8羟基喹啉氮氧化物—钴（Ⅱ）—过氧化氢化学发光体系的研究

作者合成了８－羟基喹啉氮氧化物，将其引入Ｃｏ（Ⅱ）－Ｈ２Ｏ２（ＯＨ＾－）无发光的氧化还原体系中充当化学发光的能量接受体，获得了强的化学发光效应。本文对该效体系进行了研究，建立了测定微量钴的ＣＬ分析法。     

Fluorescent Complexes of Nucleic Acids/8-Hydroxyquinoline/Lanthanum(III) and the Fluorometry of Nucleic Acids

Abstract

The ternary fluorescent complexes of nucleic acids/8-hydroxyquinoline/ lanthanum (III) were studied. Nucleic acids in the study involve natured and thermally denatured calf thymus DNA, fish sperm DNA and yeast RNA. In the range of pH 8.0–8.4 (controlled by NH₃-NH₄Cl buffer) ternary fluorescent complexes are formed which emit at 485.0 nm for calf thymus DNA and at 480.0 nm for yeast RNA (when excited at 267.0 nm) and emits at 483.0 nm for fish sperm DNA when excited at 265.0 nm. Based on the fluorescence reactions sensitive fluorometric methods for nucleic acids were proposed. Using optimal conditions, the calibration curves were linear in the range of 0.4–3.6 μg˙ml^?1 for calf thymus DNA, 0.4–4.0 μg-ml^?1 for fish sperm DNA and 0.4–4.0 μg˙ml^?1 for yeast RNA, respectively. The limits of determination (3σ) were 0.076 μg˙ml^?1 for calf thymus DNA, 0.068 μg˙ml^?1 for fish sperm DNA and 0.329 μg˙ml^?1 for yeast RNA, respectively. Five synthetic samples were determined with satisfaction.

     

8-Hydroxyquinoline Based Multipodal Systems: Effect of Spatial Placement of 8-Hydroxyquinoline on Metal Ion Recognition

The complexation behaviors of tetrapod 1,2,4,5-tetrakis(8-hydroxyquinolinoxymethyl) benzene (1) and dipod 1,2-bis(8-hydroxyquinolinoxymethyl)benzene (2) have been determined by fluorescence spectroscopy in CH₃CN–H₂O (4:1) buffered at pH 6.9 [HEPES 10 mM] and by ¹H NMR in CD₃CN-CDCl₃ (1:1) mixture. Tetrapod 1 can recognize Ag⁺(10–40 μM) even in the presence of (500 μM) of alkali and alkaline earth metal ions. However, transition metal ions interfere in the estimation of Ag⁺. Dipod 2 shows poor selectivity towards Ag⁺. The ¹H NMR based titrations of podands 1 and 2 against AgNO₃ show characterstic changes in chemical shifts in quinoline, methylene and aromatic protons. The spectral fitting of fluorescence and ¹H NMR titration data has been used to evaluate the stoichiometries of complexes and their complexation constants.     

Novel Chromogenic Chemosensors for Fluoride Anion Based on 8-Hydroxyquinoline Azo Derivatives

A series of 8-hydroxyquinoline azo derivatives with diverse conjugated structures were synthesized and studied to chromogenicaUy detect anions. All the dyes allowed selective detection for fluoride anion in CH3CN via instant deprotonation of the compounds, which was affirmed by UV-Vis absorption and 1H NMR spectra. The chromogenically responding ability increases as the substituent changes from phenyl to naphthyl or anthryl. This result is likely to be related to the enhancement of intramolecular charge transfer （ICT） induced by extension of conjugated structure.     

含氟8-羟基喹啉锌配合物的合成与发光性能

设计合成了2种含三氟甲基的8-羟基喹啉衍生物配体:(E)-2-[2-(3-三氟甲基苯基)乙烯基]-8-羟基喹啉(3a)、(E)-2-[2-(4-三氟甲基苯基)乙烯基]-8-羟基喹啉(3b)及其相应的锌配合物(4a)、(4b),并由1H NMR、IR、MS、元素分析确认了其结构。通过紫外滴定观察了金属锌与配体的配合过程,测定了它们在DMF溶液中的荧光性质;荧光光谱显示化合物3a、3b在DMF溶液中的λmax分别是491nm和513nm,4a、4b的λmax分别是585nm和599nm,而且改变三氟甲基的位置可以调节配合物的发光性能。     

A New 2-((Z)-Thiosemicarbazidomethyl)- Quinolin-8-YL Acetate Ligand and its Cu(II) Complex: Syntheses,Structures, and Characterizations

Abstract

A new ligand, 2-((Z)-thiosemicarbazidomethyl)-quinolin-8-yl acetate (C₁₃H₁₂ N₄O₂S) (L) and its Cu(II) coordination complex, [Cu(L₁)] [HL₁ = (Z)-1-((8-hyd- roxyquinolin-2-yl)methylene)thiosemicarbazide], have been synthesized, and characterized by IR, elemental analysis, ¹H NMR, MS, and X-ray single-crystal diffraction. L shows a stable three-dimensional supramolecular structure through hydrogen bonds and π-π stacking interactions. [Cu(L₁)] shows a three-dimensional network structure formed only by hydrogen bonds. In addition, the fluorescence spectra of L were measured.     

