Reversibly Switchable Fluorescent Molecular Systems Based on Metallacarborane–Perylenediimide Conjugates

Icosahedral metallacarboranes are θ-shaped anionic molecules in which two icosahedra share one vertex that is a metal center. The most remarkable of these compounds is the anionic cobalt-based metallacarborane [Co(C₂B₉H₁₁)₂]⁻, whose oxidation-reduction processes occur via an outer sphere electron process. This, along with its low density negative charge, makes [Co(C₂B₉H₁₁)₂]⁻ very appealing to participate in electron-transfer processes. In this work, [Co(C₂B₉H₁₁)₂]⁻ is tethered to a perylenediimide dye to produce the first examples of switchable luminescent molecules and materials based on metallacarboranes. In particular, the electronic communication of [Co(C₂B₉H₁₁)₂]⁻ with the appended chromophore unit in these compounds can be regulated upon application of redox stimuli, which allows the reversible modulation of the emitted fluorescence. As such, they behave as electrochemically-controlled fluorescent molecular switches in solution, which surpass the performance of previous systems based on conjugates of perylendiimides with ferrocene. Remarkably, they can form gels by treatment with appropriate mixtures of organic solvents, which result from the self-assembly of the cobaltabisdicarbollide-perylendiimide conjugates into 1D nanostructures. The interplay between dye π-stacking and metallacarborane electronic and steric interactions ultimately governs the supramolecular arrangement in these materials, which for one of the compounds prepared allows preserving the luminescent behavior in the gel state.     

现代物流业与其相关产业灰色关联度研究——基于山西省的实证分析

结合山西省2002～2006年的相关行业生产总值增加值,运用灰色系统理论方法,得到山西省现代物流业与相关产业的灰色关联系数,按照关联度的不同排序,对山西省发展现代物流业提出了切实可行的政策建议.     

基于效益最优的企业物流外包决策的量化研究

供应链管理要求相关企业进行优化合作,将非核心业务外包,其中最典型的是物流外包.目前大多数文献仅仅从定性角度出发阐述企业物流外包决策的原因,而没有将其定量化研究.尝试由基本的需求函数出发,根据企业利润最大化原则,从成本和收益的角度去量化分析企业物流外包的必然性和建立高效供应链的必要性,找到基于利润和核心竞争力的企业物流外包的动力.     

物流客户服务水平的综合评价研究

本文在客户问卷调查的基础上,结合国外有关的物流企业客户服务指标,建立了物流客户服务水平评价的指标体系,同时应用定性与定量分析相结合的方法,建立了属性综合评价的物流客户服务水平评价模型,并给出了具体的应用实例.     

Magnetic moments of hindered rotators by off‐center impurity ions

Off‐center impurity ions in solids often perform rotations around their regular lattice sites. Unlike quasifree rotors with rotational line spectra subject to textbook attention in quantum mechanics, the off‐center species are hindered rotors with spectra quantized in rotational bands. These bands occur because of tunneling through barriers arising along the orbital path. For an off‐center ion rotating along a planar orbit, such as the Li⁺ impurity nearest‐neighboring an F center in alkali halide, the hindered rotation will give rise to specific magnetic moments that couple to and quantize external magnetic fields normal to the orbital plane. We present a simple theory and estimates of Li⁺ magnetic dipoles and rotational bands to find conditions for an experimental verification. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

LiF晶体中F3^＋—F2混合色心激光器

本文报道了室温下LiF晶体中F_3~+-F_2混合色心激光器.利用一块晶体和单一泵光,输出激光波长范围从510～580nm、640～710nm.总带宽140nm.     

Effect of Mg2+ co‐doping on the scintillation performance of LuAG:Ce ceramics

Ce‐doped Lu₃Al₅O₁₂ optical ceramics co‐doped with Mg²⁺ are fabricated by solid‐state reaction method and further optimized by an air‐annealing process. Mg²⁺ co‐doping leads to a significant decrease of thermoluminescence intensity above room temperature and an increase of scintillation light yield (LY) value and fast component content even if the overall scintillation efficiency decreases. Scintillation LY of ～21900 ph/MeV has been achieved with a short shaping time of 1 μs, and the ratio of LY values for 1 μs and 10 μs shaping times was as high as 79%. The acceleration of scintillation response induced by Mg²⁺ co‐doping and the role of Ce⁴⁺ ions in the scintillation mechanism are discussed.

     

Theory of oxidation/reduction-induced valence transformations of metal ion dopants in oxide crystals mediated by oxide-vacancy diffusion: I. Thermodynamic analysis

We consider theoretically valence transformations of doping metal ions in oxide crystals induced by oxidation and reduction obtained by changes in the ambient oxygen partial pressure. Three types of oxygen vacancies are assumed to mediate transformations: neutral, singly ionized, and doubly ionized. We provide thermodynamic equilibrium analyses, yielding concentration relations among the oxygen vacancy, metal ions, holes and electrons as functions of the ambient oxygen pressure. The results suggest that experimental study of different species concentrations at thermodynamic equilibrium as functions of pressure and temperature should allow assessment of various reversible reaction constants controlling the process. In the Part II companion paper, the kinetic (diffusion) characteristics are considered in detail.     

手性3-溴-2(5H)-呋喃酮的合成及其串联的不对称Michael加成 反应的研究

研究了新的手性试剂,5-(l-孟氧基)-3-溴-呋喃酮(5a)的合成及其与亲核性醇发生的串联不对称双Michael加成/分子内亲取代反应。通过此反应,一举生成了四个新的手性中心,得到了一般方法难以合成的含有多个手性中心的丁内酯并螺－环丙烷类化合物8a～8d。详细报道了8a～8d的合成方法以及它们的[α]、IR、UV、^1^HNMR、^13^CNMR、MS、元素分析等结构分析数据。此不对称双Michael加成/分子内亲核取代反应可以为某些新的光学活性螺－环内丙烷类化合物以及某些复杂结构的分子提供合成策略。     

运筹学在整车物流智能调度决策支持系统中的研究与应用

本文基于整车物流智能调度决策支持系统的研发、实施与运维的成功应用,论述运筹学在智能化上的应用路径以及实践驱动的学术路径。该系统是国内较早在汽车物流企业实现落地的智能化调度系统,其所形成的思想理论与方法技术揭示了运筹学在智能化应用上的核心价值,以及实践驱动的学术价值,对解决“卡脖子”难题提供示范性思路。本文提出运筹学在智能化研发上“三环七步”的整体研发框架。首先,分析智能化需求的运筹学特征,详细介绍汽车整车物流的发展趋势、瓶颈及智能调度需求;其次,论述运筹学系统模型的作用与建模方法,分析汽车整车物流系统模型的决策要素、目标及约束,提出汽车整车物流智能调度的运筹学应用问题。然后,提出“模式装箱”的新装箱理论问题,明确问题的计算难解性、可解性及核心科学特征。进一步,建立汽车整车物流调度应用问题与科学问题的混合整数线性规划模型;提出求解汽车整车物流调度问题的分支定界算法,以及大规模问题求解的时空分解及滚动求解方法与技术;提出面向运筹应用的生产测试及压力测试方法,给出汽车整车物流调度的测试分析的流程与结果。此外,提出深度集成整车运输管理系统与仓库管理系统、优化算法引擎驱动的分布式、多视图、多系统融合的智能调度决策支持系统。最后,论述该系统在实施过程中的推广使用和运维情况,并对运筹学应用及实践驱动的科学研究进行总结与展望。