Interaction of echinomycin with guanine: electrochemistry and spectroscopy studies

The interaction of antitumor antibiotic, echinomycin (Echi) with guanine (Gua) was thoroughly investigated by adsorptive transfer stripping cyclic voltammetry, ultraviolet and visible adsorption spectra (UV/Vis) and Fourier-transform infrared spectroscopy (FTIR). Electrochemistry provided a simple tool for verifying the occurrence of interaction between Echi and Gua. Echi could be accumulated from the solution and give well-defined electrochemical signals in 0.1 M phosphate buffer solution (pH 7.0) only when Gua was present on the surface of the electrochemically pretreated glass carbon electrode (GCE), suggesting a strong binding of Echi to Gua. All the acquired spectral data showed that a new adduct between Echi and Gua was formed, and two pairs of adjacent intermolecular hydrogen bonds between the Ala backbone atoms in Echi and Gua (Ala-NH to Gua-N3 and Gua-NH2 to Ala-CO) played a dominating role in the interaction. Electrochemistry coupled with spectroscopy techniques could provide a relatively easy way to obtain useful insights into the molecular mechanism of drug-DNA interactions, which should be important in the development of new anticancer drugs with specific base recognition.

Crosslinkable poly (p-phenylenevinylene) derivative

To simplify the fabrication of multilayer light-emitting diodes, we prepared a p-phenylenevinylene-based polymer capped with crosslinkable styrene through a Wittig reaction. Insoluble poly(p-phenylenevinylene) derivative (PPVD) films were prepared by a thermal treatment. The photoluminescence and ultraviolet-visible (UV-vis) absorbance of crosslinked films and noncrosslinked films were studied. We also studied the solvent resistance of crosslinked PPV films with UV-vis absorption spectra and atomic force microscopy. Double-layer devices using crosslinked PPVD as an emitting layer, 2-(4-tert-butylphenyl)-5-phenyl-1,3,4-oxadiazole (PBD) in poly(methyl methacrylate) as an electron-transporting layer, and calcium as a cathode were fabricated. A maximum luminance efficiency of 0.70 cd/A and a maximum brightness of 740 cd/m(2) at 16 V were demonstrated. A 12-fold improvement in the luminance efficiency with respect to that of single-layer devices was realized.

Tunable photoluminescent and cathodoluminescent properties of ZnO and ZnO : Zn phosphors

ZnO and ZnO: Zn powder phosphors were prepared by the polyol-method followed by annealing in air and reducing gas, respectively. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectra (XPS), electron paramagnetic resonance (EPR), and photoluminescence (PL) and cathodoluminescence ( CL) spectra, respectively. The results indicate that all samples are in agreement with the hexagonal structure of the ZnO phase and the particle sizes are in the range of 1-2 mu m. The PL and CL spectra of ZnO powders annealed at 950 degrees C in air consist of a weak ultraviolet emission band ( similar to 390 nm) and a broad emission band centered at about 527 nm, exhibiting yellow emission color to the naked eyes. When the sample was reduced at the temperatures from 500 to 1050 degrees C, the yellow emission decreased gradually and disappeared completely at 800 degrees C, whereas the ultraviolet emission band became the strongest. Above this temperature, the green emission ( similar to 500 nm) appeared and increased with increasing of reducing temperatures.

Morphology-controllable synthesis and characterization of single-crystal molybdenum trioxide

Molybdenum trioxide nanobelts and prism-like particles with good crystallinity and high surface areas have been prepared by a facile hydrothermal method, and the morphology could be controlled by using different inorganic salts, such as KNO3, Ca(NO3)(2), La(NO3)(3), etc. The possible growth mechanism of molybdenum trioxide prism-like particles is discussed on the basis of the presence of HI and the modification of metal cations. The as-prepared nanomaterials are characterized by means of powder X-ray diffraction (PXRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), Fourier transformation infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and ultraviolet and visible spectroscopy (UV-vis). TEM and HRTEM micrographs show that the molybdenum trioxide nanobelts and prism-like particles have a relatively high degree of crystallinity and uniformity. BET specific surface areas of the as-prepared molybdenum trioxide nanocrystals are 67-79 m(2)g(-1). XPS analysis indicates that the hexavalent molybdenum is predominant in the nanocrystals. UV-vis spectra reveal that the direct band gap energy of the annealed molybdenum trioxide prism-like particles shows a pronounced blue shift compared to that of bulk MoO3 powder.

