铕(Ⅲ)-二苯甲酰甲烷-聚(苯乙烯-丙烯酸)配合物及其发光性质研究

研究了铕(Ⅲ)和二苯甲酰甲烷(HDBM)形成的有机配合物与聚(苯乙烯-丙烯酸)(PSAA)发生配位反应得到配位聚合物Eu(Ⅲ)-DBM-PSAA。红外光谱、紫外光谱、X光电子能谱的测试表明了Eu^3^+分别与PSAA,DBM^-发生配位,元素分析和电导率测定结果证明了一个Eu^3^+分别与PSAA中三个链节的羧基和一个DBM^-发生配位。从而得到该配合物的结构并对其荧光性进行研究,配位聚合物不能溶于普通有机溶剂,只能溶于丙三醇/异丙醇混合溶剂常温下配合物在紫外光下发出强的红光,主要是Eu离子的^5D0→^7F2的跃迁。     

聚丙烯酸-铕-二苯甲酰甲烷配合物及其荧光性质的研究

将铕的有机配合物NaEu(DBM) 4与聚丙烯酸反应获得铕配位聚合物 (PAA Eu3+ DBM) .此配位聚合物是白色固体 ,不溶于大部分有机溶剂 ,只能溶于丙三醇和异丙醇的混合溶剂 .采用红外光谱、紫外光谱、X射线光电子能谱、电导率、元素分析和荧光光谱等手段对其结构和荧光性质进行表征 ,确定其配位组成和结构即每个铕离子分别与一个DBM分子和PAA分子中二个链节羧基发生配位 .荧光光谱表明PAA Eu3+ DBM有很好的荧光性     

含稀土铕(Ⅲ)配位聚合物的研究

将铕的有机配合物NaEu(TTA)4与聚（苯乙烯-丙烯酸）（PSAA）反应制备了铕配位聚合物[Eu(Ⅲ）-TTA-PSAA]，用电导、DTA-TGA、荧光光谱等对其进行了表征。由于配合物中存在着Eu^3 分别与TTA^-和PSAA分子中羧基的配位作用，并进一步交联，因此配合物样品均不溶于大部分有机溶剂，只能溶于N，N-二甲基甲酰胺和丙三醇/异丙醇的混合溶剂，且耐热性得到提高。配合物为褐色固体，在常温、紫外光下发出红光，主要是由于Eu^3 离子的^5D0→^7F2跃进。讨论了pH值对配合物荧光强度的影响，当pH=10时，合成的配合物具有最好的荧光性。     

一维链状3-碘苯甲酸铽配合物的合成、晶体结构和性质表征（英文）

溶液法合成了配合物{[Tb（3-IBA）3（H2O）2]·0.5（4,4′-bipy）}n（3-IBA=3-碘苯甲酸根;4,4′-bipy=4,4′-联吡啶）,并通过X-射线衍射单晶结构分析、红外光谱、紫外光谱、荧光光谱以及热重分析对配合物进行了结构和性质表征。配合物晶体属三斜晶系,P1空间群。该配合物具有一维链状结构。Tb^3＋离子与8个O原子配位,其中6个O原子来自5个3-碘苯甲酸根,2个O原子来自水分子。相邻Tb^3＋离子通过2个双齿桥联的3-碘苯甲酸根联结成一维链状结构。未配位的4,4′-联吡啶分子与配位水分子之间形成氢键,并将相邻的一维链联结起来形成二维网状结构。沿a轴的分子堆积形成一维孔道,是由于相邻一维链的苯环之间部分重叠而形成的。在紫外光照射下,配合物发出很强的绿色荧光。配合物的荧光光谱中,4个峰位于490、544、583和619nm,分别对应于Tb^3＋离子的^5D4→^7F6、^5D4→^7F5、^5D4→^7F4和^5D4→^7F3跃迁。     

铕-2-甲硫基烟酸掺杂配合物的合成及荧光性质研究

由2-甲硫基烟酸(HA)与Eu(Ⅲ)合成了二元配合物和13种分别掺杂La(Ⅲ),Y(Ⅲ),Zn(Ⅱ)的三元配合物。通过红外、紫外、元素分析、荧光光谱和热重分析对配合物进行了表征。并着重研究了掺杂离子、溶剂、配合物溶液的浓度对配合物中Eu(Ⅲ)发光性能的影响。紫外光谱显示HA与铕离子配位后其吸收峰强度发生较大改变。红外光谱表明2-甲硫基烟酸中的羧基与铕离子以螯合双齿配位,且单一配合物和掺杂配合物具有相似的配位结构。荧光光谱表明La(Ⅲ),Y(Ⅲ),Zn(Ⅱ)掺杂可以提高铕配合物的荧光强度,其中La(Ⅲ)掺杂荧光强度增强最明显。配合物(Eu0.5Zn0.5)(A)2.5·3H2O以乙醇为溶剂,浓度为5×10-5mol·L-1时,其荧光强度是最强的。     

