Atmospheric oxidation chemistry of 1–methoxy 2–propyl acetate initiated by OH radicals: kinetics and mechanisms

Kinetics and mechanism of the gas-phase reaction of CH₃C(O)OCH(CH₃)CH₂OCH₃ (MPA) with OH radicals in the presence of O₂ and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311?+?G(d,p)//BH&HLYP/6-311++G(d,p)?+?0.9335×ZPE. The calculations predict that the H-abstraction from the ?CH₂?O? position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ under atmospheric conditions. This activated radicals CH₃C(O)OCH(CH₃)C(O ?)HOCH₃ will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH₃ and acetic anhydride CH₃C(O)OC(O)CH₃). In the presence of water, acetic anhydride can convert into acetic acid CH₃C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372?K are used to derive a negative activation energy (E_a= ?5.88 kJ/mol) and an pre-exponential factor (A?=?1.78×10^?12 cm³ molecule^?1 s^?1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263?1000?K can be described by k?=?5.60 × 10^?14×(T/298?K)^3.4×exp(1725.7?K/T) cm³ molecule^?1 s^?1.     

Electrical and Thermal Transport Properties of n-type Bi6Cu2Se4O6 (2BiCuSeO + 2Bi2O2Se)

New thermoelectric materials, n-type Bi₆Cu₂Se₄O₆ oxyselenides, composed of well-known BiCuSeO and Bi₂O₂Se oxyselenides, are synthesized with a simple solid-state reaction. Electrical transport properties, microstructures, and elastic properties are investigated with an emphasis on thermal transport properties. Similar to Bi₂O₂Se, it is found that the halogen-doped Bi₆Cu₂Se₄O₆ possesses n-type conducting transports, which can be improved via Br/Cl doping. Compared with BiCuSeO and Bi₂O₂Se, an extremely low thermal conductivity can be observed in Bi₆Cu₂Se₄O₆. To reveal the origin of low thermal conductivity, elastic properties, sound velocity, Grüneisen parameter, and Debye temperature are evaluated. Importantly, the calculated phonon mean free path of Bi₆Cu₂Se₄O₆ is comparable to the interlayer distance for BiO─CuSe and BiO─Se layers, which is ascribed to the strong interlayer phonon scattering. Contributing from the outstanding low thermal conductivity and improved electrical transport properties, the maximum ZT ≈0.15 at 823 K and ≈0.11 at 873K are realized in n-type Bi₆Cu₂Se_3.2Br_0.8O₆ and Bi₆Cu₂Se_3.6Cl_0.4O₆, respectively, indicating the promising thermoelectric performance in n-type Bi₆Cu₂Se₄O₆ oxyselenides.     

Evaluation of Charged Defect Energy in Two-Dimensional Semiconductors for Nanoelectronics: The WLZ Extrapolation Method

Defects play a central role in controlling the electronic properties of two-dimensional (2D) materials and realizing the industrialization of 2D electronics. However, the evaluation of charged defects in 2D materials within first-principles calculation is very challenging and has triggered a recent development of the WLZ (Wang, Li, Zhang) extrapolation method. This method lays the foundation of the theoretical evaluation of energies of charged defects in 2D materials within the first-principles framework. Herein, the vital role of defects for advancing 2D electronics is discussed, followed by an introduction of the fundamentals of the WLZ extrapolation method. The ionization energies (IEs) obtained by this method for defects in various 2D semiconductors are then reviewed and summarized. Finally, the unique defect physics in 2D dimensions including the dielectric environment effects, defect ionization process, and carrier transport mechanism captured with the WLZ extrapolation method are presented. As an efficient and reasonable evaluation of charged defects in 2D materials for nanoelectronics and other emerging applications, this work can be of benefit to the community.     

Recent Advances in Spatial Self-Phase Modulation with 2D Materials and its Applications

In recent years, spatial self-phase modulation (SSPM) with two-dimensional (2D) materials has attracted the attention of many researchers as an emerging and ubiquitous nonlinear optical effect. In this review, the state of the art of 2D material-based SSPM is summarized. SSPM measures or tunes the nonlinearity of 2D materials, and it is also an effective approach to study the band structure of 2D materials. Several modified forms of SSPM, such as high-order, white-light-excited, vector field excited, and optically nonlinearly enhanced SSPM are also presented. Subsequently, the physical origin of the SSPM formation mechanism is compared and analyzed. Furthermore, the applications of SSPM with 2D materials, including passive photonic devices, generation of Bessel beams, and identifying the mode of the orbital angular momentum, are listed. Finally, several urgent problems of the SSPM with 2D materials, potential applications, and prospects for future development are presented.     

