Different responses of E:Z‐isomers of pesticides in liquid chromatography–electrospray ionization–mass spectrometry

The mass spectrometric behavior of four pairs of stereoisomers was investigated by liquid chromatography–electrospray ionization–mass spectrometry (LC–ESI–MS). The E‐ and Z‐isomers of the pesticides chlorfenvinphos, dimethomorph, mevinphos and phosphamidon—each with one double bond—were chosen for this study. The MS response of the individual isomers was investigated by infusing the isomers individually into the MS or after the separation of isomer mixtures via high‐performance liquid chromatography(HPLC). In the case of dimethomorph, the same MS response was found for the two isomers. In contrast to that, the individual isomers of chlorfenvinphos, mevinphos and phosphamidon showed different MS response both in the single ion monitoring (SIM) mode in single quadrupole MS and multiple reaction monitoring (MRM) mode in tandem MS. The MS response of the isomers partly depends on (1) the declustering potential of the precursor ion in the SIM mode, (2) the selected transition and (3) the collision energy in the MRM mode. Consequently, quantification by summation of the peak areas of the isomers is inaccurate due to over‐ or underestimating of one of the stereoisomers. Accurate quantitative results can only be achieved when the compound‐specific MS parameters are separately determined for each isomer. This can be done by using pure isomers or by the determination of the MS parameters after HPLC separation and the measurement of the actual isomer ratio with an independent technique. Copyright © 2010 John Wiley & Sons, Ltd.     

大尺度三维几何尺寸立体视觉测量系统实现

基于立体视觉的大尺度三维几何尺寸测量技术是对外形不规则的大型物体进行几何量测量的有效方法。与传统的视觉测量技术不同,大尺度视觉测量的精度随测量距离的增加而迅速下降,同时大尺度空间下照明条件难以控制,也使得测量变得不稳定。因此如何在大测量尺度的前提下提高测量精度成为这一领域的研究难点。从立体视觉测量系统的原理出发,分析了影响系统精度的各种因素,将相位一致性变换与极线约束条件引入结构光光条中心提取之中,显著提高了图像分析的精度。研制了测量系统的样机并给出了实验结果,现场测试表明该系统可以有效地保证大尺度条件下的测量精度。     

单目多视点立体图像提取及应用

设计并实现了一种基于广角相机和平面镜的单目多视点立体图像摄像系统,给出了硬件装置的设计指标和优化方法;同时,在研究了硬件系统的标定方法基础上,实现了其在三维测距方面的应用。多枚平面镜构成的对称斗型腔体被放置在广角相机前面,物体光线经过不同平面镜反射后,投影到相机图像平面的不同区域,在相机投影平面上生成物体多个影像,形成单目多视点投影图像。该类图像等价于视点不同的多幅图像,可以使用多视点立体视觉算法实现三维测量。     

高阶控制增稳系统等效拟配参数时域在线辨识方法

现代控制增稳飞机是高达几十阶的复杂系统,将其降阶为特定形式的低阶等效系统才能与已有飞行品质规范进行比较,进而预测和评价飞机飞行品质.从时域角度出发,提出了一种高阶控制增稳系统等效拟配参数在线辨识方法.分析了时域等效系统拟配的基本方法,提出了等效系统实时在线拟配的系统框架思路,基于Tustin变换法推导了由高阶系统时域响应获取四阶等效系统参数的数学公式,应用最小二乘法在MATLAB中实现了算法编程,并用试飞数据验证了所提方法的可行性.计算结果表明,所提方法可以快速准确地实现高阶控制增稳系统的等效系统参数辨识.     

用扫描式电感耦合等离子体光谱仪测定红矾钾产品中的杂质

应用电感耦合等离子体发射光谱法测定了铬盐清洁工艺红矾钾产品中的微量元素硅、铝、铁、钙、锰、镁和氯。采用基体匹配法消除了大量基体的干扰。实验的优化条件为RF发生器的入射功率095kW;载气压力013MPa,流量12L·min-1;辅助气流量02L·min-1。元素氯用氯化银沉淀间接测定,在6%的硝酸体系中氯离子形成氯化物完全沉淀,在50℃陈化2h后进行测定。样品的加标回收率在90%～104%,RSD<4%,检出限在10-4%～10-5%。随机抽样的分析结果与标准加入法吻合较好,相对误差在-427%～ 526%。本方法用于实际样品分析,快速简单,结果令人满意。     

图像序列运动检测算法的研究及其应用

探讨了监控图像序列中进行运动检测的若干基本算法 ,结合统计方法和边缘检测筛选出运动边缘点 ,对运动边缘点逐个进行了块匹配最优搜索 ,估算出其运动矢量 .此方法在数字视频监控系统中用于运动物体检测和报警 ,不但提供了智能型监控 ,而且也有效的压缩了存储数据 ,改善了系统性能 ,有较好的实用价值 .     

