Stable Tetrabenzo-Chichibabin's Hydrocarbons: Tunable Ground State and Unusual Transition between Their Closed-Shell and Open-Shell Resonance Forms

Stable open-shell polycyclic aromatic hydrocarbons (PAHs) are of fundamental interest due to their unique electronic, optical, and magnetic properties and promising applications in materials sciences. Chichibabin's hydrocarbon as a classical open-shell PAH has been investigated for a long time. However, most of the studies are complicated by their inherent high reactivity. In this work, two new stable benzannulated Chichibabin's hydrocarbons 1-CS and 2-OS were prepared, and their electronic structure and geometry in the ground state were studied by various experiments (steady-state and transient absorption spectra, NMR, electron spin resonance (ESR), superconducting quantum interference device (SQUID), FT Raman, X-ray crystallographic etc.) and density function theory (DFT) calculations. 1-CS and 2-OS exhibited tunable ground states, with a closed-shell quinoidal structure for 1-CS and an open-shell biradical form for 2-OS. Their corresponding excited-state forms 1-OS and 2-CS were also chemically approached and showed different decay processes. The biradical 1-OS displayed an unusually slow decay to the ground state (1-CS) due to a large energy barrier (95 ± 2.5 kJ/mol) arising from severe steric hindrance during the transition from an orthogonal biradical form to a butterfly-like quinoidal form. The quick transition from the quinoidal 2-CS (excited state) to the orthogonal biradicaloid 2-OS (ground state) happened during the attempted synthesis of 2-CS. Compounds 1-CS and 2-OS can be oxidized into stable dications by FeCl(3) and/or concentrated H(2)SO(4). The open-shell 2-OS also exhibited a large two-photon absorption (TPA) cross section (760 GM at 1200 nm).     

Vibrational analysis of mononitrosyl complexes in hemerythrin and flavodiiron proteins: relevance to detoxifying NO reductase

Flavodiiron proteins (FDPs) play important roles in the microbial nitrosative stress response in low-oxygen environments by reductively scavenging nitric oxide (NO). Recently, we showed that FMN-free diferrous FDP from Thermotoga maritima exposed to 1 equiv NO forms a stable diiron-mononitrosyl complex (deflavo-FDP(NO)) that can react further with NO to form N(2)O [Hayashi, T.; Caranto, J. D.; Wampler, D. A; Kurtz, D. M., Jr.; Mo?nne-Loccoz, P. Biochemistry 2010, 49, 7040-7049]. Here we report resonance Raman and low-temperature photolysis FTIR data that better define the structure of this diiron-mononitrosyl complex. We first validate this approach using the stable diiron-mononitrosyl complex of hemerythrin, Hr(NO), for which we observe a ν(NO) at 1658 cm(-1), the lowest ν(NO) ever reported for a nonheme {FeNO}(7) species. Both deflavo-FDP(NO) and the mononitrosyl adduct of the flavinated FPD (FDP(NO)) show ν(NO) at 1681 cm(-1), which is also unusually low. These results indicate that, in Hr(NO) and FDP(NO), the coordinated NO is exceptionally electron rich, more closely approaching the Fe(III)(NO(-)) resonance structure. In the case of Hr(NO), this polarization may be promoted by steric enforcement of an unusually small FeNO angle, while in FDP(NO), the Fe(III)(NO(-)) structure may be due to a semibridging electrostatic interaction with the second Fe(II) ion. In Hr(NO), accessibility and steric constraints prevent further reaction of the diiron-mononitrosyl complex with NO, whereas in FDP(NO) the increased nucleophilicity of the nitrosyl group may promote attack by a second NO to produce N(2)O. This latter scenario is supported by theoretical modeling [Blomberg, L. M.; Blomberg, M. R.; Siegbahn, P. E. J. Biol. Inorg. Chem. 2007, 12, 79-89]. Published vibrational data on bioengineered models of denitrifying heme-nonheme NO reductases [Hayashi, T.; Miner, K. D.; Yeung, N.; Lin, Y.-W.; Lu, Y.; Mo?nne-Loccoz, P. Biochemistry 2011, 50, 5939-5947 ] support a similar mode of activation of a heme {FeNO}(7) species by the nearby nonheme Fe(II).     