Dy3+- and Eu3+-doped LaGaO3 nanocrystalline phosphors for field emission displays

Nanocyrstalline LaGaO3 and Dy3+- and Eu3+-doped LaGaO3 were prepared through a Pechini-type sol-gel process. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), photoluminescence, cathodoluminescence spectra, and lifetimes were utilized to characterize the samples. XRD reveals that the samples begin to crystallize at 900 degrees C and pure LaGaO3 phase can be obtained at 1000 degrees C. FE-SEM images indicate that the Dy3+- and Eu3+-doped LaGaO3 samples are both composed of aggregated spherical particles with sizes ranging from 40 to 80 nm. Under the excitation of ultraviolet light and low voltage electron beams (1-5 kV), the undoped LaGaO3 sample shows a strong blue emission peaking at 433 nm, and the Dy3+- and Eu3+-doped LaGaO3 samples show their characteristic emissions of Dy3+ (F-4(9/2)-H-6(15/2) and F-4(9/2)-H-6(13/2) transitions) and Eu3+ (D-5(0,1,2)-F-7(1,2,3,4) transitions), respectively. The relevant luminescence mechanisms are discussed.

Monodisperse spherical core-shell structured SiO2-CaTiO3 : Pr3+ phosphors for field emission displays

Nanocrystalline CaTiO3:Pr3+ phosphor layers were coated on nonaggregated, monodisperse, and spherical SiO2 particles by the sol-gel method, resulting in the formation of core-shell structured SiO2-CaTiO3:Pr3+ particles. X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, photoluminescence, cathodoluminescence spectra, as well as lifetimes were utilized to characterize the core-shell structured SiO2-CaTiO3:Pr3+ phosphor particles. The obtained core-shell structured phosphors consist of well dispersed submicron spherical particles with a narrow size distribution. The thickness of the CaTiO3:Pr3+ shell could be easily controlled by changing the number of deposition cycles (about 70 nm for four deposition cycles). The core-shell SiO2-CaTiO3:Pr3+ particles show a strong red emission corresponding to D-1(2)-H-3(4) (612 nm) of Pr3+ under the excitation of ultraviolet (326 nm) and low voltage electron beams (1-5 kV). These particles may be used in field emission displays.

Fabrication and photoluminescence properties of core-shell structured spherical SiO2@Gd2Ti2O7 : Eu3+ phosphors

A sol-gel technique was used to prepare Gd2Ti2O7:Eu3+-coated submicron silica spheres (SiO2@Gd2Ti2O7:Eu3+). The resulted SiO2@Gd2Ti2O7:Eu3+ core-shell particles were characterized by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy-dispersive x-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra, as well as kinetic decays. The XRD results demonstrate that the Gd2Ti2O7:Eu3+ layers begin to crystallize on the SiO2 spheres after annealing at 800 degrees C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have perfect spherical shape with narrow size distribution (average size similar to 620 nm), non-agglomeration, and smooth surface. The thickness of the Gd2Ti2O7:Eu3+ shells on the SiO2 cores could be easily tailored by varying the number of deposition cycles (60 nm for four deposition cycles). Under the irradiation of 310 nm ultraviolet, the SiO2@GdTi2O7:Eu3+ samples show strong emission of Eu3+.

