻菲罗啉衍生物的合成及其配合物稳定性研究王蕊1林海2林华宽1,*(1南开大学化学系,天津300071；2南开大学吸附与分离功能高分子材料教育部重点实验室,天津300071)摘要合成并表征了两个长链多齿配体2,9⁃二⁃(n⁃2′,5′,8′⁃三氮杂壬烷基)⁃1,10⁃菲罗啉(L1)和2,9⁃二⁃(n⁃4′,7′,10′⁃三氮杂十一烷基)⁃1,10⁃菲罗啉(L2).研究了该配体及其与过渡金属离子和稀土金属离子配合物的热力学性质.配体和金属离子的配位比都是1∶1.对两个系列配合物的规律性及其差异以及对结果的影响因素也进行了研究.结果表明,所研究的稀土配合物都具有能催化水解生物大分子的11⁃1物种.此性质表明它们是潜在的切割DNA和磷酸二酯水解酶的良好模型物.关键词：1,10⁃菲罗啉,过渡金属离子,稀土金属离子,稳定常数中图分类号：O642Synthesis and Stability of Two Novel Derivatives of1,10鄄phenanthrolineand Their ComplexesWANG,Rui1LIN,Hai2LIN,Hua⁃Kuan1,*(1Department of Chemistry,Nankai University,Tianjin300071,P.R.China;2Key Laboratory of Functional Polymer Materials for Adsorption and Separation of Ministry of Education,Nankai University,Tianjin300071,P.R.China) Abstract Two long⁃chain multidentate ligands,2,9⁃di(n⁃2′,5′,8′⁃triazanonyl)⁃1,10⁃phenanthroline(L1)and2,9⁃di(n⁃4′,7′,10′⁃triazaundecyl)⁃1,10⁃phenanthroline(L2),were synthesized and characterized using1H NMR and elementalanalysis.The thermodynamic properties of the ligands and their complexes with transition metal ions and rare earthmetal ions were investigated using potentiometric titrations.The coordination capabilities of the ligands with thetransition metal ions followed the Irving⁃William sequence:Co(II)<Ni(II)<Cu(II)>Zn(II).The stability constants of theligands with the rare earth metal ions increase from La(III)to Gd(III).The coordination ratio of the ligands and themetal ions is1∶1.The similarities and the differences between the two series of complexes were studied.In addition,the factors influencing the results were researched.The results of this study indicate that all rare earth complexes in thisstudy have the species11⁃1,which can catalyze the hydrolysis of biological macromolecules.This property means thatthey are potentially useful as a good model of hydrolysis enzyme that has the capacity to cleave DNA and diesterphosphate.Keywords:1,10⁃phenanthroline,Transition metal ions,Rare earth metal ions,Stability[Article]Received：May10,2006；Revised：July13,2006.*Correspondent,E⁃mail：hklin@；Tel：+8622⁃23502624.国家自然科学基金(20371028)和天津市自然科学基金(023605811)资助项目ⒸEditorial office of Acta Physico⁃Chimica Sinica1377Acta Phys.鄄Chim.Sin.(Wuli Huaxue Xuebao),2006Vol.22goodπ⁃electron acceptor.Because of its peculiar structure,it can easily form feed backπ⁃bond,which has good coordination capacity with transition metal ions.Consequently,experiments with regard to the complexes of divalent transition metal ions (Co2+,Ni2+,Cu2+,Zn2+)and trivalent rare earth metal ions(La3+, Nd3+,Sm3+,Eu3+,Gd3+),which were used as the possible active species of mimic enzyme were carried out[1⁃3]because of their high number of coordination bonds and their high positive charge.As a further contribution in this area,two novel1,10⁃phenanthroline⁃bridged polyamine ligands(L1,L2)were devel⁃oped and synthesized.Besides the two nitrogen atoms of the aromatic ring,1,10⁃phenanthroline,there are additional six nitrogen atoms in the molecule;therefore,the coordination ca⁃pacity is considerably improved.Protonation constants of the two ligands and stability constants of their complexes with diva⁃lent transition metal ions(Cu2+,Zn2+,Co2+,Ni2+)and trivalent rare earth metal ions(La3+,Nd3+,Sm3+,Eu3+,Gd3+)were determined. 1Experimental1.1SynthesisAll the chemicals were of analytical reagent grade and pu⁃rified before use.2,9⁃dicarboxaldehyde⁃1,10⁃phenanthroline[4]and N⁃bromoethyl⁃ethylenediamine⁃hydrochloride[5⁃6]were synthesized according to the methods described in the literature.The1H NMR spectra were recorded using a Varian UNITY⁃plus400 MHz spectrometer.The elemental analyses were carried out on a Perkin⁃Elmer240C elemental analyzer.A mixture of N⁃bromoethyl⁃ethylenediamine⁃hydrochloride (15g)and25%methylamine solution(31mL)in water(20mL) was gently refluxed by stirring for15h.Following this,the mixture was filtered.Sodium hydroxide was then added to the residue in sufficient amounts such that it does not dissolve any⁃more.Due to the strong basicity,the solution separates into two layers.The upper layer and the ethereal extract of the lower layer were combined and then dried using anhydrous potassium carbonate for one day.The precipitate was filtered.Ether,water, and excessive methylamine were removed from the filtrate by normal distillation.By vacuum distillation,2.6g of product n⁃1,4,7⁃triazaoctane was obtained at72~75℃/1.1kPa[5].2,9⁃dicarboxaldehyde⁃1,10⁃phenanthroline(2.36g,10mmol) was dissolved in absolute ethanol(50mL),which were added in drops to a mixture of n⁃1,4,7⁃triazaoctane hydrochloride(4.98 g,22mmol),triethylamine(4.92mL,132mmol),and abso⁃lute ethanol(50mL).The mixture was then stirred for12h at room temperature under a nitrogen atmosphere.The mixture was then filtered,and solid NaBH4(1.5g,40mmol)was added in portions to the filtrate in an ice⁃cold