Novel multi-responsive fluorescence switch for Hg2+ and UV/vis lights based on diarylethene-rhodamine derivative

A new multi-responsive fluorescent switch DTE-Pip-Rho 1O has been designed and synthesized in this study. For this molecule, the reactive site of spirolactam ring is far away from the diarylethene unit through the intramolecular piperazine. It exhibited high selectivity and sensitivity to Hg²⁺ in addition to obvious color change (colorless-pink) and fluorescence “off-on” (dark-orange) during this process. It is believed that the color change is due to Hg²⁺-assisted hydrolysis of rhodamine hydrazide. Therefore, the new molecule can be used as colorimentric and fluorescent chemosensor for Hg²⁺ with high selectivity. The detection limits of absorbance and fluorescence for Hg²⁺ were calculated to be 1.15?μM and 1.16?μM, respectively. The resulting DTE-Pip-Rho 1O-Hg²⁺ could also function as a reversible fluorescence photo-switch in response to UV/vis light owing to FRET mechanism. Moreover, it has been demonstrated that the photo-switchable system displayed excellent fatigue resistance and remarkable anti-photobleaching capability.     

WavePacket: A Matlab package for numerical quantum dynamics. III. Quantum-classical simulations and surface hopping trajectories

WavePacket is an open-source program package for numerical simulations in quantum dynamics. Building on the previous Part I (Schmidt and Lorenz, Comput. Phys. Commun. 2017, 213, 223] and Part II (Schmidt and Hartmann, Comput. Phys. Commun. 2018, 228, 229] which dealt with quantum dynamics of closed and open systems, respectively, the present Part III adds fully classical and mixed quantum-classical propagation techniques to WavePacket. There classical phase-space densities are sampled by trajectories which follow (diabatic or adiabatic) potential energy surfaces. In the vicinity of (genuine or avoided) intersections of those surfaces, trajectories may switch between them. To model these transitions, two classes of stochastic algorithms have been implemented: (1) Tully's fewest switches surface hopping and (2) Landau–Zener-based single switch surface hopping. The latter one offers the advantage of being based on adiabatic energy gaps only, thus not requiring nonadiabatic coupling information any more. The present work describes the MATLAB version of WavePacket 6.1.0, which is essentially an object-oriented rewrite of previous versions, allowing to perform fully classical, quantum-classical and quantum-mechanical simulations on an equal footing, that is, for the same physical system described by the same WavePacket input. The software package is hosted and further developed at the Sourceforge platform, where also extensive Wiki-documentation as well as numerous worked-out demonstration examples with animated graphics are available. © 2019 Wiley Periodicals, Inc.     

基于P2 Mo18O6-62@Tb3+溶液可逆变色-荧光开关性质对维生素C和H2O2的光谱检测

基于变色多酸P₂Mo₁₈{\mathrm{O}}_{62}^{6-}与绿光Tb³⁺之间的功能互补及分子间能量转移的原理, 在维生素C(VC)的还原下, P₂Mo₁₈{\mathrm{O}}_{62}^{6-}@Tb³⁺溶液由浅黄色变为蓝色, 发生荧光猝灭; 相反, 在H₂O₂氧化下, 溶液的蓝色褪去, 荧光得以恢复, P₂Mo₁₈{\mathrm{O}}_{62}^{6-}@Tb³⁺溶液呈现出可逆的化学响应变色及荧光开关性质. 利用紫外-可见(UV-Vis)及荧光(PL)光谱法对VC浓度进行定量检测, 分别以800 nm处的吸光度和 547 nm处荧光强度的对数值对VC浓度作图, 获得光谱法对VC检测的线性方程, 检出限分别为3.40×10^-3和0.21 μmol/L; 利用UV-Vis及PL动力学方法对VC和H₂O₂检测的响应速度进行了考察, 响应时间分别为52和320 s; 通过UV-Vis光谱及动力学方法考察了VC检测的选择性及可重复使用性.     

Periodic DFT Study of the Effects of Co-Crystallization on a N-Salicylideneaniline Molecular Switch

This work aims at better understanding the complex effects of co-crystallization on a single salicylideneaniline molecular switch, (E)-2-methoxy-6-(pyridine-3-yliminomethyl)phenol (PYV3), which can tautomerize between an enol and a keto form. A combination of periodic boundary conditions DFT and molecular wavefunction calculations has been adopted for examining a selection of PYV3 co-crystals, presenting hydrogen bonds (H-bonds) or halogen bonds (X-bonds), for which X-ray diffraction data are available. Three aspects are targeted: i) the energy (H-bond strength, enol to keto relative energy, and geometry relaxation energies), ii) the geometrical structure (PYV3 to co-crystal and enol to keto geometrical variations), and iii) the electron distribution (PYV3 to co-crystal and enol to keto Mulliken charge variations). These allow i) explaining the preference for forming H-bonds with the nitrogen of the pyridine of PYV3 with respect to the oxygens and the importance of the crystal field, ii) distinguishing the peculiar behavior of the SulfonylDiPhenol (SDP) coformer, which stabilizes the keto form of PYV3, iii) describing the relative stabilization of the enol form upon co-crystallization (with the exception of SDP) and therefore iv) substantiating the co-crystallization-induced reduction of thermochromism observed for several PYV3 co-crystals.     

