PSO-LSSVM对LIBS定量分析精度的提高

针对土壤定量分析受基体效应影响大，LIBS定量分析精度不佳等问题，采用粒子群算法对LSSVM进行优化，提高模型的精确度。选取Pb Ⅰ 405.78 nm和Cr Ⅰ 425.44 nm作为分析谱线进行分析。采集十二个不同浓度样品的特征光谱，每个浓度样品在不同点采集20组数据，将其中17组数据设为训练集，3组数据设为预测集，用LSSVM和PSO-LSSVM两种方法建立定标模型。对比两种模型的拟合相关系数（R2）、训练集均方根误差（RMSEC）和预测集均方根误差(RMSEP)。由于自吸收效应的影响，随着浓度的增加，预测值逐渐低于实际值，LSSVM定标模型的拟合程度较低，无法达到实验要求，模型性能有待提高。利用粒子群算法对LSSVM的模型参数惩罚系数和核函数参数进行优化，得到最佳的参数组合，Pb元素为(8 096.8, 138.865 7)，Cr元素为(4 908.6, 393.563 5)，用最佳的参数组合构建LSSVM的定标模型。相比于LSSVM，PSO-LSSVM定标模型的精确度更高，Pb和Cr元素的R2提高到了0.982 8和0.985 0，拟合效果明显提升。Pb和Cr元素的训练集均方根误差由0.026 0 Wt%和0.027 2 Wt%下降到0.022 4 Wt%和0.019 1 Wt%，预测集均方根误差由0.101 8 Wt%和0.078 8 Wt% 下降到0.045 8 Wt%和0.042 0 Wt%，模型的稳定性进一步提高。说明PSO-LSSVM算法能够更好地降低土壤基体效应和自吸收效应带来的影响，提高分析结果的精确度与稳定性。     

Oxotitanium(IV) complexes of some bis‐unsymmetric Schiff bases: Synthesis,structural elucidation and biomedical applications

A number of oxotitanium(IV) complexes of the type TiOL with bis‐unsymmetric dibasic tetradentate Schiff base (LH₂) containing ONNO donor atoms have been synthesized. Mono‐Schiff base (OPD‐HNP) was prepared by the condensation of 1:3 molar ratio of 2‐hydroxy‐1‐naphthaldehyde (HNP) with o‐phenylenediamine (OPD). Dibasic unsymmetric tetradentate diamine Schiff bases were prepared by the reaction of OPD‐HNP with 2‐hydroxyacetophenone, 2‐hydroxypropeophenone, benzoylacetone, acetylacetone and ethylacetoacetate. Further, titanylacetylacetonate was reacted with these ligands to obtain their metal complexes. On the basis of analytical and physiochemical data, the formation of complexes as TiOL was suggested having square pyramidal geometry. Quantum mechanical approach also confirmed this geometry. The assessment of the synthesized ligands and their complexes showed that some behave as good inhibitors of mycelial growth against selected phytopathogic fungi but weak inhibitors against some selected bacteria. A few of them also showed antioxidant properties.     

近红外光谱结合共识模型快速检测果酒的总酚含量

果酒发酵中的多酚是引起果酒口感、颜色变化的重要因素。为保证果酒品质,有必要开发一种快速监测发酵过程中多酚含量变化的技术。收集不同批次成熟期的蓝莓、桑葚为原料,分别碾压成汁,同时按比例混合二者,于小型发酵罐进行发酵。通过离线收集不同发酵时段的发酵液于离心管,高速离心后取上清液置于棕色瓶保存,共计得到48个果酒发酵样本。将上清液置于三个平行样比色皿,以傅里叶快速变换近红外光谱仪(FT-NIR)采集其透射光谱,取平均值作为该样本的光谱信号。然后将棕色瓶内的发酵液以国标法(即以标准液的吸光度值制定标准曲线)测定各样品的总酚含量,以duplex法计算样本光谱之间的距离且按2∶1的比例划分为训练集和预测集。采用间隔偏最小二乘法(iPLS)将训练集样本的透射光谱与总酚含量之间构建定量模型,间隔数从2依次变化到60个。该研究创新之处是使用共识方法融合多个已构建好的iPLS成员模型,按一定的共识规则分配权系数。通过各成员模型交互验证的残差及其残差之间的相关性来优化各成员模型的线性组合,以拉格朗日乘数法求解各成员模型的权系数,使间隔偏最小二乘-共识模型(consensual iPLS,CiPLS)的交互验证均方根误差最小。相比于全局PLS模型、划分不同间隔数量时的iPLS模型,CiPLS均具有较小的预测误差。当划分39个间隔时由三个iPLS成员模型(即14th,16th,18th)组成的共识模型误差最小为124.2,交互验证相关系数为0.944,对预测集样本的预测均方根误差为163.4,预测相关系数为0.931,预测性能均优于PLS和iPLS模型。另外,作为对比选用连续投影算法与无信息变量剔除法来优化光谱模型,其预测性能均不及本文提出的共识模型。分析各iPLS模型预测残差之间的相关性,发现共识模型主要是融合那些具有较高预测性能且模型间较低相关性的成员模型。结果表明,光谱分析结合共识方法可提高回归模型的预测精度、减少建模所需变量数,能够用于果酒总酚含量的离线快速检测。     

