穿心莲内酯硫酸酯化反应体系中四个新的衍生物的分离与表征

通过色谱方法, 从复杂的穿心莲内酯硫酸酯化反应体系中分离获得4个新的穿心莲内酯衍生物, 应用谱学方法进行了表征. 主要利用1H NMR, 13C NMR, DEPT, 1H-1H COSY, HSQC, HMBC及NOSEY等1D和2D NMR技术, 并通过与母体化合物NMR数据的对比分析, 鉴定这4个化合物分别为3,19-二羟基-8,11,13-赖百当三烯-15,16-内酯(1), 3-羟基-8,11,13-赖百当三烯-15,16-内酯-19-硫酸酯(2), 8,11,13-赖百当三烯-15,16-内酯-3,19-二硫酸酯(3), 3-羟基- 8(R)-12(S)-8(12)-环氧-13-赖百当烯-15,16-内酯-19-硫酸酯(4).     

苄嘧磺隆印迹聚合物的波谱分析及吸附性能研究

以苄嘧磺隆为模板分子, α-甲基丙烯酸为功能单体, 三甲氧基丙烷三甲基丙烯酸酯为交联剂, 二氯甲烷为致孔剂, 在20 ℃温度下, 采用紫外引发沉淀聚合方法制备了苄嘧磺隆分子印迹聚合物. 紫外光谱和核磁共振氢谱实验提示了聚合前模板分子与功能单体之间的相互作用主要是分子间氢键, 分子间氢键相互作用能和双氢键的键距由Hyperchem 7.0和Gaussian 03W软件分别计算为: －28.6163 kJ/mol和0.179～0.181 nm. 制备的印迹聚合物在高效液相色谱和吸附动力学实验中都表现出对模板分子有较强的吸附作用.     

Two-photon spectroscopic behaviors and photodynamic effect on the BEL-7402 cancer cells of the new chlorophyll photosensitizer

The spectroscopic properties of a new chlorophyll derivate photosensitizer(CDP) are studied under the excitation wavelengths at 800 and 400 nm using femtosecond pulses from a Ti:sapphire laser.The damaging effect of CDP on the BEL-7402 cancer cells is also investigated upon two-photon illumination at 800 nm.The normalized fluorescence spectra of CDP in tetrahydrofuran(THF) show that two-photon and one-photon spectra have the same distributions and the same emission bands(675 nm).The life-times of two-and one-photon induced fluorescence of this molecule are of the order of 5.0 ns.By comparing the data it is shown that there is some difference between the two lifetimes,but the differ-ence is less than one nanosecond.The two-photon absorption cross section of the molecule is also measured at 800 nm and estimated as about σ′2 ≈ 31.5×10-50 cm4·s·photon-1.The results of two-photon photodynamic therapy(TPPDT) tests show that CDP can kill all of the tested cancer cells according to the usual Eosine assessment.Our results indicate that the two-photon-induced photophysical,photo-chemical and photosensitizing processes of CDP may be basically similar to those of one-photon ex-citation.These behaviors of the sample suggest that one may find other possible methods to estimate some photosensitizers' effects in details such as their distribution in cells and the reactive targets of the sub-cellular parts of some tumor cells via two-photon excitation techniques.     

弹塑性摩擦接触问题形状设计灵敏度分析

提出了一种计算二维有限变形弹塑性摩擦接触问题形状设计灵敏度的算法. 采用主动集策略和mortar方法处理接触边线上的约束条件. 在mortar接触边线的切线和法线方向上采用相同的名义罚函数,提出基于名义罚函数的移动摩擦锥算法来正则化接触约束条件,发展了一种新的二维多体有限变形摩擦接触算法. 在此基础上, 通过将离散形式的摩擦接触问题控制方程对形状设计变量微分,得到了该路径相关问题的直接微分法解析设计灵敏度计算格式, 其节点位移灵敏度方程在每个增量步不用迭代、直接求解. 与国际上现有的二维多体有限变形摩擦接触问题的解析设计灵敏度算法相比,本算法不需分解为法向和切向推导,表达式较简洁,便于编程实现. 数值算例验证了算法的精度和有效性.      

