低电压下氮气放电的发射光谱分析

建立了一套直流放电产生氮气等离子体装置,该装置以碳纳米管修饰ITO电极为阳极,铝平板为阴极,两极间距~80 μm。在室温低电压(低于150 V)对氮气进行气体放电,利用发射光谱法对氮气放电过程中的活性物种进行了诊断研究。在直流电压下,观测到氮气发射光谱中能量最强最清晰的谱带N₂(C3Π_u),强度比较弱的Gaydon’s Green带系N₂(H₃Φ_u-G3Δ_g),以及820 nm附近氮原子的发射谱线(4p-4p0),发现氮分子的亚稳态是导致一系列激发态氮原子和氮气电离的主要因素,与交流电下(1.1 kV)产生的发射光谱相比,直流电下氮原子谱线光谱较强,且在500~800 nm范围检测到一个宽的分子谱带。考察了氧气与氢气对氮气发射光谱的影响,氧气对氮气的激发态有猝灭作用,使氮气发光强度降低,但其发射光谱图的谱型相似,都检测到氮气的第二正带系、Gaydon’s Green带系及氮原子谱线。当氮气与氢气的体积比为1∶1时,氮气的第二正带系及Gaydon’s Green带系都会受到很大的影响,说明加入的氢气可抑制氮等离子体激活,导致氮气的发光强度明显减弱,Gaydon’s Green System消失不见。碳纳米管修饰的ITO电极能使击穿电压降低,在10 V的低电压下,通过光电倍增管可观察到气体弱电离产生的光信号。     

High‐Throughput Screening in Olefin‐Polymerization Catalysis: From Serendipitous Discovery Towards Rational Understanding

High–throughput‐screening (HTS) tools and methods are used more and more, especially in industry, in the search for new, selective organometallic catalysts. In most cases, the approach is, in essence, empirical, and the strategy is to increase the number of experiments that can be run at a given place in a given time. Highly miniaturized, parallel reaction setups have been implemented for the rapid assessment of whether novel catalysts resulting from the structural amplification of a basic framework are “good” or “bad” with respect to the properties of interest, and, depending on the response, worthy of a subsequent, more‐careful evaluation. In this article, we demonstrate that it is possible to utilize these state‐of‐the‐art HTS platforms with a different strategy: the rapid generation of reliable kinetic data for mechanistic studies in view of a thorough understanding and rational catalyst design. Ziegler–Natta‐type catalytic olefin polymerization will be used throughout as an example.

     

Periodic orbits, damped transitions and targeted energy transfers in oscillators with vibro-impact attachments

We study complex damped and undamped dynamics and targeted energy transfers (TETs) in systems of coupled oscillators, consisting of single-degree-of-freedom primary linear oscillators (LOs) with vibro-impact attachments, acting, in essence, as vibro-impact nonlinear energy sinks (VI NESs). First, the complicated dynamics of such VI systems is demonstrated by computing the VI periodic orbits of underlying Hamiltonian systems and depicting them in appropriate frequency–energy plots (FEPs). Then, VI damped transitions and distinct ways of passive TETs from the linear oscillators to the VI attachments for various parameter ranges and initial conditions are investigated. As in the case of smooth stiffness nonlinearity [Y. Lee, G. Kerschen, A. Vakakis, P. Panagopoulos, L. Bergman, D.M. McFarland, Complicated dynamics of a linear oscillator with a light, essentially nonlinear attachment, Physica D 204 (1–2) (2005) 41–69], both fundamental and subharmonic TET can be realized in the VI systems under consideration. It is found that the most efficient mechanism for VI TET is through the excitation of highly energetic VI impulsive orbits (IOs), i.e., of periodic or quasiperiodic orbits corresponding to zero initial conditions except for the initial velocities of the linear oscillators. In contrast to NESs with smooth essential nonlinearities considered in previous works, VI NESs are capable of passively absorbing and locally dissipating significant portions of the energies of the primary systems to which they are attached, at fast time scale. This renders such devices suitable for applications, like seismic mitigation, where dissipation of vibration energy in the early, highly energetic regime of the motion is a critical requirement.     