Development and validation of a reversed‐phase HPLC method for CYP1A2 phenotyping by use of a caffeine metabolite ratio in saliva

CYP1A2 is important for metabolizing various clinically used drugs. Phenotyping of CYP1A2 may prove helpful for drug individualization therapy. Several HPLC methods have been developed for quantification of caffeine metabolites in plasma and urine. Aim of the present study was to develop a valid and simple HPLC method for evaluating CYP1A2 activity during exposure in xenobiotics by the use of human saliva. Caffeine and paraxanthine were isolated from saliva by liquid‐liquid extraction (chlorophorm/isopropanol 85/15v/v). Extracts were analyzed by reversed‐phase HPLC on a C₁₈ column with mobile phase 0.1% acetic acid/methanol/acetonitrile (80/20/2 v/v) and detected at 273nm. Caffeine and paraxanthine elution times were <13min with no interferences from impurities or caffeine metabolites. Detector response was linear (0.10–8.00µg/ml, R²>0.99), recovery was >93% and bias <4.47%. Intra‐ and inter‐day precision was <5.14% (n=6). The limit of quantitation was 0.10µg/ml and the limit of detection was 0.018±0.002µg/mL for paraxanthine and 0.032±0.002µg/ml for caffeine. Paraxanthine/caffeine ratio of 34 healthy volunteers was significantly higher in smokers (p<0.001). Saliva paraxanthine/caffeine ratios and urine metabolite ratios were highly correlated (r=0.85, p<0.001). The method can be used for the monitoring of CYP1A2 activity in clinical practice and in studies relevant to exposure to environmental and pharmacological xenobiotics. Copyright © 2015 John Wiley & Sons, Ltd.     

Design and development of a two‐dimensional system based on hydrophilic and reversed‐phase liquid chromatography with on‐line sample treatment for the simultaneous separation of excreted xenobiotics and endogenous metabolites in urine

In the present work we describe a two‐dimensional liquid chromatographic system (2D‐LC) with detection by mass spectrometry (MS) for the simultaneous separation of endogenous metabolites of clinical interest and excreted xenobiotics deriving from exposure to toxic compounds. The 2D‐LC system involves two orthogonal chromatographic modes, hydrophilic interaction liquid chromatography (HILIC) to separate polar endogenous metabolites and reversed‐phase (RP) chromatography to separate excreted xenobiotics of low and intermediate polarity. Additionally, the present proposal has the novelty of incorporating an on‐line sample treatment based on the use of restricted access materials (RAMs), which permits the direct injection of urine samples into the system. The work is focused on the instrumental coupling, studying all possible options and attempting to circumvent the problems of solvent incompatibility between the RAM device and the two chromatographic columns, HILIC and RP. The instrumental configuration developed, RAM‐HILIC‐RPLC‐MS/MS, allows the simultaneous assessment of urinary metabolites of clinical interest and excreted compounds derived from exposure to toxic agents with minimal sample manipulation. Thus, it may be of interest in areas such as occupational and environmental toxicology in order to explore the possible relationship between the two types of compounds. Copyright © 2015 John Wiley & Sons, Ltd.     

Eu:Lu2O3透明闪烁陶瓷的制备与性能

采用湿化学法合成了Eu原子掺量5%的Lu₂O₃陶瓷前驱体,通过SEM、XRD研究了煅烧前后前驱体和1 100 ℃煅烧4 h后粉体的形貌、结构以及物相。结果表明煅烧后的粉体为纳米类球形、高分散且结晶性良好的颗粒。颗粒尺寸为68.5 nm。使用煅烧后的粉体为原料,在1 650 ℃真空烧结30 h制备了高透过率的Eu:Lu₂O₃陶瓷,晶粒尺寸为46 μm,在611 nm处的直线透过率可以达到66.3%。此外对陶瓷的吸收曲线、光致激发和发射光谱特性以及X射线激发发射光谱进行研究。可观察到,Eu:Lu₂O₃陶瓷存在基质和激活离子两类吸收,光致发光光谱和X射线激发发射光谱均可以看出Eu:Lu₂O₃陶瓷存在极强的⁵D₀→⁷F₂跃迁发光,位于611 nm处。对比商业的BGO单晶的X射线发射光谱,可得本实验中制备的陶瓷的光输出为85 000 ph/MeV。Eu:Lu₂O₃陶瓷本身有着高X射线以及高能粒子的阻止能力,结合高光输出特性,表明Eu:Lu₂O₃陶瓷在X射线成像等领域具有巨大的潜在应用价值。     

