基于铋可饱和吸收体的超快激光产生

采用磁控溅射沉积法在微纳光纤表面上镀一层纳米级厚度的铋薄膜,制备了一种微纳光纤-铋膜结构的可饱和吸收体.在1.5μm处的非线性光调制深度为14%.将其应用到掺铒光纤激光器中,在1.5μm波段获得稳定的超快脉冲激光产生,脉宽为357 fs,输出功率为45.4 mW,单脉冲能量为2.39 nJ,信噪比为84 dB.实验结果表明,利用磁控溅射法可制备出大调制深度的可饱和吸收体,为获得高能量超短脉冲激光输出提供新方案.     

AC等离子体辅助CH4低温氧化的分子激发作用

本文采用实验测量和数值模拟结合的方法,对AC放电下He/CH4/O2混合气中激发态对甲烷裂解和低温氧化的动力学贡献进行研究。基于HP-Mech,增加反应物的放电机理以及激发态参与的化学反应及其驰豫反应,建立CH4低温氧化机理。采用化学反应动力学求解器CHEMKIN中的两段式Plasma-PSR模型模拟放电过程及化学反应过程。该动力学模型能较好地预测反应物的消耗和主要产物的生成,反应路径分析表明激发态物质CH4(v),O2(v),O2(a^1△g)等通过链式反应CH4(v)+OH→CH3+H2O,O2(v)+H→OH+O,O2(a^1△g)+H→OH+O促进活性自由基和产物的生成。     

涡流二极管空化流动的数值计算

为了研究涡流二极管内空化现象的机理特性及对其性能的影响,我们假设流体为气液混相均质,并考虑不可凝结气相,采用基于组分输运方程,求解了涡流二极管全流道内气液混相均质流的雷诺平均N-S方程以及气相组分输运方程。数值计算结果显示了空化形成时涡流二极管入口、出口及旋流腔内的流场形态,研究表明:涡流二极管空化现象主要发生在流体切向进入时旋流腔和中心管的中心部位;空化流是由于液体在中心旋流场低压条件下汽化,同时不可凝结气体由于亨利定律在旋转流场形成的压力梯度下而发生的输运效应综合形成的;空化流由于强旋涡的原因对涡流二极管的性能产生明显的影响。上述结论对涡流二极管的设计及其指导工程应用具有重要的价值。     

Copper-mediated intramolecular aza-Wacker-type cyclization of 2-alkenylanilines toward 3-aryl indoles

A copper-mediated intramolecular aza-Wacker-type cyclization was developed for the direct and efficient synthesis of 3-aryl indoles using 2-alkenylanilines in moderate to good yields with good functional group compatibility. This strategy shows the high efficiency, operational simplicity as well as broad substrate scope.     

Highly enantioselective direct Michael addition of 1,3-dicarbonyl compounds to β-fluoroalkyl-α-nitroalkenes

Cinchona alkaloid catalysts were used in the Michael addition reaction of 1,3-dicarbonyl compounds to β-fluoroalkyl-α-nitroalkenes for the first time. The catalytic system performed well over a broad scope of substrates including β-keto esters and 1,3-diketones with high diastereoselectivities and excellent enantioselectivities (up to 99% ee) under mild conditions. A wide range of useful fluorinated chiral building blocks was synthesized.     

2-Chlorotetrafluoroethanesulfinamide induced asymmetric vinylogous Mannich reaction

The generality of (S)-2-chlorotetrafluoroethanesulfinamide (CTFSA) induced asymmetric vinylogous Mannich (AVM) addition reaction has been investigated. The reaction of aldimines derived from (S)-CTFSA with 2-(tert-butyldimethylsilyloxy) furan (TBSOF) took place regioselectively at the γ-site at room temperature in DMSO under air atmosphere to give the desired addition products in syn-configuration with high diastereoselectivities (up to 98:2 dr). However, anti-configuration product as major isomer was obtained in the presence of tetra-butyl ammonium fluoride (TBAF) at −78 °C. Facile removal of the auxiliary group without epimerization demonstrated their synthetic potential for piperidone derivatives.     