<Emphasis Type="Italic">Q</Emphasis>-systems as Cluster Algebras II: Cartan Matrix of Finite Type and the Polynomial Property

We define the cluster algebra associated with the Q-system for the Kirillov–Reshetikhin characters of the quantum affine algebra \({U_q(\widehat{\mathfrak {g}})}\) for any simple Lie algebra \({\mathfrak {g}}\), generalizing the simply-laced case treated in (Kedem in Q-systems as cluster algebras. arXiv:0712.2695 [math.RT], 2007). We describe some special properties of this cluster algebra, and explain its relation to the deformed Q-systems which appeared on our proof of the combinatorial-KR conjecture. We prove that the polynomiality of the cluster variables in terms of the “initial cluster seeds”, including solutions of the Q-system, is a consequence of the Laurent phenomenon and the boundary conditions. We also define the cluster algebra associated with T-systems, or general systems which take the form of T-systems in the bipartite case. Such systems describe the recursion relations satisfied by the q-characters of Kirillov–Reshetikhin modules and also appear in the categorification picture in terms of preprojective algebras of Geiss, Leclerc and Schröer. We give a formulation of both Q-systems and generalized T-systems as cluster algebras with coefficients. This provides a proof of the polynomiality of solutions of all such “generalized T-systems” with appropriate boundary conditions.     

A pulsed EPR method to determine distances between paramagnetic centers with strong spectral anisotropy and radicals: The dead-time free RIDME sequence

Methods to determine distances between paramagnetic metal centers and radicals are scarce. This is unfortunate because paramagnetic metal centers are frequent in biological systems and so far have not been employed much as distance markers. Successful pulse sequences that directly target the dipolar interactions cannot be applied to paramagnetic metal centers with fast relaxation rates and large g-anisotropy, if no echos can be detected and the excitation bandwidth is not sufficient to cover a sufficiently large part of the spectrum. The RIDME method Kulik et al. (2002) [20] circumvents this problem by making use of the T₁-induced spin-flip of the transition-metal ion. Designed to measure distance between such a fast relaxing metal center and a radical, it suffers from a dead time problem. We show that this is severe because the anisotropy of the metal center broadens the dipolar curves, which therefore, only can be analyzed if the full curve is known. Here, we introduce five-pulse RIDME (5p-RIDME) that is intrinsically dead-time free. Proper functioning of the sequence is demonstrated on a nitroxide biradical. The distance between a low-spin Fe(III) center and a spin label in spin-labeled cytochrome f shows the complete dipolar trace of a transition-metal ion center and a spin label, yielding the distance expected from the structure.     

掺锡As2S8薄膜光折变效应及其在条波导制备中的应用研究

实验研究了Sn₁As₂₀S₇₉非晶态半导体薄膜的光折变效应及其膜厚变化的现象,归纳了沉积态样品、退火态样品和光饱和态样品的实验规律,提出和采用紫外光激励的方法试制了Sn₁As₂₀S₇₉条形波导,632.8 nm波长导模激励显示该波导具有良好的导波特性. 关键词： 光波导技术 硫属化合物玻璃 光阻断效应 光折变效应     

环氧大豆油与丙交酯星形共聚物支化度的表征

采用凝胶色谱(GPC)/示差检测器(RI)/十八角激光光散射仪(MALLS)联用技术, 对环氧大豆油(ESO)与丙交酯形成的星形共聚物(ESO-丙交酯)的结构进行了表征。实验结果表明: 随着ESO-丙交酯星形共聚物分子量的增长, 接枝数目呈现增多趋势、支化度从0.46E-4增大到0.78E-4、支化因子从0.82减小到0.15。本研究为高分子ESO-丙交酯星形支化共聚物的研究提供了科学依据。