添加氢化钙合成高分子量聚对苯二甲酰对苯二胺的研究

研究使用氢化钙代替吡啶作为酸吸收剂合成高分子量聚对苯二甲酰对苯二胺(PPTA),并与以吡啶作酸吸收剂的聚合产物进行对比以评估该研究的应用前景.尝试以氢化钙代替吡啶,考察氢化钙的加入对TPC与PPD的聚合过程及聚合产物分子量和结构的影响.研究结果表明,添加氢化钙可以聚合出高分子量PPTA.元素分析、X-射线衍射及红外光谱分析结果表明,使用氢化钙和吡啶作为酸吸收剂合成的PPTA在元素含量和结构上均相同.热重分析结果表明,使用两种酸吸收剂得到的PPTA的热分解温度都在550℃左右.这些研究结果初步证明使用氢化钙代替吡啶进行高分子量PPTA工业聚合是可行的.     

非高斯单因子短期利率模型正则化参数估计

应用正则化方法估计带约束条件非高斯单因子短期利率模型中含时间变量参数估计.基于变分原理,证明该正则化方法具有稳定性和收敛性.由于该问题是一个带有约束条件的反问题,本文应用罚方法把原问题转化为非约束条件问题以方便计算.最后,通过数值模拟确认该算法的有效性并给出实证结果.     

奇异积分算子交换子在变指数空间上的特征

The main purpose of this paper is to characterize the Lipschitz space by the boundedness of commutators on Lebesgue spaces and Triebel-Lizorkin spaces with variable exponent.Based on this main purpose, we first characterize the Triebel-Lizorkin spaces with variable exponent by two families of operators. Immediately after, applying the characterizations of TriebelLizorkin space with variable exponent, we obtain that b ∈■β if and only if the commutator of Calderón-Zygmund singular integral operator is bounded, respectively, from■ to■,from■ to■ with■. Moreover, we prove that the commutator of Riesz potential operator also has corresponding results.     

肋板结构受压构件的剪力滞效应分析

建立了肋板结构受压构件考虑剪力滞效应时的微分方程,并以该微分方程的解作为位移插值函数,得到了较为精确的有限段单元刚度矩阵,数值算例证明本方法具有好的精度,且具有一维有限元法的便利和广泛适应性。     

基于改进最小方差无失真响应角度谱算法的 气体泄漏定位方法*

针对噪声环境下微小气体泄漏难以准确定位的问题,提出了一种基于改进最小方差无失真响应角度谱算法的气体泄漏定位方法。该算法通过引入信噪比追踪加权的方式,提取受噪声影响较小且单个声源能量占优的时频支撑域,并通过Softplus激活函数自适应地调整不同频率分量对角度谱函数的贡献,增加泄漏声源占优的时频域权重;此外,引入基于时频稀疏性的分频带处理,使各子频带内存在一个主导声源能量占优,抑制低频段噪声能量的积累同时避免高频混叠现象。通过软件仿真计算以及实验验证算法的性能,结果表明改进最小方差无失真响应角度谱算法可以实现气体泄漏源的精准定位,定位结果的最大误差在3.5°以内。相比传统算法,该方法在低信噪比和低采样点数下有更高的稳定性、抗噪能力及准确率,可为气体泄漏定位的实际应用提供一定的参考价值。     

Construction of a MOF-Supported Palladium Catalyst via Metal Metathesis

A new MOF-supported heterogeneous palladium catalyst Pd/NBB-1 has been synthesized successfully through the effective metal metathesis between Pd(CF₃COO)₂ and NBB-1. NBB-1 is a two-dimensional zinc metal-organic framework constructed from 2-aminoterephthalate (NH₂−H₂BDC) and 2,2′-bipyridine-5-carboxylate (HBPC) by solvothermal method. The replacement efficiency of Pd(II) to Zn(II) is up to 72% after only 24 hours, which is beneficial to the catalytic application. Pd/NBB-1 with a low loading of 2 mol% works efficiently in the 1,4-addition reaction of arylboronic acids with α,β-unsaturated ketones in air, and its catalytic activity keeps unchanged after 3 reaction cycles. This work provides a new strategy to effectively prepare supported noble metal/MOF catalysts, which would further increase the practical applications of metal-organic frameworks.     

Red Emissive Double Aza[7]helicenes with Antiaromaticity / Aromaticity Switching via the Redox-Induced Radical Cation and Dication Species

We herein present the synthetic approach to a new antiaromatic double aza[7]helicene C that features NN-embedded polycyclic aromatic hydrocarbons (PAHs). This heteroatom-doped helicene showed a rarely obtained long-wavelength emission and far-red circularly polarized luminescence (CPL) in the solid state. These optical and chiroptical properties could be ascribed to both the NN-PAH core structure and the further extension through angular ring fusions. Such a unique electronic structure also culminated in facile chemical oxidations of neutral C to the positively charged chiral radical ( C ⋅⁺) and dication species ( C ²⁺). Interestingly, DFT computations revealed that the pyridazine central core showed an antiaromaticity-to-aromaticity switching, in contrast to the inversed transition for the helical periphery in cationic states. The reported approaches are anticipated to lead to the development of further redox-active chiral systems for potential applications in chiroptoelectronics, spintronics as well as fluorescent bioimaging.     

Frontier Molecular Orbital Engineering: Constructing Highly Efficient Narrowband Organic Electroluminescent Materials

It is of great strategic significance to develop highly efficient narrowband organic electroluminescent materials that can be utilized to manufacture ultra-high-definition (UHD) displays and meet or approach the requirements of Broadcast Television 2020 (B.T.2020) color gamut standards. This motif poses challenges for molecular design and synthesis, especially for developing generality, diversity, scalability, and robustness of molecular structures. The emergence of multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters has ingeniously solved the problems and demonstrated bright application prospects in the field of UHD displays, sparking a research boom. This Minireview summarizes the research endeavors of narrowband organic electroluminescent materials, with emphasis on the tremendous contribution of frontier molecular orbital engineering (FMOE) strategy. It combines the outstanding advantages of MR framework and donor-acceptor (D−A) structure, and can achieve red-shift and narrowband emission simultaneously, which is of great significance in the development of long-wavelength narrowband emitters with emission maxima especially exceeding 500 nm. We hope that this Minireview would provide some inspiration for what could transpire in the future.     

Linking Composition,Structure and Thickness of CoOOH layers to Oxygen Evolution Reaction Activity by Correlative Microscopy

The role of β-CoOOH crystallographic orientations in catalytic activity for the oxygen evolution reaction (OER) remains elusive. We combine correlative electron backscatter diffraction/scanning electrochemical cell microscopy with X-ray photoelectron spectroscopy, transmission electron microscopy, and atom probe tomography to establish the structure–activity relationships of various faceted β-CoOOH formed on a Co microelectrode under OER conditions. We reveal that ≈6 nm β-CoOOH(01 0), grown on [ 0]-oriented Co, exhibits higher OER activity than ≈3 nm β-CoOOH(10 3) or ≈6 nm β-CoOOH(0006) formed on [02 - and [0001]-oriented Co, respectively. This arises from higher amounts of incorporated hydroxyl ions and more easily reducible Co^III−O sites present in β-CoOOH(01 0) than those in the latter two oxyhydroxide facets. Our correlative multimodal approach shows great promise in linking local activity with atomic-scale details of structure, thickness and composition of active species, which opens opportunities to design pre-catalysts with preferred defects that promote the formation of the most active OER species.