可变高度激光里程计在室内不平整地面环境下的地图构建

针对可变高度激光雷达的结构特点提出了一种基于线、面特征的匹配算法, 并应用于存在不平整地面的结构化的室内环境. 首先提取激光点云中的边缘点和平面点, 并使用随机抽样一致性算法拟合成线段和平面; 然后根据线段与平面几何关系提出特征匹配条件, 完成特征之间的匹配; 利用特征间的匹配关系构建约束方程求解机器人位姿; 最后把机器人竖直方向位姿变换信息补偿到激光点云中, 并把纠正后的有一定高度的激光点云压缩成二维激光构建室内栅格地图. 实验结果表明, 与常用的二维激光同时定位与构图算法Gmapping对比, 在地面不平整的室内环境构建的地图得到了改善, 提高了移动机器人的构图精度.     

Controlling the thermomechanical properties of biobased ABA triblock copolymers comprising polylactide (A) and poly(1,2-propylene succinate) (B) with high molecular weight

Bis-hydroxyl-terminated poly(1,2-propylene succinate) (PPS-diols) with high molecular weight (10–40 kDa) are prepared by two-step melt polycondensation of succinic acid and 1,2-propanediol with Ti(BuO)₄ as the catalyst. By using these PPS-diols as macroinitiators, the ring-opening polymerization of d - and l -lactides is readily conducted to obtain enantiomeric ABA triblock copolymers consisting of poly(l -lactide) and PPS (B) (t-l -PPS) as well as those of poly(d -lactide) and PPS (B) (t-d -PPS) which have higher PPS compositions (20–70 wt%) in addition to high molecular weight (20–80 kD). The T_g, T_m, and ΔH_m values of the t-l -PPS copolymers as well as the stereo mixtures of t-l -PPS/t-d -PPS are controlled to linearly decrease with increasing the PPS content. The copolymers also exhibit higher elastomeric properties with increasing the PPS content. The tensile properties of the copolymer films having higher PPS contents (both the single block copolymers and stereo mixtures) are comparable to those of the oil-based thermoplastic elastomers. It is therefore concluded that these block copolymers can afford thermoplastic elastomers or flexible plastic materials having a 100% biobased content.     

Crystallization behavior and morphology of β‐nucleated isotactic polypropylene with different stereo‐defect distribution

Aiming at further investigating the combination effect of concentration of β‐nucleating agent (β‐NA) and stereo‐defect distribution on the crystallization behavior of β‐nucleated isotactic polypropylene (β‐iPP), in this study, the crystallization behavior and polymorphic morphology of twoβ‐iPP resins with nearly same average isotacticity (PP‐A and PP‐B) but different uniformities of stereo‐defect distribution were investigated by differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD) and polarized optical microscopy (POM). The results of DSC and WAXD showed that the addition of TMB‐5 increases the crystallization temperature and decreases the spherulite sizes of both PP‐A and PP‐B, and reduces their crystallization energy barriers as well; however, the polymorphic behaviors of PP‐A and PP‐B exhibit different dependence on the TMB‐5 concentration. For PP‐A with less uniform distribution of stereo‐defects, β‐phase can be observed only when the TMB‐5 concentration is no less than 0.1 wt.%, while for PP‐B with more uniform stereo‐defect distribution, addition of 0.01 wt.% TMB‐5 can induce the formation of β‐phase. Moreover, the analysis of POM indicated that the crystalline morphologies of both PP‐A and PP‐B change greatly with the TMB‐5 concentration, and the variation features of PP‐A and PP‐B are quite different from each other. PP‐B with more uniform stereo‐defect distribution was more favorable for the formation of large amount of β‐phase in the presence of wide concentration range of TMB‐5. The different polymorphic behaviors and their different dependences on the β‐NA concentration were related to the different uniformities of stereo‐defect distribution of the samples, since the distribution of stereo‐defects could restrain the regular insertion of molecular chains during crystallization and thus determine the tendency the α‐phase crystallization of the sample. Copyright © 2014 John Wiley & Sons, Ltd.     

Investigation on the dynamic crystallization and melting behavior of β‐nucleated isotactic polypropylene with different stereo‐defect distribution—the role of dual‐selective β‐nucleation agent

The selectivities of different β‐nucleating agents might be quite different from each other, which is important in determining the crystallization and properties of the obtained β‐isotactic polypropylene (β‐iPP). However, the relationship between molecular structure and dynamic crystallization behavior of β‐iPP nucleated by dual‐selective β‐nucleating agent (DS‐β‐NA) is still not clear. In this study, the dynamic crystallization and melting behavior of two β‐iPP with nearly same average isotacticity but different stereo‐defect distribution, nucleated by a DS‐β‐NA (N,N′‐dicyclohexyl‐2,6‐naphthalenedicarboxamide; trade name TMB‐5), were studied by differential scanning calorimetry, wide‐angle X‐ray diffraction, and scanning electronic microscopy. The results indicated that in the presence of TMB‐5, the dynamic crystallization and melting behavior of the samples are quite different because the joint effects of the dual selectivity of TMB‐5 and stereo‐defect distribution of the iPP under different cooling rates. Two important roles were observed: (i) slow cooling rate favors the formation of high β‐fraction; and (ii) high crystallization temperature favors the crystallization of α‐phase accelerated by TMB‐5. Generally, the dual selectivity of the DS‐β‐NA, the stereo‐defect distribution of iPP, and the cooling rate were important factors in determining the formation of β‐crystal. Copyright © 2013 John Wiley & Sons, Ltd.