water bath.After being heated and stirred for another6h at35~45℃,the solvent was removed under vacuum.The resultant white precipitate was dis⁃solved in water(10mL)containing NH4OAc(2g)and water phase was extracted with chloroform(4.80mL)and was com⁃bined with the organic phase,washed with water,and dried with MgSO4.The solvent was filtered and removed using a rotary evaporator to obtain light yellow oil that was further dissolved in a small amount of water.Following the addition of concentrated hydrochloric acid,the pH was adjusted suitably,the precipitate was filtered and recrystallized with methanol/ether.A total of2.4 g of light yellow powder2,9⁃di⁃(n⁃2′,5′,8′⁃triazanonyl)⁃1,10⁃phenanthroline(L1)was obtained.The synthesis of2,9⁃di⁃(n⁃4′, 7′,10′⁃triazaundecyl)⁃1,10⁃phenanthroline(L2)was similar to that of L1.Fig.1shows the processes involved in the preparation of ligands.L1:2,9⁃di⁃(n⁃2′,5′,8′⁃triazanonyl)⁃1,10⁃phenanthroline. Yield:35%.1H NMR(D2O,δ):δ7.79(d,2H,H3,8);δ8.06(s,2H, H5,6);δ8.58(s,2H,H4,7);δ4.80(s,4H,CH2);δ3.14(m,6H, CH3);δ3.54~3.66(m,16H,NHCH2).Elemental analysis:Calc. for C24H38N8·6HCl·3H2O,H:7.08%;C:40.52%;N:15.75%; Found,H:7.12%;C:40.39%;N:15.96%.L2:2,9⁃di⁃(n⁃4′,7′, 10′⁃triazaundecyl)⁃1,10⁃phenanthroline.Yield:33.2%.1H NMR (D2O,δ):δ7.92(d,2H,H3,8);δ8.06(s,2H,H5,6);δ8.61(s,2H, H4,7);δ4.84(s,4H,CH2);δ0.95(t,6H,CH2CH2CH3),δ1.67~1.73 (m,4H,CH2CH2CH3);δ3.07~3.11(m,4H,CH2CH2CH3),δ3.54~ 3.67(m,16H,NHCH2).Elemental analysis:Calc.for C28H46N8·6HCl·3H2O,H:7.62%;C:43.82%;N:14.60%.Found,H: 7.70%;C:43.77%;N:14.71%.1.2Potentiometric titrationsIn potentiometric experiments,all the aqueous solutions were prepared from redistilled water.The Cu(II),Zn(II),Co(II), Ni(II)nitrates were purchased from the Tianjin Third Chemistry Fig.1Processes involved in the preparation ofligands1378No.11LIN,Hua ⁃Kuan et al.：Synthesis and Stability of Two Novel Derivates of 1,10⁃phenanthroline and Their Complexes Reagent Factory,China.The La(III),Sm(III),Eu(III),Gd(III),Nd(III)perchlorates were prepared using the accurate weighing technique.All the metal ion solutions were standardized using ED TA.Titration was carried out with the help of a Beckman pH meter (model 椎71)equipped with a 39841⁃combination glass electrode.In potentiomatric titration experiments,the whole experi mental process was carried out at (25.0±0.1)℃using high ⁃purity N 2as an inert atmosphere.The concentrations of both ligands and metal ions in the experimental solutions were 0.5mmol ·L -1.The ionic strengths were maintained at I =0.1mol ·L -1by the addition of a known amount of 1mol ·L -1KNO 3.A small amount of dilute HNO 3was added to the solutes and then titrated with 0.1mol ·L -1KOH.For each system,at least three titrations were performed and at least 70experimental points were noted.The protonation constants and stability constants were calculated using the SCMAR program [7].2Results and discussion2.1Protonation constants of the ligandsIn the studied pH range (2.5~10.8),there were six stepwise protonation constants,results of which are shown in Table 1.Fig.2shows the species distribution curves.Six stepwise protonation constants can be obtained within the studied pH range.Each of the ligands contains eight nitrogen atoms.Two nitrogen atoms belong to o ⁃phenanthroline.The remaining six nitrogen atoms are located on the long ⁃chain mul ⁃tidentate side arm.Because the basicity of the nitrogen atom of o ⁃phenanthroline (p K a =4.75[8])is less than that of the secondary amine (p K a =9~10),all six protonations belong to the six nitrogen atoms on the side arm.Following the protonation of nitrogenatoms that are located on the long ⁃chain multidentate side arm,the electron cloud of the two nitrogen atoms of o ⁃phenanthroline is attracted by the positive charge of the six pro ⁃tons.The densi ⁃ties of the electron cloud of the two nitrogen atoms of phenan -throline are considerably reduced.The nitrogen atoms of o ⁃phenanthroline lose the ability to bind protons;there ⁃fore,the two nitrogen atoms of o ⁃phenanthroline cannot be protonated in the investigated pH range.From Table 1,the six stepwise protonation constants could be divided into three classes:9.95~9.39,8.65~7.12,and 5.02~3.63.The first class belongs to the two nitrogen atoms at the end of the long chain (N3).The second class forms the middle two (N2),and the third class forms the two (N1)that is bonded with the methylene linked with o ⁃phenanthroline.The electron ⁃with ⁃drawing effect of o ⁃phenanthroline reduces the basicity of N1.The positive charge of the protonated nitrogen atoms attracts the electron cloud of unprotonated nitrogen atoms;therefore,the protonation constants decrease step by step.Contrasting L1with L2,the end of the long chain of L1is methyl,whereas that of L2is propyl (the electron ⁃donating effect of propyl is stronger than that of methyl);however,the positions of other atoms are similar.So,the differences among the six stepwise protonation constants of the two ligands reduce sequen ⁃tially from N3to N1.From lg K 1to lg K 6,the differences betweenEquilibria L1L2[LH]/[L][H]9.60±0.049.95±0.04[LH 2]/[LH][H]9.39±0.039.70±0.03[LH 3]/[LH 2][H]8.51±0.038.65±0.04[LH 4]/[LH 3][H]7.12±0.047.25±0.03[LH 5]/[LH 4][H] 4.95±0.02 5.02±0.02[LH 6]/[LH 5][H]3.63±0.013.68±0.01Table 1Protonation constants of the ligands (lg K )pH=2.5~10.8,T=(25.0±0.1)℃,I =0.1mol ·L -1KNO 3,c L =0.5mmol ·L -1Fig.2Distribution curves of the protonation of the ligandsL1L21379Acta Phys.