Precipitation Behavior of Metal Ions in the Preparation of YBa2Cu3Oy and (Bi,Pb)2(Sr,Ca)4Cu3Oy Superconductive Materials in 8-Hydroxyquinoline-diethylamine Media

To prepare the YBa₂Cu₃O_y (Y-123) and (Bi, Pb)₂(Sr, Ca)₄Cu₃O_y (Bi-2223) superconductive materials, coprecipitation was used with 8-hydroxyquinoline (oxine) as precipitant to ensure complete precipitation. Various aspects of competitive reactions such as dissociation, precipitation, complex formation and association in the aqueous solution system containing metal ions, oxinate ion and diethylamine species have been explored in order to discover the optimal coprecipitation conditions of the title system. Experiments were conducted to confirm these conditions.     

8-羟基喹啉对V2O5催化氧化环己烯的调变作用

研究了8-羟基喹啉对丙酮中V2O5催化氧化环己烯合成环己烯酮的调变作用,考察了8-羟基喹啉的用量、反应温度、反应时间、溶剂和催化剂用量对环己烯氧化反应的影响,发现在该催化体系中生成的环己烯醇和环氧环己烷可转化成环己烯酮,在适当的反应条件下可抑制环己烯醇和环氧环己烷的生成.结果表明,当五氧化二钒的用量为1%,五氧化二钒与8-羟基喹啉之比为1∶2,在20℃以下反应时,过氧化氢几乎定向地将环己烯氧化成环己烯酮.认为是8-羟基喹啉与钒的配位作用促进了环己烯酮的生成.     

Novel Fluorescent Chemosensors Based on Tryptophan Unit for Cu2+ and Fe3+ in Aqueous Solution

We reported four fluorescent chemosensors containing tryptophan units. The fluorescence spectrum titration experiments suggest that chemosensors 1, 2, 3 and 4 are highly selective for Cu²⁺ and Fe³⁺ over Li⁺, Na⁺, K⁺, Co²⁺, Zn²⁺, Ni²⁺, Hg²⁺ and Cr³⁺ via forming complexes with Cu²⁺ or Fe³⁺, which is confirmed by dramatical quench of fluoreseence in aqueous solution at pH 7.4, thus making all the chemosensors suitable for Cu²⁺ and Fe³⁺ fluorescent sensors.     

Two 5-tetrazolylazo-8-hydroxyquinoline-based Zn(II) and Mn(II) complexes: syntheses,structures and optical properties

Two 5-tetrazolylazo-8-hydroxyquinoline (TTHQ) Zn²⁺ and Mn²⁺ complexes, [Zn(TTHQ)(en)]·2H₂O (en = ethylenediamine) (1) and [Mn₂(TTHQ)₂(H₂O)₆]·2H₂O (2), were synthesized and characterized by single-crystal X-ray diffraction analysis. Stacking (π–π) and hydrogen-bonding interactions are responsible for the stabilization of the supramolecular structures. UV–vis spectral changes and photoluminescent properties of TTHQ, 1 and 2 were investigated and a red emission was found. The hydrogen-bonding interaction energies in 1 and 2 were calculated using density functional theory at the WB97XD/6-31++G level.     

A Highly Selective Fluorescent Chemosensor for Cu2+

A new Zn²⁺ probe L2-Zn(L2=naphthofuran carbonylhydrazone derivant) was synthesized as a fluorescence chemosensor for Cu²⁺, by which Cu²⁺ ion could be detected with high selectivity and sensitivity in a wide pH range via a displacement “turn-off” signaling strategy. Whereas the coordination between Zn²⁺ and L2 resulted in a considerable enhancement of typical luminescence of a naphthalofuran group in complex L2-Zn, the addition of Cu²⁺ ion led to a dramatic decrease in the emission intensity of probe L2-Zn at about 503 nm(excitation at 423 nm). The competitive fluorescent experiments showed that other metal ions, such as Hg²⁺, Fe³⁺, Ag⁺, Ca²⁺, Co²⁺, Ni²⁺, Cd²⁺, Pb²⁺, Zn²⁺, Cr³⁺ and Mg²⁺ could not impact the detection of Cu²⁺. The detection limit of the novel probe L2-Zn for Cu²⁺ ion was as low as 2.3×10^-7 mol/L, which is far lower than the guideline value of 1.6×10^-5 mol/L of the United States Environmental Protection Agency.     

