含喹啉酮基团稀土配合物的合成及荧光性能研究

制得了喹啉酮羧酸衍生物(C16H15N3O6)的稀土配合物,通过红外、质谱、热重以及电化学分析表征了它们的结构,确定了配合物的化学组成为[Ln(C16H15N3O6)X]·n H2O(Ln=Ce、Te)。之后对他们的荧光性能进行研究发现:金属铈离子形成的配合物荧光强度为配体的3.0倍,同时相比于配体,配合物的最大荧光发射波长红移33.5 nm。金属铽离子形成的配合物相比于配体最大荧光发射波长红移46 nm。且两种配合物峰形明显优于单独的存在的金属离子与配体。结果表明制得的稀土有机配合物有良好的荧光性能,在光电及离子检测领域有潜在的应用价值,对生物检测和荧光成像技术的发展具有重要意义。     

三[（5-亚甲基-8-羟基喹啉）氨基乙基]胺及其稀土配合物的合成、表征和与DNA的作用

为研究三爪结构配体稀土配合物的组成、可能的配位状态及与DNA的作用方式,合成了新型三爪结构配体——三[（5-亚甲基-8-羟基喹啉）氨基乙基]胺及其5种稀土配合物.用元素分析、摩尔电导率、IR光谱和TG-DTA方法分析了该类化合物的组成和结构;通过UV光谱和荧光光谱研究了配合物与CT DNA的作用方式.结果表明,该系列配合物的组成为[REL（NO3）2]NO3.4 H2O（RE=Eu,Tb,Nd,La,Ce）,其中2个硝酸根以双齿形式与金属离子配位,总配位数为10;配合物与CT DNA之间存在着插入作用.     

甲基丙烯酸-8-羟基喹啉-Eu(Ⅲ)配合物与鲱鱼精DNA的作用机制

采用光谱法、黏度法和DNA热变性方法研究甲基丙烯酸8羟基喹啉Eu(Ⅲ)配台物(Eu(MA)_2(hq))与鲱鱼精DNA之间的作用机制和结台常数结果表明:该配台物加人鲱鱼精DNA后,特征吸收峰发生明显的减色效应,但峰位红移现象不明显;该配台物能猝灭中性红DNA体系的荧光;该配台物与鲱鱼精DNA的结台常数K_(20)=5.91×10~3L/mol,K_(35)=7.70×10~3L/mol,二者作用的物质的量比为1;该配台物与鲱鱼精DNA之间的热力学函数△rH_m~e=1.34×10~3J/mol,△rG_m~e=-2.12×10~4J/mol,△rS_m~e=76.41 J/(mol·K);鲱鱼精DNA的相对黏度增大,熔点明显升高,Eu(MA)_2(hq)与鲱鱼精DNA之间的作用模式为插人作用.     

镧与8-羟基喹啉水杨酸配合物的热化学研究

目的:由七水氯化镧与水杨酸、8-羟基喹啉反应合成多元混合配合物,并测定该合成反应的标准摩尔反应焓以及配合物的标准摩尔生成焓。方法:应用溶解量热法分别测定了七水氯化镧、水杨酸、8-羟基喹啉和配合物在298.15 K、混合量热溶剂(VDMF:VEtOH:VHClO4=1:1:0.5)中的标准摩尔溶解焓。通过设计热化学循环,根据盖斯定律计算了合成反应的标准摩尔反应焓以及配合物的标准摩尔生成焓。结果:该配合物的化学式是La(C7H5O3)2?(C9H6NO)。各物质的溶解焓分别为△sH mΘ[LaCl3?7H2O(s),298.15 K]=-96.45±0.18 kJ·mol-1,△sH mΘ[2 C7H6O3(s),298.15 K]=14.99±0.17 kJ?mol-1,△sH mΘ[C9H7NO(s),298.15 K]=-3.86±0.06 kJ?mol-1及?sH mΘ[La(C7H5O3)2·(C9H6NO)(s),298.15 K]=-117.78±0.11 kJvmol-1。反应LaCl3?7H2O(s)+2C7H6O3(s)+C9H7NO(s)=La(C7H5O3)2·(C9H6NO)(s)+3HCl(g)+7H2O(l)的标准摩尔反应焓为91.57±0.33 kJ·mol-1。La(C7H5O3)2?(C9H7NO)(s)的标准摩尔生成焓为△fHmΘ[La(C7H5O3)2·(C9H6NO)(s),298.15 K]=-2076.5±3.9 kJ·mol-1。     

