Molecular dynamics of the intramolecular 1, 3-dipolar ene reaction of a nitrile oxide and an alkene: non-statistical behavior of a reaction involving a diradical intermediate*

ABSTRACT

Potential energy surfaces and molecular dynamics of the intramolecular 1, 3-dipolar cycloaddition and ene reaction of a nitrile oxide with an alkene were performed in the gas phase and in dichloromethane with density functional theory. One hundred trajectories were propagated in the gas phase and in dichloromethane, respectively. Twenty percent of the trajectories in the gas phase involve bicyclic intermediate and the mean time gap is 472fs. A dynamically stepwise reaction is observed. In dichloromethane, more reactive trajectories were obtained and the time gap is larger than that in the gas phase.     

The maximum multiplicity of the largest k-th eigenvalue in a matrix whose graph is acyclic or unicyclic

Given a graph $G$ we are interested in studying the symmetric matrices associated to $G$ with a fixed number of negative eigenvalues. For this class of matrices we focus on the maximum possible nullity. For trees this parameter has already been studied and plenty of applications are known. In this work we derive a formula for the maximum nullity and completely describe its behavior as a function of the number of negative eigenvalues. In addition, we also carefully describe the matrices associated with trees that attain this maximum nullity. The analysis is then extended to the more general class of unicyclic graphs. Further our work is applied to re-describing all possible partial inertias associated with trees, and is employed to study an instance of the inverse eigenvalue problem for certain trees.     

基于气象卫星云图的红外吸收带火山特征分析

飞行目标在2.7和4.3 μm谱段附近具有较强的红外辐射，因此这两个波段是探测飞行目标的最佳波段, 但是由于这两个波段并非大气窗口，不被大多数遥感器包含。对这两个谱段的典型地物特性开展研究具有重要的价值，但由于缺乏必要的数据获取能力，经常面临数据缺乏的问题。世界范围内频频有各种程度的火山爆发，火山爆发时温度较高的火山口，是否对于天基红外探测系统典型目标探测有影响，其影响程度如何一直缺乏相关的分析和研究。基于大气辐射传输理论，利用多元统计分析得到波段转换模型，使用气象卫星已有波段获得红外吸收谱段数据。将火点像元视为明火和背景的混合像元，采用目标与背景分离的方式描述高温目标像元的热辐射。对高温目标辐射量，在气溶胶模式固定的情况下，选取观测天顶角、大气可降水量、大气廓线为自变量影响因子。对于背景辐射亮度关系，选取观测天顶角、大气可降水量、大气廓线、背景温度为自变量影响因子, 利用多元统计，建立相关模型。利用对地面热状态非常敏感的风云三号可见光红外扫描辐射计第3通道数据的统计特征探测火山口，获取高温目标在特定波段的表观多维特征并定量分析。火山的多维特征分析，主要从时间和空间两个维度展开。时间维度是对同一火山在不同时间的数据进行分析，空间维度上，主要统计火山口的辐射亮度和亮度温度的空间分布特征。一般气象卫星分辨率较低，单纯利用像元个数表示火山面积, 明显夸大了火山的实际面积，所以基于亚像元特性对火山进行分析，将混合像元火点视为明火和背景的组合，运用线性光谱混合模型，通过混合像元的辐射率精确计算火山高温点的面积和温度，提高定量分析精度。分析结果表明： 通过仿真手段结合多元统计分析方法建立高温目标的波段转换模型是一种可行的预研手段。在2.7~2.95 μm谱段，火山口在弱背景环境下可能会对高温目标造成干扰，而在4.2~4.45 μm谱段，火山口能量远高于一般地表类型，是不可忽视的干扰。     

The Hydrogen Bond and Beyond: Perspectives for Rotational Investigations of Non-Covalent Interactions