受限亚音速气流中倒置悬臂壁板静气弹稳定性的理论及实验研究

板壳结构在航空航天、高速列车、能量采集等诸多工程领域已经得到了广泛应用. 将悬臂壁板倒置于轴向气流中并在壁板周围流场中设置刚性壁面可有效地调控壁板的失稳速度, 是俘能器优化设计的重要措施之一. 但针对刚性壁面作用下亚音速气流中倒置悬臂壁板的失稳机制仍需要开展深入研究. 本文以受限亚音速气流中倒置的二维悬臂壁板为对象, 以理论分析及风洞实验为手段, 研究了单侧刚性壁面效应对倒置悬臂壁板静态失稳特性的影响规律. 在理论分析中, 首先应用镜像函数法来处理壁面约束条件, 基于算子理论研究获得了以Possio积分方程为表征的壁板气动力, 壁面效应实际表征为一包含移位Tricomi算子的复合算子; 然后将壁板失稳方程的求解问题转化为定区间上的函数逼近问题; 最后, 依据Wererstrass定理并利用最小二乘法求解该最优函数, 以获得系统的失稳临界参数. 在试验研究中依据压杆稳定原理设计了壁板静态失稳的测试方法并完成了风洞实验. 理论分析结果表明, 壁板会发生发散(静气动弹性)失稳, 临界动压随壁板与壁面间距的增加而增大并最终趋于稳定(无壁面情况); 通过理论与风洞实验结果的对比分析, 验证了本文气动力及理论分析的适用性及准确性. 针对倒置悬臂壁板结构的气动弹性失稳问题, 本文提出的方法不涉及系统方程的离散及特征值求解问题, 而是将其转化为了定区间上的函数逼近问题进行求解, 这为弹性结构静气动弹性失稳问题的研究提供了一个可行的新思路.      

Temporal freedom in mathematical thought: A philosophical–empirical enquiry

This paper seeks to introduce and elaborate on the notion of ‘temporal freedom’ in the context of mathematical thinking.The intention is to merge a philosophical and empirical discussion on this topic, and findings will be presented from a qualitative study in which 29 high-school students were invited to explore the symmetry group of a square during clinical interviews. The data indicate how the interviewees – who were given the opportunity to freely explore an unseen mathematical system – repeatedly brought past and future together in a tangible present during their investigations. In doing so they were exceptionally successful in engaging with advanced abstract algebra, far beyond what might have been expected at the outset.By using empirical data to exemplify an otherwise highly philosophical discussion, I hope to draw explicit attention to the temporal aspect of the human mind in mathematical action which instructional methods frequently fail to recognise, value and utilise.     

Hydrodynamics of a flexible cylinder under modulated vortex-induced vibrations

Both amplitude modulation and frequency modulation of Vortex-induced Vibration (VIV) are observed in a recent model test of a flexible cylinder under oscillatory flow, but its hydrodynamics has not yet been broached in detail. This paper employs the Forgetting Factor Least Squares (FF-LS) method for identification of time-varying hydrodynamics of a flexible cylinder under modulated VIV. The FF-LS method’s applicability to accurately identify time-varying hydrodynamic coefficients is demonstrated through an elastically mounted rigid cylinder under flow with a given modulated motion. Furthermore, we propose a framework to predict instantaneous amplitude (envelope) and frequency using time-varying hydrodynamic coefficients to establish their analytical relationship. This prediction method is further extended to a highly tensioned flexible cylinder through Fourier series expansion in the spatial domain. By performing the identification procedure for all sampled data of a flexible cylinder undergoing oscillatory flow, we obtain the corresponding time-varying hydrodynamics in the cross-flow direction considering the amplitude and frequency modulation. The results show that, under modulated VIV, hydrodynamic coefficients of the flexible cylinder also show time-varying characteristics. We further investigate differences between identified hydrodynamic coefficients and those obtained from the database of a cylinder with modulated motion under flow. Prediction results using these identified time-varying coefficients reveal that the time-varying excitation coefficients mainly influence the amplitude modulation, and the time-varying added-mass coefficients contain the major information of frequency modulation. These results further suggest including the temporal derivative of the instantaneous amplitude as one determining parameter in building databases to improve the prediction of modulated VIV.     

基于Retinex理论与概率非局部均值的红外图像增强方法

针对传统红外图像增强算法中细节模糊及过度增强的问题,提出了一种基于Retinex理论与概率非局部均值相结合的红外图像增强方法.首先通过单尺度Retinex方法调整图像中过暗与过亮部分的灰度级;然后利用概率非局部均值对图像进行分解处理得到基本层与细节层,对基本层采用直方图均衡化拉伸对比度,对细节层采用非线性函数进行增强;最后,将不同层次的结果融合得到对比度与细节增强的红外图像.用该方法对多组不同场景的红外图像进行仿真实验,并将其与多种增强方法进行主、客观对比分析,结果表明所提方法在红外图像的细节及对比度增强方面都获得了更好的效果.