2、3—二氯异丁酸基、8—羟基喹啉与希土三元固体配合物合成及表征

该文报告了Nd、Gb、Yb与2,3—二氯异丁酸基、8—羟基喹啉三元配合物的合成及其化学组成的测定。元素分析确定化合物组成为六配位的RELL（L：C4H5O2Cl2,L：C2H5NO）。并对其摩尔电导、红外光谱和热分析等性质进行了研究。     

4-氨基-1,2,4-三唑-5-酮银配合物的制备与表征

目的研究4-氨基-1，2，4-三唑-5-酮银配合物的合成方法。方法用4-氨基-1，2，4-三唑-5-酮(ATO)水溶液与硝酸银溶液反应合成制得。结果得到灰白色固体粉末状配合物，并对其进行了分析鉴定和表征，推测其结构为[Ag(C2H4N4O)(H2O)]NO3。结论反应条件温和，生成了新物质。     

稀土配合物Nd(C5H8NO3)2(C3H5N2)2Cl3·4H2O的合成、表征及性能研究

合成了稀土氯化钕与N-乙酰-DL-丙氨酸(C5H9NO3,Ac-Ala)及咪唑(C3H4N2,Im)的三元配合物,通过元素分析和化学分析确定其化学组成为Nd(C5H8NO3)2(C3H5N2)2Cl3*4H2O,并通过FTIR、UV、1H NMR、13C NMR和X-射线粉末衍射的等手段对目标配合物的结构进行了表征.根据DSC和TG-DTG曲线研究了配合物的热分解过程.配合物水溶液的荧光性质测试表示,形成配合物后,配合物水溶液发生了荧光淬灭现象,在10-2～10-4 mol/L浓度范围内荧光强度与溶液浓度呈正相关.     

基于β-Anderson型铬钼氧酸阴离子为配体的Ag(I)配合物合成及结构表征

使用常温溶液合成方法,成功合成出了2个新的基于β-Anderson阴离子{Cr(OH)6Mo6O18}3-配体的Ag(Ⅰ)离子配合物:[{Ag(C6H5NO2)2}2][Ag{Cr(OH)6Mo6O18}(H2O)2](C6H5NO2)21和(NH4)3[Ag{Cr(OH)6Mo6O18}][Ag2(H2O)2{Cr(OH)6Mo6O18}]·10H2O2,并通过元素分析、单晶X射线分析、红外表征、热重分析和X射线粉末衍射等技术确定了化合物的组成和结构.配合物1是β-Anderson{Cr(OH)6Mo6O18}3-阴离子使用桥氧桥连Ag(Ⅰ)离子,形成一维链状结构;其配阳离子是Ag(Ⅰ)离子与异烟酸吡啶环氮连接,形成线性结构的{Ag(C6H5NO2)2}+配阳离子,由于存在AgAg和吡啶环π-π弱相互作用,在晶体结构中形成双聚{Ag(C6H5NO2)2}2+2结构,并且进一步与多酸阴离子端氧弱配位连接,形成二维结构.配合物2的主体结构是由Ag+和β-Anderson结构阴离子{Cr(OH)6Mo6O18}3-通过配位键连接形成二维网状结构.     

开链冠醚配合物[Zn(C25H19N3O2)H2O]（NO3）2的合成与晶体结构

合成了开链冠醚:2,6-二(8’-喹啉氧甲基)吡啶,并研究了其与Zn(NO3)2的配位反应,得到配合物:[Zn(C25H19N3O2)H2O](NO3)2,并通过熔点、红外光谱、X-射线单晶衍射进行了表征.该配合物由配阳离子[Zn(C25H19N3)H2O]2+和两个NO3-组成,配阳离子中,Zn与开链冠醚上的两个O,三个N原子配位以外,还与一个水分子配位.Zn为六配位,配位几何构型为变形八面体.NO3-与配阳离子间除静电作用以外,还存在O-H…O氢键,增强了分子的稳定性.     

5-硝基-8-羟基喹啉合锌配合物的合成、结构及发光性质

近年来,有机电致发光材料的研究吸引了科学家的极大兴趣,8-羟基喹啉衍生物及其配合物具有较好的发光性质,许多研究人员在该方面做了研究。以5-硝基-8-羟基喹啉和Zn(NO3)2·6,H2O用常温搅拌的方式合成了锌配合物Zn(C9H5N2O3)2(CH3OH)2,对其进行了红外光谱、元素分析、X射线单晶衍射结构测定等表征。该配合物属于单斜晶系,C2/c空间群。以398,nm为激发波长,测定了配合物的荧光发射光谱,配合物在560,nm处有发射峰。与配体及其他类似配合物相比,配合物发光波长有明显的红移,能起到调控发光颜色的作用,可开发成为新的电致发光材料。     

