浓度加和模型在化学混合物毒性评估中的应用

化学污染物总是以混合物形式存在于实际环境体系中. 化学混合物的毒性评估与预测是环境化学领域当前的研究热点与难题. 要评估与预测一个化学混合物的毒性效应, 首先要证明其是否具有加和性. 目前有3个加和参考模型即浓度加和模型(CA)、独立作用模型(IA)与效应相加模型(ES)用于化学混合物毒性的加和性检验. 如果混合物效应明显偏离加和参考模型预测效应, 则认为该混合物产生毒性相互作用, 即协同或拮抗. 选择不同的加和参考模型可能得出不同的相互作用结论. ES模型最早广泛应用, 但不能解释由同一化合物构成的所谓虚拟组合现象, 应用已开始受到限制. IA模型被认为适用于具有相异作用模式的化学物构成的混合物, 而CA模型适用于相似作用模式化学物构成的混合物并能合理解释ES模型不能解释的虚拟组合现象, 常常认为是化学混合物毒性预测的标准模型. 然而, 由于CA模型目前没有坚实的理论支持, 也不能直接联系混合物毒性作用机理, 同时在浓度-效应曲线的部分区域存在不能预测的所谓“预测盲区”, 因此, CA模型也只是一个工作模型, 需谨慎使用.     

应用质量源于设计的理念优化大鼠血浆中大黄蒽醌的分析方法

应用质量源于设计理念建立一种高效液相色谱-荧光检测法(HPLC-FLD)用于测定大鼠血浆中5种大黄蒽醌。用Plackett-Burman设计考察流动相中甲醇含量、pH值、流速、柱温和进样体积对色谱峰的分离度、理论塔板数、最末洗脱峰的保留时间和拖尾因子的影响,结果显示流动相中甲醇含量、流速和柱温对色谱系统的影响显著(p<0.05)。继而采用Box-Behnken设计结合响应面法考察上述三因素对分离度、保留时间和理论塔板数的影响。用Derringer渴求函数评价了响应值的综合作用。得出最优色谱条件为:以甲醇-0.1%(v/v)磷酸水溶液(81.4:18.6, v/v)为流动相等度洗脱,流速1.1 mL/min,柱温31℃,荧光检测激发波长为440 nm,发射波长为540 nm。建立的模型显示良好的预测性。结果表明:质量源于设计的理念可有效地应用于优化高效液相色谱分析方法。     

电场响应光子晶体

光子晶体是一种介电常数周期变化、具有光子带隙、对光路可控的新型功能材料。将对外界刺激敏感性材料引入光子晶体空隙就得到可响应光子晶体。电场响应光子晶体是由电活性材料与光子晶体结构相结合所得,可以应用于反射型彩色显示并表现出其他显示技术所没有的独特优点。本文重点介绍了电场响应光子晶体器件的结构和响应机理,并按照引入电活性材料的不同将电场响应光子晶体分为基于液晶、聚电解质水凝胶、金属有机聚合物凝胶、导电聚合物以及核壳式电场响应光子晶体,总结了近几年各类电场响应光子晶体的研究进展,提出了在反射型彩色显示器件方面的应用以及存在的问题和展望。     

氧化还原电池组等效电路模型

本文综合考虑氧化还原二次电池内部的电化学反应和电池组漏电电流,建立了氧化还原电池组的等效电路模型. 以1 kW额定输出功率的全钒液流储能电池组为例,测试电池组暂态响应和自放电曲线,确定了等效电路模型的重要参数,比较模拟结果与实验结果,计算电池组的内阻和自放电电流,可知漏电电流造成的容量损失约占系统总容量损失的60%左右.     

One- and two-photon absorption properties of two metalloporphyrin complexes

The linear and nonlinear optical properties of two metalloporphyrin complexes formed by the complementary coordination of central zinc or magnesium ions to the ligand 5, 10, 15-tri-(p-tolyl)-20-phenylethynylporphyrin are theoretically investigated by using the analytic response theory at the density functional theory level. The results indicate that the studied complexes present more symmetric geometry structures than the ligand. The charge-transfer states of the two complexes in the lower energy region are all almost degenerate but those of the ligand are well separated. The ratio of the two-photon absorption cross sections of the ligand, zinc-porphyrin and magnesium-porphyrin complexes is 1.0:1.5:1.8, demonstrating that the two-photon absorption capability can be greatly increased when the ligand is coordinated with a metal ion. Moreover, several physical micro-mechanisms including electron transitions and intramolecular charge-transfer processes are discussed to explore the differences in optical property between the ligand and two complexes.     

