A sharp change in the N2 emission channel from N2O(a) → N2(g) + O(a) to N(a) + N(a) → N2(g) has been found at around 500 K in a steady-state NO + D2 reaction over stepped Pd(211) = [(S)3(111) × (100)] by means of angle-resolved desorption. The desorbing N2 is highly collimated at around 30° off normal toward the step-down direction below about 500 K due to the intermediate N2O decomposition, whereas, above 500 K, the near normally directed desorption due to the recombination of N(a) is relatively enhanced. The N2O decomposition channel is promoted when the reaction is carried out with hydrogen (deuterium) and the channel change is accelerated by quick changes of the amounts of surface hydrogen and oxygen (or NO(a)) into the opposite directions, and enhanced nitrogen removal as ammonia on the resultant hydrogen-rich surface. In the steady-state NO + CO reaction, the N2 emission channel gradually changes above 500 K toward recombination. A model for the off-normal N2 emission is briefly described. 相似文献
PM2.5 and total suspended particulate(TSP) samples were collected at Lijiang,southeastern Tibetan Plateau.China.Sixteen elements(Al,Si,S,K,Ca,Cr,Mn,Ti,Fe,Ni,Zn,As,Br,Sb,Pb and Cu) were analyzed to investigate their elemental compositions during the pre-monsoon period.The results showed that Ca was the most abundant element in both PM2.5 and TSP samples.The enrichment factors(EFs) of Si,Ti,Ca, Fe,K and Mn were all below 10 for both PM2.5 and TSP,and these elements also had lower PM2.5/TSP ratios (0.32-0.34),suggesting that they were mainly derived from crustal sources.Elements Cu,Zn,S,Br and Sb showed strong enrichment in PM2.5 and TSP samples,with their PM2.5/TSP ratios ranging from 0.66 to 0.97,indicating that they were enriched in the fine fractions and influenced by anthropogenic sources. Analysis of the wind field at 500 hPa and calculations of back trajectories indicated that Al,Si,Ca,Ti,Cr, Mn and Fe can be influenced by transport from northwestern China during the dust-storm season,and that S,K,Ni,Br and Pb reached high concentrations during westerly transport from south Asia.Combined with the principle component analysis and correlation analysis,elements of PM2.5 samples were mainly from crustal sources,biomass burning emissions and regional traffic-related sources. 相似文献
High-performance organic light-emitting diodes (OLEDs) that use phosphorescent and/or thermally activated delayed fluorescence emitters are capable of realizing 100 % electron-to-photon conversion. The host materials in these OLEDs play crucial roles in determining OLED performance. Carbazole derivatives are frequently used as host materials, among which 3,3-bis(9H-carbazol-9-yl)biphenyl ( mCBP ) is often used for lifetime testing in scientific studies. In this study, the π conjugation of the carbazole unit was expanded to enhance OLED lifetime by designing and developing two benzothienocarbazole (BTCz)-based host materials, namely m1BTCBP and m4BTCBP . Among these host materials, m1BTCBP formed a highly efficient [Ir(ppy)3]-based OLED with an operational luminescence half-life (LT50) of over 300 h at an initial luminance of approximately 12000 cd m−2 (current density: 25 mA cm−2). The LT50 value at 1000 cd cm−2 was estimated to be about 23 000 h. This performance is clearly higher than that of mCBP -based OLEDs (LT50≈8500 h). 相似文献
Recently, researchers have focused on thermally activated delayed fluorescence (TADF) for efficient future lighting and displays. Among TADF emitters, a combination of triazine and acridine is a promising candidate for realizing high-efficiency organic light-emitting devices (OLEDs). However, simultaneous development of perfect horizontal orientation (Θ=100 %) and an external quantum efficiency (EQE) of over 40 % is still challenging. Here, to obtain insights for further improvements of a triazine/acridine combination, various asymmetric spirobiacridine (SBA)-based TADF emitters with a unity photoluminescence quantum yield and high Θ ratio of over 80 % were developed. Furthermore, the substitution effects of the triazine acceptor unit on the photophysical properties were studied, including molecular orientations and OLED performance. The corresponding OLED exhibited sky-blue emission with a high EQE of over 30 %. 相似文献
End‐group analyses of the oligo‐ and polypropylenes produced with bis(phenoxy‐imine) Zr and Hf complexes with methylaluminoxane (MAO) indicate that the polymerization is initiated by two consecutive 1,2‐insertions and is terminated by a β‐H transfer following a 2,1‐insertion. Our data indicate that chain propagation occurs with prevailing 1,2‐regiochemistry but with considerable regioerrors, and with virtually no stereoselectivity.