新型吡唑啉类荧光增白剂的合成及性能研究

根据Schellhammer化学结构与荧光性的经验,在吡唑啉环的1-位引入苯并噻唑基,3-位引入吲哚基,5-位引入呋喃基,设计并合成了4种新的吡唑啉衍生物,并且通过红外光谱,^1HNMR谱、质谱和元素分析进行结构表征。化合物的荧光测定显示此类化合物具有良好的荧光性,是一类很有发展前途的蓝紫色荧光化合物。其荧光强度与取代基有关,荧光相对强度与荧光量子产率没有直接关系。     

4-苄氧基苯酚与鲱鱼精DNA相互作用的研究

在pH=7.4的Tris-HCl缓冲溶液中,采用荧光光谱法、黏度法等分析方法研究了4-苄氧基苯酚(PBP)与鲱鱼精DNA的作用方式,用摩尔比法确定了PBP与DNA的结合比为2∶1。通过热力学研究得出,在27℃时PBP与鲱鱼精DNA之间相互作用的结合常数为Kθ300.15K=2.16×105L/mol,热力学函数ΔrHθm=-6.18×104J/mol,ΔrSθm=-1.05×103J/(mol·K),ΔrGmθ300.15K=-3.04×104J/mol,结果表明该反应为焓驱动。综合实验结果确定了PBP与DNA的作用方式为部分嵌插以及静电作用。     

化学强化剂提高生物膜填料塔烟气同时脱硫脱氮性能的实验研究

对采用外加化学强化剂提高生物膜填料塔烟气同时脱硫脱氮的性能进行实验研究.结果表明,当按最优化学强化剂添加量添加硝酸镧0.25+硝酸铈0.25 mg/L、硫酸镁0.5 g/L、乙酸钠0.3 g/L时,生物膜填料塔的NOx净化效率可达61.78%,脱硫率为100%.进一步的长时间连续运行实验结果表明,在对SO2的净化效率达到100%的同时,按添加最优化学强化剂条件实验操作的生物膜填料塔的NOx净化效率明显高于对比空白实验的NOx净化效率,其NOx净化效率的平均值提高了14.78%.实验为研究形成提高生物法烟气同时脱硫脱氮性能(尤其对提高烟气脱氮效率)的新型化学强化技术方法奠定了基础.     

Syntheses,structure and photoluminescent properties of lanthanide oxalatosulfocarboxylate coordination polymers

Hydrothermal reactions of oxalic acid(H2ox) and 2-sulfobenzoic acid(H2L) with lanthanide oxide or hydroxide yielded five lanthanide oxalatosulfocarboxylates.They have a general formula [Ln2L2(ox)(H2O)6]n[Ln = La(1),Nd(2),Eu(3),Gd(4),Tb(5)].Their structures were characterized by single crystal X-ray diffraction,powder X-ray diffraction(PXRD),infrared(IR) spectroscopy,elemental analysis(EA),and thermogravimetric analysis(TGA).1-5 are isostructural coordination polymers and feature one-dimensional(1D) chains,which are extended into 3D supramolecular frameworks through inter-chain hydrogen bonds between coordinated H2O donors and oxygen acceptors from carboxylate,sulfonate and oxalate groups.In addition,the solid-state photoluminescence properties of the Nd(2),Eu(3) and Tb(5) derivatives have been measured at room temperature.The Eu and Tb-containing coordination polymers(CPs) exhibit intense red and green luminescence emissions,respectively,with lifetimes in the order of millisecond.     

Synthesis, structure and property of serial p-carboxylphenoxyacetate-lanthanide coordination polymers

Four novel lanthanide-based coordination polymers, [Ln（PBDC）（HPBDC）（H2O）3] （H=PBDC=p-carboxylphenoxyacetate; Ln = La （1）, Pr （2）, Nd （3）） and [La=（PBDC）3（H2O）4] （4）, have been prepared through hydrothermal synthetic methods. Compounds 1-3 are isomorphous and exhibit one-dimensional （1D） chain-like motifs, while compound 4 features a complicated three-dimensional （3D） architecture, which is designed and synthesized based on the inspiration from the structure characterization of compound 1. Under the similar reaction conditions, the carboxyl in compound 1 may be further deprotonated by adding the organic base of 2,2′-bipyridine. This subtle change caused a significant difference in the structures, from 1D chain of 1 to a 3D structure of 4. In addition, IR, UV-Vis, TGA and magenetic properties are also investigated in this paper.     