鄄Chim.Sin.(Wuli Huaxue Xuebao ),2006Vol.22L1and L2are 0.35,0.31,0.14,0.13,0.07,and 0.05,respectively.2.2Stability constants of ligands with Co(II),Ni(II),Cu(II),Zn(II)Table 2shows the stability constants of ligands L1and L2.Fig.3shows the species distribution curves (for example,Cu(II)).The stability constants were calculated using the three models,MLH 4,MLH 3,and MLH 2,within the investigated pH range (2.7~10.5),the three models were determined as 114,113,and 112,respectively.Their possible configurations are shown in Fig.4.From the distribution curves,it is obvious that when pH=3,the coordination does not occur,and so the ligands exist in the protonated form.With the increase in pH,the protons of the secondary amine N1dissociate.The divalent metal ion coordi ⁃nates with the nitrogen atoms of o ⁃phenanthroline and N1to form the model MLH 4.There are three five ⁃atom chelate rings in the complexes.With the further increase in pH,the two protons of N2dissociate sequentially and coordinate with the metal ion to form models MLH 3and MLH 2.The configuration is a regular octahedron.Among the six nitrogen atoms coordinated with the metal ion,the four nitrogen atoms of o ⁃phenanthroline and N1are on the plane position of the octahedron.N2is on the axial position.From the stability constants of L1and L2in Table 2,the coordination capabilities of ligands with the metal ions followed the Irving ⁃William sequence:Co(II)<Ni(II)<Cu(II)>Zn(II).As is well known,the stability constants of complexes par ⁃tially depend on the basicity of the secondary amine.As the electron ⁃donating effect of alkyl substituent increases,the basicity of the amino group is enhanced.Meanwhile,the steric hindrance weakens the coordination capability of the amino group.The two effects together determined the coordination capability.From Table 2,the six ⁃step stability constants of L1are larger than the corresponding step of L2.It shows that the effect of steric hindrance is stronger than the electron ⁃donating effect of the alkyl substituent in the coordination procedure.2.3Stability constants of ligands with La(III),Nd(III),Sm(III),Eu(III),Gd(III)The stability constants of the binary complexes of rare earth metal ions with ligands L1and L2are shown in Table 3.lg β114L1Cu(II)38.75±0.10Zn(II)38.14±0.09Co(II)37.36±0.08Ni(II)38.43±0.12L2Cu(II)37.96±0.09Zn(II)36.90±0.10lg β11333.45±0.1633.38±0.2132.27±0.1833.24±0.2332.85±0.1531.49±0.21lg β11226.27±0.2325.58±0.1824.90±0.2725.89±0.3325.89±0.1923.97±0.29Co(II)36.68±0.1231.52±0.2523.28±0.24Ni(II)37.76±0.0932.52±0.1925.31±0.21Table 2Stability constants of transition metal ions with the ligandspH=2.7~10.5,T =(25.0±0.1)℃,I =0.1mol ·L -1KNO 3,c L =0.5mmol ·L -1Fig.3Distribution curves of the Cu(II)complexes with the ligand L1at n (Cu(II))∶n (L1)=1∶1T=25.0℃,I =0.1mol ·L -1KNO 3,c L =0.5mmol ·L-1MLH 4MLH 3MLH 2Fig.4Possible configurations of binary complexes of L with Cu(II),Ni(II),Co(II),Zn(II)1380No.11LIN,Hua ⁃Kuan et al.：Synthesis and Stability of Two Novel Derivates of 1,10⁃phenanthroline and Their Complexes Fig.5shows the species distribution curves (for example,La(III)).Within the investigated pH range (2.7~10.5),by calculation of the five models,LnLH 2,LnLH,LnL,LnLH ⁃1,and LnLH ⁃2,are determined,which are represented by 112,111,110,11⁃1,and 11⁃2,respectively.Their possible configurations are shown in Fig.6.From the species distribution curves of La ⁃L1⁃H system,the ligands do not coordinate with rare earth metal ions at pH less than 6.H 6L 6+,H 5L 5+,H 4L 4+,and H 3L 3+exist in the solution.This is because that the rare earth metal ion is a hard acid;how ⁃ever,the nitrogen atom is the adjacent base.The coordination between the two is not easy.Even though the deprotonation of N1and N2occurs when pH=2~6,the binding force is so weakFig.5Distribution curves of the La(III)complexes of the ligand L1at n (La(III))∶n (L1)=1∶1T=25.0℃,I =0.1mol ·L -1KNO 3,c L =0.5mmol·L -1ConstantsLa(III)Nd(III)Sm(III)Eu(III)Gd(III)L1lg β11223.45±0.1023.50±0.1123.53±0.0923.71±0.1223.93±0.10lg β11115.35±0.1215.72±0.1516.19±0.2116.23±0.2616.39±0.24lg β110 6.84±0.157.70±0.188.19±0.208.33±0.278.35±0.19lg β11⁃1-2.33±0.20-1.60±0.21-1.23±0.25-0.48±0.16-0.55±0.20lg β11⁃2-12.23±0.28-11.16±0.24-11.02±0.27-10.08±0.19-10.16±0.25L2lg β11223.89±0.1123.97±0.1924.07±0.2324.22±0.1824.50±0.25lg β11115.86±0.2316.19±0.1616.53±0.2016.60±0.2716.78±0.31lg β1107.37±0.258.12±0.298.59±0.238.81±0.318.83±0.33lg β11⁃1-1.73±0.18-1.10±0.19-0.71±0.20-0.13±0.15-0.02±0.08lg β11⁃2-11.71±0.25-10.57±0.28-10.40±0.18-9.31±0.29-9.20±0.25Table 3Stability constants of rare metal ions with the ligandspH=2.7~10.5,T=(25.0±0.1)℃,I =0.1mol ·L -1KNO 3,c L =0.5mmol ·L-111⁃111⁃2Fig.6Possible configurations of binary complexes of L with Ln(III)1121111101381Acta Phys.