Effect of substituent groups of porphyrins on the electroluminescent properties of porphyrin‐doped OLED devices

Six tetraphenylporphyrins (TRPPH₂) with different horizontal substituents R (R = H, CH₃, OH, F, Cl, Br) were synthesized, and the organic light‐emitting diode (OLED) devices with a general configuration of ITO/TPD/Alq₃:2%TRPPH₂/Alq₃/Al were prepared. The substituted TRPPH₂ was used as the host dopant, 4,4‐bis‐(m‐tolyphenylamino)biphenyl (TPD) was used as a hole‐transporting material, and aluminum tris(8‐quinolinolato) (Alq₃) was used as an electron‐transporting material. The electroluminescent (EL) properties of these devices were studied to understand the light emitting properties of the substituted TRPPH₂. Previous studies have found that the color emitted by the devices was dependent on the TRPPH₂ dye concentration. The electronic effect of the horizontal substituents R of TRPPH₂ influenced the turn‐on voltage, brightness, and power efficiency of the devices. Also, the electroluminescence performance of the porphyrin‐doped OLED devices depended on the effectual overlaps between the emission of electron‐transporting material and the absorption of the dopants. This means that it is possible to evaluate the electroluminescence performance of the porphyrin‐doped OLED devices based on the emission of electron‐transporting material and the absorption of the dopants. Copyright © 2009 John Wiley & Sons, Ltd.     

Intramolecular Diels–Alder reaction in enyne–allenes: a computational investigation and comparison with the Myers–Saito and Schmittel reactions

The reaction mechanisms as well as substituted effect and solvent effect of the enyne–allenes are investigated by Density Functional Theory (DFT) method and compared with the Myers–Saito and Schmittel reactions. The Myers–Saito reaction of non‐substituted enyne–allenes is kinetically and thermodynamically favored as compared to the Schmittel reaction; while the concerted [4 + 2] cycloaddition is only 1.32 kcal/mol higher than the C₂? C₇ cyclization and more exothermic (Δ_RE = ?69.38 kcal/mol). For R₁ = CH₃ and t‐Bu, the increasing barrier of the C₂? C₇ cyclization is higher than that for the C₂? C₆ cyclization because of the steric effect, so the increased barrier of the [4 + 2] cycloaddition is affected by such substituted electron‐releasing group. Moreover, the strong steric effect of R₁ = t‐Bu would shift the C₂? C₇ cyclization to the [4 + 2] cycloaddition. On the other hand, for R₁ = Ph, NH₂, O^?, NO₂, and CN substituents, the barrier of the C₂? C₆ cyclization would be more diminished than the C₂? C₇ cyclization due to strong mesomeric effect; the reaction path of C₂? C₇ cyclization would also shift to the [4 + 2] cycloaddition. The solvation does not lead to significant changes in the potential‐energy surface of the reaction except for the more polar surrounding solvent such as dimethyl sulfoxide (DMSO), or water. Copyright © 2009 John Wiley & Sons, Ltd.     

Fe valence state at the surface of the Fe0.5Cu0.5Cr2S4 spinel

Here we present X‐ray absorption measurements of a vacuum cleaved Fe_0.5Cu_0.5Cr₂S₄ single crystal. Measurements at different positions on the cleaved sample surface clearly reveal a difference between the valence state of the Fe ions in the sur‐ face layers and the valency of the Fe ions present in the bulk. These results confirm the findings of recent measurements outlined previously. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Accurate standard‐based quantification of X‐ray fluorescence data using metal‐contaminated plant tissue

Quantitative X‐ray fluorescence (XRF) measurements have been conducted on naturally lead‐contaminated samples. The calibration procedure using the ratio of fluorescence to Compton scattered radiation was investigated using Monte Carlo simulation. Experimental results with low‐energy photons (14 keV) and simulations show a very good linearity of the fluorescence to Compton ratio as a function of metal concentration. Lead (Pb), iron (Fe) and zinc (Zn) are measured in samples of Phaseolus vulgaris (bean seeds) that have been grown using a nutritive solution with different Pb dopings. Naturally contaminated samples are thus obtained. The calibration must be done for fixed conditions of X‐ray energy and scattering angle, while X‐ray beam intensity and detector to sample distance can change from one sample to another. Simulation allows to evaluate the matrix effect on the calibration curve, and shows that linearity is preserved even in the presence of other heavy elements in the fluorescence spectrum. However, calibration must be done using samples with similar matrix as it affects the slope of the curve. Copyright © 2010 John Wiley & Sons, Ltd.     

Approximate symmetry reduction for perturbed nonlinear SchrSdinger equation

We investigate the one-dimensional nonlinear SchrSdinger equation with a perturbation of polynomial type. The approximate symmetries and approximate symmetry reduction equations are obtained with the approximate symmetry perturbation theory.     

Detection of subsurface defects of fused silica optics by confocal scattering microscopy

<正>A non-destructive technique for subsurface measurements is proposed by combining light scattering method with laser confocal scanning tomography.The depth and distribution of subsurface defect layers are represented in term of scattered light intensity pattern,and three types of fused silica specimens are fabricated by different grinding and polishing processes to verify the validity and effectiveness.By using the direct measurement method with such technique,micron-scale cracks and scratches can be easily distinguished,and the instructional subsurface defect depths of 55,15,and 4μm are given in real time allowing for an in-process observation and detection.     