Synthesis and structural characterization of lanthanide coordination polymers constructed from a 13-membered macrocycle

The lanthanide coordination polymers bearing a 13-membered macrocycle, [(13-EDTA-pnOH)H2] were synthesized. The products [Ln(13-EDTA-pnOH)(H2O)2·NO3]n (Ln = Eu(1), Tb(2), Dy(3)) have been obtained by MS, IR and element analyses. The solid-state structure of 1 was established by single-crystal X-ray analysis. The coordination geometry around the central metal atom in complex 1 is a nine-coor-dinated, tricapped-trigonal prism having six donor atoms (two amine nitrogen atoms, two amide oxygen atoms and two carboxymethyl oxygen atoms) from one ligand, one oxygen atom from a neighboring ligand, and two more oxygen atoms from two water molecules. The europium atoms are linked by―Eu―O―C―O―Eu―bridges to form an infinite chain.     

新的糖/茂钛化合物的合成及其生物活性研究

用4种含糖基团取代二氯化二茂钛中的氯,合成了4种新的糖/茂钛化合物:乳糖酸根一氯化二茂钛C12H21O12.C10H10TiCl,质酸根一氯化二茂钛C14H20NO11.C10H10TiCl.8H2O,乳糖酸根一质酸根二茂钛C12H21O12.C14H20NO11.C10H10Ti.26H2O和乳糖酸酰胺乙酸根一氯化二茂钛C14H24NO13C10H10TiCl.化合物都经过红外光谱、核磁共振、元素分析表征,并用MTT法研究了化合物对人体子宫颈癌细胞增殖体外实验.研究表明新合成的化合物都溶于水,对癌细胞有很好的抑制作用,糖结构的引入有明显的肝靶向效应.     

Synthesis, structure and superoxide dismutase activity of two self-assembly transition metal complexes containing a tridentate amino-Schiff base deviating from salicylaldehyde with glycine

Two new transition metal （Cu, Ni） complexes with amino-Schiff base ligand, （CgH7NO3）Cu（C14H12N2）.H2O （1） and （C9HTNO3）Ni（C3H4N2）3.H2O （2）, have been designed and synthesized in ethanol solution at room temperature. Both of the complexes have been characterized by elemental analysis, IR spectra, UV-vis spectroscopy and X-ray single crystal diffraction. For complex 1, the coordination environment of the central copper atom is a distorted square pyramid, and one-dimensional chain is formed through the inter-molecular hydrogen bonds （O4-H2W…O3, O4…H2W…O3#1 （#1： -x＋1, y, -z＋3/2）） and weak interactions （∏-∏ stacking interaction） between the phenyl rings. For complex 2, the nickel atom is 6-coordinated and in a distorted octahedral environment, and a discrete hydrogen-bond cluster （four molecules are connected by hydrogen bonds into a group） is formed via two types of intra-molecular hydrogen bonds （O-H...O, N-H...O） and inter-molecular hydrogen bonds （O-H...O, N-H...O）.     

Synthesis and properties of a Pr（Ⅲ） complex with 2-acetylbenzimidazoledehyde-glycine Schiff-base ligand

Abstract The 2-acetyl-benzimidazoledehyde-glycine Schiff-base ligand and the corresponding Pr（Ⅲ） complex Pr2L3（NO3）3· 2CH3OH （L=C11H10N3O2） were synthesized in methanol and characterized by a series of methods, including chemical analysis, elemental analysis, TOF-MS, ^1H NMR, UV-, IR-, Raman spectra, thermal analysis, and the three-dimension fluorescence excitation and emission spectra. The Pr（Ⅲ） complex exhibits extraordinary water-solubility and the Pr（Ⅲ） hydroxide appears at pH≥13. The complex also possesses specific fluorescent properties. Thus, at the excitation wavelengths 200.0-280.0 and 260-350 nm the fluorescence bands were observed at 290.0 and 400.0 nm, respectively.     

Preparation of three-dimensionally ordered macroporous perovskite materials

In this paper,we use La0.8Sr0.2MnO3 and La0.7Ca0.2Sr0.1MnO3 as examples to demonstrate a preparation method for threedimensionally ordered macroporous(3DOM) perovskite thermochromic materials.Polystyrene spheres with an average diameter of 220 nm were self-assembled into a three-dimensionally ordered colloidal crystal template.A mixed metal nitrate solution prepared using La(NO3) 3·6H2O,Ca(NO3) 2·4H2O,Sr(NO3) 2,Mn(CH3COO) 2·4H2O and an ethanol precursor was used to fill the interstitial voids of the polystyrene colloidal crystal templates.3DOM La0.8Sr0.2MnO3 and La0.7Ca0.2Sr0.1MnO3 materials were then obtained after the sphere templates were removed via drying and calcination.The results show that the framework of the 3DOM materials can have different thicknesses and pore shrinkage rates by varying the filling times.In addition,the Curie temperatures of the 3DOM and bulk La0.8Sr0.2MnO3 materials can be varied by altering the preparation method.