鄄Chim.Sin.(Wuli Huaxue Xuebao),2006Vol.22 that the coordination is hard to form.When pH>6.0,the bind⁃ing force is so strong that the metal ions can coordinate withnitrogen atoms of o⁃phenanthroline and N1,N2,and the com⁃plex LnLH2is formed.With the increase in pH,the protons ofthe secondary amine N3dissociates,and LnLH,LnL are formedone after the other.Because of the chelating effect,the com⁃plexes are very stable.With the further increase in pH,andwhen pH>8.0,the coordinated water on central rare earth metalion begins to deprotonate,and LnLH⁃1and LnLH⁃2are formedsequentially.The maximum coordination number of central rareearth metal ion is10.From the stability constants of L1and L2in Table3,it can beseen that the stability constants increase from La(III)to Gd(III), that is to say,La(III)<Nd(III)<Sm(III)<Eu(III)<Gd(III). Although all the Ln(III)ions have the same charge,the ionic radii gradually decrease from La(III)to Gd(III):La(III)106pm; Nd(III)100pm;Sm(III)96pm;Eu(III)95pm;Gd(III)94pm[9]. The electron density of Ln(III)ions gradually increases,and thereby the coordination capability of Ln(III)with ligands grad⁃ually increases.Therefore,the stability constants increase gradu⁃ally from La(III)to Gd(III).The stability constants of rare earth metal complexes of L2are larger than those of the same metal complexes of L1.The reason is that the propyl of L2has a stronger electron⁃donating effect,which enhances the coordina⁃tion capability and the stability of complexes.However,accord⁃ing to the crystal⁃field theory,the rare earth metal ions usually have smaller coordination⁃field stabilization energy(ca4.18kJ·mol-1)than the transition metal ions(逸418kJ·mol-1)[10].So, when the rare earth metal ions are coordinated with the ligand, they mainly form the electrovalent bond that has a weaker ori⁃entation effect.The ligand has accordingly a greater steric choice for coordination,which alleviates the tension that is observed during the formation of the five⁃member chelate ring. In addition,the rare earth metal ions have larger radii,as a result of which the adverse steric effect is reduced.In addition,from the graph of lg茁vs angular momentum of metal ions(Fig.7,consider the model species111,110,11⁃1for example),it is obvious that they have a good linear relation. This is in agreement with the“inclined W”regulation,which is generalized by Sinha[11].When compared with transition metals,the rare earth metal ions have larger ionic radius that reduces the steric hindrance effect of the substituent.So,the stability of the complexes of L2 is higher than that of L1,which is contrary to that of the transi⁃tion metal ions.This result indicates that the electron⁃donating effect of alkyl substituent is stronger than the effect of steric hin⁃drance in the rare earth metal ions coordination procedure.It is important to note that rare earth complexes contain the species 11⁃1that can catalyze the hydrolysis of biological macro⁃molecules,and the p K a is at about8~9,which is close to the p K a of human body.This property means that they are potentially useful as a good model of hydrolysis enzyme that has the capacity to cleave DNA and diester phosphate.References1Luo,Y.H.;Lin,H.K.;Lin,H.Transitonn Metal Chemistry,2006, 31:1032Liu,Q.;Lin,H.K.;Lin,H.Transition Metal Chemistry,2006,31: 3253Lin,H.K.;Luo,Y.H.;Lin,H.Transition Metal Chemistry,2006, 31:6904Madeja,K.J.Parkt.Chem.,1962,17:975O′Gee,R.C.;Woodburn,H.W.J.Am.Chem.Soc.,1951,23:1370 6Guo,Y.H.Ph.D.Dissertation.Tianjin:Nankai University,2002 [郭延河.博士学位论文.天津:南开大学,2002]7Sun,H.W.Ph.D.Dissertation.Tianjin:Nankai University,1998 [孙宏伟.博士学位论文.天津:南开大学,1998]8Xia,H.T.;Lin,H.K.;Chen,R.T.Chinese Journal of Inorganic Chemistry,1994,10:363[夏海涛,林华宽,陈荣悌.无机化学学报(Wuji Huaxue Xuebao),1994,10:363]9Yao,Y.B.;Xie,T.;Gao,Y.M.Handbook of physical chemistry.Shanghai:Shanghai Science and Technology Publishing Company, 1985:99⁃104[姚允斌,解涛,高英敏.物理化学手册.上海:上海科学技术出版社,1985:99⁃104]10Peppard,D.F.;Bloomquist,C.A.A.;Horwitz,E.P.;lewey,S.;Mason,G.W.J.Inorg.Nucl.Chem.,1970,32:33911Sinha,S.P.Helv.Chim.Acta,1975,58:1978Fig.7Relation of lg茁and angular momentum of metal ion1382。

