Luminescent film with terbium-complex-bridged polysilsesquioxanes

A luminescent film with terbium-complex-bridged polysilsesquioxanes has been prepared by sol-gel processing of a new bifunctional monomer that combines the role of a sol-gel molecular precursor with a Tb3+ ion coordinate donor. The emission from Tb3+ ion due to ligand-to-metal energy transfer was observed by UV excitation.

Preparation and luminescence properties of hybrid materials containing europium(III) complexes covalently bonded to a silica matrix

A new kind of luminescent organic-inorganic hybrid material (denoted Hybrid I) consisting of europium 1,10-phenanthroline complexes covalently attached to a silica-based network was prepared by a sol-gel process. 1,10-Phenanthroline grafted to 3-(triethoxysilyl)propyl isocyanate was used as one of the precursors for the preparation of an organic-inorganic hybrid materials. For comparison purposes, the hybrid material (denoted Hybrid II) in which phenanthroline was not grafted onto the silica backbone of the frameworks was also prepared. Elemental analysis; NMR, FT-IR, UV/vis absorption, and luminescence spectroscopies, and luminescence decay analysis were used to characterize the obtained hybrid materials. It is shown that the homogeneity of Hybrid I is superior to that of Hybrid II, and a higher concentration europium can be incorporated into Hybrid I than Hybrid II. Excitation at the ligand absorption wavelength (283 nm) resulted in the strong emission of the Eu3+ D-5(0)-F-7(J) (J = 0-4) transition lines as a result of the efficient energy transfer from the ligands to the EU3+ in Hybrid I. The number of water molecules coordinated to the europium ion was estimated, and the structure of the as-synthesized Hybrid I was predicted on the basis of the experimental results.

Alternate assemblies of thionine and Au-nanoparticies on an amino functionalized surface

Photoactive and electroactive thionine dyes have been introduced in high-surface-area surface-confined Au-nanoparticle superstructures by layer-by-layer deposition techniques.

Preparation, characterization and photophysical properties of layered zirconium bis(monohydrogenphosphate) intercalated with rare earth complexes

Two kinds of rare earth (RE) complexes were intercalated into zirconium bis(monohydrogenphosphate) (alpha -ZrP) by exchanging the RE complexes into the p-methyoxyaniline (PMA) preintercalated compound Zr(O3POH)(2). 2PMA (alpha -ZrP . 2PMA). Powder X-ray diffraction patterns reveal that Eu(DBM)(3)phen (DBM: dibenzoylmethane, phen: 1,10-phenanthroline) and Tb(AA)(3)phen (AA: acetylacetone) intercalated into alpha -ZrP . 2PMA. This was confirmed by the UV-visible spectra of both the RE complexes and the assemblies. At the same time, the assemblies have better luminescent properties, and the fluorescent lifetimes of RE3+ in the excited state in the assemblies are much longer than those in the complexes. The stabilities of the assemblies under UV radiation are much better than those of the RE complexes.

Preparation and luminescence properties of the ternary europium complex incorporated into an inorganic polymer matrix by a sol-gel method

Ternary europium complexes with thenoyltrifluoroacetone (TTA) and phenanthroline (phen) were incorporated into SiO2/polymer matrix by a sol-gel method. The gels exhibit the characteristic emission bands of europium ion. In addition, Eu3+ presents a longer fluorescence lifetime in gel than in the corresponding pure complex powder. Concentration effects on the luminescence intensity were investigated. The reasons that are responsible for above results are also discussed in the context.

Luminescence properties of the rare earth (Eu3+ and Tb3+) complexes with 1,10-phenanthroline incorporated in silica matrix by a sol-gel method

Europium and terbium complexes with 1,10-phenanthroline were introduced into silica gel by the sol-gel method. The luminescence behavior of the complexes in silica gels was studied compared with the corresponding solid state complexes by means of emission, excitation spectra and lifetimes. (C) 1998 Published by Elsevier Science S.A. All rights reserved.

Luminescence properties of rare earth (Eu3+ and Tb3+) complexes with conjugated carboxylic acids and 1,10-phenanthroline incorporated in silica matrix

Binary and ternary complexes of europium and terbium with conjugated carboxylic acid (nicotinic acid and 3,4-furandicarboxylic acid) and 1,10-phenanthroline were introduced into silica gel by the sol-gel method. The luminescence behavior of the complexes in silica gels was studied compared with the corresponding solid state complexes by means of emission, excitation spectra and lifetimes. The result indicated that the rare earth ions (EU3+ and Tb3+) showed fewer emission lines and slightly lower emission intensities in the silica gel than those in pure rare earth complexes. The lifetimes of rare earth ions (EU3+ and Tb3+) in silica gel doped with rare earth complexes became longer than those in pure rare earth complexes. (C) 1998 Elsevier Science S.A.