Fluorescent Detection of Cu(Ⅱ) by Chitosan-based AIE Bioconjugate

Detection of Cu(Ⅱ) is very important in disease diagnose, biological system detection and environmental monitoring. Previously, we found that the product TPE-CS prepared by attaching the chromophores of tetraphenylethylene(TPE) to the chitosan(CS) chains showed excellent fluorescent properties. In this study, we tried to use TPE-CS for detecting Cu(Ⅱ) because of the stable complexation of CS with heavy metals and the luminosity mechanism of the Restriction of Intramolecular Rotations(RIR) for aggregation-induced emission(AIE)-active materials. The fluorescence intensity changed when TPE-CS was contacted with different metal ions, to be specific, no change for Na~+, slightly increase for Hg~(2+), Pb~(2+), Zn~(2+), Cd~(2+), Fe~(2+), Fe~(3+) due to the RIR caused by the complexation between CS and metal ions. However, for Cu~(2+), an obvious fluorescence decrease was observed because of the Photoinduced-Electron-Transfer(PET). Moreover, we found that the quenched FL intensity of TPE-CS was proportional to the concentration of Cu(Ⅱ) in the range of 5 μmol/L to 100 μmol/L, which provided a new way to quantitatively detect Cu(Ⅱ) . Besides, TPE-CS has excellent water-solubility as well as absorbability(the percentage of removal, R = 84%), which is an excellent detection probe and remover for Cu(Ⅱ) .     

Synthesis of light-emmting materials bis-[2′-2″-(9H-fluoren-2-yl)-vinyl-8-hydroxyquinoline] zinc(II) and bis-[2′-4″-(4,5-diphenyl-1H-imidazol-2-yl)styryl-8-hydroxyquinoline] zinc(II)

Two novel light-emitting materials bis-[2′-2″-(9H-fluoren-2-yl)-vinyl-8-hydroxyquinoline] zinc(II) (3) and bis-[2′-4″-(4,5-diphenyl-1H-imidazol-2-yl)styryl-8-hydroxyquinoline] zinc(II) (4) containting 8-hydroxyquinoline and fluorene or imidazole moieties have been synthesized. The optical properties of these complexes were influenced by the styryl substituents, and exhibited orange-emission. They have higher fluorescence quantum yields than Alq₃, and good stabilities with thermal decomposition temperatures 395 °C and 435 °C. The single-layer OLED fabricated by 3 emitted lemon-yellow, and exhibited good device performance with a maximum luminance of 489 cd m⁻², and luminance efficiency of up to 0.41 cd A⁻¹. The single-layer OLED fabricated by 4 emitted yellow-green, and exhibited good device performance with a maximum luminance of 323 cd m⁻², and luminance efficiency of up to 0.54 cd A⁻¹.     

Synthesis,characterization, crystal structure and biological activities of supramolecular compounds of Mn(II) and Zn(II) with dipicolinic acid and 8-hydroxyquinoline

Two compounds, (8-H₂Q)₂[Mn(dipic)₂] · 6H₂O (1) and (8-H₂Q)₂[Zn(dipic)₂] · 6H₂O (2) (8-HQ = 8-hydroxyquinoline (oxine), H₂dipic = dipicolinic acid), have been prepared and characterized by elemental, spectroscopic (IR and UV–Vis), and thermal analyses, magnetic measurements and single crystal X-ray diffraction techniques. Compounds 1 and 2 consist of two 8-hydroxyquinolinium cations, one bis(dipicolinato)M(II) anion (M = Mn(II) and Zn(II)) and six uncoordinated water molecules. Both 1 and 2 crystallize in the monoclinic space group C2/c. In the complex anion, each dipic ligand is tridentate through N of pyridine and oxygens of the carboxylate groups. Crystal packing of 1 and 2 is a composite of intermolecular hydrogen bonding interactions. The in vitro antibacterial and antifungal activities of 1 and 2 were evaluated by the agar well diffusion method by MIC (Minimal Inhibition Concentration), looking for compounds which display high-inhibitory effect against gram positive bacteria and fungi. No growth inhibition was observed against tested gram negative bacteria.     