The polymerization of propylene mediated by bis(phenoxy‐imine) Zr and Hf complexes with MAO. 相似文献
We report the potential of a small Ca2+-dependent deoxyribozyme as a novel biomaterial to distinguish RNA foldings. It is found that an immobilized deoxyribozyme using avidin-biotin interaction cleaves the target site within only single-stranded RNAs. The RNA cleavage reaction is also detected using the deoxyribozyme SPR sensor chip. Furthermore, we develop a novel NAPzyme (nucleic acid peptide deoxyribozyme) with its RNA cleavage function in the absence of divalent metal ions. 相似文献
Using a tailored high triplet energy hole transport layer (HTL) is a suitable way to improve the efficiency and extend the lifetime of organic light-emitting devices (OLEDs), which can use all molecular excitons of singlets and triplets. In this study, dibenzofuran (DBF)-end-capped and spirobifluorene (SBF) core-based HTLs referred as TDBFSBF1 and TDBFSBF2 were effectively developed. TDBFSBF1 exhibited a high glass transition temperature of 178 °C and triplet energy of 2.5 eV. Moreover, a high external quantum efficiency of 22.0 %, long operational lifetime at 50 % of the initial luminance of 89,000 h, and low driving voltage at 1000 cd m−2 of 2.95 V were achieved in green phosphorescent OLEDs using TDBFSBF1 . Further, a high-hole mobility μh value of 1.9×10−3 cm2 V−1 s−1 was recorded in TDBFSBF2 . A multiscale simulation successfully reproduced the experimental μh values and indicated that the reorganization energy was the primary factor in determining the mobility differences among these SBF core based HTLs. 相似文献
Isotactic polypropylene-based graft copolymers linking poly(methyl methacrylate), poly(n-butyl acrylate) and polystyrene were successfully synthesized by a controlled radical polymerization with isotactic polypropylene (iPP) macroinitiator. The hydroxylated iPP, prepared by propylene/10-undecen-1-ol copolymerization with a metallocene/methyl-aluminoxane/triisobutylaluminum catalyst system, was treated with 2-bromoisobutyryl bromide to produce a Br-group containing iPP (PP-g-Br). The resulting PP-g-Br could initiate controlled radical polymerization of methyl methacrylate, n-butyl acrylate and styrene by using a copper catalyst system, leading to a variety of iPP-based graft copolymers with a different content of the corresponding polar segment. These graft copolymers demonstrated unique mechanical properties dependent upon the kind and content of the grafted polar segment. 相似文献
The Rh(II)-catalyzed intramolecular C H insertion reactions of N,N-dialkyl-α-diazo-α-(diethylphosphono)acetamides 2a , f–j in CHCl3 or ClCH2CH2Cl were found to give monocyclic and bicyclic α-phosphono-β-lactams, 3a and 3f–j , in 43–67% yields via regiospecific α-C H insertion of the N-alkyl groups. Similar treatment of N-benzyl-N-isopropyl-α-diazo-α-(diethylphosphono)acetamide ( 2b ) and the corresponding N-isobutyl-N-methylacetamide 2d in ClCH2CH2Cl afforded mixtures of β-lactams 3b (35%) and and 3b ′ (16%), β-lactam 3d (47%), and γ-lactam 4d (10%), respectively, each of which is formed by the competitive C H insertion reaction between benzylic and isopropyl α-C H bonds and between methyl α-C H and methine β-C H bonds, respectively. For the formation of β-lactams, the selectivity in the rhodium-mediated C H insertion in ClCH2CH2Cl follows the order methyl > methine > benzylic α-C H bond on N-substituents. The N,N-dibutyl-α-diazo homologue 2c and Nα[α-diazo-α-(diethylphosphono)acetyl]-2-methylindoline ( 2k ) exclusively produced γ-lactams 4c (67%) and 4k (81%) via insertion into the methylene β-C H and methyl β-C H bonds. tert-Butyl N-[α-diazo-α-(dibenzylphosphono)acetyl]-piperidine-2-carboxylate ( 2m ) on similar treatment, followed by deprotection of the benzyl ester afforded the 7-phosphono carbacepham 6 in 32% overall yield. Similar Rh(II)-catalyzed cyclization of N-methyl-N[4-benzyloxy-α-(diethylphosphono)-phenyl(diethyl-phosphono)methyl]-α-diazo-acetamide ( 2n ) led to 1-[4′-benzylphenyl(diethylphosphono)methyl] -3-(diethyl-phosphono)azetidin-2-one ( 3n ) in 78% yicld. The phosphono group at C-7 of 3f was converted into the acetylamino group via a four-step reaction. Application of chiral rhodium(II) carboxylates 12a–c to the insertion reactions of 2b , c produced α-phosphono-β-and γ-lactams, 3b and 4c , in 6–24% ee and 25–29% ee, respectively. 相似文献