On the validity of planar, thick curved beam models derived with respect to centroidal and neutral axes

Most dynamic analyses of planar curved beams found in the literature are carried out based on a curved beam model which assumes that the neutral axis coincides with the centroidal axis of the curved beam. This assumption leads to governing equations of motion which are relatively simple with analysis results that have acceptable accuracy for shallow curved beams. However, when a curved beam is not shallow and/or its cross section is not doubly symmetric, the offset distance between the neutral and centroidal axes may be large enough to influence the in-plane dynamics of the curved beam even for small motion. In this paper, the validity of this underlying assumption for modeling a linear curved beam is examined. To this end, two sets of equations of motion governing the in-plane dynamics of a planar curved beam are derived, in a consistent manner for comparison, based on the linear strain-displacement relations and Hamilton’s principle. The first set of equations is derived from the displacement components measured with reference to the neutral axis of the curved beam while the second set is derived with respect to the centroidal axis of the cross section. The curved beam is considered extensional and the effects of rotary inertia and radial shear deformation are included. In addition to the curvature parameter that characterizes the wave motion for both curved beam models, an eccentricity parameter is introduced in the first model to account for the offset between the neutral and centroidal axes. The dynamic behavior predicted by each curved beam model is compared in terms of the dispersion relations, frequency spectra, cutoff frequencies, natural frequencies and modeshapes, and frequency responses. In order to ensure that the comparison is accurate, the wave propagation technique is applied to obtain exact wave solutions. It is shown that, when the curvature parameter is not small, the underlying assumption has a substantial impact on the accuracy of the linear dynamic analysis of a curved beam.     

人行桥标准行人激励荷载的构建与验证

基于Young和Ebrahimpour等学者对行人步行荷载竖向激励特征的研究成果,利用傅立叶级数模型构建了行人正常步行状态下的标准荷载激励,并从曲线形状和引起人行桥动力反应两方面与8组实测的步行荷载进行比较,验证了标准步行荷载的准确性。通过理论分析进一步讨论了均方根加速度动力反应arms与动载因子ci和相位角φi的关系,并给出了具有参考价值的结论。     

X荧光能谱分析中探测器响应函数建立方法

在X荧光能谱测量及分析过程中,通过建立探测器响应函数,可以实现对X荧光能谱中的全能峰峰形描述,有助于提高X荧光能谱分析速度、准确度和自动化程度。在X荧光能谱测量中,针对半导体探测器建立响应函数模型的理论与建模技术,文中对三种典型探测器响应函数建模方法,以及全能峰标准差、法诺因子等关键参数的求取进行了论述,并对已有研究进行了总结和比较。最后,对X荧光能谱测量中探测器响应函数建模方法给出了建议。     

ASYMPTOTIC BEHAVIOR OF THE ECKHOFF APPROXIMATION IN BIVARIATE CASE

The paper considers the Krylov-Lanczos and the Eckhoff approximations for recovering a bivariate function using limited number of its Fourier coefficients. These approximations are based on certain corrections associated with jumps in the partial derivatives of the approximated function. Approximation of the exact jumps is accomplished by solution of systems of linear equations along the idea of Eckhoff. Asymptotic behaviors of the approximate jumps and the Eckhoff approximation are studied. Exact constants of the asymptotic errors are computed. Numerical experiments validate theoretical investigations.     

金纳米粒子催化鲁米诺-异烟肼化学发光反应及其分析应用

研究发现, 在金纳米粒子存在下, 异烟肼与鲁米诺反应可产生强的化学发光. 采用响应曲面优化法中的Box-Behnken设计, 对试剂浓度进行了优化. 在优化的实验条件下, 相对化学发光强度与异烟肼的质量浓度在5.0× 10^－9～3.0×10^－7 g/mL范围内呈线性关系. 方法的检出限为4.1×10^－9 g/mL异烟肼, 相对标准偏差为1.3% (1.0×10^－7 g/mL异烟肼溶液, n＝11). 该方法已用于片剂、注射液和人血清中异烟肼含量的测定. 同时, 对化学发光反应的可能机理也进行了讨论.