Sulfonylation of 1,4-Diazabicyclo[2.2.2]octane: Charge-Transfer Complex Triggered C−N Bond Cleavage

A novel charge-transfer complex triggered sulfonylation of 1,4-diazabicyclo[2.2.2]octane (DABCO) with mild reaction conditions has been developed. The formation of a charge-transfer complex between electron-withdrawing (hetero)aryl sulfonyl chloride and DABCO allows the synthesis of N-ethylated piperazine sulfonamide in good yields. The reaction has a high functional group tolerance. Spectroscopic studies confirmed the charge-transfer complex formation between sulfonyl chlorides and DABCO, which facilitates the C−N bond cleavage of DABCO.     

东祁连山高寒灌丛六种灌木植物的光谱特征分析

高寒灌丛是青藏高原生态系统的重要组成部分,研究高寒灌丛对青藏高原生态系统的系统研究具有重要的意义。但是长期以来,由于地处偏远而交通欠发达、加之生长条件严酷,造成青藏高原高寒灌丛相关研究较为困难。遥感探测技术,可以克服地理及环境造成的困难,而且可以进行大面积、无损的探测,因此,可以采用遥感探测技术进行青藏高原的高寒灌丛研究。传统的高分辨率遥感探测技术,由于常常采用的是RGB三个波段,对不同植物的辨别精度低,对应植物的NDVI指数和RVI指数差异性较小,不能有效区分各类植被。同时,高光谱反射率曲线和辐照度曲线,蕴含上千波段的光谱信息,若选择某一单一波段来进行植被探测,则光谱信息损失非常大,反应出来的灌丛特征不明显,结果置信度低。为了区别高寒灌丛植被,利用高光谱技术对灌丛开展光谱特征分析,为青藏高原灌丛的遥感探测提供理论支持。本研究借助美国FieldSpec4高分辨率地物光谱仪,在东祁连山马牙雪山景区内采集头花杜鹃（Rhododendron capitatum Maxim.）、鬼见愁（Caraganajubata (Pall.) Poir.）、金露梅（Potentillafruticosa L.）、高山柳（Salix cupularis）、甘肃瑞香（Daphne tangutica Maxim.）和鲜黄小檗（Berberisdiaphana）六种典型灌木植物的室内光谱数据,通过反射率（REF）、吸收率（ABS）及其一阶微分（GREF和GABS）的变换,进一步提高灌木植物光谱曲线间的可辨析度,分析并筛选出敏感波段,而后通过各个波段之间的相互组合计算NDVI′值和RVI′值,并且以TM设置波段计算的NDVI值和RVI值作为参考,筛选出优于TM波段且差值最大的波段组合确定为最优模型。结果表明：(1）灌木植物对太阳辐射吸收形成的光谱特征曲线与大多数植物相似,但与草本植物相比,灌木植物的第一个波谷发生了左移现象;(2）灌木植物在某些敏感波段中反映出独有的光谱特征,通过REF,ABS,GREF和GABS变换,可以进一步扩大,利用这一特点可以筛选出敏感波段,进行灌丛分类和识别;(3）六种灌木植物光谱值差异较大,且数值相对较为稳定的波段有550～680,860～1 075,1 375～1 600和1 900～2 400 nm,因此可选取这四个波段为敏感区进行灌木植物识别;(4）利用575～673和874～920 nm敏感波段的REF均值或者685～765,556～590,635～671和1 117～1 164 nm敏感波段的GABS面积,计算的NDVI值和RVI值可以有效辨别六种灌木植物。     

货运动车组装载门凹陷对隧道内会车压力波的影响

随着我国技术经济水平的提高,电子商务产业快速发展,货运动车组应运而生。采用有限体积方法和重叠网格方法,以及SST k-ω高雷诺数湍流模型,数值模拟研究时速350 km的货运动车组在隧道内交会的压力波,探究货运动车组车体结构即装载门凹陷对隧道内交会压力波的影响。实车试验结果验证了本文数值模拟方法的准确性。研究结果表明,凹陷的装载门使平直车身处的最大正压值增大约20%~30%,且有无凹陷的装载门中心最大正压值的差异百分比维持在35%~80%,最大负压值差异百分比在20%~25%。     

15×10~4m~3超大型油罐应力测试与数值模拟分析

兰州原油末站大型油罐群,是我国首次在饱和黄土地基修建的大型储油设施。依托其中一座15×104 m3超大型非锚固油罐,开展了现场充水测试罐壁静态应力的试验研究。通过粘贴在油罐罐壁的应变计,测试充水过程中罐壁应力的变化规律,并采用有限元对15×104 m3超大型油罐进行应力分析。测试结果表明:罐壁的环向应力随充水水位的增加基本呈线性关系。数值模拟计算表明,罐壁环向应力最大值发生在第二圈罐壁和第三圈罐壁相连接的位置。由于罐壁上部设置了抗风圈和加强圈,有效地控制了罐壁的径向位移,使罐壁环向应力和竖向轴向应力在加强圈和抗风圈附近发生波动。将有限元数值模拟计算的罐壁环向应力分布情况与实测应力进行比较,两者总体吻合较好。上述研究结果可为超大型储罐在黄土地基的设计和建造提供技术依据和设计参数验证。     

Energy Band and Josephson Dynamics of Spin-Orbit Coupled Bose——Einstein Condensates

We theoretically investigate the energy band structure and Josephson dynamics of a spin-orbit coupled Bose-Einstein condensate in a double-well potential. We study the energy band structure and the corresponding tunneling dynamics of the system by properly adjusting the SO coupling, Raman coupling, Zeeman field and atomic interactions. The coupled effects of SO coupling, Raman coupling, Zeeman field and atomic interactions lead to the appearance of complex energy band structure including the loop structure. Particularly, the emergence of the loop structure in energy band also depends on SO coupling, Raman coupling, Zeeman field and atomic interactions. Correspondingly, the Josephson dynamics of the system are strongly related to the energy band structure. Especially, the emergence of the loop structure results in complex tunneling dynamics, including suppression-revival transitions and self-trapping of atoms transfer between two spin states and two wells. This engineering provides a possible means for studying energy level and corresponding dynamics of two-species SO coupled BECs.     