Influence of the Degree of Deacetylation of Chitosan and BMP-2 Concentration on Biocompatibility and Osteogenic Properties of BMP-2/PLA Granule-Loaded Chitosan/β-Glycerophosphate Hydrogels

Compositions based on chitosan/β-glycerophosphate hydrogels with highly porous polylactide granules can be used to obtain moldable bone graft materials that have osteoinductive and osteoconductive properties. To eliminate the influence of such characteristics as chain length, degree of purification, and molecular weight on a designed material, the one-stock chitosan sample was reacetylated to degrees of deacetylation (DD%) of 19.5, 39, 49, 55, and 56. A study of the chitosan/β-glycerophosphate hydrogel with chitosan of a reduced DD% showed that a low degree of deacetylation increased the MSCs (multipotent stromal cells) viability rate in vitro and reduced the leukocyte infiltration in subcutaneous implantation to Wistar rats in vivo. The addition of 12 wt% polylactide granules resulted in optimal composite mechanical and moldable properties, and increased the modulus of elasticity of the hydrogel-based material by approximately 100 times. Excessive filling of the material with PLA (polylactide) granules (more than 20%) led to material destruction at a ~10% strain. Osteoinductive and osteoconductive properties of the chitosan hydrogel-based material with reacetylated chitosan (39 DD%) and highly porous polylactide granules impregnated with BMP-2 (bone morphogenetic protein-2) have been demonstrated in models of orthotopic and ectopic bone formation. When implanted into a critical-size calvarial defect in rats, the optimal concentration of BMP-2 was 10 μg/mL: bone tissue areas filled the entire material’s thickness. Implantation of the material with 50 μg/mL BMP-2 was accompanied with excessive growth of bone tissue and material displacement beyond the defect. Significant osteoinductive and osteoconductive properties of the material with 10 μg/mL of BMP-2 were also shown in subcutaneous implantation.     

基于深度学习的ELM实时识别研究

基于深度学习的方法，在HL-2A装置上开发出了一套边缘局域模(ELM)实时识别算法。算法使用5200次放电数据(约24.19万数据切片)进行学习，得到一个深度为22层的卷积神经网络。为衡量算法的识别能力，识别了HL-2A装置自2009年实现稳定ELMy H模放电以来所有历史数据(约26000次放电数据)，共识别出1665次H模放电，其中误识别35次，误报率为2.10%。在实际的1634次H模放电中，漏识别4次，漏识别率为0.24%。该误报率和漏报率可以满足ELM实时识别的精度要求。识别算法在实时控制环境下，对单个时间点的平均计算时间为0.46ms，可以满足实时控制的计算速度要求。     

Highly Luminescent Red Phosphorescent OLED with Interfacial Layers for Hole Transport and Electron Injection

Four kinds of red phosphorescent organic light-emitting devices were fabricated and compared to investigate the effect of interfacial layers for hole transport and electron injection. 1 nm-thick LiF in the device A and C and 1 nm-thick Cs₂CO₃ in the device B and D were deposited as an electron injection layer between the anode and the electron transport layer, and 5 nm-thick layer of dipyrazion[2,3-f:2′,2′-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile[HATCN] was inserted as a hole transport interfacial layer between the hole injection layer and the hole transport layer only in the device C and D. Under a luminance of 1000 cd/m², the power efficiencies were 7.6 lm/W and 8.5 lm/W in the device A and B, and 8.6 lm/W and 13.4 lm/W in the device C and D. The quantum efficiency of the device D was 15.8% under 1000 cd/m² which was somewhat lower than those of the device A and C, but a little higher than that of the device B. The luminance of the device D was much higher than those of the other devices at a given votage. The luminance of the device D at 7 V was 23,710 cd/m², which was 13.0, 3.4, and 4.0 times higher than those of the device A, B, and C at the same voltage, respectively.