Luminescence properties of the ternary rare earth complexes with beta-diketones and 1,10-phenanthroline incorporated in silica matrix by a sol-gel method

Ternary complexes of rare earth Eu(dbm)(3).phen and Tb(acac)(3).phen (dbm = dibenzoylmethanide, acac = acetylacetone and phen = 1,10-phenanthroline) were introduced into silica gel by the sol-gel method. The result indicated that the rare earth ions (EU3+ and Tb3+) showed fewer emission lines and slightly lower emission intensities in the silica gel than in the pure rare earth complexes. The lifetimes of rare earth ions in silica gel (Eu3+ and Tb3+) doped with Eu(dbm)(3).phen and Tb(acac)(3).phen were longer than those in purl Eu(dbm)(3).phen and Tb(acac)(3).phen. A very small amount of rare earth complexes doped in a silica gel matrix can retain excellent luminescence properties. (C) 1997 Elsevier Science S.A.

Interaction of brilliant cresyl blue and methylene green with DNA studied by spectrophotometric and voltammetric methods

The binding behavior of two cationic dyes, brilliant cresyl blue (BCB) and methylene green (MG) to calf thymus DNA was studied by spectrophotometric and voltammetric methods. A red shift of the adsorption spectra and hypochromism accompany the binding of BCB and MG to calf thymus DNA. In 5 x 10(-2) mol dm(-3) NaCl, 5 x 10(-3) mol dm(-3) tris-HCl pH 6.87 buffer solution, the apparent binding constants are: K-BCB+ 3.0 x 10(4)M(-1) (N = 4.13) and K-MG+ = 8.8 x 10(4)M(-1) (n = 4.44). Electrochemical studies show that the formal potentials shift negatively upon addition of DNA, indicating that the oxidized forms of the dyes have stronger affinity to DNA than the reduced ones. K-BCB+/K-BCBH and K-MG+/K-MGH are evaluated to be 10.39 and 7.04. respectively. Our investigation suggests that the two cationic dyes interact with DNA predominantly via electrostatic interaction.

ELECTROCATALYTIC OXIDATION OF REDUCED NICOTINAMIDE COENZYMES AT ORGANIC DYE-MODIFIED ELECTRODES

Chemically modified electrodes (CMEs) were prepared by adsorbing different dyes, including methylene blue (MB), toluidine blue (TB) and brilliant cresyl blue (BCB), onto glassy carbon electrodes (GCE) with anodic pretreatment. The electrochemical reactions of adsorbed dyes are fairly reversible at low coverages. The CMEs are more stable in acid solutions than in alkaline ones, which is mainly due to decomposition of the dyes in the latter media. They exhibit an excellent catalytic ability for the oxidation of nicotinamide coenzymes (NADH and NADPH). The formation of a charge transfer complex between the coenzyme and the adsorbed mediator has been demonstrated using a rotating disk electrode. The charge transfer complex decomposition is a slow step in the overall electrode reaction process. Some kinetic parameters are estimated. Dependence of the electrocatalytic activity of the CMEs on the solution pH is discussed.

STUDY ON DYE TRANSFER ACROSS THE LIQUID-LIQUID INTERFACE

I. INTRODUCTIONStudies on the electrochemical phenomena at the liquid-liquid interface are a developing area in electrochemistry and electroanalytical chemistry. The exploration for new ion transfer systems is very important in the development of this area. Dyes are a large group of reagents used widely in analytical chemistry. But no paper deals with the tran,fer processes of dyes at the liquid-liquid (L/L) interface so far.

海洋红藻多管藻和松节藻的化学成分及抗氧化活性研究

海洋生物具有产生丰富多样的次生代谢产物的能力，其中红藻门松节藻科海藻卤代次生代谢产物以其结构新颖、生物活性独特引起了天然产物化学家的重视。 本论文对海洋红藻多管藻和松节藻进行了化学成分研究，综合利用各种色谱学方法 (硅胶柱层析、反相硅胶柱层析、凝胶Sephadex LH-20柱层析、半制备高效液相色谱以及重结晶等) 和现代波谱学技术 (IR、UV、EI-MS、FAB-MS、HR-ESI-MS、CD、1H-NMR、13C-NMR、DEPT、1H-1H COSY、HSQC、HMBC等)，共分离鉴定了100个化合物，发现25个新化合物。 从多管藻中分离鉴定38个化合物 (24个溴酚化合物)，其中7个新化合物 (均为溴酚化合物)，包括1个菲并呋喃结构溴酚 (P1), 2个二氢菲结构溴酚 (P2, P3)，1个含 5,7-dihydrodibenzo[c,e]oxepine 结构溴酚 (P4)和3个简单溴酚 (P5, P6, P7)。P1 (urceolatin) 属首例报道的具有菲并呋喃结构的天然产物，从该种中分离的化合物P12 和 P13 可能是其生源合成的前体。P2和P3为第二例报道的具有二氢菲结构的溴酚化合物。 从松节藻中分离并鉴定了62 个化合物，其中18 个为溴酚类新化合物，44 个为已知化合物。化合物具有多变的取代基团，包括2 个脲基吡咯烷酮溴酚化合物 (R1, R2), 4 个γ-脲基丁酸溴酚化合物 (R3-R6)，5 个酰胺溴酚化合物 (R7, R8, R9, R13, R14)，1 个溴酚砜化合物 (R12), 1 个Xanthene 溴酚化合物 (R10)和5 个简单溴酚化合物 (R11, R15, R16, R17, R18)。R1、R2 是首例报道的含有脲基吡咯烷酮片段的天然产物，R10 为首次报道的溴代Xanthene 类天然产物。 对分离到的化合物进行了清除DPPH 和ABTS两种自由基活性的筛选。结果发现溴酚类天然产物具有显著的DPPH自由基清除活性，其中R3 的IC50 仅为3.3 μM, 其活性强度约为阳性对照BHT (IC50 为82.1 μM) 的24倍。另外，溴酚类天然产物对ABTS自由基有较强的清除活性，R2 的TEAC（Trolox efficency activity capacity）值为5.2 mM，约为阳性对照 (ascorbic acid, 1.02 mM) 的 5 倍。初步的构效关系研究发现，稠环分子、多羟基和邻位甲氧基等结构特点能有效增强DPPH 自由基清除活性；特殊取代基如脲基、吡咯烷酮等含有氮原子的基团，能有效增强ABTS 自由基清除活性，多羟基、溴代等结构特点也使其活性有所增强。 本研究结果丰富了海藻卤代化合物的结构类型，为多管藻和松节藻的合理利用提供了一定的科学依据。

