Highly uniform and monodisperse beta-NaYF4 : Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprism crystals: Hydrothermal synthesis and luminescent properties

beta-NaYF4:Ln(3+) (Ln = Eu, Tb, Yb/Er, and Yb/Tm) hexagonal microprisms with remarkably uniform morphology and size have been synthesized via a facile hydrothermal route. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and photoluminescence (PL) spectra as well as kinetic decays were used to characterize the samples. It is found that sodium citrate as a shape modifier introduced into the reaction system plays a critical role in the shape evolution of the final products. Furthermore, the shape and size of the products can be further manipulated by adjusting the molar ratio of citrate/RE3+ (RE represents the total amount of Y3+ and the doped rare earth elements such as Eu3+, Tb3+, Yb3+/Er3+, or Yb3+/Tm3+). Under the excitation of 397 nm ultraviolet light, NaYF4:xEu(3+) (x = 1.5, 5%) shows the emission lines of Eu3+ corresponding to D-5(0-3) -> F-7(J) (J = 0-4) transitions from 400 to 700 nm (whole visible spectral region) with different intensity, resulting in yellow and red down-conversion (DC) light emissions, respectively.

Synthesis and characterization of high-quality ZnS, ZnS : Mn2+, and ZnS : Mn2+/ZnS (core/shell) luminescent nanocrystals

High-quality ZnS, ZnS:Mn2+, and ZnS:Mn2+/ZnS (core/shell) nanocrystals (NCs) were synthesized via a high-boiling solvent process and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectra. The monodisperse ZnS NCs (size = 8 nm), which self-assembled into several micrometer-sized domains, were achieved by adopting poly(ethylene glycol) (PEG) in the reaction process (without using a size-selection process). The obtained ZnS:Mn2+ and ZnS:Mn2+/ZnS core/shell NCs are highly crystalline and quasimonodisperse with an average particle size of 6.1 and 8.4 nm, respectively. All of the as-formed NCs can be well dispersed in hexane to form stable and clear colloidal solutions, which show strong visible emission (blue for ZnS and red-orange for ZnS:Mn2+ and ZnS:Mn2+/ZnS) under UV excitation. The growth of a ZnS shell on ZnS:Mn2+ NCs, that is, the formation of ZnS:Mn2+/ZnS core/shell NCs, resulted in a 30% enhancement in the PL intensity with respect to that of bare ZnS:Mn2+ NCs due to the elimination of the surface defects.

Solvent effects on spectrophotometric titrations and vibrational spectroscopy of 5,10,15-triphenyl-20-(4-hydroxyphenyl)porphyrin in aqueoius DMF

The spectrophotometric titration by sodium hydroxide of 5,10,15-triphenyl-20-(4-hydroxyphenyl)porphyrin ((OH)(1)PH2) is studied as a function of solvent composition of DMF-H2O binary solvent mixture ([OH-] = 0.04 M). Combining the structure changes of the porphyrin and the "four orbital" model of Gouterman, many features of the optical spectra of this deprotonated para-hydroxy-substituted tetraphenylporphyrin in different composition of binary solvent mixtures can be rationalized. In highly aqueous solvents, the changes of the titration curves are shown to be mainly due to hydrogen-bonding of the oxygen of the phenoxide anion group by the hydroxylic solvent, Which decreases the energy of the phenoxide anion pi orbital. Thus the phenoxide anion pi orbital cannot cross over the porphyrin Tr orbital being a different HOMO. However, its energy is close to that of the porphyrin pi orbitals. As a result, in the visible region, no charge-transfer band is observed, while in the visible-near region, the Soret peak split into two components. In nonaqueous solvents, the changes are mainly attributed to further deprotonation of pyrrolic-Hs of (OH) 1PH2 by NaOH and coordination with two sodium ions to form the sodium complex of (OH) 1PH2, which turns hyperporphyrin spectra of deprotonated of phenolic-H of (OH)(1)PH2 into three-banded spectra of regular metalloporphyrin.