5-硝基-1,10-邻菲罗啉的合成及性质研究

收稿日期：０００２１ — ５１６
基金项目：州市 “ １人才培养计划资助项目．杭１ ” ３作者简介：存进（９０）男，江瑞安人，教授，江大学博士研究生，要从事稀土发光材料的合成与性质研究． — ｉｃ２５徐１７，浙副浙主Ｅｍａｌｊ１：ｘ７
Ｖｏ１９ＮＯ．．４
Ｊ１０Ｏｕ．２ｌ
ＤＯＩ０３６／．ｓｎ１７３Ｘ．０００．０：ｌ．９９ｊｉｓ．６４２２２１．４０２
５硝基一，邻菲罗啉的合成及性质研究一１１一０
徐存进
（杭州师范大学材料与化学化３学院，江杭州３０３）＿－浙】０６
中图分类号：０２．２Ｔ５．６６３；Ｑ２３２
文章编号：１７３Ｘ（０００ — ２５０６４２２２１）４０４３
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自２０世纪４０年代初Ｗｅｓｍａ口发现用近紫外光可以激发某些具有共轭体系的有机配体稀土配合ｉｓｎ
计未经校正；ｌｓＡ１１ＦａｈＥ１２型元素分析仪；ｉｏｕＶ一１２ＰＵｎｃ２０Ｃ型紫外可见分光光度仪；ｔｃｉ４０Ｈｉｈ— ５０型ａＦ荧光光谱仪测定荧光光谱和磷光光谱，发光源为氙灯，缝ｓｉ２５ｎ２５ｎ倍增管电压７０Ｖ，激狭ｌ．ｍ／．ｍ，ｔ０扫描速率２０ｎｍｉ．定磷光光谱时用液氮致冷，度为７Ｂ４ｍ／ｎ测温７Ｋ；ＲＵＫＥＮＳ一７型红外光谱仪，ＲＴＥＯＲ２

镝芳香族羧酸与邻菲罗啉配合物的合成、结构、热分解机理及动力学的研究

镝芳香族羧酸与邻菲罗啉配合物的合成、结构、热分解机理及动力学的研究本文以苯甲酸及其衍生物为第一配体,以1,10-邻菲啰啉为第二配体，合成了17种新型镝的配合物,分别是:[Dy（BA）3phen]2、[Dy（o-MBA）3phen]2、[Dy（m-MBA）3phen]2·H2O、[Dy（p-MBA）3phen]2、[Dy（o-MOBA）3phen]2·1.5H2O、[Dy（m-MOBA）3phen]2、[Dy（p-MOBA）3phen]2、[Dy（o-NBA）3phen]2、[Dy（m-NBA）3phen]2·4H2O、[Dy（p-NBA）3phen]2·3H2O、[Dy（o-ClBA）3phen]2、[Dy（m-ClBA）3phen]2、[Dy（p-ClBA）3phen]2·2H2O、[Dy（2,4-DClBA）3phen]2·H2O、[Dy（p-FBA）3phen]2、[Dy（o-FBA）3phen]2、[Dy（p-ABA）3phen·H2O]·1.5 H2O。

稀土席夫碱邻菲罗啉三元配合物的合成及活性研究

Ｐｒ。，Ｎｄ。。＿，Ｓｍ。。＿）ｗａｓｓｙｎｔｈｅｓｉｚｅｄｗｉｔｈｃｏｏｒｄｉｎａｔｅｒｅａｃｔｉｏｎｃｏｎｔａｉｎｉｎｇＳｃｈｉｆｆｂａｓｅ，ｐｈｅｎａｎｔｈｒｏＩｉｎｅａｎｄｒａｒｅｅａｒｔｈ
（ＣｏｌｌｅｇｅｏｆＬｉｆｅＳｃｉｅｎｃｅａｎｄＣｈｅｍｉｓｔｒｙ，ＴｉａｎｓｈｕｉＮｏｒｍａｌＵｎｉｖｅｒｓｉｔｙ，Ｔｉａｎｓｈｕｉ７４１００１）ＡｂｓｔｒａｃｔＲａｒｅｅａｒｔｈＳｃｈｉｆｆｂａｓｅａｎｄｐｈｅｎａｎｔｈｒｏｌｉｎｅｔｅｒｎａｒｙｃｏｍｐｌｅｘｅｓＲＥＭ（ｏ — ｐｈｅｎ）２Ｃ１・２Ｈ２Ｏ（Ｍ — Ｌａ ” ，
２Ｈ２Ｏ的抑菌活性最好。
关键词稀土邻菲罗啉三元配合物结构表征抑菌活性
中图分类号：０６２２．６
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ＳｙｎｔｈｅｓｉｓａｎｄＢｉｏｌｏｇｉｃａｌＡｃｔｉｖｉＣｏｍｐｌｅｘｅｓｗｉｔｈ
摘要
以席夫碱ＩＮ，Ｎ，双（２，４一二羟基苯甲醛）缩邻苯二胺］（Ｉ）和邻菲罗啉为配体，与稀土金属离子配位合
成了稀土席夫碱邻菲罗啉三元配合物ＲＥＭ（ｏ — ｐｈｅｎ）２Ｃ１・２Ｈ２Ｏ（Ｍ－二Ｌａ、Ｐｒ、Ｎｄ ”、Ｓｍａ。。），并利用红外光谱、紫外可见光谱、元素分析和摩尔电导率仪对其结构进行了分析表征，同时将该类配合物应用于生物活性抑菌试验。结果表明，所有配合物对大肠杆菌、金黄色葡萄球菌和白色念珠菌都有较好的抑菌作用，且配合物ＲＥＳｍ（ｏ — ｐｈｅｎ）２Ｃ１・

稀土配合物Tb_p_MBA_3phen的有机电致发光(精)

稀土配合物Tb_p_MBA_3phen的有机电致发光1 实验 1.1 材料的合成按1∶3∶1的摩尔比分别称取TbCl3·6H2O、对甲基苯甲酸(p-MBA)和1,10-邻菲口罗啉(phen)。

将TbCl3·6H2O和两种配体分别溶于适量的95% 乙醇中。

用1 mol·L-1的NaOH水溶液将配体的乙醇水溶液的pH值调节至6~7,然后在不断搅拌的情况下,将混合配体溶液逐滴加到TbCl3·6H2O的乙醇溶液中,其间有白色沉淀产生。

