UV–vis photodegradation of dyes in the presence of colloidal Q-CdS

The interaction of the dyes Safranin-O (SO) and Orange II (OII) with aqueous colloidal Q-CdS clusters, which emit single fluorescence bands with maximum wavelengths at 481 nm (excitonic band) or 559 nm (trapped band), has been studied. This was carried out by monitoring both the photodegradation of the dye in the presence of the clusters and the quenching of the clusters fluorescence by the dyes. The photolysis experiments were carried out by excitation either at 520 nm (the wavelength at which the dyes, but not the clusters absorb light) or at 350 nm (the wavelength at which the clusters strongly absorb light, and the dyes have absorbance minima). At 520 nm, photodegradation of SO could be observed, which follows a first-order kinetics (for trapped-band clusters) and a second-order kinetics (for excitonic-band clusters). For the excitation wavelength of 350 nm, photodegradation of either of the dyes could not be observed. The Stern–Volmer plots for the quenching of the excitonic band-clusters fluorescence by SO show an upward curvature, pointing to the occurrence of more than one species acting as the fluorescence quencher, whereas the Stern–Volmer plots for the quenching of the trapped band-clusters fluorescence by SO are linear, indicating that only one species acts as a fluorescence quencher. Lambert–Beer type plots (absorbance vs. concentration) are linear for SO in water and in trapped band-clusters solutions, but a similar study of SO in excitonic band-clusters solution show the occurrence of a new band, which can be assigned to a ground-state dimer of the dye. The latter can be used to explain both the upward curvature of the Stern–Volmer plots and the second-order kinetics observed for SO photodegradation in the SO-excitonic band-clusters system. The Stern–Volmer plots for the quenching of both fluorescence bands by OII are linear.     

Large-scale synthesis of size-controllable Ag nanoparticles by reducing silver halide colloids with different sizes

By reducing the colloidal silver halide, we successfully synthesized a series of micro-nano Ag particles.     

Antimicrobial activity of silver nanoparticle colloids of different sizes and shapes against Streptococcus mutans

Research on Chemical Intermediates - Silver nanoparticles stabilized with chitosan biopolymer are a new antibacterial agent for treatment of caries. To determine whether the size and morphology of...     

Synthesis and luminescence of polyphosphazenes with carbazolyl side chains

Two new blue‐light‐emitting polyphosphazenes ( 1 and 2 ) containing carbazolyl groups as side chains were synthesized from a highly reactive macromolecular intermediate by a nucleophilic substitution reaction. Molecular structural characterization for the polymers was presented by ¹H NMR, IR, and ultraviolet–visible spectra, gel permeation chromatography, and differential scanning calorimetry. The polymers exhibited excellent solubility in common organic solvents and were thermally stable. A fluorescence analysis of the two materials in tetrahydrofuran showed a strong blue light emitting. The quantum yields of the polyphosphazenes were 0.55 for 1 and 0.64 for 2 , relative to quinoline (in 0.1 N H₂SO₄). An electroluminescent diode was fabricated, and a bright blue light was observed; the maximum external quantum efficiency was about 0.026% at an applied forward voltage of 23 V. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3428–3433, 2001     

Seeded growth of titania colloids with refractive index tunability and fluorophore-free luminescence

Titania is an important material in modern materials science, chemistry, and physics because of its special catalytic, electric, and optical properties. Here, we describe a novel method to synthesize colloidal particles with a crystalline titania, anatase core and an amorphous titania-shell structure. We demonstrate seeded growth of titania onto titania particles with accurate particle size tunability. The monodispersity is improved to such an extent so that colloidal crystallization of the grown microspheres becomes feasible. Furthermore, seeded growth provides separate manipulation of the core and shell. We tuned the refractive index of the amorphous shell between 1.55 and 2.3. In addition, the particles show luminescence when trace amounts of aminopropyl-triethoxysilane are incorporated into the titania matrix and are calcined at 450 °C. Our novel colloids may be useful for optical materials and technologies such as photonic crystals and optical trapping.     

