Metal-free synthesis of 1,2,3-benzotriazines

The recent molecular iodine catalyzed [1,2]-rearrangement of aryl amines and 3-amino-1H-indazolesfor the synthesis of 1,2,3-benzotriazines is highlighted.     

Influence of carbon templates and Yb concentration on red and green luminescence of uniform Y2O3:Yb/Er hollow microspheres

Uniform Yb³⁺ and Er³⁺-codoped Y₂O₃ hollow microspheres were synthesized via urea co-precipitation using carbon spheres as templates. Intense red emission (⁴F_9/2→⁴I_15/2) and weak green emission (²H_11/2, ⁴S_3/2→⁴I_15/2) of Er³⁺ were observed for the Yb³⁺ and Er³⁺-codoped Y₂O₃ hollow microspheres under 980 nm infrared excitation. The integrated intensity of visible emission and the ratio of red to green were found to be strongly dependent on the amount of carbon sphere templates and the concentration of Yb³⁺ ions. The amount of carbon sphere templates also plays an important role in adjusting the size of crystallite. Multi-phonon relaxation resulted from the absorbents (OH⁻ and CO₃²⁻) on the surface of the crystallite, and efficient occur of energy transfer processes and cross-relaxation between Er³⁺ and Yb³⁺ are responsible for the enhancement of intensity ratio of red to green emission. Interestingly, for higher concentration of Yb³⁺ ions, the green emission is assigned to a three-phonon process in Y₂O₃:Yb/Er hollow microspheres, which also could result in the increase of the red to green emission ratio. An explanation to account for these behaviors was presented.     

CuI/Al双层电极的有机场效应晶体管

制备了CuI/Al为源极和漏电极的并五苯基场效应晶体管.相对于纯金属(Al, Au)电极的晶体管,所研制的晶体管的迁移率、阈值电压VT、开关电流比I_on/I_off等参数都有明显改善.研究发现,在Al电极与并五苯半导体之间引入CuI作为空穴注入层,能够明显降低Al电极与并五苯之间的空穴注入势垒.紫外-可见光谱和X射线光电子能谱数据表明,这种空穴注入势垒的降低源自并五苯和Al向CuI的电子转移. 关键词： 有机场效应晶体管 CuI/Al双层源漏电极 电子转移     

日光辐射光还原合成左旋多巴胺功能化的荧光发射的银纳米簇和铁离子检测

以左旋多巴胺(L-3,4-dihydroxyphenylalanine,DOPA)为稳定剂,采用日光辐射光还原法,合成了强荧光发射的银纳米簇(silver nanoclusters,Ag NCs)。透射电镜分析表明,所合成的Ag NCs表现亚纳米非晶态结构。Ag NCs在可见-近红外波长范围内(400~750 nm)有明显光吸收带,最大荧光激发和发射峰分别为550和630 nm,荧光量子产率为2.3%(相对于罗丹明B)。Ag NCs的荧光强度与合成时的日光辐射时间、DOPA浓度以及pH值等因素有关。进一步优化了合成Ag NCs的条件。基于荧光猝灭原理,所合成的DOPA功能化的Ag NCs能选择性地灵敏响应Fe3+。修饰在Ag NCs表面的配体DOPA能够选择性地结合Fe3+,导致Ag NCs显著聚集,伴随荧光猝灭。Ag NCs具有的较高量子产率和红荧光发射特性,有利于提高Fe3+的分析灵敏度。     

新型噻唑并[3,2-a]嘧啶类化合物的合成

5-乙氧羰基-4-芳基-6-甲基-3,4-二氢嘧啶-2-酮与丁炔二酸二甲酯反应, 合成了系列新的噻唑并[3,2-a]嘧啶类化合物, 反应具有时间短、收率高、后处理简单等优点. 采用NMR (1H, 13C, COSY, HSQC和HMBC), IR等多种谱学技术, 结合元素分析对产物进行详细表征, 通过对目标产物的1,3-偶极环加成的衍生化产物进行X射线单晶衍射而确定目标产物的结构.     

区域和立体选择性合成新型螺羟吲哚类化合物

2-芳亚甲基苯并[4,5]咪唑并[2,1-b]噻唑-3-酮与甲亚胺叶立德(经靛红与肌氨酸反应在线生成)进行l,3-偶极环加成反应, 合成了8个新的螺羟吲哚类化合物. 采用元素分析, NMR, IR, 质谱以及X射线单晶衍射等多种谱学技术对产物进行详细表征, 而产物的晶体结构表明了此类反应具有高度的立体选择性和区域选择性.     