混合完毕,继续搅拌反应5 h,静置过夜。

抽滤,用少量乙醇洗涤沉淀3次,经红外灯下烘干得到白色粉末状固体产物。

经元素分析和单晶结构分析确定这种配合物的组成为Tb(p-MBA)3phen[7]。

1.2 器件的制备图1为所用材料的分子式及器件的结构图。

我们用聚乙烯咔唑(PVK)作为空穴传输材料, 8-羟基喹啉铝(AlQ)分别作为电子传输材料,铽配合物 Tb(p-MBA)3phen为发光材料, LiF为电极修饰材料制备了单层、双层有机电致发光器件: 1. ITO/ PVK: Tb(p-MBA)3phen/Al; 2. ITO/PVK: Tb (p-MBA)3phen/AlQ/LiF/Al。

为了改善配合物的成膜性和导电性,引入了聚合物材料PVK,用PVK作为基质材料与铽配器件2结构与所用材料的分子结构图合物混合采用旋涂的方法制得发光层。

器件的制备方法简单,并且避免了由真空热蒸发而引起铽配合物的分解。

另外, PVK还是很好的空穴传输材料, 这样就提高了器件的空穴注入性能,更有利于铽配合物的发光。

首先把PVK和Tb(p-MBA)3phen溶于氯仿中, 分别配成浓度为10和1 mg·ml-1的溶液,按体积比1∶2分别取两种溶液,制成质量比为5∶1的混合溶液。

分别把Tb(p-MBA)3phen的氯仿溶液和质量比5∶1的混合溶液旋涂在石英玻璃上,用SPEX Fluo- rolog-3荧光光谱仪测量他们的光致发光光谱。

5-氯-2-甲氧基苯甲酸与1,10-邻菲哕啉稀土配合物的合成、表征及热分解机理

ｆｏｅｃｎｅｓｅｔｈｗｅｈｔｏｌ２ｅ￣ｄａｃａａｔｒｔｕｒｓｅｃｆｈｕｉｎ．ｈｌｒｓｅｃｐｃｒｓｏｄｔａｍｐｅｕａｃｘ（）ｍｉｅｈｒｃｅｉｉｆｏｅｃｎｅｏｅＥ ” ｏｓＴｅｓｃｌｔ
ｅｅｎａａａｙｉ．ｔｅｍｏｒｖｍｅｒｄｉｅｅｔｌｔｅｍｏｒｖｍｅｒ．ｆｒｎｉｓａｎｎｃｏｉｔｌｍｅｔＩｎｌｓｓｈｒｇａｉｔｙ— ｆｒｎｉｈｒｇａｉｔｙｄｉｅｅｔａａｌｃｎｉｇａｌｒｍｅｒｙ
ｔｅｒＩｒｐｒｉｓａｅｄｓｕｓｄｂｅｍｏａｉｔｈｍａｏｅｔｒｉｃｓｅｙｔｒｇｒｖｍｅｒｐｅｈｙ—ｄｆｅｎｉＩｃｎｉｇｃｌｒｔｉｅｒｔａｎｎａｏｉｒａｓｍｅｙ，ＦｕｉｒｒｎｆＩｏｒａｓｃｒｅｔｍ
Ｆｂｕｒｅｒａｙ
、ｗ、．ｘ．ｋ．ｄ．Ｉ＾）ｒｌ，ｂｐｕｅｕＣＩｗｈ
பைடு நூலகம்
［ｔｌ］Ａｒｉｅｃ
５氯．－基苯甲酸与１１－一２甲氧，０邻菲哕啉稀土配合物的合成、表征及热分解机理
张洁王娟芬张建军・
（石药集团河北中润制药有限公司，石家庄００４；河北师范大学实验中心，５０１石家庄００１）５０６
（Ｇ— ＴＤＣ）ｉｆｒｄ（）ｓｅｔ，ｌａｉｌＵｓｅｔ，ｎｌｒｃｎｕｔｎｅｔｃｎｕｓＴｅＴＤＧ－Ｓ，ｎｒｅＩｐｃｒｕｔｖｏｅＶ）ｐｃｒａｄｍｏａｏｄｃａｃｅｈｉｅ．ｈａＲａｒｔ（ａｑ

丁二酸、1,10-菲啰啉构筑稀土配合物的合成、表征及与DNA作用的光谱学研究

丁二酸、1,10-菲啰啉构筑稀土配合物的合成、表征及与DNA作用的光谱学研究李小芳;冯小强;杨声;朱元成【期刊名称】《发光学报》【年(卷),期】2016(037)005【摘要】首次合成丁二酸-1,10-菲啰啉稀土配合物,并运用光谱法研究配合物与DNA之间的作用机制,为新型抗癌药物的设计开发提供依据。

以1,10-菲啰啉( phen)和丁二酸( SA)为配体构筑了3种稀土( La3+,Nd3+, Eu3+)配合物,采用元素分析、红外和紫外光谱及热重分析对配合物性质进行表征测试,确定其化学组成为(RE)2(SA)(phen)·2H2O (RE=La,Nd,Eu)。

同时,通过光谱法探讨了这3种配合物分别与DNA作用的机理以及稀土离子种类对作用强度的影响。

配合物与DNA作用时,可观察到较明显的吸收峰红移和较大的减色效应现象,同时,中性红( NR)荧光竞争实验发现配合物都能不同程度地猝灭NR -DNA体系的荧光。

这3种配合物对DNA均具有较强的插入作用,作用强度为：La(Ⅲ)>Nd(Ⅲ)>Eu (Ⅲ)。

计算了DNA与配合物的结合比、结合常数及一些热力学参数,得出DNA 与Eu配合物、Nd配合物、La配合物的结合比分别为4∶1,2∶1和8∶1,ΔrGm <0、ΔrSm >0,表明这3种配合物与DNA之间的反应均能够自发进行,且作用是熵驱动的。

