Synthesis and properties of a thiophene-substituted diaza[7]helicene for application as a blue emitter in organic light-emitting diodes

Carbazole-based diaza[7]helicene substituted by thiophene groups, 2,12-dithiophene-5,15-dihexyl-5,15-diaza[7]helicene (6), was synthesised successfully and confirmed by ¹H NMR, ¹³C NMR, High Resolution Mass Spectrometry, Time of Flight Mass Spectrometry. Compound 6 exhibited good solubility and excellent thermal stability with no melting point and a high decomposition temperature of 453.64 °C. A doped device with a structure of ITO/NPB (50 nm)/CBP: 10% 6 (30 nm)/Bphen (20 nm)/Mg:Ag (150 nm)/Ag (50 nm) emitted the blue light at 460 nm with Commission Internationale de LEclairage (CIE) coordinate of (0.176, 0.26). The maximum brightness and external quantum efficiency (EQE) were 2306 cd m^?2 and 0.41%, respectively.     

Synthesis and Solution Behavior Studies of a Bifunctional Fluorenyl Dioxotetraamine and Its Copper(II) Complex

The fluorenyl dioxotetraamine L⁴ was designed and prepared. The solution behavior of L⁴ and its interaction with the Cu^II ion were studied by pH potentiometric, fluorimetric and spectrophotometric titration. In the dioxane/water solution, it was found that the molecule L⁴ showed an “off‐on” or “on‐off” fluorescent response in the absence or presence of the Cu^II ion with the increase of the pH value. Moreover, influenced by the Cu^II ion, the fluorescence of the dioxotetraamine L⁴ can be almost quenched when the pH value was slightly higher than 4.0, which is rarely reported and useful to detect the Cu^II ion under acidic condition.     

A Potential Method Using Ge{iPrNC[N(SiMe3)2]NiPr}2, (Et3Si)2Te and Anhydrous Hydrazine for Germanium Tellurides

A germanium(II)‐guanidine derivative of formula Ge{iPrNC[N(SiMe₃)₂]NiPr}₂ ( 1 ) was synthesized and characterized by ¹H NMR, ¹³C NMR, elemental analysis, and X‐ray diffraction method. Thermal property was also studied to identify its thermal stability and volatility. More importantly, compound 1 was synthesized to develop a new method for germanium tellurides, where anhydrous hydrazine was introduced to prompt the activity of germanium(II) guanidines (or derivatives) towards (Et₃Si)₂Te. Solution reaction of compound 1 , (Et₃Si)₂Te, and anhydrous hydrazine was investigated to pre‐identify the feasibility of this combination for ALD process. The EDS data of the black precipitate from this reaction verified the potential of this method to manufacture germanium tellurides.     

Unraveling the Mechanism for the Sharp‐Tip Enhanced Electrocatalytic Carbon Dioxide Reduction: The Kinetics Decide

The electrocatalytic reduction reaction of carbon dioxide can be significantly enhanced by the use of a sharp‐tip electrode. However, the experimentally observed rate enhancement is many orders of magnitudes smaller than what would be expected from an energetic point of view. The kinetics of this tip‐enhanced reaction are shown to play a decisive role, and a novel reaction‐diffusion kinetic model is proposed. The experimentally observed sharp‐tip enhanced reaction and the maximal producing rate of carbon monoxide under different electrode potentials are well‐reproduced. Moreover, the optimal performance shows a strong dependence on the interaction between CO₂ and the local electric field, on the adsorption rate of CO₂, but not on the reaction barrier. Two new strategies to further enhance the reaction rate have also been proposed. The findings highlight the importance of kinetics in modeling electrocatalytic reactions.     

Nanographite-based fluorescent biosensing of Salmonella enteritidis by applying deoxyribonuclease-assisted recycling

Microchimica Acta - The authors describe a low-cost and sensitive method for the fluorometric determination of Salmonella enteritidis (S. enteritidis). It is based on the use of nanographite (NG)...     

Crystallization kinetics and the fine morphological evolution of poly(ethylene oxide)/ionic liquid mixtures

The overall crystallization kinetics and spherulite morphologies of miscible poly(ethylene oxide)(PEO)/1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_6]) mixtures were studied by differential scanning calorimetry(DSC),polarized optical microscopy(POM) and rheological measurements. The finer crystal structures were further detected by wide angle X-ray diffraction(WAXD) and small angle X-ray scattering(SAXS). Crystallization of PEO is largely suppressed by [BMIM][PF_6] addition especially at higher ionic liquid(IL) concentrations above 20 wt%. Both the overall crystallization rate and the spherulite growth decrease with the increase of IL content and crystallization temperature; however, the crystallization mechanism keeps unchanged as evidenced by the similar Avrami exponent n and WAXD results. The addition of [BMIM][PF_6] could induce more nuclei to some extent, but the induction time of crystallization is evidently prolonged,and a linear to non-linear transition of the spherulite growth(R ∝ t to R ∝ t~(1/2)) can be observed. At higher IL concentration,the spherulite texture changes apparently from particular serrated to branch surface due to the diffusion-controlled growth and the dilution effect, which also as a main factor contributes to the increasing trend of the long period of crystals.     