Luminescent CdSe and CdSe/CdS core-shell nanocrystals synthesized via a combination of solvothermal and two-phase thermal routes

A new solvothermal route has been developed for synthesizing the size-controlled CdSe nanocrystals with relatively narrow size distribution, and the photoluminescence (PL) quantum yields (QYs) of the nanocrystals can reach 5-10%. Then the obtained CdSe nanocrystals served as cores to prepare the core/shell CdSe/CdS nanocrystals via a two-phase thermal approach, which exhibited much higher PL QYs (up to 18-40%) than the CdSe core nanocrystals. The nanocrystal samples were characterized by ultraviolet-visible (UV-vis) absorption spectra, PL spectra, wide-angle Xray diffraction (WAXD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).

VIV-UV excited luminescent properties of LnCa4O(BO3)3 : RE3+(Ln = Y, La, Gd; Re=Eu, Tb, Dy, Ce)

Calcium lanthanide oxyborate doped with rare-earth ions LnCa(4)O(BO3)(3):RE3+ (LnCOB:RE, Ln = Y, La, Gd, RE = Eu, Tb, Dy, Cc) was synthesized by the method of solid-state reaction at high temperature. Their fluorescent spectra were measured from vacuum ultraviolet (VUV) to visible region at room temperature. Their excitation spectra all have a broadband center at about 188 nm, which is ascribed to host absorption. Using Dorenbos' and J phi rgensen's work [P. Dorenbos, J. Lumin. 91 (2000) 91, R. Resfeld, C.K. J phi rgensen. Lasers and Excite States of Rare Earth [M], Springer, Berlin, 1977, p. 45], the position of the lowest 5d levels E(Ln,A) and charge transfer band E-ct were calculated and compared with their excitation spectra.Eu3+ and Tb3+ ions doped into LnCOB show efficient luminescence under VUV and UV irradiation. In this system, Ce3+ ions do not show efficient luminescence and quench the luminescence of Tb3+ ions when Tb3+ and Ce3+ ions are co-doped into LnCOB. GdCOB doped with Dy3+ shows yellowish white light under irradiation of 254 nm light for the reason that Gd ions transfer the energy from itself to Dy.

A wide-bandgap semiconducting polymer for ultraviolet and blue light emitting diodes

A novel wide-bandgap conjugated polymer (PDHFSCHD) consisting of alternating dihexylfluorene and rigidly twisted biphenyl units has been synthesized. The new fluorene-based copolymer composed of rigid twisting segments in the main-chain exhibits an optical bandgap of as high as 3.26 eV, and a highly efficient ultraviolet emission with peaks at 368 nm and 386 nm. An electroluminescence device from PDHFSCHD neat film as an active layer shows UV emission which peaks at 395 nm with a turn on voltage below 8 V By optimizing the device conditions, a peak EL quantum efficiency of 0.054% and brightness of 10 cd.m(-2) was obtained. Furthermore, blending a poly(dihexylfluorene) in the PDHFSCHD host gave pure blue emission peaking at 417 nm, and 440 nm without long wavelength emission from aggregated species. Efficient energy transfer from PDHFSCHD to PDHF was demonstrated in these blended systems. Depressed chain-aggregation of PDHF in the PDHFSCHD host can correspond to pure blue emission behaviors.

Luminescence properties of RP1-xVxO4: A (R=Y, Gd, La; A=Sm3+Er3+ x=0, 0.5, 1) thin films prepared by pechini sol-gel process

Thin film phosphors with compositions of RP1-xVxO4: A (R = Y, Gd, La; A = Sm3+, Et3+; x = 0, 0.5, 1) have been prepared by a Pechini sol-gel process. X-Ray diffraction, atomic force microscopy (AFM), photoluminescence excitation and emission spectra were utilized to characterize the thin film phosphors. The results of XRD showed that a solid solution formed in YVxP1-xO4: A film series from x = 0 to x = 1 with zircon structure, which also held for GdVO4: A film. However, LaVO4: A film crystallized with a different structure, monazite. AFM study revealed that the phosphor films consisted of homogeneous particles ranging from 90 to 400 nm depending on the compositions. Upon short ultraviolet excitation, the films exhibit the characteristic Sm(3+ 4)G(5/2)-H-6(J) (J=5/2, 7/2, 9/2) emission in the red region and Er3+ H-2(11/2), S-4(3/2)-I-4(15/2) emission in the green region, respectively With the increase of x values in YVxP1-xO4: SM3+ (Er3+) films, the emission intensity Of SM3+ (Er3+) increases due to the increase of energy transfer probability from VO43- to Sm3+ (Er3+). Due to the structural effects, the Sm3+ (Er3+) shows similar spectral properties in YVO4 and GdVO4 films, which are much different from those in LaVO4 film.