不同围压作用下非均匀岩石水压致裂过程的数值模拟

从岩石细观非均匀性的特点出发，提出一个描述非均匀材料渗流和破裂相互作用的数值模型。在这个数值模型中，单元的力学、水力学性质根据统计分布而变化，以体现材料的随机不均质性，材料在开裂破坏过程中流体压力传递通过单元渗流，损伤耦合迭代来实现。算例表明，该模型能较好地模拟出岩石类材料在水力压裂作用下，微结构非均匀分布和不同围压比对破裂模式、失稳压力的影响，非均匀性导致试件的开裂压力、失稳压力明显不同，裂纹扩展路径不规则发展，模拟结果和实验结果较为一致。     

主动控制压电旋转悬臂梁的参数振动稳定性分析

在工程实际中旋转机械由于制造和加工误差,装配的不均匀性等原因,往往会脉动运行,这将使得机械系统发生参数振动. 当脉动参数满足一定关系时,这种参数振动将会失稳,进而影响机械结构的正常运转. 本文针对这一问题,引入压电材料对 脉动旋转悬臂梁系统的振动进行控制,研究主动控制悬臂梁系统的参数振动优化设计问题,采用 Hamilton 变分原理与一阶 Galerkin 离散相结合的方法,建立了受速度反馈传感器主动控制的压电旋转悬臂梁的一阶近似线性控制方程. 运用多尺度方法,得到了压电旋转悬臂梁系统在发生1/2亚谐波参数共振时稳定性边界的控制方程,并利用直接分析方法验证了解析摄动解的正确性. 将摄动解中临界阻尼比和轮毂角速度脉动幅值的无量纲参数作为评价系统稳定性能的指标. 通过数值算例,分析了轮毂半径、轮毂角速度平均值和脉动幅值、梁长以及速度传感器的反馈增益系数对系统稳定性区域的影响. 研究结果表明,梁长、轮毂半径、脉动幅值会降低系统稳定性,反馈增益系数可以提高系统稳定性,而轮毂角速度平均值与系统稳定性之间有非单调的关系. 为进一步设计压电旋转机械结构提供了理论依据.      

主动射流控制水翼空化的数值模拟与分析

为了改善高速流动工况下水翼吸力面上流场的空化特性,提出了水翼表面主动射流对绕水翼周围流动加以控制的方法.基于密度分域滤波的FBDCM混合湍流模型联合Zwart-Gerber-Belamri空化模型,分析了来流空化数为0.83,来流攻角为8°,射流位置距水翼前缘为x=0.19c时,主动射流对于水翼吸力面上流动的空化特性和水动力特性影响.对回射流的强度进行了量化分析,以探究回射流与流场空化特性的关系.数值分析结果表明,在射流水翼吸力面上的时均空泡体积为原始水翼的1/15,使得流场内空化流动由云空化状态转变为较为稳定的片空化状态,显著地削弱了云空化的发展.此外,射流极大地改善了水翼的水动力性能,使得水翼的升阻比较原始水翼提高了22.9%,空泡的脱落频率减少了26.2%,空泡脱落所引起的振幅减小了9.1%.射流大幅降低了水翼吸力面上低压区面积,水翼吸力面上流体的逆向压力减小,回射流强度降低;同时,射流使水翼吸力面上的边界层减薄,增强了流动的抗逆压梯度能力,一定程度上阻挡了回射流向水翼前缘的流动,这也从机理上分析了主动射流抑制空化的原因.      

Self-supported metal sulphide nanocrystals-assembled nanosheets on carbon paper as efficient counter electrodes for quantum-dot-sensitized solar cells

Developing efficient counter electrodes (CEs) and quantum dots made of earth-abundant and non-toxic elements is essential but still challenging for quantum dot-sensitized solar cells (QDSSCs). Here, we report a facile strategy to prepare self-supported and robust CoS₂ and NiS nanocrystals-assembled nanosheets directly grown on carbon paper (MSx NS@CP) as efficient counter electrodes for QDSSCs. Such CEs integrate the merits of fast electron transfer from interconnected conductive scaffold, efficient mass transfer from hierarchically vertical nanosheet on 3D open substrate, as well as abundant highly active catalytic sites from metal sulphide nanocrystal units. As a result, QDDSCs based on such CoS₂ NS@CP and NiS NS@CP CEs achieve a PCE of 8.88% and 7.53%, respectively. The detailed analyses suggest that CoS₂ NS@CP has the highest catalytic activity and shows the lowest charger transfer resistance, leading to the highest PCE. These findings may inspire the design and exploration of other self-supported efficient CEs by integrating highly active catalysts onto 3D conductive networks for efficient QDSSCs.