Effect of nano-TiO(2)on MP-25 resin

MP-25 resin is a chlorine-containing polymer widely used in coatings. The effects of two types of nano-TiO2 (P-25 and RM301 LP) on MP-25 were studied with saline immersion, UV irradiation, and electrochemical impedance spectroscopy. UV irradiation was evaluated in terms of gloss change and X-ray photoelectron spectroscopy (XPS). The results indicate that, compared to pigment R-930 TiO2, P-25 reduced the immersion resistance and accelerated UV aging of the MP-25 coating, whereas RM301 LP showed the opposite effects. XPS analysis showed that MP-25 resin degraded under UV irradiation via dechlorination and C-C bond breakage, similarly to poly(vinyl chloride), but RM301 LP could inhibit the aging of MP-25 to a certain extent. A skin effect of oxygen and chlorine was identified in MP-25 resin by XPS. RM301 LP could improve the impedance of the MP-25 coating because of its excellent fill capacity. Hence, rutile nano-TiO2 RM301 LP represents an excellent additive for MP-25 resin. (c) 2007 Wiley Periodicals, Inc.

A homogeneous DNA hybridization system by using a new luminescence terbium chelate

Homogeneous DNA hybridization assay based on the luminescence resonance energy transfer (LRET) from a new luminescence terbium chelate, N,N,N-1,N-1-[2,6-bis(3'-aminomethyl-1'-pyrazolyl)-4-phenylpyridine]tetrakis(acetic acid) (BPTA)-Tb3+ (lambda(ex) = 325 nm and lambda(em) = 545 nm) to an organic dye, Cy3 (A,. = 548 nm and A,. = 565 nm), has been developed. In the system, two DNA probes whose sequences are complementary to the two different consecutive sequences of a target DNA are used; one of the probes is labeled with the Tb3+ chelate at the T-end, and the other is with Cy3 at the 5'-end. Labeling of the Tb3+ chelate is accomplished via the linkage of a biotin-labeled DNA probe with the Tb3+ chelate-labeled streptavidin. Strong sensitized emission of Cy3 was observed upon excitation of the Tb3+ chelate at 325 run, when the two probe DNAs were hybridized with the target DNA. The sensitivity of the assay was very high compared with those of the previous homogeneous-format assays using the conventional organic dyes; the detection limit of the present assay is about 30 pM of the target DNA strand.

Biomimetic emulators of high potential peroxygenases: Implications in bioremediation and metabolic studies

Nowadays, classical (bio)remediation processes are affected by some economical and environmental drawbacks. These approaches often seem to be inadequate, particularly in the perspective of sustainable green processes. Since immobilized metalloporphines can emulate the active site of peroxidases and peroxygenases, their use in several bioremediation processes has been analyzed in this work. The described catalytic reactions use bioinspired, homogenized or heterogenized, commercial porphines and showed a remarkable ability to catalyze substrates oxidation at the expenses of different oxidants such as Oxone and hydrogen peroxide. The biomimetic catalysts have been also investigated about their peroxidase- and peroxygenase-like catalysis and ability to emulate lignolytic peroxidases action and substrate specificity. The adducts showed a remarkable ability to catalyze veratryl alcohol (widely recognized as a simple model compound of lignin) oxidation at the expenses of H2O2. In the perspective of broadening industrial applications of the described catalysts, the oxidation of several pollutants such as durable textile dyes and inorganic sulfides, has been attempted with quite promising results, and some findings open the way toward industrial scaling-up. Accordingly, the inexpensiveness of the synthesis and the mild operational conditions allow these adducts to be proposed as applicable catalysts also for industrial large-scale processes. Besides, these synthetic models are helpful also to understand the behavior of pharmaceuticals, antifungal drugs in this case, in the environment, and to predict the drug metabolism by cytochromes P450. The biomimetic catalysts, for the studied cases, also proved to be much more efficient than the corresponding enzymes.