Growth and vibrational spectra of doped KMgF3 single crystal

The different ions doped KMgF3 single crystals are prepared by the vertical Bridgman method. The near-infrared absorption spectra for different parts of all as-growth crystals indicate that there is the best transparency in middle part. The correlation between the vibronic frequencies of Eu2+ and the site displacement of Cu+ co-doped ions is firstly studied, which indicates that Cu+ ions replace the site of the Mg2+ ions. The co-doped Eu2+ counteracts the charge misfit causing by the replacement of Mg2+ with Cu+. The overlapping of the emission spectra of the Eu2+ and the excitation spectra of the Cu+ results in the energy transfer from Eu2+ to Cu+.

Copolymerization of CO2 and propylene oxide under rare earth ternary catalyst: design of ligand in yttrium complex

Copolymerization of carbon dioxide and propylene oxide was carried out employing (RC6H4COO)(3)Y/glycerin/ZnEt2 (R = -H, -CH3, NO2, -OH) ternary catalyst systems. The feature of yttrium carboxylates (ligand, substituent and its position on the aromatic ring) is of great importance in the final copolymerization. Appropriate design of substituent and position of the ligand in benzoate-based yttrium complex can adjust the microstructure of aliphatic polycarbonate in a moderate degree, where the head-to-tail linkage in the copolymer is adjustable from 68.4 to 75.4%. The steric factor of the ligand in the yttrium complex is crucial for the molecular weight distribution of the copolymer, probably due to the fact that the substituent at 2 and 4-position would disturb the coordination or insertion of the monomer, lead the copolymer with broad molecular distribution. Based on the study of ultraviolet-visible spectra of the ternary catalyst in various solvents, it seems that the absorption band at 240-255 nm be closely related to the active species of the rare earth ternary catalysts.

Photochromic behavior and luminescent properties of novel hybrid organic-inorganic film doped with Preyssler's heteropoly acid H-12[EuP5W30O110] and polyvinylpyrrolidone

A novel hybrid photochromic composite film composed of Preyssler's heteropoly acid H-12[EuP5W30O110] (EuP5W30) and polyvinylpyrrolidone (PVP) was prepared by dip-coating method. Atomic force microscopy (AFM) was used to investigate the surface topography. The change of characteristic peak in the infrared spectra (IR) was investigated. The TG curve showed three steps of weight loss and approximately revealed the composition of the hybrid film. Ultraviolet-visible adsorption spectra (UV-VIS) and electron resonance spectrum (ESR) were used to investigate the photochromic behavior and mechanism of hybrid film. The photoluminescent behavior of the film at room temperature was investigated to show the characteristic Eu3+ emission pattern of D-5(o)-F-7(J). The occurrence of photoluminescent activity confirms the potential for creating luminescent thin film with polyoxometalates (POMs).

The optical spectroscopic properties of rare earth-activated barium orthophosphate in VUV-Vis range

The optical properties of rare earth ions-activated barium orthophosphate phosphors, Ba-3(PO4)(2):RE (RE = Ce3+, Sm3+, Eu3+, Eu2+, and Tb3+), were investigated in vacuum ultraviolet (VLTV)-Vis range. A band-band transition Of PO43- in Ba-3(PO4)(2) is observed in the region of 150-170 nm. The partial reduction of Eu3+ to Eu2+ was observed and confirmed by luminescent spectra under the VUV-UV excitation. It is proposed that the electronegative defects that formed by aliovalent substitution of Eu3+ on the Ba2+ site in the host are responsible for the reduction process.