Al-Zn-Mg-Cu合金双级时效析出行为的TEM研究

Al-Zn-Mg-Cu合金是一种时效强化高强变形铝合金,长期以来广泛应用于航空航天等工业领域[1,2].其性能主要由时效过程中的时效析出相决定.研究不同时效状态下合金时效析出相的显微组织结构,对明确组织与性能的关系、确定合理的热处理工艺、改善合金的综合性能具有重要的理论意义和工程实用价值.     

荧光素钠与牛血清蛋白相互作用的荧光光谱研究及其分析应用

采用荧光光谱研究了荧光素钠与牛血清蛋白(BSA)间的相互作用, 根据荧光淬灭相关方程分别计算了淬灭速率常数、结合常数、结合位点数及热力学参数, 确定了BSA对荧光素钠的淬灭机理及作用方式, 根据能量转移理论求得荧光素钠与BSA的结合距离及能量转移率, 结合三维、同步荧光光谱研究了荧光素钠对BSA构象的影响|在一定范围内荧光素钠的淬灭程度与BSA浓度成正比, 据此建立一种荧光素钠测定蛋白的方法, 线性范围为0.15×10^－7～15× 10^－7 mol•L^–1, 方法具有高灵敏度, 检测极限为0.146×10^－8 mol•L^–1, 文中还考察了不同pH值和干扰物质对于测定结果的影响, 用于人血清中总蛋白含量测定结果与考马斯亮蓝法基本一致.     

Asymmetric cycloaddition of β,γ-unsaturated α-ketoesters with electron-rich alkenes catalyzed by a chiral Er(OTf)3/N,N'-dioxide complex: highly enantioselective synthesis of 3,4-dihydro-2H-pyrans

The asymmetric inverse-electron-demand hetero-Diels-Alder (HDA) reactions of β,γ-unsaturated α-ketoesters with electron-rich alkenes were investigated, with an N,N'-dioxide/erbium(III) complex employed as the catalyst. Quantitative conversion of the β,γ-unsaturated α-ketoesters and excellent enantioselectivities (up to >99% ee) and diastereoselectivities (up to >99:1 d.r.) were observed for a broad range of substrates by using a 0.5-0.05 mol% catalyst loading under mild reaction conditions. The reaction could be scaled up to the gram scale with the same results. In addition, this was the first application of Er(OTf)(3) to the asymmetric inverse-electron-demand HDA reaction and it behaved as an efficient catalyst. Moreover, the synthetic utility of this methodology was demonstrated with the synthesis of key intermediates of some natural products.     

Nd3+:Gd3Sc2Al3O12 晶场能级及拟合

Nd³⁺ :GSAG是性能优良的942 nm激光晶体.用提拉法成功生长Nd³⁺ :GSAG单晶,研究其室温透射光谱,辨认位置高达29967 cm^-1的68个Nd³⁺晶场能级.对这些能级拟合了自由离子及晶场Hamilton参量,拟合标准偏差为16.7 cm^-1,表明实验与计算能级符合很好.获得的Hamilton参量可用于计算Nd³⁺ :GSAG中Nd³⁺的     

双(N 氧化吡啶 2-甲醛)缩1,2-丙二胺镍配合物的合成和晶体结构

合成所得双(N-氧化吡啶-2-甲醛)缩1,2-丙二胺的镍(II)配合物[Ni(piopn)(H_2O)_2](ClO_4)_2的晶体属空间群C_s~4-C_c, 晶胞参数a=0.7397(3) nm, b=1.3187(7) nm, c=2.5502(14) nm, β=102.18(4)°. 用分子轨道理论的近似方法分析了该配合物的电子结构和分子轨道, 探讨了分子的结构特征与红外光谱的关系.     

Insight into copper-catalyzed decarboxylative thiolation of carboxylic acids in the gas phase

Organocopper complexes bearing bidentate nitrogen ligands were synthesized in the gas phase by electrospray ionization mass spectrometry. Gas-phase decarboylative thiolation reaction was carried out in the ion-trap analyzer by collision-induced dissociation and ion-molecule reaction. The carboxylic acids were finally converted to thioethers as a neutral loss via collision-induced dissociation. During this process, copper acetate acted as a catalyst, and the valence state change of copper was observed. Meanwhile, the mechanism of decarboxylative thiolation was examined. This reaction was also suitable for different carboxylic acids and bidentate nitrogen ligands in the gas phase.     

N—乙基—N—苄基苯胺合成方法的改进

以苯胺和乙醇为原料，采用ＲａｎｅｙＮｉ为催化剂，合成了Ｎ－乙基苯胺，再在相转移催化剂作用下，经苄基化反应得到标题化合物，第一步合成方法的收率比通常方法的收率提高约３０％。     

近50年鄱阳湖流域降水时空特征及其对水文过程的驱动

依照鄱阳湖流域79个国家气象站的逐月降水资料(1961~2010年),基于BCC-CSM全球气候系统模式预估数据(2014~2050年),对鄱阳湖流域降水变化趋势和空间分布变化趋势进行分析。选取赣江外洲站1961~2010年逐日径流量和1960~2010年年代径流量、输沙量数据,利用HBV水文模型、SPSS统计软件对赣江流域面雨量及径流量进行相关性分析,探讨降水特征对水文过程的驱动性。结果表明:1961~2010年间鄱阳湖流域降水量总体略呈上升趋势,降水日数呈下降趋势,降水强度增加、降水时间分布不均匀性更加明显,旱涝等极端事件发生更为频繁;年内变化特征为分布不均匀,以4~6月为汛期,其中6月降水量最大;空间分布特征总体表现为东部降水大于西部,丘陵地区降水大于平原地区;降水变化为径流量、输沙量变化等水文响应的主要驱动力,赣江流域面雨量及径流量呈显著线性相关,相关系数高达0.909。未来37年降水呈现略上升趋势,但趋势不显著。若鄱阳湖流域长期存在高能源需求及高温室气体排放,则洪涝灾害发生将更为频繁。研究为预测鄱阳湖流域水资源科学管理提供科学依据。     

A multi-objective optimization method for uncertain structures based on nonlinear interval number programming method

A multi-objective optimization method for uncertain structures is developed based on nonlinear interval number programming (NINP) method. The NINP method is employed to transform each uncertain objective function into a deterministic single-objective optimization problem. Using the constraint penalty function method, a deterministic multi-objective and non-constraint optimization problem is formulated in terms of penalty functions. Then the micro multi-objective genetic algorithm and the intergeneration projection genetic algorithm are adopted as outer layer and inner optimization operator to solve the nesting optimization problem, respectively. Finally, four numerical examples are provided to demonstrate the effectiveness of the present method.     

Acetonitrile derivatives as carbonyl synthons. One-pot preparation of diheteroaryl ketones via a strategy of sequential SNAr substitution and oxidation

The anion of 2-aryl acetonitrile derivatives reacted with a variety of heteroaryl chlorides or bromides in an S(N)Ar manifold to afford intermediate anions which were susceptible to oxidation. The addition of sodium peroxide and aqueous NH(4)OAc solution effected oxidation to afford aryl heteroaryl ketones in good yields. Aryl acetonitrile derivatives are thus umpolung-type synthons of the corresponding aryl carbonyl functionality.