Phase mismatching analysis of third-harmonic generation in BBO crystal

<正>Phase mismatching for third-harmonic generation(THG) in barium metaborate(BBO) crystal is investigated in detail.Upon using BBO crystal in the TypeⅠ(oo→e) scheme,in the two independent planes (principal section of the crystal and the plane normal to principal section),when the input second-harmonic beam deviates from the expected direction,phase mismatching occurs and the angle deviation produces different effects on the conversion efficiency.We numerically simulate these two cases of phase mismatching and identify the relation between the conversion efficiency and the deviation angle in the air.The computational results indicate that the phase matching tolerance in the principal section is 0.2°(in the air),while the phase matching tolerance in the plane normal to principal section is 4.5°(in the air).After conducting a lab experiment,the results agree perfectly with the computational results,indicating that the deviation angle in the principal section has a greater effect on the conversion efficiency.     

Observation of B(s)(0) → D(s)(*)+ D(s)(*)- using e+ e- collisions and a determination of the B(s)-B(s) width difference ΔΓ(s)

We have made the first observation of B(s)(0)→D(s)(*)+ D(s)(*)- decays using 23.6 fb(-1) of data recorded by the Belle experiment running on the Υ(5S) resonance. The branching fractions are measured to be B(B(s)(0)→D(s)+ D(s)-)=(1.03(-0.32-0.25)(+0.39+0.26))%, B(B(s)(0)→D(s)(*±) D(s)(?))=(2.75(-0.71)(+0.83)±0.69)%, and B(B(s)(0)→D(s)*+ D(s)*-)=(3.08(-1.04-0.86)(+1.22+0.85))%; the sum is B[B(s)(0)→D(s)(*)+ D(s)(*)-]=(6.85(-1.30-1.80)(+1.53+1.79))%. Assuming B(s)(0)→D(s)(*)+ D(s)(*)- saturates decays to CP-even final states, the branching fraction determines the ratio ΔΓ(s)/cosφ, where ΔΓ(s) is the difference in widths between the two B(s)-B(s) mass eigenstates, and φ is a CP-violating weak phase. Taking CP violation to be negligibly small, we obtain ΔΓ(s)/Γ(s)=0.147(-0.030)(+0.036)(stat)(-0.041)(+0.042)(syst), where Γ(s) is the mean decay width.     

Seed‐mediated growth method for electroless deposition of AgNPs on glass substrates for use in SERS measurements

In this work, an electroless deposition method for silver nanoparticles (AgNPs) on glass substrates was developed for use in surface‐enhanced Raman scattering (SERS) measurements. To obtain evenly distributed AgNPs of suitable size on the glass substrates, a seeding procedure was utilized as a pretreatment before the electroless deposition of AgNPs. The AgNPs thus formed were affected by both the seeding and growing procedures. To optimize the procedures for preparation of SERS substrates, several factors, including reaction time, the concentration of silver ions, and the concentration of reducing agents (glucose) for seeding and growing procedures, were varied. The morphologies of the seeds and the resulting AgNPs on the glass substrates were characterized by field‐emission scanning electron microscopy (FE‐SEM) and correlated with the SERS signals from probing with para‐nitrothiophenol (pNTP). The results indicated that only the seeding time and the concentration of silver ions significantly influenced the distribution and sizes of the Ag seeds on the substrates. In the growing procedures, both the concentration of silver nitrate and the reducing agent affected the morphologies of the resulting AgNPs and, hence, the SERS signals. The substrates prepared using this newly developed method offer 2–5 times improvement of the SERS signals compared to substrates prepared without seed treatment. Also, the AgNPs prepared by this method can be easily controlled to designated sizes with even spatial and size distributions. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman and surface‐enhanced Raman spectroscopic studies of the 15‐mer DNA thrombin‐binding aptamer

Aptamers are single‐stranded oligonucleotides that selectively bind to their target molecules owing to their ability to form secondary structures and shapes. The 15‐mer (5′‐GGTTGGTGTGGTTGG‐3′) DNA thrombin‐binding aptamer (TBA) binds to thrombin following the formation of a quadruplex structure via the Hoogsten‐type G–G interactions. In the present study, Raman and SERS spectra of TBA and thiolated TBA (used to facilitate covalent bonding to metal nanoparticle) in different conditions are investigated. The spectra of the two analogs exhibit vibrations, such as the C8N7 H2 deformation band at ∼1480 cm⁻¹ of the guanine tetrad, that are characteristic of the quadruplex structure in the presence of K⁺ ions or at low temperature. Interestingly, SERS spectra of the two analogs differ markedly from their respective normal Raman spectra, possibly due to changes in the conformation of the aptamer upon binding, as well as to the specific interaction of individual vibrational modes with the metal surface. In addition, the SERS spectra of the thiolated aptamer show significant changes with different concentrations, which may be due to different orientation of the molecule with respect to the metal surface. This study provides useful information for the development of label‐free aptamer‐based SERS sensors and assays. Copyright © 2009 John Wiley & Sons, Ltd.