有序介孔Sn-SBA-15负载铂催化剂上丙烷脱氢性能的提高

丙烷脱氢制丙烯能够将低级烷烃转变成烯烃,是有效扩大丙烯来源的生产工艺.铂锡催化剂用于丙烷催化脱氢的主要缺点是稳定性差、选择性低,通过稳定锡的氧化态可以大大改善催化剂的脱氢性能及稳定性.本文采用一锅水热合成法制备了一系列高比表面积具有高度有序介孔结构的Sn掺杂的Sn-SBA-15材料,并作为载体负载铂催化剂用于丙烷脱氢反应.同时利用传统浸渍法(IM)合成了Sn/SBA-15-IM材料作为对比.结合X射线衍射(XRD)、BET比表面积和孔体积测试、红外光谱(FT-IR)、X射线光电子能谱、H2程序升温脱附(H2-TPD)、热重分析(TGA)、扫描电镜和透射电镜等多种物理化学表征手段研究了Sn-SBA-15材料和催化剂的结构性质及其丙烷脱氢反应性能.XRD和BET比表面积和孔体积测试结果表明,水热合成法原位引入助剂Sn不影响载体SBA-15的有序孔道结构,同时能够保持较大的比表面积.传统浸渍法引入Sn会堵塞载体孔道,载体比表面积及孔道有序度下降.Sn掺杂进入SBA-15骨架能够增强Sn物种与载体的相互作用,有利于Sn物种在反应过程中保持氧化态,提高催化剂丙烷脱氢反应的活性及选择性.当Sn掺杂量增至2.0 wt％时,Pt,Sn组分与载体之间的相互作用减弱,催化剂中Sn0物种所占比例增多,导致催化剂丙烷脱氢性能下降.在丙烷脱氢反应过程中,一锅法引入Sn的催化剂上反应活性和稳定性明显优于浸渍法引入Sn的催化剂.其中,Pt/0.5 Sn-SBA-15催化剂表现出最优的丙烷脱氢性能,丙烷转化率为43.8％,丙烯选择性为98.5％.     

Simple and rapid surface-enhanced Raman Spectroscopy assay for safranine T and its application in highly sensitive determination of mercury (Ⅱ)

A simple and sensitive surface-enhanced Raman spectroscopy (SERS) method for the detection of safranine T (ST) and Hg²⁺ using silver nanoparticles (AgNPs) as substrate was developed. ST can absorb on the surface of AgNPs through electrostatic interaction, the electromagnetic effect combined with chemical adsorption effect give a notable Raman enhancement for ST. The presence of Hg²⁺ well decreased the absorbed ST molecules on AgNPs, leading to a significant decrease of SERS signals thus enabling to detect Hg²⁺. The determination conditions for SERS, including the amount of AgNPs, the concentration of NaCl, the concentration of HCl, the concentration of ST and the reaction time, were optimised. Under the optimised experimental conditions, good linear responses were obtained for ST and Hg²⁺ in the concentration ranges of 0.01–4.0 μmol L^?1 (3.5–1403.4 ng mL^?1) and 0.01–2.0 μmol L^?1 (2.0–401.2 ng mL^?1), the limit of detection were 3.0 nmol L^?1 (1.1 ng mL^?1) and 2.0 nmol L^?1 (0.4 ng mL^?1), respectively. The present method was subsequently applied to the determination of ST in tomato sauces and Hg²⁺ in environmental waters, the recoveries of ST and Hg²⁺ in spiked samples are 95.5–107.8% and 91.4–110.8 %, respectively.     

Flow Bifurcations in a Thin Gap Between Two Rotating Spheres

This paper presents the use of a parameter continuation method and a test function to solve the steady, axisymmetric incompressible Navier–Stokes equations for spherical Couette flow in a thin gap between two concentric, differentially rotating spheres. The study focuses principally on the prediction of multiple steady flow patterns and the construction of bifurcation diagrams. Linear stability analysis is conducted to determine whether or not the computed steady flow solutions are stable. In the case of a rotating inner sphere and a stationary outer sphere, a new unstable solution branch with two asymmetric vortex pairs is identified near the point of a symmetry-breaking pitchfork bifurcation which occurs at a Reynolds number equal to 789. This solution transforms smoothly into an unstable asymmetric 1-vortex solution as the Reynolds number increases. Another new pair of unstable 2-vortex flow modes whose solution branches are unconnected to previously known branches is calculated by the present two-parameter continuation method. In the case of two rotating spheres, the range of existence in the (Re ₁ , Re ₂ ) plane of the one and two vortex states, the vortex sizes as a function of both Reynolds numbers are identified. Bifurcation theory is used to discuss the origin of the calculated flow modes. Parameter continuation indicates that the stable states are accompanied by certain unstable states. Received 26 November 2001 and accepted 10 May 2002 Published online 30 October 2002 Communicated by M.Y. Hussaini     

Mach Wave Radiation by Mixing Layers. Part II: Analysis of the Source Field

In Part II a large-scale sound source in a time-developing planar free mixing layer is studied using an acoustic analogy approach. It is shown that only the non-compact character of the source resembles well the character of the corresponding source in a spatially developing flow. A model based on a continuous assembly of wave packets is derived and applied to direct numerical simulation results of two supersonic time-developing mixing layers undergoing transition to turbulence. The analysis predicts two distinctive dominant Mach wave sources in agreement with the direct analysis of Part~I. The first dominates during the stage of the Λ-vortex structure and the second just prior to the final breakdown to a fine-scale structure. The convective velocity of the second Mach wave source is higher than the first and thus its Mach angle of radiation is higher. The second source has a reduced strength at the higher free-stream Mach number. Directivity and frequency spectra compare well with the results of Part I, demonstrating that the assumptions inherent in the analogy are quite reasonable. Received 5 August 1997 and accepted 6 April 1998