Co-Ni/FeMn双层膜中磁化强度对交换偏置的影响

固定CoNiFeMn双层膜中反铁磁层的厚度,改变CoNi铁磁层的成分来调节磁化强度,从而研究铁磁层的饱和磁化强度对CoNiFeMn双层膜中交换偏置的影响.研究表明,CoNiFeMn界面的交换耦合能U不是一个常量,而是随(MFM)12的增加而线性增加.其原因是铁磁层磁矩通过界面相互作用在反铁磁层中形成的局域交换磁场,在磁场冷却时影响反铁磁层的自旋结构或磁畴结构及双层膜中的交换偏置 关键词： 交换偏置 磁化强度     

Structural,spectroscopic, luminescence sensing and TD–DFT theoretical studies of a CuP2N-type complex

Luminescent cuprous complexes are an important class of coordination compounds due to their relative abundance, low cost and ability to display excellent luminescence. The title heteroleptic cuprous complex, [2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl-κ²P,P′](2-phenylpyridine-κN)copper(I) hexafluoridophosphate, rac-[Cu(C₄₄H₃₂P₂)(C₁₁H₉N)]PF₆, conventionally abbreviated rac-[Cu(BINAP)(2-PhPy)]PF₆ ( I ), where BINAP and 2-PhPy represent 2,2′-bis(diphenylphosphanyl)-1,1′-binaphthyl and 2-phenylpyridine, respectively, is described. In this complex, the asymmetric unit consists of a hexafluoridophosphate anion and a heteroleptic cuprous complex cation, in which the cuprous centre in a CuP₂N coordination triangle is coordinated by two P atoms from the BINAP ligand and by one N atom from the 2-PhPy ligand. Time-dependent density functional theory (TD–DFT) calculations show that the UV–Vis absorption of I should be attributed to ligand-to-ligand charge transfer (LLCT) characteristic excited states. It was also found that the paper-based film of this complex exhibited obvious luminescence light-up sensing for pyridine.     

Synthesis, structure and nuclease activity of copper complexes of disubstituted 2,2′-bipyridine ligands bearing ammonium groups

A series of Cu(II) complexes of disubstituted 2,2′-bipyridine bearing ammonium groups [Cu(L¹⁻⁴)₂Br]⁵⁺ (1–4, L¹ = [5,5′-(Me₂NHCH₂)₂-bpy]²⁺, L² = [5,5′-(Me₃NCH₂)₂-bpy]²⁺, L³ = [4,4′-(Me₂NHCH₂)₂-bpy]²⁺, L⁴ = [4,4′-(Me₃NCH₂)₂-bpy]²⁺ and bpy = 2,2′-bipyridyl) were synthesized, of which complexes 1 and 4 were structurally characterized. Both coordination configurations of Cu(II) ions can be described as distorted trigonal bipyramid. The interaction between all complexes and CT-DNA was evaluated by thermal-denaturation experiments and CD spectroscopy. Results show that the complexes interact with CT-DNA via outside electrostatic interactions and their binding ability follows the order: 1 > 2 > 3 > 4. In the absence of any reducing agents, the cleavage of plasmid pBR322 DNA by these complexes was investigated and the hydrolysis kinetics of DNA was studied in Tris buffer (pH 7.5) at 37 °C. Obtained pseudo-Michaelis–Menten kinetic parameters: 15.0, 13.6, 2.01 and 1.69 h⁻¹ for 1, 2, 3 and 4, respectively, indicate that complexes 1 and 2 exhibit very high DNA cleavage activities. According to their crystal data, the high nuclease activity may be attributed to the strong interaction of the metal moiety and two ammonium groups with phosphate groups of DNA.     

Regiospecific organocatalytic asymmetric aldol reaction of methyl ketones and alpha,beta-unsaturated trifluoromethyl ketones

[structure: see text]. The aldol reaction of methyl ketones and alpha,beta-unsaturated trifluoromethyl ketones occurred under mild conditions with the combination of proline-derived N-sulfonylamide and trifluoroacetic acid as the catalyst to give the corresponding unsaturated alpha-trifluoromethyl tertiary alcohols in high yields with good enatioselectivities.