机理转移法合成星形梳状聚丁二烯-g-聚甲基丙烯酸甲酯共聚物的研究

结合活性负离子聚合与原子转移自由基聚合(ATRP),采用机理转移法制备了一系列窄分布且分子量可控的星形梳状聚丁二烯-g-聚甲基丙烯酸甲酯接枝共聚物(SC-(PB-g-PMMA)).首先通过阴离子聚合,制备星形聚丁二烯,后经甲酸-过氧化氢原位环氧化对链中部分双键进行环氧化,再与原位生成2-溴异丁酸发生酯化反应,得到具有链中活性溴的星形大分子引发剂(SPB-Brn).然后,利用该大分子引发剂,采用CuCl/CuCl2/PMDETA催化体系,通过ATRP聚合单体MMA,合成出星形梳状SC-(PB-g-PMMA)聚合物.通过GPC,1H-NMR和FTIR等分析手段对合成的星形大分子引发剂及星形梳状聚合物进结构表征,证实得到目标产物,并同时研究了聚合物的热力学性质与溶液性质.     

基于二乙醇胺配体的[Dy2Co8]型配合物的合成、晶体结构和磁性分析

以二乙醇胺为配体合成了一种具有[Dy₂Co₈]核结构的配合物[Dy₂Co₈（L）₄（HL）₄（HCOO）₄（OH）₂Cl₂（CH₃OH）₂]Cl₂·4CH₃OH·2H₂O（1）（H₂L=二乙醇胺）,并对其进行了X射线单晶衍射、红外光谱、元素分析和磁性表征。该配合物属于三斜晶系,P1空间群。晶体学数据：a=1.160 4（8）nm,b=1.322 7（9）nm,c=1.465 3（9）nm,α=71.181（7）°,β=67.638（7）°,γ=65.939（7）°。在晶体结构中,每一个Dy（Ⅲ）都是九配位,而每一个Co（Ⅱ）均为六配位。     

Synthesis and Crystal Structure of a New [Mn_2Ni_2] Cubane Complex

A new Mn2Ni2 cubane complex has been synthesized and characterized by single-crystal X-ray diffraction,FT IR spectra and elemental analysis.The title compound [MnIII2NiII2(hmp)4(N3)4(O2CR)2](hmp-is the anion of 2-pyridinemethanol and O2CR-is α-na-phthaleneacetate)crystallizes in the monoclinic system,space group P21/c with a = 10.519(5),b = 22.109(10),c = 23.235(9),β = 106.096(17)o,C48H42Mn2N16Ni2O8,Mr = 1198.28,V = 5192(4)3,Dc = 1.533 g/cm3,F(000)= 2448,μ = 1.258 cm1,Z = 4,the final R = 0.0875 and wR = 0.2020 for 3398 reflections with I > 2σ(I).X-ray diffraction analysis reveals that each Mn(III)center is octahedrally coordinated by two nitrogen atoms of azide anions and three oxygen atoms from three 2-pyridinemethanol anion ligands together with one oxygen atom from naphthaleneacetate.Each Ni(II)is octahedrally coordinated by two nitrogen atoms of 2-pyridinemethanol anion ligands as well as three oxygen atoms from three 2-pyridinemethanol anion ligands and one oxygen atom from naphthaleneacetate.     

纺锤形介孔纳米二氧化锰的控制合成

在KMnO₄和葡萄糖水溶液体系中, 用一步水热法控制合成了介孔MnCO₃纳米纺锤体, 通过焙烧MnCO₃前驱体可以得到介孔纳米MnO₂, 且保持了原有的纺锤体形貌. 用X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱、扫描电镜(SEM)、透射电镜(TEM)和N₂吸附-脱附(BET)对制备的样品进行了形貌和结构的表征. 并对反应时间、反应物浓度等对产物形貌的影响进行了研究. 实验结果表明, 反应时间和葡萄糖的浓度对MnCO₃前驱体的尺寸和形貌具有重要影响, MnCO₃纵横比可从1.35:1到2.89:1之间改变. 并初步探讨了介孔MnO₂纺锤体的生长机制, MnO₂ 孔的形成是由于焙烧葡萄糖降解形成的纳米碳颗粒所致.     

Structural modification of C60 films induced by 300-keV Xe-ion irradiation

The structural modification of C 60 films induced by 300-keV Xe-ion irradiation was investigated.The irradiated C 60 films were analysed using Fourier transform infrared spectroscopy,the Raman scattering technique,ultraviolet/visible spectrophotometry and atomic force microscopy.The analysis results indicate that the Xe-ion irradiation induces polymerization and damage of the C 60 molecule and significantly modifies the surface morphology and the optical property of the C 60 films.The damage cross-section for the C 60 molecule was also evaluated.     