四氯合钯(II)喹诺酮配合物的合成及与DNA的作用和抗增殖活性

在酸性条件下, 分别合成了四氯合钯(II)离子与2种喹诺酮(诺氟沙星, NFLX＝C16H18N3O3F; 环丙沙星, CPLX＝C17H18N3O3F)离子形成的配合物(NFLXH)2[PdCl4]•2H2O (1)和(CPLXH)2[PdCl4]•2H2O (2). 用元素分析、IR、UV以及摩尔电导测定等方法对其进行了表征. 配合物1的晶体结构经X射线单晶衍射确定, 结构参数: 三斜晶系, P-1空间群, a＝0.84561(17) nm, b＝0.94191(19) nm, c＝1.2832(3) nm; α＝111.26(3)°, β＝97.23(3)°, g＝96.38(3)°, V＝0.9312(4) nm3, Z＝1, 最后吻合因子R＝0.040, wR＝0.088. 利用紫外光谱法、荧光光谱法对配合物与小牛胸腺DNA (ct-DNA)的作用进行了研究, 研究表明, 配合物对DNA的作用模式为插入作用, 与DNA的结合常数Kb分别为: Kb(1)＝2.06×104, Kb(2)＝2.43×104. 其后测试了配合物对体外肿瘤细胞的抗增殖活性. 经采用四甲基偶氮唑蓝分析法(MTT法)测试后发现配合物1和2对人肺腺癌A549细胞、人原髓细胞白血病HL-60细胞的增殖抑制作用显著强于相应的喹诺酮分子本身, 其中配合物2对人肺腺癌A549细胞增殖有明显的抑制作用, 抑制率可高达(95.4±3.7)%, 半数抑制浓度(IC50, 72 h)为(124.5±10.3) μmol•L－1.     

酸性络蓝K双波长信号系数光度法测定钙镁

基于在氢氧化钠溶液中,钙、镁均与酸性络蓝K(ACBK)形成暗红色配合物,提出了测定钙和镁的双波长信号系数光度法.该法不仅消除了钙、镁之间的吸收干扰,且消除了一定量的共存离子的干扰.利用褪色法与生色法的吸光度之和作为信号吸光度,使方法的灵敏度大为提高.测定钙、镁总量时,分别用钙、镁吸收曲线正峰与负峰上的等吸收波长470.5 nm(λPa)及559.5 nm(λNa)处测定吸光度APa和ANa,求得总量的信号系数fs为2.439.于λPa470.5 nm处测得任一浓度钙、镁试液的吸光度APa′,其信号吸光度As=fsAλPa′.测定镁时,以试剂ACBK褪色对钙配合物生色的完全相消干扰的波长539 nm(Pa)作为测定波长,负峰波长583 nm为Na.按相同方法测得镁的信号系数fs为4.148.     

对三氟甲基苯甲酸和2，2′-联吡啶双核铽配合物的合成、晶体结构及发光性质

A new dinuclear complex [Tb₂(BA)₆(2,2′-bipy)₂] (BA=4-(trifluoromethyl)benzoic acid, 2,2′-bipy=2,2′-bipyridine) has been synthesized. The complex was characterized by X-ray single-crystal structure analysis. The complex is a dimer with an inversion center. In the complex, two Tb3+ ions are linked by four carboxylate groups of BA ligands in bridging-bidentate coordination mode. Each Tb³⁺ ion is eight-coordinated with two nitrogen atoms from one 2,2′-bipy molecule, four oxygen atoms from four bridging-bidentate BA ligands and two oxygen atoms from one chelating-bidentate BA ligand. Intermolecular hydrogen bonds are formed in the crystal. The complex exhibits strong green fluorescence under ultraviolet light and the fluorescence spectrum consists of four lines peaking at 489, 545, 584 and 620 nm, which are corresponding to the ⁵D₄→⁷F_j (j=6～3) transitions of Tb³⁺ ion, respectively. CCDC: 727763.     

Synthesis, characterization and DNA-binding studies of ruthenium(II) mixed-ligand complexes containing dipyrido[1,2,5]oxadiazolo[3,4-b]quinoxaline

A novel ligand dipyrido[1,2,5]oxadiazolo[3,4-b]quinoxaline (dpoq) and its complexes [Ru(bpy)₂(dpoq)]²⁺ and [Ru(phen)₂(dpoq)]²⁺ (bpy = 2,2′-bipyridine; phen = 1,10-phenanthroline) have been synthesized and characterized by elemental analysis, electrospray mass spectra and ¹H NMR. The interaction of Ru(II) complexes with calf thymus DNA (CT-DNA) was investigated by absorption spectroscopy, fluorescence spectroscopy, thermal denaturation and viscosity measurements. Results suggest that two Ru(II) complexes bind to DNA via an intercalative mode.