Tb0.3Dy0.7(Fe0.9T0.1)1.95合金的结构、自旋重取向和穆斯堡尔谱

系统研究了室温下Tb_0.3Dy_0.7(Fe_0.9T_0.1)_1.95(过渡金属元素T=Mn，Fe，Co，B，Al，Ga)合金中ⅢA族金属和过渡金属元素T替代Fe对结构、自旋重取向和穆斯堡尔谱的影响.结果发现，不同金属T替代Fe，Tb_0.3Dy_0.7(Fe_0.9T_0.1)_1.95，合金具有相同的MgCu₂型立方Laves相结构；Al，Ga替代使Tb_0.3Dy_0.7(Fe_0.9T_0.1)_1.95合金的易磁化方向在{110}面逐渐偏离了立方晶体的主对称轴，即自旋重取向，B，Mn，Co替代未使易磁化轴发生明显转动；Al，Ga元素替代使超精细场H_hf略有下降，B，Mn替代对超精细场H_hf的影响不大，而Co元素替代使超精细场H_hf有较大增加；所有元素替代使同质异能移IS有所增加；B，Al，Ga和Mn替代使四极劈裂Q_s增加，而Co替代使四极劈裂Q_s下降. 关键词： 立方Laves相 自旋重取向 穆斯堡尔谱     

Motion of influential players can support cooperation in Prisoner’s Dilemma

We study a spatial Prisoner’s dilemma game with two types (A and B) of players located on a square lattice. Players following either cooperator or defector strategies play Prisoner’s Dilemma games with their 24 nearest neighbors. The players are allowed to adopt one of their neighbor’s strategy with a probability dependent on the payoff difference and type of the given neighbor. Players A and B have different efficiency in the transfer of their own strategies; therefore the strategy adoption probability is reduced by a multiplicative factor (w < 1) from the players of type B. We report that the motion of the influential payers (type A) can improve remarkably the maintenance of cooperation even for their low densities.     

Theoretical Study on the Excited-state Intramolecular Hydrogen Abstraction Reactions of Butanal

The excited-state intramolecular hydrogen abstraction reactions of butanal have been investigated using the CAS-MP2/6-311＋G^＊//CASSCF/6-31G^＊ methods. Calculated results show that the hydrogen transfer induced fluorescence quenching of the n,π^＊-excited state of covalent butanal with three paths： （1） The first path corresponds to direct S0-react reconstitution, which involves the first S1 decay by partial hydrogen atom transfer. （2） The second stepwise mechanism can be viewed as a full hydrogen atom transfer followed by a partial hydrogen atom back transfer, electron transfer （near S1/S0 or S0-TS） and finally a proton transfer to S0-react. （3） On the triplet surface, the surface crossing to the singlet state would be clearly much efficient at the T1/S0 region due to the large SOC value of 8.3 cm^-1. The S0-react decay route from T1/S0 was studied with an intrinsic reaction coordinate （IRC） calculation at the CASSCF level, resulting in the S0-React minimum.     

Fe3+掺杂TiO2光催化纤维材料的制备及表征

以棉花纤维为模板制备了一系列Fe3+掺杂的、具有中空纤维结构的TiO2光催化材料(Fe3+/TiO2), 利用热重分析(TG)、扫描电子显微镜(SEM)、X射线衍射(XRD)、zeta电位、红外光谱(IR)和紫外-可见光谱(UV-Vis)等技术对其形貌、晶体结构及表面结构、光吸收特性等进行了表征. 以亚甲基蓝(MB)溶液的脱色降解为模型反应, 考察了不同Fe3+掺杂量的样品在太阳光下的光催化性能. 结果表明, 用模板法制备的Fe3+/TiO2中空纤维结构材料表面存在大量纳米微粒(平均尺寸约12 nm); Fe3+可能均匀分散于锐钛矿结构的TiO2中, 部分取代Ti4+的晶格位置, 既拓宽了TiO2的光谱响应范围, 又形成了TiO2晶体结构的缺陷, 使其表面带负电荷. 在太阳光条件下, 该纤维结构材料较纯TiO2对MB溶液具有更好的光催化脱色降解效果, 且Fe3+的掺入量显著影响该纤维材料的催化性能; 当Fe3+掺杂量为0.15%(w), 在500 ℃焙烧2 h所得中空纤维材料的催化性能最好, 2 h即可使MB溶液的脱色降解率达93%; 重复使用5次仍可使MB溶液的脱色降解率保持在90%以上, 且该催化剂材料易于离心分离去除. 因此, 以该模板合成法, 通过Fe3+的掺杂有望使TiO2成为一种低或无能耗、高活性的绿色环保型催化材料.     

共价作用于自组装膜修饰电极表面的多巴胺电化学行为研究

在过去的半个世纪里,由于多巴胺 (DA)在神经传导中的重要作用,引起了分析工作者尤其是电分析工作者的广泛兴趣.