地表水总有机碳含量紫外-可见光谱检测方法

总有机碳是以碳含量评价水质有机污染的指标,可以反映水体受污染程度。目前地表水总有机碳检测多采用现场取样后实验室分析检测方法,该方法存在费时费力、操作复杂、二次化学污染等缺点。紫外-可见光谱法具有环保、操作简便、可实时在线原位检测等优点,在地表水总有机碳检测中具有很好的应用前景。针对总有机碳检测问题,采用了一种基于自适应增强学习的区间偏最小二乘回归方法,该方法将总有机碳吸收光谱波段分为若干子区间,初始化训练样本权重, 依次在各子区间建立偏最小二乘回归模型,根据子区间模型预测误差率计算该子区间预测结果的权重系数,并更新下一子区间训练样本权重,最后将各子区间模型预测结果线性加权得到总有机碳的检测结果。实验配制总有机碳标准溶液浓度25～150 mg·L-1共43个样品,第一时间段采集35个总有机碳标准样品光谱分为训练集和测试集,建立并验证总有机碳检测算法模型。为评价算法模型鲁棒性,在另一时间段采集剩余的8个标准样品光谱进行反测验证。实验结果表明,采用基于自适应增强学习的区间偏最小二乘回归法建立的总有机碳定量模型具有较高的精度和鲁棒性,分组验证和反测验证的预测均方根误差分别为1.304和1.533 mg·L-1,均优于偏最小二乘回归和极限学习机方法。为进一步验证该方法的有效性,使用该建模方法预测生活污水的总有机碳含量。实际地表水样本取样于河北石家庄藁城污水处理厂排污口污水及河北先河公司园区的生活污水,经稀释后共获得50组地表水样本,采用SPXY方法分为训练集33组水样,测试集17组水样。在实际水样检测中,采用净信号分析方法进行光谱预处理,降低总有机碳与其他水质参数间的交叉干扰;分组验证预测均方根误差为3.26 mg·L-1,平均绝对值百分比误差为3.46%。综上所述,基于自适应增强学习的区间偏最小二乘回归方法,可以快速准确地对地表水中总有机碳进行检测,为在线水质总有机碳检测提供了方法支撑。     

Co助剂对甲烷脱氢芳构化反应中Mo/MCM-22催化剂积碳行为的影响

 甲烷在Co-Mo/MCM-22催化剂上进行无氧脱氢芳构化反应的评价结果表明,Co的添加大大提高了Mo/MCM-22催化剂的催化活性和稳定性. 采用程序升温表面加氢反应、程序升温表面二氧化碳反应和热重分析等方法对催化剂表面的积碳物种进行了表征. 结果表明,反应后的催化剂表面主要存在两种积碳物种,H2主要与高温峰对应的积碳发生反应,而CO2对高温峰对应的积碳和低温峰对应的积碳都产生影响. Co的添加对高温峰对应的积碳和低温峰对应的积碳都有明显的抑制作用.     

太阳系界面动态磁场问题的H(curl,Ω)有限元最优误差估计

本文利用具有最优插值逼近的界面棱边元来逼近太阳系界面动态磁场问题,采用界面对齐的三角剖分对区域进行划分且跳转接口被δ-带包围.利用界面棱边元的性质,得到了关于动态磁场的最优误差估计,收敛结果为O(τ+h),其中τ和h分别是时间和空间方向的剖分步长.最后,对太阳系界面模型的动态磁场进行了数值模拟.     

孔型硅光子晶体中折叠式马赫-曾德尔干涉仪(英文)

设计了基于孔型硅光子晶体的折叠式马赫-曾德尔干涉仪.它由一个光反射器和几个光分束器构成.在干涉仪中,窄光束依赖自准直效应进行传输.利用时域有限差分法研究了折叠式马赫-曾德尔干涉仪的特性.结果表明,在0.255～0.270c/a的归一化频率范围内,干涉仪的两个透射谱均为正弦形且强度互补,透射谱的透射峰间距随着干涉仪两臂的光程差的增大而减小.该折叠式干涉仪结构紧凑,尺寸比非折叠式光子晶体马赫-曾德尔干涉仪要小许多,有望作为信道解复用器应用于光子芯片中.     

Effect of microstructure on ~3He migration in TiT_(1.9) films

Two kinds of films were prepared to study the effect of microstructure on helium migration in Ti tritides. Both films showed different release behaviors and helium bubble distributions. In the film consisting of columnar grains, a twolayered structure was observed. Inclusions with a strip feature were found at the grain boundary, and no helium bubbles were distributed in these inclusions. However, helium preferred to migrate to the boundaries of these inclusions. Bubble linkage as a ribbon-like feature developed parallel to the film surface in the film consisting of columnar grains. More cracks were developed at the grain boundaries of the film consisting of columnar grains, although the helium content in the film consisting of columnar grains was less than that in the film consisting of equiaxed grains. A surface region with a small number of bubbles, or "depleted zone", was observed near the surface. The cracks extending to the film surface were the pathways of the critical helium released from the film. The helium migration was strongly influenced by the grain microstructure.