【总页数】8页(P616-623)【作者】李小芳;冯小强;杨声;朱元成【作者单位】天水师范学院化工学院，甘肃天水 741001;天水师范学院化工学院，甘肃天水 741001;定西师专化学系，甘肃定西743000;天水师范学院化工学院，甘肃天水 741001【正文语种】中文【中图分类】O629.74【相关文献】1.2-（4-羟基苯基）咪唑并［4，5-f］［1，10］菲啰啉的合成、表征及抑菌活性研究 [J], 曹虹;董风英;王艳丽;李宁;赵鑫;孙晓风;孙云明2.芳香胺氮氧化物合贵金属配合物研究Ⅱ、1,10-菲啰啉-N-氧化物与金(Ⅲ)、铂(Ⅳ)和钯(Ⅱ)的配合物的合成与表征 [J], 龚钰秋;姜美春;孙鑫泉3.甲酰基甲酸缩氨基硫脲和1,10-菲啰啉的过渡金属配合物的合成、表征及杀菌活性 [J], 刘树祥;高恩庆;田君濂;毕思玮;张建民;李桂芝4.1，10－菲啰啉－1－氧化物与重稀土丙烯酸盐配合物的合成及表征 [J], 李长正;闫福林;李红星;孙建辉;祝振富5.协萃络合物结构的研究——二(1-苯基-3-甲基-4-三氟乙酰基吡唑啉酮-5)-(1,10菲啰啉)合钴(Ⅱ)的合成、表征与晶体结构的测定 [J], 王科志;黄春辉;翁诗甫;徐光宪;韩玉真;贺存恒;郑启泰因版权原因，仅展示原文概要，查看原文内容请购买。

稀土-姜黄素-菲啰啉配合物荧光和抑菌活性研究

稀土-姜黄素-菲啰啉配合物荧光和抑菌活性研究许军鹏;刘景旺;达文燕;宋玉民;朱早龙【期刊名称】《中国稀土学报》【年(卷),期】2009()1【摘要】合成了稀土与姜黄素和1,10-菲啰啉的稀土三元配合物和稀土与姜黄素的稀土二元配合物,通过元素分析、摩尔电导、热重-差热分析、IR、UV-Vis和1HNMR方法,确定配合物的化学组成分别为:REL3L′及REL3.2H2O(RE=Sm,Eu,Dy,L=姜黄素,L′=1,10-菲啰啉)。

同时研究了配合物在室温下的荧光性质,结果显示稀土三元、二元配合物都表现出配体(L)的特征发射且发射强度大于配体(L),三元配合物的荧光强于二元配合物。

抗菌活性试验结果表明,稀土三元、二元配合物对枯草杆菌和大肠杆菌都表现出很好的抑制作用,而且稀土三元配合物REL3L′对所选菌种的抑菌性明显强于稀土二元配合物REL3.2H2O和配体姜黄素。

【总页数】8页(P68-75)【关键词】稀土配合物;姜黄素;荧光性质;抑菌活性【作者】许军鹏;刘景旺;达文燕;宋玉民;朱早龙【作者单位】西北师范大学化学化工学院;天津师范大学化学与生命科学学院;西北师范大学生命科学学院【正文语种】中文【中图分类】O641.33【相关文献】1.邻菲啰啉及其配合物对人参锈腐病菌的抑菌活性 [J], 申凤善;李熙英;张莲姬2.聚(苯乙烯-丙烯酸)载体铁邻菲啰啉(5-硝基邻菲啰啉)配合物的合成及其对丁二烯聚合的催化活性 [J], 曲雅焕;于广谦;李玉良;尹作瑞3.苯甲酸系列邻菲啰啉硝酸根稀土四元混配配合物的合成、表征和抗菌活性研究[J], 赵曙辉;咸春颖;李文刚;黄象安4.钇、镱氯代苯甲酸与1,10-邻菲啰啉三元配合物的合成及抑菌活性 [J], 韩华;刘媛媛;陈志民;王淑萍;王瑞芬;赵宝华5.铒-对甲苯磺酰组氨酸-邻菲啰啉三元配合物的合成及其抑菌活性 [J], 李晓慧;王卫东;李煜林;陆江林因版权原因，仅展示原文概要，查看原文内容请购买。

稀土离子-1,10-菲罗啉桥联多胺二元配合物的稳定性研究

稀土离子-1,10-菲罗啉桥联多胺二元配合物的稳定性研究汪中明;周志芬;林华宽;徐猛;刘天府;朱守荣;孙宏伟;陈荣悌【期刊名称】《化学学报》【年(卷),期】2001(59)5【摘要】在(25±0.1)℃,I=0.1 mol@dm-3NaClO4的条件下,用pH电位滴定法测定了配体N,N'-二取代基-1,10-菲罗啉-2,9-二甲胺(L1～L6,取代基分别对应于甲基、乙基、正丙基、正丁基、异丙基、叔丁基)在水溶液中分别与稀土离子Ln[Ln=La(Ⅲ),Ce(Ⅲ),Pr(Ⅲ),Nd(Ⅲ),Sm(Ⅲ),Eu(Ⅲ),Gd(Ⅲ),Tb(Ⅲ),Dy(Ⅲ),Ho(Ⅲ)]的二元配合物的稳定常数.提出了配合物在溶液中的可能结构.对金属离子和取代基的大小对配合物稳定性的影响进行了详细的讨论.运用线性回归,对有放射性的Pm(Ⅲ)与相应配体的二元配合物的稳定常数进行了推测.【总页数】6页(P701-706)【作者】汪中明;周志芬;林华宽;徐猛;刘天府;朱守荣;孙宏伟;陈荣悌【作者单位】南开大学化学系,;南开大学化学系,;南开大学化学系,;南开大学化学系,;南开大学化学系,;南开大学化学系,;南开大学化学系,;南开大学化学系,【正文语种】中文【中图分类】O6【相关文献】1.新型1，10-菲罗啉铅配合物的合成、晶体结构及性质研究 [J], 冯建华;吴刚;李会会2.2,9-二(n-2′,5′-二氮杂庚基)-1,10-菲罗啉镍(Ⅱ)配合物的合成、晶体结构及生物活性研究 [J], 李风华;刘天府;吴红星;林华宽;江冬青;朱守荣3.两个新型的1,10-菲罗啉桥联多胺配体及其配合物的合成与热力学性质 [J], 李玉玲;林海;林华宽4.铽与苯乙酮酸、2,2′-联吡啶、1,10-菲口罗啉、三苯基氧膦铽三元配合物的合成、结构表征及荧光性能的研究 [J], 张彦辉;孙波;裴娟;耿啸天;王云友;颜剑波5.稀土离子与2,9-二甲基-1,10-菲罗啉的α-氨甲基吡啶衍生物的二元配合物的稳定性研究 [J], 刘天府;汪中明;周志芬;林华宽;朱守荣;徐猛;陈荣悌因版权原因，仅展示原文概要，查看原文内容请购买。