Effect of silver nanoparticles on luminescent properties of europium complex in di-ureasil hybrid materials

Organic-inorganic hybrids containing luminescent lanthanide complex Eu(tta)(3)Phen (tta = thenoyltrifluoroaceton, phen = 1,10-phenanthroline) and silver nanoparticles have been prepared via mixing rare earth complex and nanoparticles with the precursors of di-ureasil using a sol-gel process. The obtained hybrid materials with transparent and elastomeric features were characterized by transmission electron microscope, solid-state Si-29 magic-angle spinning NMR spectra, diffuse reflectance, UV-visible absorption and photoluminescence spectroscopies. The effect of the silver nanoparticles on the luminescence properties was investigated. The experimental results showed that the luminescence intensity of the Eu(tta)(3)phen complex could be enhanced by less than ca. 9.5 nM of silver nanoparticles with the average diameter of 4 nm, and reached its maximum at the concentration of ca. 3.6 nM. Further increasing the concentration of the silver nanoparticles (> 9.5 nM) made the luminescence quenched. The enchancement and quench mechnism was discussed.

A simple and effective route for the preparation of poly(vinylalcohol) (PVA) nanofibers containing gold nanoparticles by electrospinning method

Poly(vinyl alcohol) (PVA) nanofibers containing gold nanoparticles have been simply obtained by electrospinning a solution containing gold nanoparticles without the additional step of introducing other stabilizing agents. The optical property of gold nanoparticles in PVA aqueous solution was observed by UV-visible absorption spectra. Morphology of the Au/PVA nanofibers and distribution of the gold nanoparticles were characterized by transmission electron. microscopy (TEM). The structure transformation was characterized from PVA to PVA/Au composite by Fourier transform infrared spectroscopy (FTIR).

Electrosynthesis and characterization of 1,2-dibenzyl C-60: A revisit

A reinvestigation of the reaction between C-60(2-) and benzyl bromide in benzonitrile containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) has shown that there are more reaction products than previously reported. Use of a silica rather than a "Buckyclutcher I" column for HPLC purification led to isolation of two previously unattained products in the reaction mixture, one of which was identified as 1,2-(PhCH2)(2)C-60 by UV-vis and NMR. The earlier incorrectly assigned 1,2-(PhCH2)(2)C-60 was identified as the methanofullerene C61HPh by X-ray single-crystal diffraction. The electrochemistry of genuine 1,2-(PhCH2)(2)C-60 shows that its first reduction potential in PhCN containing 0.1 M TBAP is cathodically shifted by 100 mV with respect to E-1/2 for reduction of 1,4-(PhCH2)(2)C-60, indicating that the addition pattern significantly affects the electrochemistry of derivatized C-60. Visible and near-IR spectra of the monoanion and dianion of 1,2-(PhCH2)(2)C-60 are also reported.

UV-vis spectrophotometric titrations and vibrational spectroscopic characterization of meso-(p-hydroxyphenyl)porphyrins

Sequentially spectrophotometric titrations by sodium hydroxide of meso-tetraphenylporphyrin derivatives bearing one, two, three, or four p-hydroxyl groups result in new types of spectra. The strong new bands appear in the visible region with splitting or broadening of the Soret band and its significant loss of oscillator strength. To understand the molecular origin of these phenomena, the Resonance Raman (RR) and Fourier Transform Infrared (FTIR) experiments are carried out. The results demonstrate that the charges of the deprotonated para-hydroxy substituted meso-tetraphenylporphyrins are localized on the substituents, not delocalized into the pi system of the porphyrin macrocycles and that the ground states of the macrocycles remain essentially unperturbed. Both the related behavior of diprotonated tetrakis(p-(dimethylamino)phenyl) porphyrin and protonated Schiff base porphyrins show that the new bands considered as hyperporphyrin spectra are due to pi(phenoxide anion) --> pi*(porphyrin) transitions, where pi is an orbital on the phenoxide anion substitutent and pi* is a LUMO on the porphyrin.

In situ circular dichroic electrochemical study of bilirubin and bovine serum albumin complex

The electrooxidation of bilirubin (BR) and bovine serum albumin (BSA) complexes was studied by in situ circular dichroism (CD) spectroelectrochemistry. The result showed that the mechanism of the whole electrooxidation process of this complex corresponded to electrochemical processes (EE mechanism) in aqueous solution. Some parameters of the process were obtained by double logarithm method, differential method and nonlinear regression method. In visible region, CD spectra of the two enantiomeric components of the complex and their fraction distribution against applied potentials were obtained by singular value decomposition least-square (SVDLS) method. Meanwhile, the distribution of the five components of secondary structure was also obtained by the same method in far-UV region. The peak potential gotten from EE mechanism corresponds to a turning point for the component transition, beyond which the whole reaction reaches a new equilibrium. Under applied positive potentials, the enantiomeric equilibrium between M and P form is broken and M form transfers to its enantiomer of P, while the fraction of alpha-helix increases and that improves the transition to P form.