Simulation and optimization of a polymer directional coupler electro-optic switch with push-pull electrodes

Structural model and design technique are proposed for a polymer directional coupler electro-optic switch with rib waveguides and push-pull electrodes, of which the electric field distribution is analyzed by the conformal transforming method and image method. In order to get the minimum mode loss and the minimum switching voltage, the parameters of the waveguide and electrode are optimized, such as the core with, core thickness, buffer layer between the core and the electrode, coupling gap between the waveguides, electrode thickness, electrode width and electrode gap. Switching Characteristics are analyzed, which include the output power, insertion loss, and crosstalk. To realize normal switching function, the fabrication error, spectrum shift, and coupling loss between a single mode fiber (SMF) and the waveguide are discussed. Simulation results show that the coupling length is 3082 μm, push-pull switching voltage is 2.14 V, insertion loss is less than 1.17 dB, and crosstalk is less than −30 dB for the designed device.     

Spectral anomalies of focused hollow Gaussian beams at the geometrical focal plane

On the basis of diffraction integral and the expansion of the hard-aperture function into a finite series of complex Gaussian functions, an approximate expression for spatially fully coherent polychromatic hollow Gaussian beams passing through aperture lens is obtained. Detailed numerical results indicate that remarkable spectral changes always occurs near the points where the field amplitude has zero value. The effects of truncation parameter, Fresnel number and the beam order on spectral shifts and spectral switches are investigated numerically.     

Flexible integration of optical switch with optical power splitting and attenuating functions for optical fiber-based networking applications

A flexible integration of optical switch with optical power splitting and attenuating functions has been proposed to optimally serve optical fiber-based networking applications. In this switch, an etched binary-slope sidewall reflector is electrostatically actuated in and out of the plane to manipulate optical signals between input and output optical fibers. The fabrication process is a simple combination of a bulk-silicon micromachining process and silicon-to-glass anodic bonding where fiber alignment grooves, reflectors and actuators are fabricated on the same silicon substrate. Ball-lensed fibers are assembled with the device to achieve high coupling efficiency. Performances of the fabricated devices are measured and discussed. The switching time is less than 9 ms at 31 V. The excess loss of the device is less than 3 dB and the controllable attenuation range is up to 38 dB at 139 V, respectively. Moreover, polarization-dependent loss is less than 0.7 dB in the whole attenuation and splitting range.     

Ultrafast dynamics and temperature effects on the quantum efficiency of the ring-opening reaction of a photochromic indolylfulgide

The ultrafast ring-opening reaction of the molecular switch 1,2-Dimethyl-3-indolylfulgide dissolved in acetonitrile is investigated by temperature dependent quantum efficiency measurements and time-resolved transient absorption spectroscopy in the ultraviolet and visible spectral range. The photoreaction is found to be thermally activated with an activation energy of about 1640 cm^− 1. The transient absorption signal is bi-exponential with the time constants τ₁ = 0.7 ps and τ₂ = 12 ps. The fast time constant is due to solvation dynamics, while the main component τ₂ is attributed to the excited state lifetime and product formation. A long-lived intermediate state in the photoreaction can be excluded.     

基于磁开关的全固态、高功率、长脉冲发生器的初步研究

大多数电容储能型脉冲功率装置的共同特点是采用了气体开关, 由于气体绝缘恢复的限制和电极的烧蚀, 使得其重复频率都不太高, 而且寿命有限. 而目前广泛研究的磁脉冲压缩技术在脉冲功率系统的长寿命、高平均功率和高重复频率运行方面具有很大的应用前景. 通过对BOOST电路、LC谐振电路和磁脉冲压缩电路详细的理论分析和计算机模拟, 设计了由BOOST电路, LC谐振电路, 脉冲变压器, 磁压缩系统, 负载五大部分组成的脉冲发生器电路系统模型, 使用Pspice软件对系统进行了模拟、优化, 得到了电压幅值为55kV, 脉宽为500ns的输出脉冲.     

衍射扭曲高斯-谢尔模型光束在远场的光谱移动和光谱开关

从部分相干光的传输理论出发,研究了被光阑衍射扭曲高斯-谢尔模型光束远场的光谱变化规律。结果表明,扭曲高斯-谢尔模型光束在远场也会出现光谱移动和光谱开关效应。与衍射高斯-谢尔模型光束情况相比,光谱移动和光谱开关效应不仅与光束空间相关性、截断参量和源光谱谱宽有关,光束的扭曲因子也会对衍射扭曲高斯-谢尔模型光束远场的光谱移动和光谱开关效应产生影响。通过数值计算结果详细讨论了光束扭曲因子影响衍射扭曲高斯-谢尔模型远场光谱的规律。