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第１１卷第３期
２１００年６月
北华大学学报（自然科学版）
ＪＵＮＬＯＥＨＡＵＩＥＳＴＮｔｒｌｃｅｃ）ＯＲＡＦＢＩＵＮＶＲＩＹ（ａｕａＳｉｅｎ
Ｖ０．１．ＪｌＮｏ３
Ｊｎ２１ｕ．００
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摘要：乙醇一在水混合体系中合成了１１一，０菲哕啉（ｈｎ的三种稀土配合物Ｎ（ｈｎ（ＨＣ０）（Ｏ）１，ｐｅ）ｄｐｅ）ＣＯ：Ｎ（）
Ｅ（ｈｎ（Ｏ）（）Ｈ（ｈｎＮ，３３．ｕｐｅ）Ｎ，２，ｏｐｅ）（Ｏ）（）采用Ｔ — ＴＧＤＧ和ＤＡ技术研究了配合物在静态氮气中的热分解Ｔ过程，用Ａｈｒ并ｃａ法和Ｃａ．ｅｆｒｏｔＲｄｅｓｎ法对各配合物的非等温热力学数据进行了分析，推断出各反应的热分解反应机理及热分解反应动力学方程式，计算出了其表观活化能（）Ｅ和指前因子的对数值（ｎ）１Ａ．关键词：稀土配合物；，０菲哕啉；１１一热分解动力学中图分类号：６３０４文献标志码：Ａ
ＷＡＮＪａ－ｈｎ，ＧｉｎｚｏｇＹＵＡｕｑｎ，ＨＡｉａＸＩＮＨｏ — ｕＺＯＨａ— ｎ，ＮＧｎ —ｅｇｙＹｏｇｈｎ
（ｏｌｅｏｈｍｉｒｎｈｍｉｌｎｉｅｎ，ｉｏｉｇＮｒａｎｅｉＤｌｎ１６２，ｈｎ）ＣｌｇＣｅｓｙａｄＣｅｃｇｎｒｇＬｎｎｏｍｌｉｍ＠，ａｉ１０９ＣｉｅｆｔａＥｅｉａＵｖａａ
ｐｏｓｂｅｒａｔｎｍｅｈｎｓｆｔｅｔｅａｅｏｏｉｉｎｎｉｅｉｑａｉｎｗｅｅｓｇｅｔｄ，ｎａｕｓｏｓｉｌｅｃｉｃａｉｍｓｏｈｈｒｌｄｃｍｐｓｔｓａｄｋｎｔｅｕｔｏｒｕｇｓｅａｄｖｌｅｆｏｍｏｃ
ｔｅｍａｅｏｏｉｏｓｏｈｏｌｘｓｗｅｅｓｕｉｄｉｔｔｃｎｔｏｅｙＴＧ— ｈｒｌｄｃｍｐｓｔｎｆｔｅｃｍｐｅｅｒｔｄｅｎｓａｉｉｒｇｎｂｉＤＴＧｎａｄＤＴＡｔｏｓＴｈｏ — ｍｅｈｄ．ｅｎｎ
文章编号：０９４２（０００－２８０１０－８２２１）３０１－４
稀土一，Ｏ菲哕啉配合物的热分解动力学研究１１一
王建忠，袁厚群，赵海燕，永恒邢
（辽宁师范大学化学化工学院，辽宁大连１６２）１０９
稀土元素因其特殊的电子构型而表现出其他元素所不具备的光、磁等特性，电、在工业、化学、化及生医学上有着广泛的应用¨ ，其与芳香族羧酸、氮杂芳环配体形成的配合物可用于发光及功能材料等方面，
引起了人们广泛的关注．近年来，人们对以ｐｅ作为第一配体，ｈｎ以苯甲酸、Ｊ水杨酸、］吡啶羧酸类Ｈ别等其他芳香羧酸类作为第二配体的稀土三元配合物的研究报道较多．但大多数报道仅限于对配合物结构的研究和对所合成配合物热分解过程的简单描述，而对该类配合物热分解动力学方面的研究报道很少］．
ＳｕｉｓｏｈｅＴｈｒａｃｍｐｓｔｏｎｔｓｏｎｈａｉｅｔｄｅｎｔｅｍｌＤｅｏｏｉｉｎＫｉｅｉｆＬａｔｎｄｃＣｏｐｅｅｔ１－ｈｎｌｅａｇｎｍｌｘｓｗｉｈ１，０ｐｅｏｉｓＬｉａｄｎ
ａｔａｉｎｒｉ（ａｄｐｅｅｐｎｎｉｃｒ（ｎｗｒｉｎｒｓｅｔｅｙ１Ａ）ｅｅｇｅｅｐｃｖｌ．ｉｏｓｘａｆｏｖｉ
Ｋｅｒ：ｌｎｈｎｄｏｌｘ；１ｐｅｏｉｅ；ｈｒａｅｏｏｉｉｎｙｗｏｄｓａｔａｉｅｃｍｐｅ１，０一ｈｎｌｎｔｅｌｄｃｍｐｓｔｏｍ