Spectra and long-lasting properties of Sm3+-doped yttrium oxysulfide phosphor

We reported, for the first time to the best of our knowledge, the Sm3+ -doped yttriurn oxysulfide phosphors has reddish orange long-lasting phosphorescence. The phosphor show prominent luminescence in reddish orange due to the electronic transitions of (4)G(5/2) --> H-6(J) (J = 5/2, 7/2, 9/2), the afterglow color of this type of phosphors is a mixture of the three above mentioned electronic transition emissions and have a little different when the concentration of the Sm3+ dopant changes. Synthesis procedure of the Sm3+-yttrium oxysulfide reddish orange phosphor through the flux fusion method with binary flux compositions was presented. The synthesized phosphors were analyzed using X-ray diffraction (XRD) to interpret the structural characterization. The XRD analysis result reveal that the Y2O2S:Sm3+ phosphor synthesized with a binary flux composition containing (S and Na2CO3 at a ratio of 1: 1 at 30 wt.% of total raw material) at 1050degreesC for 3 h was in single-phase. Luminescence properties of the Y2O2S:Sm3+ long-lasting phosphor was analyzed by measuring the excitation spectra, emission spectra and afterglow decay curve. The mechanism of the strong afterglow from Y2O2S:Sm3+ was also discussed in this paper.

Long-lasting properties of rare earth-doped Y2O2S phosphors

The aim of this presentation is to report a new result of afterglow materials. The Y2OS: Ln(3+) (Ln = Sm, Tm) phosphors show bright reddish orange and orange-yellow colors when excited by UV or visible light. The main spectroscopic characterizations of Sin(3+) and Tin(3+) in yttrium oxysulfide and their long-lasting phosphorescence were measured and discussed in this presentation. Their long-lasting phosphorescence can be seen by the naked eyes clearly for about one hour in the dark room after the Irradiation light sources were removed. XRD and photoluminescence (PL) spectra as well as the luminance decay were used to characterize these long-lasting phosphorescence phosphors. The results of XRD indicate that the products synthesized through the flux fusion method tinder 1050 degreesC, for 6 It have a good crystallization without any detectable amount of impurity phase. Both the PL spectra and luminance decay results reveal that these phosphors have efficient luminescent and good long-lasting properties. We believe that the experimental data gathered in our present work will be. useful in finding some new long-lasting phosphors with different colors.

Luminescence properties of rare earth ions in cadmium metasilicate

The luminescence properties of CdSio(3):RE3+ phosphors doped with various rare earth ions are reported. The series of rare earth ions doped CdSiO3 phosphors are prepared by the conventional high-temperature solid-state method, and characterized by XRD and photoluminescence (PL) spectra. The results of XRD measurement indicate that the products fired under 1050 degreesC for 3 h have a good crystallization without any detectable amount of impure phase. The PL spectra measurement results show that CdSiO3 is a novel self-activated luminescent matrix. When rare earth ions such as Y3+, La3+, Gds(3+), Lus(3+), Ce3+, Nd3+, Ho3+, Era(3+), Tm3+ and Yb3+ are introduced into the CdSi03 host, one broadband centered at about 420 nm resulted from traps can be observed. In the case of other earth ions which show emissions at the visible spectrum region, such as Pr3+, Sm3+, Eu3+, Tb3+ and Dy3+, the mixture of their characteristic line emissions with the similar to 420 nm strong broadband luminescence results in various emitting colors. As a consequence, different emitting colors can be attairied via introducing certain appropriate active ions into the CdSiO3 matrix. In additional, this kind of phosphors shows good long-lasting properties when excited by UV light. All the results show that CdSiO3 is a potential luminance matrix.

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.

beta-cyclodextrin controlled assembling nanostructures from gold nanoparticles to gold nanowires

In this Letter, P-cyclodextrin (P-CD) was employed as stabilizer in the synthesis of gold nanoparticles. Gold nanoparticles were synthesized by the reduction of HAuCl4 by NaBH4 in the presence of P-CD. Varying the ratio of P-Cl) to HAuCl4, isolated gold nanoparticles could be assembled into nanowires. The nanoparticles and nanowires were characterized by transmission electron microscopy, UV/visible spectroscopy, infrared spectroscopy and X-ray photoelectron spectroscopy. The decreased relative intensity of skeletal and ring vibration in FT-IR spectra and the negative shift of the Au4f(7/2) binding energy in XPS spectra confirmed that beta-CD was chemisorped on An nanoparticles via hydroxyl group.