新型含噻吩基8-羟基喹啉锌配合物的合成及光电性能简

设计合成了含噻吩基的新型配体(E)-2-[2-(3-噻吩基)乙烯基]-8-羟基喹啉(4)及相应的锌配合物5,产物结构经核磁共振、红外光谱和元素分析进行表征. 利用X射线单晶衍射仪测定了中间体(E)-2-[2-(3-噻吩基)乙烯基]-8-乙酰氧基喹啉(3)和配体4的单晶结构,结果表明中间体3晶体分子间并无明显的氢键作用,分子间呈交错堆叠;配体4分子之间由硫氢氧键弱作用相互排列形成网状结构. 通过核磁滴定及紫外和荧光滴定模拟了配体4在溶液中与金属锌的配位过程. 固体荧光寿命研究结果表明,配合物5的荧光寿命为18.8 ms. 通过电致发光器件研究发现,配合物5作为发光层具有良好的电致发光性能,同时具有较好的电子传输能力.     

调控发光波长:新型2-取代8-羟基喹啉衍生物金属锌配合物的合成与特性研究

设计合成了2-[(2'-芴基)-乙烯基]-8-羟基喹啉(6)、2-[(2'-菲基)-乙烯基]-8-羟基喹啉(7)及其金属锌配合物8和9; 用UV-Vis, FT-IR, ESI-MS, ¹H NMR和元素分析确认了化合物6和7的结构; 并用四甲基偶氮唑盐微量酶反应比色法(MTT法)研究了其调控骨髓间质干细胞增殖的作用, 结果表明, 化合物6和7对干细胞有明显的增殖作用. 用FT-IR, FAB-MS和元素分析表征了金属锌配合物结构, 光致发光光谱测试结果表明, 化合物8的发光峰值为602 nm, 发黄光; 化合物9的发光峰值为628 nm, 发橙红色光.     

Synthesis of fluorescent dendritic 8-hydroxyquinoline ligands and investigation on their coordinated Zn(II) complexes

A series of luminescent PAMAM dendrons emanating from 8-hydroxyquinoline have been synthesized and their coordination with Zn(II) was investigated for the first time. The obtained dendritic Zn(II) complexes were soluble in common organic solvents. It was found that the luminescence intensity of G2 dendron 6 was higher than that of G1 dendron 4. Furthermore, when they were coordinated with Zn(II), red-shift was observed and the intensities of the coordinated Zn(II) complexes were higher than that of the corresponding ligands.     

Novel polymeric metal complexes as dye sensitizers for Dye-sensitized solar cells based on poly thiophene containing complexes of 8-hydroxyquinoline with Zn(II),Cu(II) and Eu(III) in the side chain

Novel polymeric metal complexes as dye sensitizer for dye-sensitized solar cells (DSSCs) based on poly thiophene containing complexes of 8-hydroxyquinoline with Zn(II),Cu(II), and Eu(III) in the side chain have been synthesized according to the Stille coupling method and characterized by FTIR, GPC, and Elemental analysis. The UV-vis absorption spectroscopy, photoluminescence spectroscopy, cyclic voltammetry, and the applications in dye-sensitized solar cells (DSSCs) are also determined and studied. The DSSCs fabricated by PZn(Q)₂-co-3MT, PCu(Q)₂-co-3MT, and PEu(Q)₃-co-3MT exhibit good device performance with a power conversion efficiency of up to 0.56%, 0.78%, and 1.16%, respectively, under simulated AM 1.5 G solar irradiation (100 mW/cm²). They possess excellent stabilities and their thermal decomposition temperatures are 340 °C, 400 °C, and 540 °C, respectively, indicating polymeric metal complexes are suitable for the fabrication processes of optoelectronic devices.     

Complexation of Al(III) by 8-Hydroxyquinoline and Drastic Fluorescence Enhancement in Reverse Micelles

Complexation of Al^IIIby 8-hydroxyquinoline and fluorescence behavior of the quinolinate(s) were studied in reverse micellar systems at low water content, and compared to aqueous media. Two surfactants were used: one was cationic (CTAC: cetyltrimethylammonium chloride) and the other was anionic (AOT: sodium bis(2-ethylhexyl)sulfosuccinate). The results obtained in the CTAC/dichloromethane system (W= [H₂O]/[surfactant] = 0.9) showed that complexation occurred very likely in the oil phase and no micellar effect was observed. On the contrary, in the presence of AOT, specific micellar effects were observed due to the presence of the anionic polar heads: stabilization of the positively charged 1:1 and 1:2 chelates, at the expense of the neutral water-insoluble 1:3 chelate which is formed in aqueous solutions under similar conditions;drastic fluorescence enhancement factorsof 120 and 100 in AOT/heptane (W= 1.5) and AOT/dichloromethane (W= 1.6), respectively. Such factors have never been reported so far in either hydroorganic or direct micellar systems. In return, the length of time for the production of the complex(es) is increased because of the microheterogeneity of the medium and the small sizes of the water pools.