铽（III）-噻吩甲酰三氟丙酮-电化学聚合漆酚配合物的研究

研究了铽（III）和噻吩甲酰三氟丙酮（HTTA）形成的配合物与电化学聚合方 法得到的聚合漆酚（EPU）发生配位反应及pH = 10.2时形成配合物Tb(III)-TTA- EPU的组分和结构。红外光谱、X光电子能谱的测试表明Tb~(3+)分别与EPU，TTA~- 发生配位。元素分析和电感偶合等离子体发射光谱（AES）测定结果证明了每个 Tb~(3+)分别与EPU分子中1个链节单元的羟基和3个TTA~-发生配位，从而得到配合 物的结构。动态机械热分析（DMTA）表明发生配位反应后该配合物进一步交联，从 而难溶于大部分有机溶剂，其玻璃化转变温度和耐热性能均得到很大提高。我们对 其荧光性质进行了研究，发现常温下配合物在紫外光下发生强的荧光，主要是Tb~ (3+)离子的~5D_4→~7F_5的跃迁。讨论了溶剂、pH值对配合物荧光强度的影响。当 pH = 10.2时，合成的配合物有最好的荧光性质。     

含稀土铕(Ⅲ)配位聚合物的研究——铕(Ⅲ)噻吩甲酰三氟丙酮苯乙烯丙烯酸共聚物的研究

研究了铕 (Ⅲ )和噻吩甲酰三氟丙酮 (HTTA)形成的有机配合物与苯乙烯 丙烯酸共聚物 (PSAA)在不同pH值时发生配位反应得到配位聚合物NaEu(Ⅲ ) TTA PSAA的 3种样品 (a)、(b)、(c) .红外光谱、紫外光谱、X光电子能谱、DTA TG等测试手段证实Eu3+ 分别与PSAA、TTA- 发生配位 .元素分析和电导率测定结果证明了配位组成和结构在不同的pH条件下发生变化 .结果表明 ,配合物试样 (a)、(b)、(c)中Eu3+ 的含量分别为11 89%、12 5 5 %和 13 4 1% .由于配合物中存在着Eu3+ 分别与TTA- 和PSAA分子中羧基的配位作用并进一步交联 ,因此配合物样品均不溶于大部分有机溶剂 ,只能溶于N ,N 二甲基甲酰胺和丙三醇和异丙醇的混合溶剂 ,而且耐热性能均提高 .该配合物均是褐色固体 .荧光光谱表明 ,样品在常温、紫外光下发出强的红光 ,主要是Eu离子的5D0 →7F2 的跃迁 .讨论了溶剂、pH值对配合物荧光强度的影响 .当pH =10时 ,合成的配合物有最好的荧光性质 .     

邻苯二甲酸铽配合物与铕离子间能量传递

本文应用红外光谱、紫外吸收光谱、稳态和时间分辨荧光光谱研究了邻苯二甲酸铽及邻甲基苯甲酸铽配合物的发光性能,配位体结构以及铕离子对配合物发光的猝灭方式,并探讨了溶剂、pH值对发光强度和寿命的影响。     

铽（III）-噻吩甲酰三氟丙酮-电化学聚合漆酚配合物的研究

研究了铽（III）和噻吩甲酰三氟丙酮（HTTA）形成的配合物与电化学聚合方 法得到的聚合漆酚（EPU）发生配位反应及pH = 10.2时形成配合物Tb(III)-TTA- EPU的组分和结构。红外光谱、X光电子能谱的测试表明Tb~(3+)分别与EPU,TTA~- 发生配位。元素分析和电感偶合等离子体发射光谱（AES）测定结果证明了每个 Tb~(3+)分别与EPU分子中1个链节单元的羟基和3个TTA~-发生配位,从而得到配合 物的结构。动态机械热分析（DMTA）表明发生配位反应后该配合物进一步交联,从 而难溶于大部分有机溶剂,其玻璃化转变温度和耐热性能均得到很大提高。我们对 其荧光性质进行了研究,发现常温下配合物在紫外光下发生强的荧光,主要是Tb~ (3+)离子的~5D_4→~7F_5的跃迁。讨论了溶剂、pH值对配合物荧光强度的影响。当 pH = 10.2时,合成的配合物有最好的荧光性质。     

铽多元配合物的合成及其性质研究

通过铽金属醇盐与丙烯酸、β二酮配体反应,合成了4种具有聚合活性的含铽配合物单体,通过元素分析红外光谱、紫外光谱,确定了它们的组成和结构。热分析表明,这些铽配合物单体没有熔点,起始分解湿度在190－200℃之间。在溶液及状态下研究了这些含铽多元配合物的荧光性质,在紫外光激发下,它们均能发射铽离子的特征荧光,溶剂的极性和配体的三线态能级会影响它们的光强度;粉末状态下,这些铽多元络合物的荧光单色性较好。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.