Laser-induced luminescence of barite after thermal treatment

The photoluminescence (PL) of barite is a noncharacteristic property and cannot be used for the investigation of its structure. After thermal treatment of barite at 600°C several luminescent centers were observed, providing information about different impurities. UO ₂ ²⁺ was determined from the vibrational structure and the long decay time of the luminescence band. Two different types of uranyl were detected, thin films of uranyl mineral (most probably, reserfordin) and a solid solution of uranyl ion in barite crystal. Characteristic green luminescence of UO ₂ ²⁺ may be used as indicative feature for the prospecting of uranium deposits and for the sorting of barite ores with the aim of cleaning from harmful U impurities. Eu²⁺ was determined from the spectral position, the half-width and the characteristic decay time of the luminescence band. Mn²⁺ and Ag⁺ were determined by comparing luminescence bands spectral parameters to those of synthesized BaSO₄−Mn and BaSO₄−Ag. Fe³⁺ or Mn⁴⁺ were determined from the spectral-kinetic parameters of the luminescence bands. Dedicated to Professor Lisa Heller-Kallai on the occasion of her 65^th birthday     

Delayed luminescence of luminol initiated by a membrane-bound peroxidase

The luminescense of the luminol-H₂O₂ system was initiated by either free or membrane-bound horseradish peroxideae (HRP). The instantaneous luminescene decayed rapidly and was followed by the delayed luminescence in the presence of excess luminol. The delayed luminescence was characterized by a chain reaction, in which luminescence intensity increased exponentially. Membrane-bound HRP demonstrated that the delayed luminescence took place even in the absence of HRP if the instantaneous luminescence was initiated by HRP. A mechanism for the nonenzymatic luminescence is proposed and discussed.     

偏硅酸镉的自激活发光

利用高温固相法合成了一种具有自激活发光行为的CdSiO3基质.对样品进行了X射线衍射分析和光谱分析.光谱分析结果表明,在偏硅酸镉的发射光谱中存在三个自激活发光峰,它们分别位于380,467和560nm处,另外,通过热释光谱技术讨论了偏硅酸镉中的缺陷及相关机理.在热释光谱中有两个明显的热释峰,分别位于448和563K,它们的陷阱深度分别为0 58和0 61eV,表明了在偏硅酸镉中存在着不同的陷阱,这些陷阱的存在导致了偏硅酸镉的自激活发光.     

电化学法合成强荧光CdTe量子点

采用电化学方法产生的H2Te为碲源(Te2-),快速合成了水溶性强荧光的CdTe量子点.该方法具有操作简单、安全、快速廉价和可大量制备等优点.合成过程中考察了合成温度,pH值和配体比例对制备CdTe量子点的影响.在最优化的实验条件下,电化学方法合成的巯基丙酸配位的CdTe荧光量子产率可达到55％;通过紫外可见光谱(UV...     

Remarkable luminescence properties of lanthanide complexes with asymmetric dodecahedron structures

The distorted coordination structures and luminescence properties of novel lanthanide complexes with oxo‐linked bidentate phosphane oxide ligands—4,5‐bis(diphenylphosphoryl)‐9,9‐dimethylxanthene (xantpo), 4,5‐bis(di‐tert‐butylphosphoryl)‐9,9‐dimethylxanthene (tBu‐xantpo), and bis[(2‐diphenylphosphoryl)phenyl] ether (dpepo)—and low‐vibrational frequency hexafluoroacetylacetonato (hfa) ligands are reported. The lanthanide complexes exhibit characteristic square antiprism and trigonal dodecahedron structures with eight‐coordinated oxygen atoms. The luminescence properties of these complexes are characterized by their emission quantum yields, emission lifetimes, and their radiative and nonradiative rate constants. Lanthanide complexes with dodecahedron structures offer markedly high emission quantum yields (Eu: 55–72 %, Sm: 2.4–5.0 % in [D₆]acetone) due to enhancement of the electric dipole transition and suppression of vibrational relaxation. These remarkable luminescence properties are elucidated in terms of their distorted coordination structures.     

Synthesis, structural features, absorption spectra, redox behaviour and luminescence properties of ruthenium(ii) rack-type dinuclear complexes with ditopic, hydrazone-based ligands

The isomeric bis(tridentate) hydrazone ligand strands 1 a-c react with [Ru(terpy)Cl3] (terpy=2,2':6',2'-terpyridine) to give dinuclear rack-type compounds 2 a-c, which were characterised by several techniques, including X-ray crystallography and NMR methods. The absorption spectra, redox behaviour and luminescence properties (both in fluid solution at room temperature and in rigid matrix at 77 K) of the ligand strands 1 a-c and of the metal complexes 2 a-c have been studied. Compounds 1 a-c exhibit absorption spectra dominated by intense pi-pi* bands, which, in the case of 1 b and 1 c, extend within the visible region, while the absorption spectra of the rack-type complexes 2 a-c show intense bands both the in the UV region, due to spin-allowed ligand-centred (LC) transitions, and in the visible, due to spin-allowed metal-to-ligand charge-transfer (MLCT) transitions. The energy position of these bands strongly depends on the ligand strand: in the case of 2 a, the lowest energy MLCT band is around 470 nm, while in 2 b and 2 c, it lies beyond 600 nm. Ligands 1 a-c undergo oxidation processes that involve orbitals based mainly on the CH3--N--N== fragments. The complexes 2 a-c undergo reversible metal-centred oxidation, while reductions involve the hydrazone-based ligands: in 2 b and 2 c, the bridging ligand is reduced twice and in 2 a once before reduction of the peripheral terpy ligands takes place. Ligands 1 a-c exhibit luminescence from the lowest-lying 1pi-pi* level. Only for complex 2 a does emission occur; this may be attributed to a 3MLCT state involving the bridging ligand. Taken together, the results clearly indicate that the structural variations introduced translate into interesting differences in the spectroscopic, luminescence and redox properties of the ligand strands as well as of the rack-type metal complexes.     

