Characterization of Functional Groups in Estuarine Dissolved Organic Matter by DNP-enhanced 15N and 13C Solid-State NMR

Estuaries are key ecosystems with unique biodiversity and are of high economic importance. Along the estuaries, variations in environmental parameters, such as salinity and light penetration, can modify the characteristics of dissolved organic matter (DOM). Nevertheless, there is still limited information about the atomic-level transformations of DOM in this ecosystem. Solid-state NMR spectroscopy provides unique insights into the nature of functional groups in DOM. A major limitation of this technique is its lack of sensivity, which results in experimental time of tens of hours for the acquisition of ¹³C NMR spectra and generally precludes the observation of ¹⁵N nuclei for DOM. We show here how the sensitivity of solid-state NMR experiments on DOM of Seine estuary can be enhanced using dynamic nuclear polarization (DNP) under magic-angle spinning. This technique allows the acquisition of ¹³C NMR spectra of these samples in few minutes, instead of hours for conventional solid-state NMR. Both conventional and DNP-enhanced ¹³C NMR spectra indicate that the ¹³C local environments in DOM are not strongly modified along the Seine estuary. Furthermore, the sensitivity gain provided by the DNP allows the detection of ¹⁵N NMR signal of DOM, in spite of the low nitrogen content. These spectra reveal that the majority of nitrogen is in the amide form in these DOM samples and show an increased disorder around these amide groups near the mouth of the Seine.     

Dynamic Visualization of Free Radicals at Single Oxygen Bubbles using Chemiluminescence

The generation of free radicals is a key process in the formation and the collapse of the bubbles in water, however, the direct and dynamic observation of the radicals in this process at single bubbles has never been achieved. Here, the hydroxyl (OH^.) and oxygen (O₂^.−) radicals at single oxygen bubbles are continuously traced using chemiluminescence (CL), in which these radicals at the bubble react with the surrounding luminol in the solution emitting the light. Varied increase trends of luminescence are observed in the generation of a bubble, floating, short parking at the water/air interface and the final explosion, revealing the complexity in the distribution of radicals at the bubble unprecedentedly. Despite more radicals are observed at the bubble generated at a deep position under the water for the stabilization, almost the same amount of radicals are included in the bubbles that is independent on the water pressure during the production of the bubble. This rich information collected from the dynamic study of bubbles illustrates the complicated generation and distribution process of radicals at the bubbles, and will facilitate the understanding of the function about the bubbles.     

H-ZSM-5分子筛不同孔道处的酸位在甲醇制烯烃反应中的催化作用

甲醇制烯烃(MTO)作为一条由煤、天然气和生物质等含碳资源制备重要有机化学品的非石油路线,近年来备受关注.作为MTO催化剂,分子筛的骨架拓扑结构和酸性质对于其催化活性、反应路径和产物分布等具有重要的影响.H-ZSM-5分子筛是一种典型的MTO反应催化剂,酸位可以分布在MFI拓扑结构的直孔道、正弦孔道和交叉位点处.虽然目前已普遍认可MTO反应遵循芳烃/烯烃双循环烃池机理,分子筛的催化性能与其骨架中酸中心的位置相关,但对于H-ZSM-5分子筛不同孔道位置处的酸中心在甲醇制烯烃反应中的催化作用仍缺乏足够认识.本文采用密度泛函理论计算和分子动力学模拟方法,对H-ZSM-5分子筛不同孔道处(包括正弦孔道、直孔道和交叉腔)酸位中心上的MTO反应网络(包括芳烃循环、烯烃循环和芳构化)及甲醇原料和烯烃/芳烃产物的扩散行为进行了比较研究.结果表明,与正弦孔道和直孔道相比,芳烃循环和芳构化反应在交叉腔的酸中心上因具有较低的能垒而更易进行.相比之下,在正弦孔道和直孔道中,多甲基苯的生成受到显著限制,而烯烃循环却可以在三种酸中心(正弦孔道、直孔道和交叉腔)上以相近的能垒和相似的几率进行.芳烃循环生成乙烯和丙烯的几率相近,而烯烃循坏产物以丙烯和较高的烯烃产物为主.落位于H-ZSM-5交叉腔的酸中心能促进芳烃中间体如多甲基苯的生成,推动芳烃循环,提高乙烯选择性,而正弦孔道和直孔道中的酸中心则能增强烯烃循环,生成较多的丙烯和较高的烯烃产物.因此,H-ZSM-5分子筛对MTO的催化性能(包括活性和产物选择性等),可以通过有目的地调节酸中心在分子筛骨架中的位置分布(即铝落位)而得到有效调变和提升.本文阐明了H-ZSM-5分子筛酸中心在MTO反应中的催化作用与其骨架中的落位之间的有机联系,为高效甲醇转化分子筛催化剂的设计和性能提升提供了参考思路.     

Identification of source terms in wave equation with dynamic boundary conditions

This paper studies an inverse hyperbolic problem for the wave equation with dynamic boundary conditions. It consists of determining some forcing terms from the final overdetermination of the displacement. First, the Fréchet differentiability of the Tikhonov functional is studied, and a gradient formula is obtained via the solution of an associated adjoint problem. Then, the Lipschitz continuity of the gradient is proved. Furthermore, the existence and the uniqueness for the minimization problem are discussed. Finally, some numerical experiments for the reconstruction of an internal wave force are implemented via a conjugate gradient algorithm.     