In the last decade, experiment and theory have expanded our vision of non-covalent interactions (NCIs), shifting the focus from the conventional hydrogen bond to new bridging interactions involving a variety of weak donor/acceptor partners. Whereas most experimental data originate from condensed phases, the introduction of broadband (chirped-pulse) microwave fast-passage techniques has revolutionized the field of rotational spectroscopy, offering unexplored avenues for high-resolution studies in the gas phase. We present an outlook of hot topics for rotational investigations on isolated intermolecular clusters generated in supersonic jet expansions. Rotational spectra offer very detailed structural data, easily discriminating the isomeric or isotopic composition and effectively cancelling any solvent, crystal, or matrix bias. The direct comparison with quantum mechanical predictions provides insight into the origin of the inter- and intramolecular interactions with much greater precision than any other spectroscopic technique, simultaneously serving as test-bed for fine-tuning of theoretical methods. We present recent examples of rotational investigations around three topics: oligomer formation, chiral recognition, and identification of halogen, chalcogen, pnicogen, or tetrel bonds. The selected examples illustrate the benefits of rotational spectroscopy for the structural and energetic assessment of inter-/intramolecular interactions, which may help to move from fundamental research to applications in supramolecular chemistry and crystal engineering.     

Oxidative dehydrogenation of n-octane over a vanadium–magnesium oxide catalyst: Influence of the gas hourly space velocity

Oxidative dehydrogenation (ODH) of n-octane was carried out over a vanadium–magnesium oxide catalyst in a continuous flow fixed bed reactor. The catalyst was characterized by ICP–OES, powder XRD and SEM. The catalytic tests were carried out at different gas hourly space velocities (GHSVs), viz. 4000, 6000, 8000, and 10,000 h^?1. The best selectivity for octenes was obtained at the GHSV of 8000 h^?1, while that for C8 aromatics was attained at the GHSV of 6000 h^?1 at high temperatures (500 and 550 °C). The catalytic testing at the GHSV of 10,000 h^?1 showed the lowest activity, while that at the GHSV of 4000 h^?1 consistently showed the lowest ODH selectivity. Generally, the best ODH performance was obtained by the catalytic testing at the GHSVs of 6000 and 8000 h^?1. No phasic changes were observed after the catalytic testing.     

New lower bounds on the radius of spatial analyticity for the KdV equation

The radius of spatial analyticity for solutions of the KdV equation is studied. It is shown that the analyticity radius does not decay faster than $t^{?1/4}$ as time t goes to infinity. This improves the works of Selberg and da Silva (2017) [30] and Tesfahun (2017) [34]. Our strategy mainly relies on a higher order almost conservation law in Gevrey spaces, which is inspired by the I-method.     

Preparation,structure elucidation,and antioxidant activity of new bis(thiosemicarbazone) derivatives

Schiff-base–bearing new bis(thiosemicarbazone) derivatives were prepared from terephthalaldehyde and various thiosemicarbazides. FT–IR, ¹H NMR, ¹³C NMR, and UV–Vis spectroscopic methods and elemental analysis were used to elucidate the identification of the synthesized molecules. The in vitro antioxidant activity of the synthesized compounds was analysed with the 1,1-diphenyl-2-picryl hydrazyl free-radical–trapping process. The synthesized compounds exhibited lower antioxidant activity than the standard ascorbic acid. IC₅₀ values of the synthesized molecules measured from 3.81 ± 0.01 to 29.05 ± 0.11 μM. Among the synthesized compounds, compound 3 had the best antioxidant activity. Moreover, this study explained the structure–activity relationship of the synthesized molecules with different substituents in radical trapping reactions.     

Distinguishability and Disturbance in the Quantum Key Distribution Protocol Using the Mean Multi-Kings’ Problem

We introduce a quantum key distribution protocol using mean multi-kings’ problem. Using this protocol, a sender can share a bit sequence as a secret key with receivers. We consider a relation between information gain by an eavesdropper and disturbance contained in legitimate users’ information. In BB84 protocol, such relation is known as the so-called information disturbance theorem. We focus on a setting that the sender and two receivers try to share bit sequences and the eavesdropper tries to extract information by interacting legitimate users’ systems and an ancilla system. We derive trade-off inequalities between distinguishability of quantum states corresponding to the bit sequence for the eavesdropper and error probability of the bit sequence shared with the legitimate users. Our inequalities show that eavesdropper’s extracting information regarding the secret keys inevitably induces disturbing the states and increasing the error probability.