Application of thermal treatment of zircon for the interpretation of luminescence centers

The photoluminescence (PL) of zircon is characterized by a broad structureless spectral band down to 4.6 K, which does not enable correct interpretation of the nature of the luminescence centres (LC). By applying step-like thermal treatment, a radiation treatment and timeresolved spectroscopy, seven pure bands were separated and their individual spectral-kinetic properties were determined.The yellow PL is connected with three LC:

Crystal structure and luminescence of antimony(III) bromide with aniline

The atomic structure of antimony(III) bromide crystals with anilinium was determined by X-ray diffraction analysis of (C₆H₅NH₃)₂SbBr₅ (a = 19.704(3) Å, b = 7.914(1) Å, c = 25.556(4) Å; space group Pbca, Z = 8, ρ_calc = 2.365 g/cm³). The crystal structure consists of infinite chains of [SbBr₅]^2? complex anions formed by sharing six vertices and the anilinium (C₆H₅NH₃)⁺ cations, through which the chains are linked in layers by N-H...Br hydrogen bonds. The geometrical aspects that determine the luminescent spectral properties of the complex are discussed.     

具有新型梯形双金属链的铕羧酸-膦酸配合物的晶体结构及其发光性质研究

采用溶剂热反应,成功合成一例基于羧酸-膦酸配体的铕配位聚合物,[Eu(5-pnc)(H2O)0.5]·H2O(1).晶体结构分析表明,聚合物1具有三维超分子网络结构,其中二聚体[Eu2(μ3-O)2]通过两个O-P-O和两个O-C-O单元构成梯形双金属链,沿着a轴无限延伸,这些梯形双金属链通过有机膦酸配体交联.研究了配...     

Specific features of tetrahydrofuran copolymerization with lactones

Mechanistic features of the cationic copolymerization of lactones with cyclic ethers are studied for β-propiolactone (PL) with tetrahydrofuran (THF) and ?-caprolactone (CL) with THF. It is shown that, in the PL-THF system at [THF]₀ > [THF]_e, the copolymer is considerably enriched with the more basic THF whereas at [THF]₀ < [THF]_e anomalous enrichment of the copolymer with the less basic PL is observed. The mechanism of this phenomenon, which is applicable to many other cases and causes the formation of block copolymers from some heterocyclic monomers, is considered. At concentrations below equilibrium, THF is incorporated in the copolymer as pairs of units due to the effect of the penultimate unit on the thermodynamics of its addition.     

Aromatic compounds in molecular phase of Baltic amber-synchronous luminescence analysis

Synchronous luminescence analysis was performed in order to identify aromatic compounds in solvent extracts of Baltic amber. The investigated extracts were obtained, for comparisons, as products of extraction by various techniques and solvents. Methylene chloride and ethanol were applied independently for extraction at the ambient temperature (conservative extraction), as well as at the temperature of solvent boiling (extraction in Soxhlet apparatus). Ethanol, as the solvent, was also used for extraction in an ultrasonic bath and for the decoction process. The extraction, by techniques mentioned, of the analysed amber has resulted in products generally containing the same groups of aromatics: mainly naphthalenes, phenanthrenes and anthracenes. Among phenanthrenes, in all samples the retene was also identified, being one of the characteristic links of the diagenetic chain of chemical transformations of vegetal precursors. The identification of a series of individual compounds made, using the synchronous luminescence technique, was verified by the record of conventional emission and excitation spectra. Presented identified compounds were also confirmed by the results of GC-MS analysis. The luminescence analysis was also performed comparatively for fossil resin from Galicia, Spain (Cretaceous) older than Baltic amber (Tertiary, Eocene). The obtained preliminary results of synchronous luminescence analysis suggest the possibility of diversification in this manner of fossil resins of various ages by characterisation of aromatisation degree and alkyl substitution of aromatic rings. It is since well known that aromatisation progress is an indicator of a natural process of maturation of fossil organic matter. However, a greater number of samples should be taken to further testify to the investigations.