Plankton growth dynamic driven by plankton body size in deterministic and stochastic environments

In this paper, we establish a new phytoplankton–zooplankton model by considering the effects of plankton body size and stochastic environmental fluctuations. Mathematical theory work mainly gives the existence of boundary and positive equilibria and shows their local as well as global stability in the deterministic model. Additionally, we explore the dynamics of V-geometric ergodicity, stochastic ultimate boundedness, stochastic permanence, persistence in the mean, stochastic extinction, and the existence of a unique ergodic stationary distribution in the corresponding stochastic version. Numerical simulation work mainly reveals that plankton body size can generate great influences on the interactions between phytoplankton and zooplankton, which in turn proves the effectiveness of mathematical theory analysis. It is worth emphasizing that for the small value of phytoplankton cell size, the increase of zooplankton body size can not change the phytoplankton density or zooplankton density; for the middle value of phytoplankton cell size, the increase of zooplankton body size can decrease zooplankton density or phytoplankton density; for the large value of phytoplankton cell size, the increase of zooplankton body size can increase zooplankton density but decrease phytoplankton density. Besides, it should be noted that the increase of zooplankton body size cannot affect the effect of random environmental disturbance, while the increase of phytoplankton cell size can weaken its effect. There results may enrich the dynamics of phytoplankton-zooplankton models.     

面向绿色智能制造的高维多目标动态作业车间调度优化

在当前环境问题日益严峻情况下,绿色智能制造受到广泛关注。在动态柔性作业车间基础上考虑不同机器状态下的能耗情况、机器使用节能方法,构建以极小化总能耗、最大完工时间、机器总负荷和产品质量稳定性为目标的高维多目标绿色动态柔性作业车间调度模型,并设计改进的灰狼优化IMOGWO算法求解该问题。首先,采用反向学习初始化种群策略,以扩大种群多样性;然后,依据多目标问题和标准GWO算法的特点提出多级官员领导机制,并引入POX交叉和逆序变异算子;最后,改进精英保留策略用于多目标优化算法。为证明算法的有效性,设计两组仿真实验分别对三种算法进行比较。实验结果表明,运用本文改进的IMOGWO算法求解多目标问题有更好的收敛性和分布性。     

Controlling the Trajectory of Swallowtail Gaussian Beams in Dynamic Parabolic Potentials

The propagation dynamics of finite-energy Swallowtail beams in a dynamic parabolic potential, including uniformly moving, accelerating, and oscillating potentials, are investigated. The strong influence of dynamic potentials on the propagation trajectory of Swallowtail beams is demonstrated and various effective manipulations of the beams, including trajectory control, are validated. The intensity and the focal position can also be affected. In addition, the extension to 2D scenarios is also presented. The results theoretically provide more diverse manipulation possibilities for Swallowtail beams, and thus may broaden their potential applications in trajectory and particle manipulation.     

[2+3] Amide Cages by Oxidation of [2+3] Imine Cages – Revisiting Molecular Hosts for Highly Efficient Nitrate Binding

The pollution of groundwater with nitrate is a serious issue because nitrate can cause several diseases such as methemoglobinemia or cancer. Therefore, selective removal of nitrate by efficient binding to supramolecular hosts is highly desired. Here we describe how to make [2+3] amide cages in very high to quantitative yields by applying an optimized Pinnick oxidation protocol for the conversion of corresponding imine cages. By NMR titration experiments of the eight different [2+3] amide cages with nitrate, chloride and hydrogen sulfate we identified one cage with an unprecedented high selectivity towards nitrate binding vs. chloride (S=705) or hydrogensulfate (S>13500) in CD₂Cl₂/CD₃CN (1 : 3). NMR experiments as well as single-crystal structure comparison of host-guest complexes give insight into structure-property-relationships.     

基于动态神经元网络的激光陀螺输出误差模型

惯性敏感器误差补偿技术对提高武器装备的性能具有重要的意义,而误差补偿的关键在于误差模型的辨识。由于动态神经元网络是在前馈网络的节点引入前馈和反馈环节,理论上已证明其具有很强的动态逼近能力,可用来描述任意的非线性动态系统。根据惯性敏感器误差的动态特性,本探讨将动态神经元网络引入到激光陀螺误差建模中去,详细介绍了网络结构和对应的动态梯度算法。通过仿真算例说明,动态神经元网络在激光陀螺输出误差建模时具有一定的优点：网络收敛速度快、较好的跟踪性能、稳定性好。     

Interaction of elastic waves with a periodic array of collinear inplane cracks

A boundary integral equation method is applied to the study of the interaction of plane elastic waves with a periodic array of collinear inplane cracks. Numerical results are presented for the dynamic stress intensity factors. The effects of the wave type, wave frequency, wave incidence angle, and crack spacing on the dynamic stress intensity factors are analyzed in detail. The project supported by the Committee of Science and Technology of Shanghai and Tongji University