紧致方法对流动换热及静态分岔的模拟

发展了基于投影法的紧致方法求解流动换热问题,对顶盖驱动流和侧壁加热的方腔内自然对流换热问题进行了数值模拟。与其它传统方法相比,紧致方法能在较少的网格结点下获得精度较高的计算结果。进一步,采用所发展的紧致方法对不同工况下的Rayleigh-Benard对流及其静态分岔现象进行了数值模拟。数值计算结果表明当长宽比变大时,底部努塞尔数会有小幅度增加。当长宽比为8时,用所发展的紧致方法不同的初场可以得出三种不同的流场和温度场。与基于QUICK格式的SIMPLE算法相比,所发展的紧致方法可以多预测一种静态分岔现象。     

Perturbation method of studying the EI Nifio oscillation with two parameters by using the delay sea-air oscillator model

The EI Nio-southern oscillation (ENSO) is an interannual phenomenon involved in tropical Pacific oceanatmosphere interactions. In this paper, we develop an asymptotic method of solving the nonlinear equation using the ENSO model. Based on a class of the oscillator of the ENSO model, a approximate solution of the corresponding problem is studied employing the perturbation method.     

Simple near‐infrared photodetector based on charge transfer complexes formed in molybdenum oxide doped N,N′‐di(naphthalene‐1‐yl)‐N,N′‐diphenyl‐benzidine

We have demonstrated a simple near‐infrared (NIR) photodetector (PD) based on charge transfer complex (CTC) formed in molybdenum trioxide (MoO₃) doped N,N′‐di(naphthalene‐1‐yl)‐N,N′‐diphenyl‐benzidine (NPB), which shows a photocurrent of about 0.35 A/cm² at –3 V under 980 nm illumination. The existence of CTC formation promotes photocurrent generation which is investigated by comparison with MoO₃ doped 2‐methyl‐9,10‐di(2‐naphthyl)anthracene (MADN) film which has no CTC absorption. It can be evolved that this kind of simple‐structure photodetector has potential application in the near‐infrared (NIR) detection area. It is shown in this Letter that although both MoO₃ and NPB have larger energy gaps of about 3 eV and weak absorption in the NIR region, the charge transfer complexes formed by mixing the two materials show an extra absorption band and good photoelectric response in the NIR region.

     

Palladium-catalyzed intramolecular decarboxylative coupling of arene carboxylic acids/esters with aryl bromides

Give me a ring? An efficient approach has been developed for the intramolecular decarboxylative coupling of arene carboxylic acids/esters with aryl bromides catalyzed by palladium (see scheme). From a synthetic viewpoint, this method is highly attractive because the catalyst loading is low, the optimized reaction conditions are mild, and the substrate scope is broad.     

Tunability of UV electroluminescence for n-ZnO:Al/n −-ZnO/i-MgO/n-GaN heterostructured light-emitting diodes

n-ZnO:Al/n ^?-ZnO/i-MgO/n-GaN heterostructured diodes have been fabricated by radio frequency magnetron sputtering. The electroluminescence (EL) of the n-ZnO:Al/n ^?-ZnO/i-MgO/n-GaN diodes has been investigated. All EL spectra are dominated by ultraviolet (UV) emission peaked at around 368 nm. However, EL performances of the devices can be tuned through controlling the electrical parameters of ZnO:Al films. With the variation of the ZnO:Al films, EL spectra could evolve into random lasing action from conventional EL. The electrical parameters of the corresponding ZnO:Al films were researched, and the related UV emission mechanism is discussed in terms of the energy-band theory of the heterojunctions.     

The growth of high-quality and self-separation GaN thick-films by hydride vapor phase epitaxy

About 1.2 mm thick GaN bulk crystals were obtained by combining a pulsed NH₃-flow modulation (PFM) method and a self-separation method of short-shutting NH₃ flow when using hydride vapor phase epitaxy (HVPE). High crystal quality of bulk GaN was evaluated by X-ray rocking curves (XRC) and the full width at half maximum (FWHM) values were 110, 72 and 83 arcsec for (002), (102) and (100) reflection planes, respectively. The PFM method is proved to be effective in reducing cracks and keeping the surface smooth. And the method of short-shutting NH₃ flow can lead to GaN thick layer separate from sapphire substrate when cooling from the high growth temperature. Growth and separation mechanisms were investigated. Two states were found in PFM method. With PFM method modulating between high quality state and low stress state, 300 μm thick GaN layers without cracks were obtained. Study of spontaneous separation mechanism revealed that the separation attributed to formation of voids inside the GaN layer.     

一类泛函微分方程半正问题的正周期解

运用Krasnosel’skii不动点理论研究了一类含参泛函微分方程半正问题正周期解的存在性．获得了当参数充分小时正周期解的存在性结果以及半正问题正周期解存在的充分条件．丰富了一阶泛函微分方程解的存在性理论．     

厄尔尼诺/拉尼娜-南方涛动非线性扰动模型孤子的渐近解法

研究了一类厄尔尼诺/拉尼娜-南方涛动(ENSO)随机扰动模型. 首先, 利用特殊的待定系数方法得到了无扰动ENSO模型下的孤子精确解. 然后利用渐近理论和方法构造了随机扰动ENSO模型的近似解, 并举例说明得到的渐近解具有较好的精度.