Electron-donating alkoxy-group-driven synthesis of heteroleptic tris(phthalocyaninato) lanthanide(III) triple-deckers with symmetrical molecular structure

Reaction of heteroleptic bis(phthalocyaninato) lanthanide compounds [(Pc)M{Pc(OC8H17)8}] [H2Pc=unsubstituted phthalocyanine; H2Pc(OC8H17)8 = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyanine] with monomeric complexes [(Pc)M(acac)] (Hacac=acetylacetone), both of which generated in situ, led to the isolation of heteroleptic phthalocyaninato-[2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato] lanthainde(III) triple-decker complexes [(Pc)M{Pc(OC8H17)8}] (M=Gd-Lu) (1-8) as the sole product. Heterodinuclear analogues [(Pc)Lu{Pc(OC8H17)8}M(Pc)] (M=Gd-Yb) (9-15) were obtained in a similar manner from the reaction of [(Pc)M{Pc(OC8H17)8}] (M=Gd-Yb) and [(Pc)Lu(acac)]. The molecular structures of the herterodinuclear compound [(Pc)Lu{Pc(OC8H17)8}Er(Pc)] (13) and its homodinuclear counterparts [(Pc)M{Pc(OC8H17)8}M(Pc)] (M=Er, Lu) (5, 8) have been determined by X-ray diffraction analysis; these structures exhibit a symmetrical molecular structure with one inner planar Pc(OC8H17)8 ligand and two outer domed Pc ligands. In addition to various spectroscopic analyses, the electrochemistry of these compounds has also been studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) methods, revealing the gradually enhanced pi-pi interactions among the phthalocyanine rings in the triple-deckers along with the lanthanide contraction.     

Wearable Thermocells Based on Gel Electrolytes for the Utilization of Body Heat

Converting body heat into electricity is a promising strategy for supplying power to wearable electronics. To avoid the limitations of traditional solid‐state thermoelectric materials, such as frangibility and complex fabrication processes, we fabricated two types of thermogalvanic gel electrolytes with positive and negative thermo‐electrochemical Seebeck coefficients, respectively, which correspond to the n‐type and p‐type elements of a conventional thermoelectric generator. Such gel electrolytes exhibit not only moderate thermoelectric performance but also good mechanical properties. Based on these electrolytes, a flexible and wearable thermocell was designed with an output voltage approaching 1 V by utilizing body heat. This work may offer a new train of thought for the development of self‐powered wearable systems by harvesting low‐grade body heat.     

Jump Detection in Regression Surfaces

Abstract

We consider the problem of locating jumps in regression surfaces. A jump detection algorithm is suggested based on local least squares estimation. This method requires O(Nk) computations, where N is the sample size and k is the window width of the neighborhood. This property makes it possible to handle large data sets. The conditions imposed on the jump location curves, the jump surfaces, and the noise are mild. We demonstrate this method in detail with some numerical examples.     

Helical Self-Assembly of Optically Active Phthalocyanine Derivatives: Effect of Zn?O Coordination Bond on Morphology and Handedness of Nanostructures

Two optically active phthalocyanine derivatives with eight peripheral chiral (S)-4′-(2-methylbutoxy)biphenyl moieties on the β-position of the phthalocyanine ring are synthesized. The circular dichroism (CD) spectra show signals in the Q absorption region for both compounds 1 and 2 in chloroform solution, indicating the effective chiral-information transfer from the peripheral chiral (S)-4′-(2-methylbutoxy)biphenyl side chains to the phthalocyanine chromophore at the molecular level. Their self-assembling properties are further investigated by using electronic absorption and Fourier transform infrared spectroscopy, transmission electronic microscopy, scanning electronic microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Experimental results reveal the effect of the metal-coordination bond on molecular packing models in these nanostructures, which in turn results in the self-assembled nanostructures with different morphologies, from nanosheets for 1 to helical nanofibers for 2 . In addition, good semiconducting properties of the nanostructures fabricated from phthalocyanine derivatives 1 and 2 are revealed by current–voltage measurements.     

Jump-Preserving Regression and Smoothing using Local Linear Fitting: A Compromise

This paper deals with nonparametric estimation of a regression curve, where the estimation method should preserve possible jumps in the curve. At each point x at which one wants to estimate the regression function, the method chooses in an adaptive way among three estimates: a local linear estimate using only datapoints to the left of x, a local linear estimate based on only datapoints to the right of x, and finally a local linear estimate using data in a two-sided neighbourhood around x. The choice among these three estimates is made by looking at differences of the weighted residual mean squares of the three fits. The resulting estimate preserves the jumps well and in addition gives smooth estimates of the continuity parts of the curve. This property of compromise between local smoothing and jump-preserving is what distinguishes our method from most previously proposed methods, that mainly focused on local smoothing and consequently blurred possible jumps, or mainly focused on jump-preserving and hence led to rather noisy estimates in continuity regions of the underlying regression curve. Strong consistency of the estimator is established and its performance is tested via a simulation study. This study also compares the current method with some existing methods. The current method is illustrated in analyzing a real dataset.     

船用惯性导航系统可靠性验收试验的研究与实现

我国船用惯导系统经过多年来的发展，其可靠性（ＭＴＢＦ）水平已达到××××小时以上。在国内现有的条件下，如何对此类机电一体化的高可靠、小子样产品的可靠性指标进行有效、经济、实用的验收呢？本文在综合分析现有的几种试验方法的基础上，结合多年的可靠性验收工作的实践，阐述了一套适合国情，行之有效的可靠性交收试验方法     

橡胶粒子和刚性纳米粒子对注塑级硬质聚氯乙烯复合材料断裂行为的影响

采用核壳型丙烯腈-苯乙烯-丁二烯共聚物(ABS)和纳米碳酸钙(CaCO3)协同改性聚氯乙烯(PVC),制备了注塑级硬质PVC纳米复合材料.通过透射电镜(TEM)、扫描电镜(SEM)、力学性能测试研究了其结构与性能,并采用有限元模拟方法研究了ABS与纳米CaCO3粒子对复合材料断裂行为的影响.当CaCO3含量低于12 p...     

Mg/Al型水滑石吸附硼的实验研究

采用共沉淀法制备了几种不同摩尔比的镁铝水滑石(LDHs),并对其进行了XRD、FT-IR表征.将其应用于吸附溶液中的硼,比较了它们对硼的吸附容量,最终选择了具有较高吸附容量的Mg4Al-LDH作为硼吸附荆.对Mg4Al-LDH吸附硼的实验条件进行了系统研究,得到了较高吸附容量下的实验条件.试验结果表明该等温吸附过程可用Langmuir吸附等温模型准确描述.     

The influence of temperature on crosshatching

The influence of temperature on crosshatching on ablating cone models made of wax and camphor is studied. Ablation experiments are carried out in supersonic tunnels. The relation between temperature and the wavelength of crosshatching is obtained. The effect of pressure on the wavelength of crosshatching is verified. The influence of temperature and pressure on the initial position of the appearance of crosshatching and on the time required for both the apperance of croosshatching and the formation of stable crosshatching are obtained and analyzed.