Measuring grain rotation at the nanoscale

In this paper, we introduced a method to measure grain rotation of nanomaterials under external stress using a high pressure diamond anvil cell and the Laue microdiffraction technique at a synchrotron facility. We used tungsten carbide marker crystals to investigate grain rotation activities of 3 and 500?nm nickel media. Our results show that the grain rotation of 3 and 500?nm nickel nanocrystals increase with pressure and finally rotation of 500?nm nickel tends to stop at a lower pressure/stress level than 3?nm nickel. 3?nm nickel nanocrystals show a higher rotation magnitude than 500?nm nickel nanocrystals. Our measurements show an effective method to study the grain rotation of nanomaterials especially in ultrafine nanocrystals.     

An efficient indium-mediated 2-bromoallylation of aldehydes at low temperature in aqueous DMF

An efficient synthesis of 2-bromohomoallylic alcohols was carried out via an indium-mediated Barbier-type 2-bromoallylation of aldehydes in moderate yields. The reaction was performed at low temperature (−20 °C) in aqueous DMF in order to minimize decomposition of 2-bromoallylindium reagent to allene.     

Magnetoabsorption spectra of magnetoexciton transitions in GaAs/Ga0.7Al0.3As quantum wells

The internal transitions and absorption spectra of confined magnetoexcitons in GaAs/Ga0.TA10.aAs quan- tum wells have been theoretically investigated under magnetic fields along the growth direction of the semiconductor heterostructure. The magnetoexciton states are obtained within the effective-mass ap- proximation by using a variational procedure. The trial exciton-envelope wavefunctions are described as hydrogeniclike polynomial functions. The internal transition energies are investigated by studying the allowed magnetoexcitonic transitions using terahertz radiation circularly polarized in the plane of the quantum well. The intraexcitonic magnetoabsorption to 2p^± like magnetoexciton states as functions of the coefficients are obtained for transitions from 1s-like applied magnetic field.     

苯/二联苯为桥的噻吩-吡咯-噻吩结构:分子构型及电致变色性质

A series of multi-branched dithienylpyrrole (SNS) monomers with rigid phenyl (PhSNS) and biphenyl rings (BPhSNS) as bridges were designed and synthesized, and were fabricated to form cross-linked polymers (pPhSNS, pBPhSNS) by electrochemical polymerization. Cyclic voltammetry (CV) results showed that PhSNS and BPhSNS exhibited similar oxidative properties except for one new higher-potential oxidative peak appearing in the curves of PhSNS. Theoretical calculations indicated that it should be attributed to the different steric configuration between the two dithienylpyrrole (SNS) units in PhSNS. One SNS unit possessed a larger twist angle (40.2°) between thiophene and pyrrole rings than the other one (21.2°), which indicated that PhSNS possessed a relatively larger energy gap (~0.4 eV) between HOMO-1 and HOMO than BPhSNS, for which HOMO and HOMO-1 levels were of almost the same energy. However, both PhSNS and BPhSNS showed similar onset oxidation potentials. The CV curves of pPhSNS and pBPhSNS showed that they presented similar oxidative properties, which enabled their corresponding electrochemical polymers to exhibit similar electrochromic properties. The UV-vis spectra of the corresponding polymers showed that both pPhSNS and pBPhSNS possessed similar optical absorption and similar multicolor switching between yellow (-0.8 V), greyish-green (0.9 V) and gray (1.1 V) colors. Besides, pPhSNS and pBPhSNS showed fast switching times of 0.57 s and 0.93 s at 1100 nm, respectively and reasonable contrasts of 46% and 31% at 1100 nm, respectively. These investigations may help understand the relationship between structural configuration and the electrochemistry/electrochromic properties for polymer electrochromic (PEC) materials research.     

Phase Transfer Catalyzed Anomeric Nucleophilic Substitutions with D-Xylopyranosyl Halides

Abstract

Anomeric pairs of per-O-acetylated-D-xylopyranosyl halides were individually treated with a wide variety of nucleophiles under mild PTC conditions. Thus, 2,3,4-tri-O-acetyl-α-D-xylopyranosyl bromide 1 provided exclusively the β-D-xylopyranosyl anomers 2-11 in good to excellent yields (65-95%). Alternatively, under the same PTC conditions, 2,3,4-tri-O-acetyl-β-D-xylopyranosyl chloride 13 afforded solely the inverted α-D-anomers 15 (82%) and 16 (67%) upon treatment with thiophenol and sodium azide, respectively. Similarly, 2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl chloride 19 provided the analogous products 20 (63%) and 21 (31%) upon treatment with thiophenol and sodium azide. In the presence of tetrabutylammonium chloride as PTC catalyst, β-xylopyranosyl chloride 13 was shown to slowly equilibrate to the α-chloride 14. Therefore, care must be taken to avoid PTC catalyst for which counter anions can cause anomerization of the starting glycosyl halides.     

Synthesis and characterization of thermally crosslinkable hole‐transporting polymers for PLEDs

Two new thermally crosslinkable hole‐transporting polymers, X‐PTPA and X‐PCz, were synthesized via Yamamoto coupling reactions. The number‐averaged molecular weights (M_n) of X‐PTPA and X‐PCz were found to be 45,000 and 48,000, respectively, and therewith, polydispersity indices were of 1.8 and 1.7, respectively. Thermally crosslinked X‐PTPA and X‐PCz exhibit excellent solvent resistance and stable optoelectronic properties. The UV–visible maximum absorption peaks of X‐PTPA and X‐PCz in the thin film state are at 389 and 322 nm, respectively. The HOMO levels of X‐PTPA and X‐PCz are estimated to be ?5.27 and ?5.39 eV, respectively. Multilayered devices (ITO/crosslinked X‐PTPA or X‐PCz/SY‐PPV/LiF/Al) were fabricated with SY (SuperYellow) as the emitting layer. The maximum efficiency of the multilayered device with a crosslinked X‐PTPA layer is approximately three times higher than that of the device without a crosslinked X‐PTPA layer and much higher than that of the crosslinked X‐PCz device. This result can be explained by the observations that crosslinked X‐PTPA produces increased electron accumulation within the emitter, SY, and also efficient exciton formation due to improved charge balance. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5111–5117     

Theoretical mechanisms of the superoxide radical anion catalyzed by the copper‐zinc superoxide dismutase

The disproportionation of superoxide radical anions catalyzed by copper‐zinc superoxide dismutase was investigated in detail using density functional theory. The structures of each stationary point and the transition states were located so that the reaction pathways were determined. The results indicate that the reactions proceed by two steps both for the oxidized process of superoxide radical anion and the reduced one. The rate for the determining step of the reaction (2) is in very good agreement with the experimental value. The solvation effect on the reaction was also discussed. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

DFT study of the structure and property of small organic hole‐transporting molecules

In this article, all calculations are performed at B3LYP/6‐31G** level. For each one of the molecule, including triphenylamine (TPA), N,N′‐diphenyl‐N,N′‐bis(3‐methyllphenyl)‐(1,1′‐biphenyl)‐4,4′‐diamine (TPD), biphenyl (Bp), and their derivatives (TPAs, TPDs, Bps, respectively), the geometry is optimized for both neutral and radical‐cation states. Their reorganization energy is then compared. It seems that it is the monomer, TPAs, and not the central biphenyl moiety that determines the properties of TPDs. However, this is contradictory of some previous results. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011