Nucleophilic Activation of Sulfur Hexafluoride by N-Heterocyclic Carbenes and N-Heterocyclic Olefins: A Computational Study

Sulfur hexafluoride (SF₆) is considered as a potent greenhouse gas, whose effective degradation is challenging. Here we report a computational study on the nucleophilic activation of sulfur hexafluoride by N-heterocyclic carbenes and N-heterocyclic olefins. The result shows that the activation of SF₆ is both thermodynamically and kinetically favorable at mild condition using NHOs with fluoro-substituted azolium and sulfur pentafluoride anion being formed. The Gibbs free energy barrier during the activation of SF₆ has a linear relationship with the energy of HOMO of substrates, which could be a guideline for applying those compounds that feature higher energy in HOMO to activate SF₆ in high efficiency.     

Spatially modulated polarimetry based on a vortex retarder and Fourier analysis

We report a spatially modulated polarimetry scheme by using a zero-order vortex half-wave retarder(ZVHR)and a spatial Fourier analysis method.A ZVHR is employed to analyze the input polarized light and convert it into a vectorial optical field,and an analyzer is set after the ZVHR to form an hourglass intensity pattern due to the spatial polarization modulation.Then,the input light’s Stokes parameters can be calculated by spatial Fourier analysis of the hourglass pattern with a single shot.The working principle of the polarimeter has been analyzed by the Stokes-Mueller formalism,and some quantitative measuring experiments of different polarization states have been demonstrated.The experimental results indicate that the proposed polarimeter is accurate,robust,and simple to use.     

A Ru(II)-Based Nanoassembly Exhibiting Theranostic PACT Activity in NIR Region

Photoactivated chemotherapy (PACT) has appealing merits over traditional chemotherapy as well as photodynamic therapy (PDT) by virtue of its spatial and temporal control on drug activity and oxygen-independent mechanisms of action. However, the short photoactivation wavelengths, e.g., visible light–activated Ru(II)-based PACT agents, limit the clinical application severely. In this work, a facile construction of supramolecular nanoparticles from a poly(ethylene glycol) (PEG)-modified [Ru(dip)₂(py-SO₃)]⁺ (abbreviated as Ru-PEG, dip = 4,7-diphenyl-1,10-phenanthroline, py-SO₃ = pyridine-2-sulfonate) and 1,3-phenylenebis(pyren-1-ylmethanone) (BP) is shown. While Ru-PEG may undergo photoinduced ligand dissociation and release anticancer species of [Ru(dip)₂(H₂O)₂]²⁺, BP has extremely large two-photon absorption cross sections (δ₂) in the NIR region and intense fluorescence over the wavelengths where Ru-PEG has strong absorption. Thus, two-photon excitation of BP followed by an efficient Förster resonance energy transfer (FRET) from BP to Ru-PEG may lead to a potent inactivation against cisplatin-resistant cancer cells and 3D multicellular tumor spheroids (MCTSs). The residue fluorescence of BP also allows the cellular uptake of the particles to be visualized. This work provides a universal and convenient strategy to realize theranostic PACT in the ideal phototherapeutic window of 650–900 nm.     

三维位势问题的梯度边界积分方程的新解法

三维位势问题的边界元分析中,关于坐标变量的边界位势梯度的计算是一个困难的问题. 已有一些方法着手解决这个问题,然而,这些方法需要复杂的理论推导和大量的数值计算. 本文提出求解一般边界位势梯度边界积分方程的辅助边值问题法. 该方法构造了与原边界值问题具有相同解域的辅助边值问题,该辅助边值问题具有已知解,因此通过求解此辅助边值问题,可获得梯度边界积分方程对应的系统矩阵,然后将此系统矩阵应用于求解原边值问题,求解过程非常简单,只需求解一个线性系统即可获得原边值问题的解. 值得注意的是,在求解原边值问题时,不再需要重新计算系统矩阵,因此辅助边值问题法的效率并不很差. 辅助边值问题法避免了强奇异积分的计算,具有数学理论简单、程序设计容易、计算精度高等优点,为坐标变量梯度边界积分方程的求解提供了一个新的途径. 3个标准的数值算例验证了方法的有效性.